Sulfonate, oxime sulfonate, imide sulfonate, amide sulfonate, acid generating agent containing said compound, and photoresist containing said acid generating agent

Abstract

Provided are new compounds that are free of perfluoromethyl and perfluoromethylene groups, are easily decomposed by light irradiation, and generate sulfonic acid having high acid strength.　The present invention is a compound that is a salt of an anion represented by formula (a-1) or (a-2) and a cation. In the formula, R1 represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group, or a group in which two or more of said groups are bonded via a linking group. R10 represents a fluorine atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group. R20 represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, an optionally substituted heterocyclic group, or a group having a group in which said group and a linking group are bonded. n is 0 or 1.

Description

Sulfonates, oximesulfonates, imidosulfonates, amidosulfonates, acid generators containing the compounds, and photoresists containing the acid generators

[0001] The present invention relates to a novel sulfonate, a novel oxime sulfonate, a novel imide sulfonate, a novel amido sulfonate, an acid generator containing the novel compound, and a photoresist containing the acid generator.

[0002] Compounds that decompose upon irradiation with light to generate acid (so-called acid generators) are used in various fields. For example, in the field of semiconductor resists, they are used to change the solubility in a developer of chemically amplified resists used in photolithography. Furthermore, in the fields of paints, adhesives, casting materials for various parts, sealing materials, and the like, they are used to initiate cationic polymerization of cationic curable compounds and cause them to cure.

[0003] Known examples of the acid generator include compounds represented by the following formulae (X-1) and (X-2) (see Patent Documents 1 and 2). These compounds have a perfluoromethyl group or a perfluoromethylene group at the α-position of the sulfonic acid group, and are therefore capable of generating sulfonic acid with high acid strength.

[0004] JP 2006-306856 A JP 2008-297255 A

[0005] However, in Europe, due to the strengthening of PFAS (Per and Polyfluoroalkyl Substances) regulations, the use of compounds having a perfluoromethyl group or a perfluoromethylene group, such as the compounds represented by the formulas (X-1) and (X-2), is restricted, and alternatives are being sought.

[0006] Therefore, an object of the present invention is to provide a novel compound that does not have a perfluoromethyl group or a perfluoromethylene group and that easily decomposes upon irradiation with light to generate a sulfonic acid having high acid strength. Another object of the present invention is to provide an acid generator containing the novel compound. Another object of the present invention is to provide a photoresist containing the acid generator. Another object of the present invention is to provide a method for producing an electronic device or an optical device using the photoresist.

[0007] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, it was found that compounds that are salts of anions represented by the following formulas (a-1) or (a-2) with cations, compounds represented by the following formulas (b-1) or (b-2), compounds represented by the following formulas (c-1) or (c-2), and compounds represented by the following formulas (d-1) or (d-2) all do not have a perfluoromethyl group or a perfluoromethylene group at the α-position of the sulfonic acid group, but decompose upon irradiation with light to generate sulfonic acids with high acid strength. The present invention was completed based on these findings.

[0008] That is, the present invention provides a compound which is a salt of an anion represented by the following formula (a-1) or (a-2) and a cation: (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0009] The present invention also provides a compound represented by the following formula (b-1) or (b-2): (In the formula, R １R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ２ , R ３ are the same or different and represent an organic group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0010] The present invention also provides a compound represented by the following formula (c-1) or (c-2): (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ４ , R ５ R may be the same or different and represent a hydrocarbon group which may have a substituent. ４ , R ５ may be bonded to each other to form a ring together with the adjacent carbon atoms. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group is bonded to a linking group. L represents a single bond or a linking group. n represents 0 or 1.

[0011] The present invention also provides a compound represented by the following formula (d-1) or (d-2): (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ６ , R ７R may be the same or different and represent a hydrocarbon group which may have a substituent. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0012] The present invention also provides an acid generator containing the compound.

[0013] The present invention also provides a photoresist comprising the acid generator and an acid-reactive compound.

[0014] The present invention also provides a method for producing an electronic device or an optical device, which comprises a step of forming a pattern by photolithography using the photoresist.

[0015] The compounds of the present invention are compounds that are salts of anions represented by formula (a-1) or (a-2) and cations, compounds represented by formula (b-1) or (b-2), compounds represented by formula (c-1) or (c-2), and compounds represented by formula (d-1) or (d-2), and are compounds that rapidly decompose upon irradiation with light to generate sulfonic acids represented by formula (A-1) or (A-2) described below. The compounds of the present invention are capable of generating sulfonic acids having acid strengths equal to or greater than those generated by conventional acid generators having perfluoromethyl and perfluoromethylene groups. Furthermore, by using a photoresist containing a compound having the above properties, it is possible to produce resist films having high-resolution patterns with good precision. Furthermore, by using the obtained resist film to subject a substrate to etching (e.g., dry etching using a reactive gas or plasma), it is possible to produce semiconductor devices having high-resolution patterns (e.g., wiring patterns, circuit patterns, etc.) with good yield.

[0016] [Sulfonate] The sulfonate of the present invention is a compound that is a salt of an anion represented by the following formula (a-1) or (a-2) and a cation. (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0017] The hydrocarbon group includes a (monovalent) aliphatic hydrocarbon group, a (monovalent) alicyclic hydrocarbon group, a (monovalent) aromatic hydrocarbon group, and a (monovalent) group formed by combining these groups.

[0018] The aliphatic hydrocarbon group may be a group having 1 to 20 carbon atoms (=C １－２０ The aliphatic hydrocarbon group includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms (=C １－２０ ) saturated aliphatic hydrocarbon groups are preferred, and examples thereof include alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. The unsaturated aliphatic hydrocarbon groups include alkyl groups having 2 to 20 carbon atoms (=C ２－２０ ) unsaturated aliphatic hydrocarbon groups are preferred, and examples thereof include alkenyl groups having 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as a vinyl group, an allyl group, or a 1-butenyl group; and alkynyl groups having 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as an ethynyl group or a propynyl group.

[0019] The alicyclic hydrocarbon group includes C ３－２０Alicyclic hydrocarbon groups are preferred, and examples thereof include 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl group, adamantyl group, tricyclo[5.2.1.0] group, and the like. ２，６ ] decan-8-yl group, tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ] Bridged cyclic hydrocarbon groups such as dodecan-3-yl group and the like are also included.

[0020] The aromatic hydrocarbon group may be C ６－１４ (Especially C ６－１０ ) Aromatic hydrocarbon groups are preferred, such as phenyl and naphthyl groups.

[0021] Examples of the monovalent group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include C groups such as a benzyl group and a phenylethyl group. ７－１８ Examples include an aralkyl group.

[0022] Furthermore, an aromatic or non-aromatic heterocyclic ring may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

[0023] Examples of the substituent that the hydrocarbon group may have include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (e.g., C １－４ Alkoxy group, C ６－１０ Aryloxy group, C ７－１６ Aralkyloxy group, C １－４ acyloxy group, etc.), a thio group, a substituted thio group (e.g., a C １－６ Alkylthio group, C ６－１０ arylthio group, and the substituents include, for example, a hydroxyl group, a cyano group, an alkoxy group, a hydroxyalkoxy group, a sulfo group, a carboxyl group, and the like), a carboxyl group, a substituted oxycarbonyl group (for example, C １－４ Alkoxycarbonyl group, C ６－１０ Aryloxycarbonyl group, C７－１６ aralkyloxycarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, etc. １－６ C such as an aliphatic acyl group, an acetoacetyl group, or a benzoyl group ７－１４ aromatic acyl group), substituted or unsubstituted carbamoyl group (e.g., carbamoyl, methylcarbamoyl, etc. １－４ C such as alkyl-substituted carbamoyl and phenylcarbamoyl groups ６－１０ Examples of the hydrocarbon group include a group containing a perfluoromethyl group or a perfluoromethylene group (e.g., C １－１０ It may have a haloalkyl group.

[0024] The heterocyclic group is a monovalent heterocyclic group. A monovalent heterocyclic group is a group obtained by removing one hydrogen atom from the structural formula of a heterocycle. The heterocycle includes aromatic heterocycles and non-aromatic heterocycles. The heterocycle constituting the heterocyclic group includes aromatic heterocycles and non-aromatic heterocycles. Examples of such heterocycles include 3- to 20-membered rings (preferably 3- to 10-membered rings, particularly preferably 4- to 6-membered rings) having carbon atoms and at least one heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) as ring-constituting atoms, and condensed rings thereof. Specifically, heterocycles containing an oxygen atom as a heteroatom (for example, three-membered rings such as an oxirane ring; four-membered rings such as an oxetane ring; five-membered rings such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, and a γ-butyrolactone ring; six-membered rings such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring, and a morpholine ring; fused rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-chromene ring, a chroman ring, and an isochroman ring; 3-oxatricyclo[4.3.1.1 ４，８ ] undecan-2-one ring, 3-oxatricyclo[4.2.1.0 ４，８] nonan-2-one ring and the like), heterocycles containing a sulfur atom as a heteroatom (for example, 5-membered rings such as a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, and the like; 6-membered rings such as a 4-oxo-4H-thiopyran ring, and the like; fused rings such as a benzothiophene ring, and the like), heterocycles containing a nitrogen atom as a heteroatom (for example, 5-membered rings such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring, and the like; 6-membered rings such as an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, and the like; indole ring, indoline ring, quinoline ring, acridine ring, a naphthyridine ring, a quinazoline ring, and a fused ring such as a purine ring, and the like).

[0025] The substituent that the heterocyclic group may have includes, in addition to the substituent that the hydrocarbon group may have, alkyl groups (e.g., C groups such as methyl groups and ethyl groups). １－４ alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, 1-butenyl groups, etc.) ２－４ alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc. ２－４ alkynyl group, etc.), C ３－８ cycloalkyl groups, aryl groups (e.g., phenyl groups, naphthyl groups, biphenyl groups, etc.) ６－１５ aryl groups) and the like.

[0026] The R １ As the sulfonic acid group, a group having a molecular weight of 100 or more (for example, 100 to 200, preferably 100 to 150) is preferred, since this group suppresses the diffusibility of the generated sulfonic acid and has the effect of improving pattern resolution when used in a photoresist.

[0027] The R １ is preferably a saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a group in which two or more of the above groups are linked via a linking group.

[0028] The linking group is a divalent group having one or more atoms, and examples thereof include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), a sulfonyl group (—SO ２ -), an ester bond (-COO- or -OCO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and a group in which a plurality of these bonds are linked together.

[0029] Examples of the divalent hydrocarbon group include groups obtained by removing one hydrogen atom from the structural formula of the monovalent hydrocarbon group. Among these, for example, C groups such as methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, and trimethylene group are preferred. １－５ Alkylene group; C such as cyclopentylene group, cyclohexylene group ３－６ Cycloalkylene group: C such as phenylene group, phenylenebis(methylene) group, biphenylene group, naphthylene group ６－１０ An arylene group is preferred.

[0030] Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the structural formula of the heterocycle. Among these, groups in which two hydrogen atoms have been removed from the structural formula of a heterocycle containing a nitrogen atom as a heteroatom, such as a pyridylene group or a quinolylene group, are preferred.

[0031] The divalent hydrocarbon group or the divalent heterocyclic group may have an electron-withdrawing group (e.g., a carboxyl group, １－５ Alkyl ester group, nitro group, halogen atom, C １－１４ It may have an alkyl group such as an acyl group, a cyano group, a tosyl group, or a mesyl group.

[0032] The linking group is preferably an ether bond (-O-) or an ester bond (-COO- or -OCO-).

[0033] The R １０ The aromatic hydrocarbon group in is a monovalent aromatic hydrocarbon group, and C ６－１４ (Especially C ６－１０) Aromatic hydrocarbon groups are preferred, and examples thereof include a phenyl group and a naphthyl group. The aromatic hydrocarbon group may have a substituent. Examples of the substituent include the same examples as the substituents that the hydrocarbon group may have (e.g., a halogen atom, etc.).

[0034] The R １０ The aromatic heterocyclic group in the formula (I) is a monovalent aromatic heterocyclic group, which is a group obtained by removing one hydrogen atom from the structural formula of an aromatic heterocyclic ring. Examples of the aromatic heterocyclic ring include five-membered rings such as a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a furan ring, and a thiophene ring; six-membered rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring; and condensed rings such as a quinoline ring and a benzofuran ring. The aromatic heterocyclic group may have a substituent. Examples of the substituent include the same examples as the substituents that the heterocyclic group may have (e.g., alkyl groups, etc.).

[0035] The R １０ Among these, a fluorine atom or an aromatic hydrocarbon group which may have a substituent is preferred, and a fluorine atom is particularly preferred, in that it has excellent photosensitivity and generates a sulfonic acid with high acid strength, thereby improving the resolution of the photoresist.

[0036] The R ２０ represents a hydrogen atom or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), or a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, or a group in which the above group and a linking group are bonded. ２０ The hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the linking group in １ These are the same as the hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the linking group in the above R ２０In the formula (I), the group having a group in which the group and a linking group are bonded is a monovalent group having a group in which one or more of the groups (hydrocarbon groups which may have a substituent, heterocyclic groups which may have a substituent) and one or more of the linking groups are bonded, and may be a group in which two or more of the groups (hydrocarbon groups which may have a substituent, heterocyclic groups which may have a substituent) are bonded via the linking group, a group in which one of the groups (hydrocarbon groups which may have a substituent, heterocyclic groups which may have a substituent) is bonded to the linking group, or a group in which the linking group is bonded to a group in which two or more of the groups (hydrocarbon groups which may have a substituent, heterocyclic groups which may have a substituent) are bonded via the linking group.

[0037] R in formula (a-1) ２０ Among these, a halogen atom, or a group in which an alicyclic hydrocarbon group or an aliphatic hydrocarbon group is bonded to an aliphatic hydrocarbon group or an aromatic hydrocarbon group via a linking group, or a group in which an alicyclic hydrocarbon group is bonded to a linking group, is preferred, from the viewpoint of having excellent photosensitivity and generating a sulfonic acid with high acid strength, thereby obtaining the effect of improving the resolution of a photoresist; a chlorine atom or bromine atom, or a group in which an alicyclic hydrocarbon group is bonded to an aliphatic hydrocarbon group via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group via an ester bond, or a group in which two or more aliphatic hydrocarbon groups are bonded to an ester group, or a group in which an alicyclic hydrocarbon group is bonded to an ester group is particularly preferred; and a chlorine atom, or a group in which an alicyclic hydrocarbon group is bonded to an aliphatic hydrocarbon group via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group via an ester bond, or a group in which two or more aliphatic hydrocarbon groups are bonded to an ester group, or a group in which an alicyclic hydrocarbon group is bonded to an —OCO— is particularly preferred.

[0038] R in formula (a-2) ２０Among these, a hydrogen atom, or a group in which an alicyclic hydrocarbon group or an aliphatic hydrocarbon group is bonded to an aliphatic hydrocarbon group or an aromatic hydrocarbon group via a linking group, or a group in which an alicyclic hydrocarbon group is bonded to a linking group, is preferred, in that they have excellent photosensitivity and generate a sulfonic acid with high acid strength, thereby achieving the effect of improving the resolution of the photoresist. Particularly preferred are a hydrogen atom, or a group in which an alicyclic hydrocarbon group is bonded to an aliphatic hydrocarbon group via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group via an ester bond, or a group in which two or more aliphatic hydrocarbon groups are bonded to each other via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to -OCO-.

[0039] Therefore, as the anion represented by the formula (a-1) where n=0, an anion represented by the following formula (a-1a-1) or (a-1a-2) is preferred, and an anion represented by the following formula (a-1a-3) or (a-1a-4) is particularly preferred. １０ is the same as above.

[0040] In the formulas (a-1a-1) and (a-1a-3), X represents a halogen atom. The halogen atom is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom, in that it has the effect of improving the resolution of the photoresist.

[0041] In the formulas (a-1a-1) and (a-1a-3), R １ａ represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a group in which two or more hydrocarbon groups are bonded via a linking group. １ａ is preferably a hydrogen atom, an optionally substituted saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, or a group in which two or more of the above groups are linked via a linking group, in that it has the effect of improving the resolution of the photoresist, and is most preferably a optionally substituted saturated aliphatic hydrocarbon group.

[0042] In the formulas (a-1a-1) and (a-1a-3), R １ｂrepresents a hydrogen atom, a hydrocarbon group which may have a substituent, or a group in which two or more hydrocarbon groups are bonded via a linking group. １ｂ is preferably a hydrogen atom, an optionally substituted saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, or a group in which two or more of the above groups are linked via a linking group, in that the effect of improving the resolution of the photoresist is obtained, and is most preferably a hydrogen atom.

[0043] As the anion represented by the formula (a-1) where n=1, anions represented by the following formula (a-1b-1) or (a-1b-2) are preferred. As the anion represented by the following formula (a-1b-1), anions represented by the following formulas (a-1b-3) to (a-1b-5) are particularly preferred. As the anion represented by the following formula (a-1b-2), an anion represented by the following formula (a-1b-6) is particularly preferred. In the following formulas, R １０ is the same as above.

[0044] In the formulas (a-1b-1) to (a-1b-6), X １ represents a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group is bonded to a linking group. As the halogen atom, a chlorine atom or a bromine atom is preferred, and a chlorine atom is particularly preferred, in that the effect of improving the resolution of the photoresist can be obtained. １ In the above, the hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the group having a group in which the above group and a linking group are bonded are each ２０ The hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the group having a group in which the above group and a linking group are bonded in the above X are the same as those in the above X, and therefore the explanation thereof will be omitted. １In the above, the optionally substituted hydrocarbon group, the optionally substituted heterocyclic group, or the group having a group in which the above group is bonded to a linking group is preferably a group in which an alicyclic hydrocarbon group or an aliphatic hydrocarbon group is bonded to an aliphatic hydrocarbon group or an aromatic hydrocarbon group via a linking group, or a group in which an alicyclic hydrocarbon group is bonded to a linking group, in that the effect of improving the resolution of the photoresist is obtained, and particularly preferably a group in which an alicyclic hydrocarbon group is bonded to an aliphatic hydrocarbon group via an ester bond, a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group via an ester bond, a group in which two or more aliphatic hydrocarbon groups are bonded to each other via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to —OCO—.

[0045] In the formula (a-1b-1), R １ｃ represents a (monovalent) hydrocarbon group which may have a substituent, or a (monovalent) group in which two or more hydrocarbon groups are bonded via a linking group.

[0046] R １ｃ is preferably a (monovalent) saturated or unsaturated aliphatic hydrocarbon group which may have a substituent, a (monovalent) alicyclic hydrocarbon group which may have a substituent, or a (monovalent) group in which two or more of the above groups are bonded via a linking group, in that the effect of improving the resolution of the photoresist can be obtained.

[0047] The anion represented by the formula (a-2) where n=1 is preferably an anion represented by the following formula (a-2-1), and particularly preferably anions represented by the following formulas (a-2-2) to (a-2-4). １ , R １０ is the same as above.

[0048] In the formulae (a-1b-3) to (a-1b-5), (a-2-2) and (a-2-3), R １ｄ represents a divalent hydrocarbon group.

[0049] R １ｄis preferably a divalent saturated or unsaturated aliphatic hydrocarbon group, in that it has the effect of improving the resolution of the photoresist. Examples of the divalent saturated hydrocarbon group include linear or branched alkylene groups having 1 to 5 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of the divalent unsaturated hydrocarbon group include linear or branched alkenylene groups having 2 to 5 carbon atoms, such as vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene.

[0050] R １ｄ Among these, a divalent saturated hydrocarbon group is preferable, a linear or branched alkylene group is particularly preferable, a linear alkylene group having 1 to 3 carbon atoms is most preferable, and a linear alkylene group having 2 to 3 carbon atoms is particularly preferable.

[0051] In the formulae (a-1b-4), (a-1b-5) and (a-2-3), R １ｅ represents a (monovalent) saturated or unsaturated aliphatic hydrocarbon group which may have a substituent.

[0052] R １ｅ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms which may have a substituent, or a linear or branched alkenyl group having 2 to 5 carbon atoms which may have a substituent, in that the effect of improving the resolution of the photoresist can be obtained.

[0053] In the formulas (a-1b-3) and (a-2-2), ring Z represents a (monovalent) alicyclic hydrocarbon group, a (monovalent) aromatic hydrocarbon group, a (monovalent) aromatic heterocyclic group, or a (monovalent) non-aromatic heterocyclic group. These groups may have a substituent.

[0054] Ring Z is preferably a (monovalent) alicyclic hydrocarbon group which may have a substituent, and particularly preferably a (monovalent) bridged cyclic hydrocarbon group which may have a substituent, in that the effect of improving the resolution of the photoresist can be obtained.

[0055] In the formulas (a-2-1) to (a-2-4), X ２represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded. ２ In the above, the hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the group having a group in which the above group and a linking group are bonded are each ２０ The hydrocarbon group which may have a substituent, the heterocyclic group which may have a substituent, and the group having a group in which the above group and a linking group are bonded in the above X are the same as those in the above X, and therefore the explanation thereof will be omitted. ２ In the above, the optionally substituted hydrocarbon group, the optionally substituted heterocyclic group, or the group having a group in which the above group is bonded to a linking group is preferably a group in which an alicyclic hydrocarbon group or an aliphatic hydrocarbon group is bonded to an aliphatic hydrocarbon group or an aromatic hydrocarbon group via a linking group, or a group in which an alicyclic hydrocarbon group is bonded to a linking group, in that the effect of improving the resolution of the photoresist is obtained, and particularly preferably a group in which an alicyclic hydrocarbon group is bonded to an aliphatic hydrocarbon group via an ester bond, a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group via an ester bond, a group in which two or more aliphatic hydrocarbon groups are bonded to each other via an ester bond, or a group in which an alicyclic hydrocarbon group is bonded to —OCO—.

[0056] The cation constituting the sulfonate is not particularly limited, and may be a monovalent cation or a polyvalent cation having a valence of 2 or more. In the present invention, among these, a monovalent or divalent cation is preferred, and a monovalent cation is particularly preferred.

[0057] The cations include inorganic cations and organic cations.

[0058] When the sulfonate is a salt of an anion represented by formula (a-1) or (a-2) and an inorganic cation, it is called an inorganic sulfonate.

[0059] The inorganic sulfonate can be suitably used, for example, as a raw material for an organic sulfonate.

[0060] When the sulfonate is a salt of an anion represented by formula (a-1) or (a-2) and an organic cation, it is called an organic sulfonate.

[0061] The organic sulfonate can be suitably used as an acid generator.

[0062] Examples of the inorganic cation include alkali metal ions such as sodium ion, potassium ion, and lithium ion; and alkaline earth metal ions such as calcium ion, magnesium ion, and barium ion.

[0063] Examples of the organic cation include onium cations such as sulfonium ion, iodonium ion, selenium ion, ammonium ion, and phosphonium ion.

[0064] Examples of the sulfonium ion include sulfonium ions represented by the following formula (s):

[0065] In the formula (s), R １１ , R １２ R may be the same or different and represent a monovalent hydrocarbon group, a monovalent heterocyclic group, or a monovalent group formed by bonding two or more of the above groups via a single bond or a linking group. １１ , R １２ are connected to each other and adjacent S ＋ may form a ring together with

[0066] R １１ , R １２ The monovalent hydrocarbon group and the monovalent heterocyclic group in R １ Examples of the hydrocarbon group and heterocyclic group in the above formula are the same as those in the above formula. The above group may have a substituent, and the substituent may be R １ Examples of the substituents that may be possessed by the hydrocarbon group and heterocyclic group in the above formula are the same as those of the substituents that may be possessed by the hydrocarbon group and heterocyclic group in the above formula.

[0067] R １１ , R １２ are connected to each other and adjacent S ＋ The ring that may be formed together with ＋The heterocycle is a heterocycle containing at least the S ＋ In addition, the heterocycle may contain a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). The heterocycle is, for example, a 5- or 6-membered heterocycle, and includes an aromatic heterocycle and a non-aromatic heterocycle. Furthermore, the heterocycle may be condensed with an aromatic hydrocarbon ring.

[0068] The benzene ring shown in the formula (s) may have an alkyl group (e.g., C １－５ alkyl groups) and aryl groups (e.g., C ６－１５ An aromatic hydrocarbon ring may be condensed to the benzene ring. Furthermore, a substituent may be condensed to the benzene ring, the alkyl group or aryl group condensed to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring. Examples of the substituent include a hydroxyl group, SF ５ groups, halogen atoms, silyl groups, substituted oxy groups (e.g., C １－４ Alkoxy group, C ６－１５ Aryloxy group, C ７－１６ Aralkyloxy group, C １－４ acyloxy group, etc.), substituted thio group (e.g., C １－６ Alkylthio group, C ６－１５ arylthio groups).

[0069] The sulfonium ion may be bonded to an acid-reactive compound described later, i.e., the sulfonium ion may contain the acid-reactive compound described later in its structure.

[0070] Of the sulfonium ions represented by the formula (s), triarylsulfonium ions represented by the following formula (s-1) and sulfonium ions represented by the following formula (s-2) are preferred.

[0071] Ring Z in formula (s-2) is a heterocycle containing at least a sulfur atom as a heteroatom. The heterocycle may contain other heteroatoms (e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.) in addition to the sulfur atom. The heterocycle is, for example, a 5- or 6-membered heterocycle, and includes aromatic heterocycles and non-aromatic heterocycles. Furthermore, an aromatic hydrocarbon ring may be condensed with the heterocycle.

[0072] Specific examples of the sulfonium ion represented by the formula (s-2) are shown below: The benzene ring shown in the formula below may also have the same substituents as above bonded thereto.

[0073] Examples of the iodonium ion include an iodonium ion represented by the following formula (i):

[0074] The benzene ring shown in the formula (i) may have an alkyl group (e.g., C １－５ alkyl groups) and aryl groups (e.g., C ６－１５ An aromatic hydrocarbon ring may be condensed to the benzene ring. Furthermore, a substituent may be condensed to the benzene ring, the alkyl group or aryl group condensed to the benzene ring, or the condensed ring of the benzene ring and the aromatic hydrocarbon ring. Examples of the substituent include a hydroxyl group, SF ５ groups, halogen atoms, silyl groups, substituted oxy groups (e.g., C １－４ Alkoxy group, C ６－１５ Aryloxy group, C ７－１６ Aralkyloxy group, C １－４ acyloxy group, etc.), substituted thio group (e.g., C １－６ Alkylthio group, C ６－１５ arylthio groups).

[0075] Specific examples of the iodonium ion include aryliodonium ions such as p-cumenyl(p-tolyl)iodonium ion, diphenyliodonium ion, di-p-tolyliodonium ion, bis(4-tert-butylphenyl)iodonium ion, bis(4-dodecylphenyl)iodonium ion, bis(4-methoxyphenyl)iodonium ion, and (4-octyloxyphenyl)phenyliodonium ion.

[0076] Examples of the selenium ion include arylselenium ions such as triphenylselenium ion, tri-p-tolylselenium ion, tri-o-tolylselenium ion, tris(4-methoxyphenyl)selenium ion, 1-naphthyldiphenylselenium ion, tris(4-fluorophenyl)selenium ion, tri-1-naphthylselenium ion, and tri-2-naphthylselenium ion.

[0077] Examples of the ammonium ion include quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tetraoctylammonium ion, trimethylhexylammonium ion, and trimethyloctylammonium ion.

[0078] Examples of the phosphonium ion include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0079] As the organic cation, a sulfonium ion or an iodonium ion is preferred, and an arylsulfonium ion or an aryliodonium ion is particularly preferred, from the viewpoint of excellent photosensitivity.

[0080] The sulfonate rapidly decomposes upon irradiation with light to generate sulfonic acid. When the sulfonate contains the anion represented by formula (a-1), it generates a sulfonic acid represented by formula (A-1) below. When the sulfonate contains the anion represented by formula (a-2), it generates a sulfonic acid represented by formula (A-2) below. The sulfonic acid is a compound represented by the formula (A-2) below. １０ science fiction ４ group or SF ５ It exhibits high acid strength due to its group. (In the formula, R １ , R １０ , R ２０ , n is the same as above)

[0081] The gas phase acidity ΔG (Kcal / mol) of the sulfonic acid is, for example, 300 or less, preferably 295 or less, particularly preferably 290 or less, and particularly preferably 285 or less. The lower limit of the gas phase acidity ΔG (Kcal / mol) is, for example, 250, but may also be 260, 270, or 275. Here, "gas phase acidity" refers to acidity in the gas phase and is defined by the International Union of Pure and Applied Chemistry (IUPAC) as the Gibbs energy change associated with acid dissociation. The gas phase acidity can be calculated using known calculation software. The smaller the gas phase acidity value, the greater the acid strength.

[0082] [Oxime Sulfonate] The oxime sulfonate of the present invention is a compound represented by the following formula (b-1) or (b-2). (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ２ , R ３ are the same or different and represent an organic group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0083] The —N═CR of the oxime sulfonate ２ R ３ The moieties other than the group represented by are the same as the corresponding moieties of the sulfonate salt, and therefore, description thereof will be omitted.

[0084] R ２ , R ３Examples of the organic group in the formula (I) include a hydrocarbon group (R), an RO group, an RCO group, an ROCO group, an RS group (wherein each of the R groups represents a hydrocarbon group), a carboxyl group, a cyano group, an isocyanate group, a carbamoyl group, an isothiocyanate group, a substituted amino group, a heterocyclic group, and a group in which two or more of these groups are bonded via a single bond.

[0085] R in the formula (b-1) ２ , R ３ The organic group in the formula (b-2) may be a group in which two or more hydrocarbon groups (R) are bonded via a divalent group represented by the following formula (L-1): ２ , R ３ The organic group in the formula (L-1) may be a group in which two or more hydrocarbon groups (R) are bonded via a divalent group represented by the following formula (L-2).

[0086] R in the formulas (L-1) and (L-2) １ , R １０ , R ２０ , n is the same as above.

[0087] The hydrocarbon group (R) and the heterocyclic group are each R １ Examples of the hydrocarbon group and heterocyclic group in R ２ , R ３ The hydrocarbon group in may have a substituent, and the substituent is R １ Examples of the substituents that may be possessed by the hydrocarbon group in the above formula are the same as those of the substituents that may be possessed by the hydrocarbon group in the above formula.

[0088] R ２ , R ３ Preferably, one of R is a hydrocarbon group which may have a substituent. ２ , R ３ The other is preferably an electron-withdrawing group, particularly preferably a group selected from a cyano group, an RCO group (R represents a hydrocarbon group), an isocyanate group, a carbamoyl group, and an isothiocyanate group, and particularly preferably a cyano group.

[0089] As the compound represented by the formula (b-1) where n=0, the compound represented by the following formula (b-1a-1) or (b-1a-2) is preferred, and the compounds represented by the following formulas (b-1a-3) and (b-1a-4) are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acid with high acid strength, thereby improving the resolution of the photoresist. ２ , R ３ , R １０ , R １ａ , R １ｂ , X is the same as above.

[0090] As the compound represented by the formula (b-1) where n=1, the compound represented by the following formula (b-1b-1) or (b-1b-2) is preferred, in that it has excellent photosensitivity and generates a sulfonic acid with high acid strength, thereby obtaining the effect of improving the resolution of the photoresist. Furthermore, as the formula (b-1b-1), the compounds represented by the following formulas (b-1b-3) to (b-1b-5) are particularly preferred. As the formula (b-1b-2), the compound represented by the following formula (b-1b-6) is particularly preferred. In the formulas below, R ２ , R ３ , R １０ , R １ｃ , R １ｄ , R １ｅ , X １ and ring Z is the same as defined above.

[0091] Among the compounds represented by formula (b-2), the compound represented by formula (b-2-1) below is preferred, and the compounds represented by formulas (b-2-2) to (b-2-4) below are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acids with high acid strength, thereby improving the resolution of photoresists. １ , R ２ , R ３ , R １０ , R １ｄ , R １ｅ , ring Z, X ２ is the same as above.

[0092] The oxime sulfonate rapidly decomposes upon irradiation with light to generate sulfonic acid. When the oxime sulfonate is a compound represented by formula (b-1), it generates sulfonic acid represented by formula (A-1). When the oxime sulfonate is a compound represented by formula (b-2), it generates sulfonic acid represented by formula (A-2). The sulfonic acid is a compound represented by formula (B-1) represented by formula (B-2). １０ science fiction ４ group or SF ５ It exhibits high acid strength due to its group.

[0093] [Imidosulfonate] The imidosulfonate of the present invention is a compound represented by the following formula (c-1) or (c-2). (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ４ , R ５ R may be the same or different and represent a hydrocarbon group which may have a substituent. ４ , R ５ may be bonded to each other to form a ring together with the adjacent carbon atoms. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group is bonded to a linking group. L represents a single bond or a linking group. n represents 0 or 1.

[0094] The portions of the imide sulfonate other than the imide ring are the same as the corresponding portions of the sulfonate salts, and therefore, the description thereof will be omitted.

[0095] The linking group for L is a divalent group having one or more atoms, and examples thereof include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), a sulfonyl group (—SO2-), an ester bond (—COO— or —OCO—), an amide bond (—CONH—), a carbonate bond (—OCOO—), and groups in which a plurality of these are linked together.

[0096] Among these, L is preferably a single bond, since it has excellent photosensitivity and generates a sulfonic acid having high acid strength, thereby improving the resolution of the photoresist.

[0097] R ４ , R ５ The hydrocarbon group in R １ Examples of the monovalent hydrocarbon group in R ４ , R ５ The hydrocarbon group in R may have a substituent. １ Examples of the substituent that the monovalent hydrocarbon group in the formula (I) may have are the same as those of the substituent that the monovalent hydrocarbon group in the formula (I) may have.

[0098] R ４ , R ５ However, examples of the ring that may be formed by linking together with adjacent carbon atoms include alicyclic hydrocarbon rings, aromatic hydrocarbon rings, and heterocyclic rings.

[0099] The alicyclic hydrocarbons include C ３－２０ Alicyclic hydrocarbon groups are preferred, for example, C cyclohexane, bicyclohexane, etc. ３－１２ Cycloalkane ring; C such as cyclohexene ３－１２ Cycloalkene ring: norbornane, norbornene, adamantane, tricyclo[5.2.1.0 ２，６ ] decane, tricyclo[4.3.1.1 ２，５ ]undecane, tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]dodecane, perhydro-1,4-methano-5,8-methanonaphthalene and the like.

[0100] Examples of the aromatic hydrocarbon ring include benzene, naphthalene, and anthracene.

[0101] Examples of the heterocyclic ring include the same heterocyclic rings as those forming the heterocyclic group.

[0102] As the compound represented by the formula (c-1) where n=0, the compound represented by the following formula (c-1a-1) or (c-1a-2) is preferred, and the compounds represented by the following formulas (c-1a-3) and (c-1a-4) are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acid with high acid strength, thereby improving the resolution of the photoresist. ４ , R ５ , R １０ , R １ａ , R １ｂ , L and X are the same as above.

[0103] As the compound represented by formula (c-1) where n=1, the compound represented by formula (c-1b-1) or (c-1b-2) below is preferred, in that it has excellent photosensitivity and generates a sulfonic acid with high acid strength, thereby obtaining the effect of improving the resolution of the photoresist. Furthermore, as the compound represented by formula (c-1b-1), the compounds represented by formulas (c-1b-3) to (c-1b-5) below are particularly preferred. As the compound represented by formula (c-1b-2), the compound represented by formula (c-1b-6) below is particularly preferred. In the following formulas, R ４ , R ５ , R １０ , R １ｃ , R １ｄ , R １ｅ , ring Z, L, X １ is the same as above.

[0104] Among the compounds represented by formula (c-2), the compound represented by formula (c-2-1) below is preferred, and the compounds represented by formulas (c-2-2) to (c-2-4) below are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acids with high acid strength, thereby improving the resolution of photoresists.１ , R ４ , R ５ , R １０ , R １ｄ , R １ｅ , ring Z, L, X ２ is the same as above.

[0105] The imide sulfonate rapidly decomposes upon irradiation with light to generate sulfonic acid. When the imide sulfonate is a compound represented by formula (c-1), it generates sulfonic acid represented by formula (A-1). When the imide sulfonate is a compound represented by formula (c-2), it generates sulfonic acid represented by formula (A-2). The sulfonic acid is a compound represented by formula (c-2) represented by formula (A-2). １０ science fiction ４ group or SF ５ It exhibits high acid strength due to its group.

[0106] [Amidosulfonate] The amidosulfonate of the present invention is a compound represented by the following formula (d-1) or (d-2). (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ６ , R ７ R may be the same or different and represent a hydrocarbon group which may have a substituent. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

[0107] The portions of the amidosulfonate other than the amide group are the same as the corresponding portions of the sulfonate salts, and therefore, the description thereof will be omitted.

[0108] R ６ , R ７ The hydrocarbon group in R １Examples of the monovalent hydrocarbon group in R ６ , R ７ The hydrocarbon group in R may have a substituent. １ Examples of the substituent that the monovalent hydrocarbon group in the formula (I) may have are the same as those of the substituent that the monovalent hydrocarbon group in the formula (I) may have.

[0109] As the compound represented by the formula (d-1) where n=0, the compound represented by the following formula (d-1a-1) or (d-1a-2) is preferred, and the compounds represented by the following formulas (d-1a-3) and (d-1a-4) are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acid with high acid strength, thereby improving the resolution of the photoresist. ６ , R ７ , R １０ , R １ａ , R １ｂ , X is the same as above.

[0110]

[0111] As the compound represented by formula (d-1) where n=1, a compound represented by formula (d-1b-1) or (d-1b-2) below is preferred, in that it has excellent photosensitivity and generates a sulfonic acid with high acid strength, thereby obtaining the effect of improving the resolution of the photoresist. Furthermore, as the compound represented by formula (d-1b-1), compounds represented by formulas (d-1b-3) to (d-1b-5) below are particularly preferred. As the compound represented by formula (d-1b-2), a compound represented by formula (d-1b-6) below is particularly preferred. In the following formulas, R ６ , R ７ , R １０ , R １ｃ , R １ｄ , R １ｅ , X １ and ring Z is the same as defined above.

[0112] As the compound represented by formula (d-2), a compound represented by the following formula (d-2-1) is preferred, and compounds represented by the following formulas (d-2-2) to (d-2-4) are particularly preferred, in that they have excellent photosensitivity and generate sulfonic acid with high acid strength, thereby improving the resolution of the photoresist. １ , R ６ , R ７ , R １０ , R １ｄ , R １ｅ , ring Z, X ２ is the same as above.

[0113] The amidosulfonate rapidly decomposes upon irradiation with light to generate sulfonic acid. When the amidosulfonate is a compound represented by formula (d-1), it generates sulfonic acid represented by formula (A-1). When the amidosulfonate is a compound represented by formula (d-2), it generates sulfonic acid represented by formula (A-2). The sulfonic acid is a compound represented by formula (d-1) １０ science fiction ４ group or SF ５ It exhibits high acid strength due to its group.

[0114] [Acid Generator] The acid generator of the present invention contains the sulfonate, oxime sulfonate, imido sulfonate, or amido sulfonate, which rapidly decomposes upon irradiation with light to generate sulfonic acid.

[0115] The acid generator has excellent solubility in a solvent (e.g., PGMEA), and the amount of the acid generator (or the sulfonate, or the oxime sulfonate, or the imide sulfonate, or the amide sulfonate) that dissolves in 100 parts by weight of PGMEA at room temperature and normal pressure is, for example, 1 part by weight or more, preferably 5 parts by weight or more, and particularly preferably 10 parts by weight or more. The upper limit is, for example, 30 parts by weight.

[0116] The acid generator has excellent sensitivity to light and rapidly generates sulfonic acid when irradiated with light. The wavelength of the light is, for example, 1 to 1000 nm. Examples of the light include infrared light, visible light, ultraviolet light, X-rays, electron beams, and EUV (Extreme Ultraviolet).

[0117] Because the acid generator has the above properties, it can be suitably used as an acid generator for photoresists (for example, chemically amplified resists) or as a cationic polymerization initiator for cationic polymerizable compounds.

[0118] [Photoresist] The photoresist of the present invention contains the acid generator and an acid-reactive compound.

[0119] The acid generator and the acid-reactive compound may be contained in the photoresist as separate compounds, or the acid-reactive compound may be incorporated into the acid generator and contained in the photoresist in an integrated state.

[0120] When the photoresist contains the acid generator and the acid-reactive compound as separate compounds, the content of the acid generator is, for example, 0.001 to 20 wt %, preferably 0.01 to 15 wt %, and particularly preferably 0.05 to 7 wt % of the content of the acid-reactive compounds (the total amount when two or more types are contained).

[0121] When the content of the acid generator is 0.001% by weight or more of the content of the acid-reactive compound, excellent sensitivity can be exhibited not only to light rays on the longer wavelength side but also to light rays with wavelengths of 20 nm or less.Furthermore, when the content is 20% by weight or less of the content of the acid-reactive compound, the effect of improving the resolution of the photoresist can be obtained.

[0122] Even when the photoresist contains an integrated product of the acid generator and the acid-reactive compound, the content ratio of the acid generator and the acid-reactive compound in the photoresist is preferably in the same range as when the acid generator and the acid-reactive compound are contained as separate compounds.

[0123] The acid-reactive compound is a polymeric compound whose solubility in an alkaline developer changes under the action of an acid. The photoresist of the present invention may contain one or more of the acid-reactive compounds alone or in combination.

[0124] The acid-reactive compounds include those that are readily soluble in an alkaline developer and react with a crosslinker in the presence of an acid to produce a compound that is poorly soluble or insoluble in the alkaline developer, and those that are poorly soluble or insoluble in an alkaline developer and whose solubility in the alkaline developer increases due to the action of an acid.

[0125] Therefore, the photoresist contains the following composition (1) and composition (2): composition (1): a composition containing the acid generator and a negative-type photosensitive resin (QN) that is readily soluble in an alkaline developer and generates a compound that is poorly soluble or insoluble in the alkaline developer in the presence of an acid; and composition (2): a composition containing the acid generator and a positive-type photosensitive resin (QP) that is poorly soluble or insoluble in an alkaline developer and whose solubility in the alkaline developer increases under the action of an acid.

[0126] The negative photosensitive resin (or negative chemically amplified resin; QN) may be, for example, a composition containing a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

[0127] The phenolic hydroxyl group-containing resin (QN1) is a resin containing a phenolic hydroxyl group that is readily soluble in an alkaline developer and that becomes poorly soluble or insoluble in the alkaline developer upon reaction with a crosslinking agent, and examples thereof include novolak resins, polyhydroxystyrenes, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and a (meth)acrylic acid derivative, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, and phenol-dicyclopentadiene condensation resins. These may be used alone or in combination of two or more.

[0128] The phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low molecular weight compound as part of its components.

[0129] The phenolic hydroxyl group-containing resin (QN1) has a weight average molecular weight (Mw) of, for example, 2,000 to 20,000, as converted into polystyrene, as measured by GPC.

[0130] The crosslinking agent (QN2) is a compound that can crosslink the phenolic hydroxyl group-containing resin (QN1) with, for example, the acid generated from the acid generator, and examples thereof include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, poly(hydroxystyrene)-based epoxy compounds, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenolic compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenolic compounds, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group-containing urea resins, carboxymethyl group-containing phenolic resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds and carboxymethyl group-containing phenolic compounds. These can be used alone or in combination of two or more.

[0131] The content of the crosslinking agent (QN2) is, for example, 10 to 40 mol % relative to the total acidic functional groups in the phenolic hydroxyl group-containing resin (QN1), from the viewpoint of efficiently making the phenolic hydroxyl group-containing resin (QN1) less soluble or insoluble in an alkaline developer.

[0132] Examples of the positive photosensitive resin (or positive chemically amplified resin; QP) include an alkali-soluble resin into which an acid-dissociable group has been introduced as a protecting group (protected group-introduced resin; QP1).

[0133] The protecting group-introduced resin (QP1) is a resin in which some or all of the hydrogen atoms of acidic functional groups (such as phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, etc.) in an alkali-soluble resin have been substituted with acid-dissociable groups.

[0134] The protecting group-introduced resin (QP1) itself is a resin that is insoluble or poorly soluble in an alkaline developer, and the acid (H ＋ X － When the acid-dissociable group is dissociated by the reaction with the hydroxy group, the resin is converted into an alkali-soluble resin that is readily soluble in an alkali developer.

[0135] The alkali-soluble resin is, for example, a resin having an HLB value of 4 to 19 (preferably 5 to 18, and particularly preferably 6 to 17).

[0136] The alkali-soluble resins include phenolic hydroxyl group-containing resins, carboxyl group-containing resins, and sulfonic acid group-containing resins.

[0137] Examples of the phenolic hydroxyl group-containing resin include the same resins as the above-mentioned phenolic hydroxyl group-containing resin (QN1).

[0138] The carboxyl group-containing resin is not particularly limited as long as it is a polymer having a carboxyl group, and examples thereof include a homopolymer of a carboxyl group-containing vinyl monomer (Ba) and a homopolymer of a carboxyl group-containing vinyl monomer (Ba) and a hydrophobic group-containing vinyl monomer (Bb).

[0139] An example of the carboxyl group-containing vinyl monomer (Ba) is (meth)acrylic acid.

[0140] The hydrophobic group-containing vinyl monomer (Bb) may be C １－２０ Examples thereof include (meth)acrylic acid esters (Bb1) such as alkyl (meth)acrylates and alicyclic group-containing (meth)acrylates, and aromatic hydrocarbon monomers (Bb2) such as hydrocarbon monomers having a styrene skeleton and vinylnaphthalene.

[0141] The sulfonic acid group-containing resin is not particularly limited as long as it is a polymer having a sulfonic acid group, and can be obtained, for example, by vinyl polymerization of a sulfonic acid group-containing vinyl monomer (Bc) such as vinyl sulfonic acid or styrene sulfonic acid, and, if necessary, a hydrophobic group-containing vinyl monomer (Bb).

[0142] Examples of the acid-dissociable group contained in the protecting group-introduced resin (QP1) include 1-substituted methyl groups such as a methoxymethyl group, a benzyl group, and a tert-butoxycarbonylmethyl group; 1-substituted ethyl groups such as a 1-methoxyethyl group and a 1-ethoxyethyl group; 1-branched alkyl groups such as a tert-butyl group; silyl groups such as a trimethylsilyl group; germyl groups such as a trimethylgermyl group; alkoxycarbonyl groups such as a tert-butoxycarbonyl group; acyl groups; and cyclic acid-dissociable groups such as a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuranyl group. These groups may be contained alone or in combination of two or more.

[0143] The introduction rate of the acid-dissociable group in the protecting group-introduced resin (QP1) [the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protecting group-introduced resin (QP1)] cannot be generally defined depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, and more preferably 15 to 100%.

[0144] The weight average molecular weight (Mw) of the protecting group-introduced resin (QP1) measured by GPC in terms of polystyrene is, for example, 1,000 to 150,000, and preferably 3,000 to 100,000.

[0145] The photoresist of the present invention can be prepared, for example, by dissolving the acid generator in an organic solvent and mixing the solution with a photosensitive resin.

[0146] In addition to the acid generator and photosensitive resin, the photoresist of the present invention may optionally contain one or more other components, such as organic solvents, pigments, dyes, photosensitizers, dispersants, surfactants, fillers, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, surface modifiers, plasticizers, and drying accelerators.

[0147] The organic solvent may be any solvent capable of dissolving the photosensitive resin and imparting good coating properties to the photoresist, but it is preferable to use one having a boiling point of 200° C. or less, since this allows the photoresist to be easily dried after application. Examples of such organic solvents include aromatic hydrocarbons such as toluene; alcohols such as ethanol and methanol; ketones such as cyclohexanone, methyl ethyl ketone, and acetone; esters such as ethyl acetate, butyl acetate, and ethyl lactate; and glycol monoether monoesters such as propylene glycol monomethyl ether acetate (PGMEA). These may be used alone or in combination of two or more.

[0148] The organic solvent preferably contains at least one selected from the group consisting of ketones, esters (particularly, chain esters), and glycol monoether monoesters.

[0149] The photoresist of the present invention is suitable for g-line (436 nm), h-line (405 nm), i-line (365 nm); KrF, ArF, F ２ The photoresist contains a sulfonium salt that has high photosensitivity to light having wavelengths such as ultraviolet rays, X-rays, electron beams, and EUV. Therefore, by using the photoresist of the present invention, a resist film having a high-resolution fine pattern can be produced by photolithography using light having the wavelengths described above.

[0150] As a method for forming a pattern by photolithography using the photoresist, for example, a method including the following steps 1 to 3 can be mentioned.

[0151] Step 1: forming a coating film of the photoresist on a substrate; Step 2: irradiating the coating film with light to transfer a pattern; Step 3: performing alkaline development.

[0152] (Step 1) This step is a step of forming a coating film of the photoresist on a substrate to be etched. The coating film of the photoresist can be formed by applying the photoresist to the substrate using a known method such as spin coating, curtain coating, roll coating, spray coating, or screen printing, and then drying the applied photoresist.

[0153] The photoresist may be dried by natural drying, but since the sulfonium salt has thermal stability, it can also be dried by heating (for example, heating at a temperature of 50° C. or higher and lower than 130° C. for 1 to 5 minutes), which is easy to work with.

[0154] The thickness of the coating film is, for example, 1 to 1000 nm.

[0155] (Step 2) This step is a step of transferring a pattern to the coating film obtained through step 1 by irradiating the coating film with light through a photomask having a pattern, for example.

[0156] The light used for the light irradiation is a light that decomposes the sulfonium salt contained in the coating film to form an acid (H ＋ X － ;X － The wavelength of the light is preferably 450 nm or less (e.g., 1 to 450 nm), more preferably 400 nm or less, even more preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 30 nm or less. Examples of the light include g-line (436 nm), h-line (405 nm), i-line (365 nm); KrF, ArF, F ２ Excimer lasers such as ultraviolet, X-ray, electron beam, EUV, etc.

[0157] After the light irradiation, it is preferable to heat the film at a temperature of 60 to 200° C. for about 0.1 to 120 minutes, since this makes it possible to increase the difference in solubility in an alkaline developer between the exposed and unexposed areas.

[0158] (Step 3) This step is a step in which the photoresist coating film that has been subjected to step 2 is subjected to an alkaline development treatment.

[0159] Examples of the alkaline developer used in the alkaline development treatment include an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, sodium hydrogen carbonate, and an aqueous solution of tetramethylammonium salt.

[0160] The alkaline developer may contain methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone, or the like.

[0161] The alkaline development treatment is carried out by applying the alkaline developer to the coating film by a method such as dipping, showering, or spraying.

[0162] The temperature of the alkaline developer is, for example, 25 to 40° C. The alkaline development time is determined appropriately depending on the thickness of the photoresist coating, but is, for example, about 1 to 5 minutes.

[0163] In alkaline development treatment, a large difference in solubility between exposed and unexposed areas of the photoresist coating film is preferable from the viewpoint of forming a highly accurate fine pattern. This is because the presence of a large amount of development residue is likely to cause problems such as abnormal wiring shape. Furthermore, since the photoresist of the present invention contains a sulfonium salt having a carboxyl group as described above, the developability of the resist during alkaline development can be improved and development residue can be reduced. Therefore, defect-free products can be produced with a high yield.

[0164] Through step 3, a resist film having a highly accurate fine pattern can be formed on a substrate. By etching a substrate using the resist film thus obtained, a highly accurate electronic or optical device can be manufactured.

[0165] Examples of the electronic device include display devices such as organic EL displays and liquid crystal displays; input devices such as touch panels; light-emitting devices; sensor devices; and MEMS (Micro Electro Mechanical Systems) devices such as optical scanners, optical switches, acceleration sensors, pressure sensors, gyroscopes, microchannels, and inkjet heads.

[0166] The optical devices include, for example, optical waveguides, metalenses, semiconductor lasers, and the like.

[0167] [Cationic Polymerization Initiator] The cationic polymerization initiator of the present invention contains the sulfonate, the oxime sulfonate, the imide sulfonate, or the amide sulfonate, which rapidly decomposes upon irradiation with light to generate sulfonic acid.

[0168] The cationic polymerization initiator has excellent solubility in a solvent (e.g., PGMEA), and the amount of the cationic polymerization initiator (or the sulfonate, or the oxime sulfonate, or the imide sulfonate, or the amide sulfonate) dissolved in 100 parts by weight of PGMEA at room temperature and normal pressure is, for example, 1 part by weight or more, preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more. The upper limit is, for example, 30 parts by weight.

[0169] The cationic polymerization initiator has excellent sensitivity to light, and when irradiated with light, it quickly generates sulfonic acid. The wavelength of the light is, for example, 1 to 1000 nm. Examples of the light include g-line (436 nm), h-line (405 nm), i-line (365 nm); KrF, ArF, F ２ Excimer lasers such as ultraviolet, infrared, visible light, X-ray, electron beam, EUV, etc.

[0170] [Curable Composition] The curable composition of the present invention contains the cationic polymerization initiator and a cationic polymerizable compound as a resin component. The cationic polymerization initiator and the cationic polymerizable compound may each be contained alone or in combination of two or more.

[0171] The content of the cationic polymerization initiator is, for example, 0.05 to 20 parts by weight, and preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationic polymerizable compound.

[0172] The cationically polymerizable compound is a compound having one or more cationically polymerizable groups selected from an epoxy group, an oxetanyl group, a vinyl ether group, etc. The epoxy group is a group containing a three-membered cyclic ether skeleton, and the oxetanyl group is a group containing a four-membered cyclic ether skeleton.

[0173] Examples of the cationically polymerizable compound include a compound having an epoxy group as a cationically polymerizable group (=epoxy compound), a compound having an oxetanyl group as a cationically polymerizable group (=oxetane compound), a compound having a vinyl ether group as a cationically polymerizable group (=vinyl ether compound), a compound having an epoxy group and an oxetanyl group as cationically polymerizable groups, a compound having an epoxy group and a vinyl ether group as cationically polymerizable groups, and a compound having an oxetanyl group and a vinyl ether group as cationically polymerizable groups.

[0174] (Epoxy Compound) Examples of epoxy compounds include epoxy-modified siloxane compounds, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), and aliphatic epoxy compounds (aliphatic epoxy resins).

[0175] <Epoxy-Modified Siloxane Compound> Examples of the epoxy-modified siloxane compound include epoxy-modified silicone and epoxy-modified polyorganosilsesquioxane.

[0176] <Alicyclic Epoxy Compound> The alicyclic epoxy compound includes known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and is not particularly limited, and examples thereof include the following compounds: (1) Compounds having an alicyclic epoxy group (= an epoxy group consisting of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring in the molecule) (2) Compounds having an alicyclic ring and a glycidyl ether group

[0177] Examples of the compound (1) having an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy Examples thereof include cis-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanemetadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, and ethylenebis(3,4-epoxycyclohexanecarboxylate).

[0178] Examples of the compound (2) having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, examples include hydrogenated compounds of bisphenol A epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]propane ... Examples of such epoxy compounds include hydrogenated compounds of bisphenol F type epoxy compounds such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane and bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; and hydrogenated products of trisphenolmethane type epoxy compounds.

[0179] <Aromatic Epoxy Compound> Examples of the aromatic epoxy compound include epibis-type glycidyl ether epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high-molecular-weight epibis-type glycidyl ether epoxy resins obtained by further addition reaction of these epibis-type glycidyl ether epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol B, etc.]; Examples of suitable epoxy resins include novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols [e.g., bisphenol F, bisphenol S, etc.] with aldehydes [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] with epihalohydrin; and epoxy compounds in which two phenol skeletons are bonded to the 9-position of a fluorene ring and a glycidyl group is bonded, directly or via an alkyleneoxy group, to the oxygen atom obtained by removing the hydrogen atom from the hydroxyl group of each of the phenol skeletons.

[0180] <Aliphatic Epoxy Compound> Examples of the aliphatic epoxy compound include glycidyl ethers of q-valent alcohols (q is a natural number) that do not have a cyclic structure; glycidyl esters of monovalent or polyvalent carboxylic acids [for example, acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of fats and oils having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized products of polyolefins (including polyalkadiene), such as epoxidized polybutadiene. Examples of the q-valent alcohol not having a cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The q-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, or the like.

[0181] (Oxetane Compound) Examples of the oxetane compound include 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and bis(vinyloxymethyl)oxetane. bis([1-ethyl(3-oxetanyl)]methyl)ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 1,4-bis([(3-ethyl-3-oxetanyl)methoxy]methyl)benzene, 3-ethyl-3([(3-ethyloxetan-3-yl)methoxy]methyl)oxetane, xylylene bisoxetane, and the like.

[0182] (Vinyl Ether Compound) Examples of the vinyl ether compound include aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxybutyl vinyl ether; and polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0183] In addition to the above components, the curable composition may contain one or more other components as needed. Examples of other components include sensitizers, sensitization aids, antioxidants, stabilizers, surfactants, solvents, rheology control agents, leveling agents, silane coupling agents, fillers, conductive particles, polymerization inhibitors, light stabilizers, plasticizers, defoamers, foaming agents, UV absorbers, tackifiers, cure retarders, ion adsorbents, pigments, dyes, fluorescent materials, mold release agents, antistatic agents, flame retardants, radically polymerizable compounds, polyimide resins, polyamide resins, phenoxy resins, poly(meth)acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, and SEBS. The content of these components (the total amount when two or more components are contained) is, for example, about 0.05 to 50 wt %, preferably 0.05 to 10 wt %, and particularly preferably 0.1 to 5 wt % of the total amount of the curable composition (100 wt %).

[0184] The curable composition can be produced by uniformly mixing the cationic polymerization initiator, the cationic polymerizable compound, and other components added as necessary using commonly known mixing equipment such as a planetary mixer, a homogenizer, a three-roll mill, a bead mill, etc. The components may be mixed simultaneously or sequentially.

[0185] The use of the curable composition is not particularly limited, and examples thereof include paints, coating agents, inks, positive resists, resist films, liquid resists, photosensitive materials, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, filling materials, sealing materials, encapsulants, and materials for optical shaping.

[0186] The curable composition contains a cationic polymerization initiator that generates sulfonic acid with excellent acid strength, and therefore can rapidly form a cured product upon irradiation with light. Furthermore, the curable composition contains a cationic polymerization initiator with excellent solvent solubility, and therefore precipitation of the cationic polymerization initiator can be suppressed even when the curable composition is stored in a low-temperature environment (for example, a temperature environment of 0°C or lower, preferably a temperature environment of -25°C or lower) after preparation. Therefore, there is ample time between preparation and use, and the composition is easy to handle.

[0187] [Cured Product] The cured product of the present invention is a cured product of the curable composition.

[0188] The cured product can be obtained by curing the curable composition.

[0189] The curable composition can be cured by irradiating it with light. The light can be any type of light, as long as it has enough energy to induce decomposition of the salt contained in the acid generator. Preferably, light having a wavelength in the ultraviolet to visible light range is obtained from a low-pressure, medium-pressure, high-pressure, or ultra-high-pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He—Cd laser, KrF excimer laser, ArF excimer laser, F2 laser, or the like. High-energy radiation such as electron beams and X-rays can also be used. The irradiation time for the light depends on the intensity of the energy beam and the transmittance of the light through the curable composition, but is typically about 0.1 to 10 seconds at room temperature. If necessary, the composition may be subjected to a heat treatment at room temperature to 150°C for several seconds to several hours after light irradiation.

[0190] The above-described configurations and combinations of the present invention are merely examples, and additions, omissions, substitutions, and modifications of the configurations are possible as appropriate without departing from the spirit of the present invention. Furthermore, each aspect disclosed in this specification can be combined with any other feature disclosed in this specification.

[0191] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0192] The structures of the compounds obtained in the Preparation Examples, Production Examples, and Examples are as follows: １ H-NMR and １９ This was confirmed by F-NMR.

[0193] Preparation Example 1 (Synthesis of Acid-Reactive Compound) Under a nitrogen atmosphere, 168.6 g of 2-ethyladamantan-2-yl methacrylate, 85.5 g of 3-hydroxy-1-adamantyl methacrylate, 172.1 g of 2-oxotetrahydrofuran-3-yl methacrylate, and 510 g of propylene glycol methyl ether acetate were charged into a flask to obtain a monomer solution. 14.86 g of 2,2'-azobisisobutyronitrile, 2.6 g of 2-mercaptoethanol, and 127 g of propylene glycol monomethyl ether acetate were mixed to obtain an initiator solution. Under a nitrogen atmosphere, 292 g of propylene glycol methyl ether acetate was charged into a separate flask and heated to 80°C with stirring. Thereafter, the above monomer solution and initiator solution were simultaneously added dropwise to the flask over a period of 4 hours. After the dropwise addition was completed, the reaction solution was stirred for 2 hours while maintaining the temperature at 80°C, and then cooled to room temperature to obtain a polymerization solution. The obtained polymerization solution was added dropwise to 12 kg of vigorously stirred methanol, and the precipitated copolymer was separated by filtration. The copolymer was washed twice with 3 kg of methanol and then vacuum dried at 50°C for 20 hours to obtain 384 g of a white powdery copolymer. The obtained copolymer was analyzed by GPC and found to have a weight average molecular weight (Mw) of 6,000 in terms of polystyrene. This copolymer was used as an acid-reactive compound.

[0194] Preparation Example 2: 1.2 g of 1-propene-1,3-sultone and 10 mL of carbon tetrachloride were added to a reaction vessel, and 12 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration: 0.1 M) was added thereto. The mixture was reacted at 50°C for 72 hours while irradiating with UV light using a high-pressure mercury lamp. The temperature was then returned to room temperature, and 10 mL of water was added, followed by separation into an organic layer (1) and an aqueous layer (1). The aqueous layer (1) obtained by separation was further extracted three times with 10 mL of diethyl ether, and the resulting organic layer (2) was combined with the organic layer (1) and washed three times with 20 mL of water. Thereafter, the solvent was distilled off from the organic layer (3) obtained by the separation operation under reduced pressure, and the residue was purified by silica gel column chromatography to isolate a compound represented by the following formula (F-1a) (=compound (F-1a)) (yield 39%) and a compound represented by the following formula (F-1a') (=compound (F-1a')) (yield 11%).

[0195]

[0196] Preparation Example 3 A compound represented by the following formula (F-1b) (=compound (F-1b)) and a compound represented by the following formula (F-1b') (=compound (F-1b')) were isolated in the same manner as in Preparation Example 2, except that 1.4 g of 1-butene-1,4-sultone was used instead of 1.2 g of 1-propene-1,3-sultone.

[0197]

[0198] Preparation Example 4 A compound represented by the following formula (F-1c) (=compound (F-1c)) was synthesized in the same manner as in Preparation Example 2, except that 1.4 g of ethyl vinylsulfonate was used instead of 1.2 g of 1-propene-1,3-sultone.

[0199]

[0200] Preparation Example 5: Instead of 12 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration 0.1 M), 4-chlorophenyltetrafluoro-λ ６A compound represented by the following formula (F-1d) (=compound (F-1d)) was obtained in the same manner as in Preparation Example 2, except that 2.6 g of sulfanyl chloride was used.

[0201]

[0202] Preparation Example 6: Instead of 12 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration 0.1 M), 4-chlorophenyltetrafluoro-λ ６ A compound represented by the following formula (F-1e) (=compound (F-1e)) was obtained in the same manner as in Preparation Example 2, except that 2.6 g of 1-butene-1,4-sultone was used instead of 1.2 g of 1-propene-1,3-sultone.

[0203]

[0204] Preparation Example 7 Instead of 12 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration 0.1 M), 5-bromopyridin-2-yltetrafluoro-λ ６ A compound represented by the following formula (F-1f) (=compound (F-1f)) was obtained in the same manner as in Preparation Example 2, except that 3.0 g of sulfanyl chloride was used.

[0205]

[0206] Preparation Example 1 2.8 g of compound (F-1a) and 50 mL of an acetonitrile-water mixed solvent (acetonitrile:water=10:1 (weight ratio)) were placed in a reaction vessel, and 50 g of a 15% aqueous sodium hydroxide solution was added little by little. After the addition, the mixture was stirred at room temperature for an additional 5 hours. The reaction solution was filtered, and the filtrate was concentrated to obtain 1.0 g of a white solid (yield 31%). １ H-NMR and １９ It was confirmed by F-NMR that the obtained white solid was a compound represented by the following formula (F-2) (=compound (F-2)).

[0207]

[0208] Production Example 2 2.8 g of compound (F-1a) and 100 mL of toluene were added to a reaction vessel, and 2.8 g of potassium hydroxide was added thereto and stirred at room temperature for 24 hours. The reaction solution was filtered, and the filtrate was concentrated to obtain a pale brown liquid. 50 mL of an acetonitrile-water mixed solvent (acetonitrile:water=10:1 (weight ratio)) was added to the obtained pale brown liquid, and 50 g of a 15% aqueous potassium hydroxide solution was added thereto little by little. After the addition, the mixture was stirred at room temperature for an additional 5 hours. The reaction solution was filtered, and the filtrate was concentrated to obtain 0.9 g of a white solid (yield 30%). １ H-NMR and １９ It was confirmed by F-NMR that the obtained white solid was a compound represented by the following formula (F-3) (=compound (F-3)).

[0209]

[0210] Production Example 3 A compound represented by the following formula (F-4) (=compound (F-4)) was obtained in the same manner as in Production Example 1, except that compound (F-1b) was used instead of compound (F-1a).

[0211]

[0212] Production Example 4 A compound represented by the following formula (F-5) (=compound (F-5)) was obtained in the same manner as in Production Example 2, except that compound (F-1b) was used instead of compound (F-1a).

[0213]

[0214] Production Example 5 A compound represented by the following formula (F-6) (=compound (F-6)) was obtained in the same manner as in Production Example 1, except that compound (F-1c) was used instead of compound (F-1a).

[0215]

[0216] Production Example 6 A compound represented by the following formula (F-7) (=compound (F-7)) was obtained in the same manner as in Production Example 2, except that compound (F-1c) was used instead of compound (F-1a).

[0217]

[0218] Production Example 7 A compound represented by the following formula (F-8) (=compound (F-8)) was obtained in the same manner as in Production Example 1, except that compound (F-1a') was used instead of compound (F-1a).

[0219] Production Example 8 A compound represented by the following formula (F-9) (=compound (F-9)) was obtained in the same manner as in Production Example 1, except that compound (F-1b′) was used instead of compound (F-1a).

[0220] Production Example 9 A compound represented by the following formula (F-10) (=compound (F-10)) was obtained in the same manner as in Production Example 1, except that compound (F-1d) was used instead of compound (F-1a).

[0221] Production Example 10 A compound represented by the following formula (F-11) (=compound (F-11)) was obtained in the same manner as in Production Example 1, except that compound (F-1e) was used instead of compound (F-1a).

[0222] Production Example 11 A compound represented by the following formula (F-12) (=compound (F-12)) was obtained in the same manner as in Production Example 1, except that compound (F-1f) was used instead of compound (F-1a).

[0223] Production Example 12 Based on the method described in a non-patent document (R. J. Terjeson, et. al., Inorg. Chem., Vol. 27, 1988, 2916), a compound represented by the following formula (F-13) (=compound (F-13)) was obtained.

[0224] Production Example 13 Based on the method described in a non-patent document (R. J. Willenbring, et al., Can. J. Chem., Vol. 67, 1989, 2037), a compound represented by the following formula (F-14) (=compound (F-14)) was obtained.

[0225] Synthesis of Production Example 14 (G-3) 0.4 g of ethyl 4-pentenoate and 50 mL of hexane were added to a reaction vessel and cooled to -40°C. 50 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration: 0.1 M) was added thereto, and then a hexane solution of triethylborane (concentration: 0.1 M) was added dropwise using a syringe. The mixture was then reacted at -40°C for 3 hours. After that, the temperature was returned to room temperature, and 10 mL of water was added, and the organic layer (1) and the aqueous layer (1) were separated.

[0226] The aqueous layer (1) obtained by separation was further extracted three times with 10 mL of diethyl ether, and the obtained organic layer (2) was combined with the organic layer (1) and washed three times with 20 mL of water.

[0227] Thereafter, the solvent was distilled off from the organic layer (3) obtained by the separation operation under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a compound represented by the following formula (F-15a) (=compound (F-15a)) (yield: 78%):

[0228] 2.9 g of compound (F-15a) and 1.5 g of sodium sulfite were placed in a reaction vessel, and 50 mL of a 50% aqueous ethanol solution was added thereto. The mixture was then heated under reflux for 70 hours and reacted. The mixture was then returned to room temperature and concentrated. The resulting residue was extracted with ethanol, and the organic layer was concentrated again to obtain a compound represented by the following formula (F-15b) (=compound (F-15b)) (yield 60%).

[0229] 3.3 g of (F-15b), 2.3 g of ethyldiisopropylaminocarbodiimide hydrochloride, and 0.1 g of dimethylaminopyridine were added to a reaction vessel and the atmosphere was purged with nitrogen. 50 mL of THF was added and the mixture was stirred. The mixture was cooled to 0°C in an ice bath, and 1.7 g of 1-adamantanemethanol was added thereto, followed by stirring at room temperature for 12 hours. 10 mL of water was then added to terminate the reaction, and the solvent was evaporated under reduced pressure. The mixture was extracted three times with 50 mL of ethyl acetate. The resulting organic layer was washed with saturated sodium carbonate and then washed five times with water. The solvent was evaporated under reduced pressure to give sodium 3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorosulfanylmethyl)-propanesulfonate as a pale yellow solid (2.7 g; yield 57%).

[0230] Synthesis of Production Example 15 (G-4) to Production Example 19 (G-8) The compounds described below were synthesized by a method similar to Production Example 14. Synthesis of Production Example 15 (G-4) The same procedure as in Production Example 14 was carried out, except that 0.3 g of ethyl acrylate was used instead of 0.4 g of ethyl 4-pentenoate, to give sodium 1-(1-adamantanemethyloxycarbonyl)-2-(pentafluorosulfanyl)-ethanesulfonate as a pale yellow solid (1.6 g; yield 36%).

[0231] Synthesis of Production Example 16 (G-5) The same procedure as in Production Example 14 was performed except that 0.5 g of methyl 4-vinylbenzoate was used instead of 0.4 g of ethyl 4-pentenoate, to give sodium 1-{4-(1-adamantanemethyloxycarbonyl)phenyl}-2-(pentafluorosulfanyl)-ethanesulfonate as a pale yellow solid (1.9 g; yield 36%).

[0232] Synthesis of Production Example 17 (G-6) The same procedure as in Production Example 14 was carried out, except that 1.2 g of 4-fluorophenyl tetrafluorosulfanyl chloride synthesized based on the method described in a non-patent document (T. Umemoto, et. al., Beilstein. J. Org. Chem., 2012, Vol. 8, 461) was used instead of 50 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration: 0.1 M), to obtain sodium 3-(1-adamantanemethyloxycarbonyl)-1-(4-fluorophenyltetrafluorosulfanylmethyl)-propanesulfonate as a pale yellow solid (2.1 g; yield 38%).

[0233] Synthesis of Production Example 18 (G-7) The same procedure as in Production Example 14 was carried out, except that 1.6 g of pentafluorophenyl tetrafluorosulfanyl chloride synthesized based on the method described in a non-patent document (T. Umemoto, et. al., Beilstein. J. Org. Chem., 2012, Vol. 8, 461) was used instead of 50 mL of a hexane solution of pentafluorosulfanyl chloride (pentafluorosulfanyl chloride concentration: 0.1 M), to obtain sodium 3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorophenyl tetrafluorosulfanylmethyl)-propanesulfonate as a pale yellow solid (2.7 g; yield 43%).

[0234] Synthesis of Production Example 19 (G-8) The same procedure as in Production Example 14 was performed except that 1.3 g of 2-hydroxyethyl methacrylate was used instead of 1.7 g of 1-adamantanemethanol, to give sodium 3-{2-(methacryloyloxy)ethoxycarbonyl}-1-(pentafluorosulfanylmethyl)-propanesulfonate as a white solid (1.8 g; yield 41%).

[0235] Example 1: 3.0 g of compound (F-3) and 2.0 g of 1-adamantanecarboxylic acid chloride were placed in a reaction vessel, and the atmosphere was purged with nitrogen. 30 mL of acetonitrile was added thereto and stirred. The mixture was cooled to 0°C in an ice bath, and 1.1 g of 2,6-lutidine was added dropwise thereto. The mixture was then stirred at room temperature for 8 hours. After the reaction, 30 mL of water and 50 mL of dichloromethane were added thereto and stirred for 1 hour. After removing the aqueous layer by separation, the organic layer was washed twice with 10 mL of water, and the solvent was distilled off under reduced pressure. The resulting solid was recrystallized from 2-propanol to obtain potassium 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonate, represented by the following formula (G-1), as a white solid (2.2 g; yield 48%).

[0236] To a reaction vessel were added 3.0 g of triphenylsulfonium chloride and 4.6 g of compound (G-1), and then 50 mL of dichloromethane and 50 mL of water were added, followed by stirring at room temperature for 10 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed five times with 50 mL of water. The organic layer was concentrated under reduced pressure, and the resulting solid was recrystallized from a dichloromethane-ether mixed solvent to obtain triphenylsulfonium 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonate, represented by the following formula (S-1), as a white solid (6.2 g; yield 90%).

[0237]

[0238] Example 2 The same procedure as in Example 1 was carried out except that 1.0 g of methacrylic acid chloride was used instead of 2.0 g of 1-adamantanecarboxylic acid chloride, and triphenylsulfonium 3-methacryloyloxy-2-(pentafluorosulfanyl)-1-propenesulfonate was obtained as a white solid (5.1 g; yield 86%).

[0239] Example 3 The same procedure as in Example 1 was carried out, except that 3.2 g of compound (F-2) was used instead of 3.0 g of compound (F-3), to obtain triphenylsulfonium 1-chloro-3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)propanesulfonate as a white solid (5.8 g; yield 80%).

[0240] Example 4 The same procedure as in Example 1 was carried out, except that 3.2 g of compound (F-2) was used instead of 3.0 g of compound (F-3) and 1.0 g of methacrylic acid chloride was used instead of 2.0 g of 1-adamantanecarboxylic acid chloride, to obtain triphenylsulfonium 1-chloro-3-methacryloyloxy-2-(pentafluorosulfanyl)propanesulfonate as a white solid (5.1 g; yield 81%).

[0241] Example 5 The same procedure as in Example 1 was carried out except that 4.8 g of compound (F-5) was used instead of 3.0 g of compound (F-3), and triphenylsulfonium 4-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-butenesulfonate was obtained as a white solid (6.3 g; yield 90%).

[0242] Example 6 The same procedure as in Example 1 was carried out, except that 3.4 g of compound (F-4) was used instead of 3.0 g of compound (F-3) and 1.0 g of methacrylic acid chloride was used instead of 2.0 g of 1-adamantanecarboxylic acid chloride, to obtain triphenylsulfonium 1-chloro-4-methacryloyloxy-2-(pentafluorosulfanyl)butanesulfonate as a white solid (5.1 g; yield 79%).

[0243] Example 7 The same procedure as in Example 1 was carried out, except that 3.4 g of compound (F-4) was used instead of 3.0 g of compound (F-3), to give triphenylsulfonium 4-(1-adamantanecarbonyloxy)-1-chloro-2-(pentafluorosulfanyl)butanesulfonate as a white solid (6.4 g; yield 87%).

[0244] Example 8 The same procedure as in Example 1 was carried out, except that 4.2 g of compound (F-10) was used instead of 3.0 g of compound (F-3), to give triphenylsulfonium 3-(1-adamantanecarbonyloxy)-1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)propanesulfonate as a white solid (5.8 g; yield 71%).

[0245] Example 9 The same procedure as in Example 1 was carried out, except that 4.3 g of compound (F-11) was used instead of 3.0 g of compound (F-3), to give triphenylsulfonium 4-(1-adamantanecarbonyloxy)-1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)butanesulfonate as a white solid (6.3 g; yield 76%).

[0246] Example 10 The same procedure as in Example 1 was carried out, except that 4.3 g of bis(4-tert-butylphenyl)iodonium chloride was used instead of 3.0 g of triphenylsulfonium chloride, to give bis(4-tert-butylphenyl)iodonium 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonate as a white solid (7.2 g; yield 88%).

[0247] Example 11 The same procedure as in Example 1 was carried out, except that 3.2 g of compound (F-2) was used instead of 3.0 g of compound (F-3), and 4.3 g of bis(4-tert-butylphenyl)iodonium chloride was used instead of 3.0 g of triphenylsulfonium chloride, to give bis(4-tert-butylphenyl)iodonium 1-chloro-3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)propanesulfonate as a white solid (6.9 g; yield 81%).

[0248] Example 12 3.0 g of triphenylsulfonium chloride and 3.2 g of compound (F-2) were added to a reaction vessel, and then 50 mL of dichloromethane and 50 mL of water were added, followed by stirring at room temperature for 10 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed five times with 50 mL of water. The organic layer was concentrated under reduced pressure, and the resulting solid was recrystallized from a dichloromethane-ether mixed solvent to obtain triphenylsulfonium 1-chloro-3-hydroxy-2-pentafluorosulfanylpropanesulfonate as a white solid (5.0 g; yield 89%).

[0249] Example 13 The same procedure as in Example 12 was carried out except that 3.4 g of compound (F-4) was used instead of 3.2 g of compound (F-2), and triphenylsulfonium 1-chloro-4-hydroxy-2-pentafluorosulfanylpropanesulfonate was obtained as a white solid (5.0 g; yield 88%).

[0250] Example 14 The same procedure as in Example 12 was carried out except that 3.9 g of sodium 1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)ethanesulfonate was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium 1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)ethanesulfonate as a white solid (5.7 g; yield 88%).

[0251] Example 15 The same procedure as in Example 12 was carried out except that 3.9 g of sodium 1-chloro-2-(5-bromopyridin-2-yltetrafluorosulfanyl)ethanesulfonate was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium 1-chloro-2-(5-bromopyridin-2-yltetrafluorosulfanyl)ethanesulfonate as a white solid (5.0 g; yield 75%).

[0252] Example 16 The same procedure as in Example 12 was carried out except that 2.9 g of compound (F-6) was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium 1-chloro-2-pentafluorosulfanylethanesulfonate as a white solid (4.6 g; yield 87%).

[0253] Example 17 The same procedure as in Example 12 was carried out except that 3.4 g of sodium 1-bromo-2-pentafluorosulfanylethanesulfonate was used instead of 3.2 g of compound (F-2), to obtain triphenylsulfonium 1-bromo-2-pentafluorosulfanylethanesulfonate as a white solid (5.0 g; yield 87%).

[0254] Example 18 The same procedure as in Example 12 was carried out except that 2.4 g of compound (F-13) was used instead of 3.2 g of compound (F-2), and triphenylsulfonium pentafluorosulfanyl methanesulfonate was obtained as a white solid (4.4 g; yield 91%).

[0255] Example 19 The same procedure as in Example 12 was carried out except that 2.7 g of compound (F-7) was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium pentafluorosulfanyl methanesulfonate as a white solid (4.2 g; yield 85%).

[0256] Example 20 The same procedure as in Example 12 was carried out except that 2.6 g of compound (F-14) was used instead of 3.2 g of compound (F-2), and triphenylsulfonium pentafluorosulfanyl methanesulfonate was obtained as a white solid (4.5 g; yield 90%).

[0257] Example 21 The same procedure as in Example 12 was carried out except that 4.2 g of compound (F-9) was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium 1-chloro-3-hydroxy-2-(4-chlorophenyltetrafluorosulfanyl)propanesulfonate as a white solid (4.3 g; yield 66%).

[0258] Example 22 The same procedure as in Example 12 was carried out except that 3.2 g of compound (F-8) was used instead of 3.2 g of compound (F-2), and triphenylsulfonium 2-chloro-3-hydroxy-1-pentafluorosulfanylpropanesulfonate was obtained as a white solid (4.1 g; yield 73%).

[0259] Example 23 The same procedure as in Example 12 was carried out, except that 3.4 g of compound (F-9) was used instead of 3.2 g of compound (F-2), to give triphenylsulfonium 2-chloro-4-hydroxy-2-pentafluorosulfanylpropanesulfonate as a white solid (3.5 g; yield 61%).

[0260] Example 24: To a reaction vessel, 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride and 1.7 g of N-hydroxyphthalimide were added and dissolved in 50 mL of chloroform. This was cooled to 0°C, and 1.1 g of triethylamine was slowly added dropwise with stirring. The temperature was then raised and the mixture was stirred at 50°C for 8 hours. To this reaction solution, 50 mL of chloroform and 50 mL of water were added and the mixture was stirred for 1 hour. After stirring, the mixture was left to stand and the aqueous layer was removed, and the organic layer was removed under reduced pressure to obtain a yellow oil. The obtained yellow oil was further recrystallized from methanol to obtain N-[3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyloxy]phthalimide as a pale yellow solid (3.0 g; yield 53%).

[0261] Example 25 The same procedure as in Example 24 was carried out, except that 3.8 g of 1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)-ethanesulfonyl chloride was used instead of 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride, to give N-[1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)ethanesulfonyloxy]phthalimide as a pale yellow solid (2.2 g; yield 44%).

[0262] Example 26 The same procedure as in Example 24 was carried out except that 1.8 g of 4-methoxybenzoyl cyanide oxime was used instead of 1.7 g of N-hydroxyphthalimide, to give N-[3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyloxy]-4-methoxybenzimidoyl cyanide as a pale yellow solid (3.4 g; yield 58%).

[0263] Example 27 The same procedure as in Example 24 was carried out, except that 3.8 g of 1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)-ethanesulfonyl chloride was used instead of 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride, and 1.8 g of 4-methoxybenzoyl cyanide oxime was used instead of 1.7 g of N-hydroxyphthalimide, to give N-[1-chloro-2-(4-chlorophenyltetrafluorosulfanyl)-ethanesulfonyloxy]-4-methoxybenzimidoyl cyanide as a pale yellow solid (2.6 g; yield 50%).

[0264] Example 28: 1.3 g of N-methylhydroxylammonium hydrochloride was added to a reaction vessel and dissolved in 10 mL of methanol. 15 mL of a 10% solution of potassium hydroxide in methanol was added dropwise while stirring at 0°C. 2.4 g of 8-methoxycoumarin-3-carboxylic acid chloride dissolved in 10 mL of THF was then added and stirred for 1 hour. The reaction solution was returned to room temperature and stirred for another 1 hour, after which the reaction solution was distilled off under reduced pressure. The residue was extracted with 20 mL of ethyl acetate and 20 mL of saturated brine. The organic layer was separated and the solvent was distilled off to obtain N-methyl-N-hydroxy-8-methoxycoumarin-3-carbonylamide (=Compound (G-2)) as a white solid (1.8 g; yield 72%).

[0265] The same procedure as in Example 24 was carried out, except that 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride was changed to 4.8 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-chloropropanesulfonyl chloride and 1.7 g of N-hydroxyphthalimide was changed to 2.5 g of compound (G-2), to obtain N-methyl-N-[3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-chloropropanesulfonyloxy]-8-methoxycoumarin-3-carbonylamide as a pale yellow solid (3.6 g; yield 52%).

[0266] Example 29 The same procedure as in Example 28 was carried out, except that 4.8 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-chloropropanesulfonyl chloride was changed to 4.3 g of 2-{(5-bromopyridin-2-yl)tetrafluorosulfanyl}-1-chloroethanesulfonyl chloride, to give N-methyl-N-[2-{(5-bromopyridin-2-yl)tetrafluorosulfanyl}-1-chloroethanesulfonyloxy]-8-methoxycoumarin-3-carbonylamide as a yellow solid (3.1 g; yield 48%).

[0267] Examples 30 to 32 The compounds listed in the table were synthesized according to the method of Example 1.

[0268] Example 33: 3.0 g of triphenylsulfonium chloride and 4.8 g of compound (G-3) were added to a reaction vessel, and then 50 mL of dichloromethane and 50 mL of water were added, followed by stirring at room temperature for 10 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed five times with 50 mL of water. The organic layer was concentrated under reduced pressure, and the resulting solid was recrystallized from a dichloromethane-diisopropyl ether mixed solvent to obtain triphenylsulfonium 3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorosulfanylmethyl)-propanesulfonate as a white solid (5.4 g; yield 75%).

[0269] Example 34 The same procedure as in Example 33 was carried out except that 5.3 g of compound (G-5) was used instead of 4.8 g of compound (G-3), to give triphenylsulfonium 1-{4-(1-adamantanemethyloxycarbonyl)phenyl}-2-(pentafluorosulfanyl)-ethanesulfonate as a white solid (6.2 g; yield 81%).

[0270] Example 35 The same procedure as in Example 33 was carried out except that 4.5 g of compound (G-4) was used instead of 4.8 g of compound (G-3), to give triphenylsulfonium 1-(1-adamantanemethyloxycarbonyl)-2-(pentafluorosulfanyl)-ethanesulfonate as a white solid (5.5 g; yield 80%).

[0271] Example 36 The same procedure as in Example 24 was carried out, except that 4.4 g of 1-(1-adamantanemethyloxycarbonyl)-2-(pentafluorosulfanyl)-ethanesulfonyl chloride was used instead of 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride, to give N-[1-(1-adamantanemethyloxycarbonyl)-2-pentafluorosulfanylethanesulfonyloxy]phthalimide as a pale yellow solid (3.3 g; yield 58%).

[0272] Example 37 The same procedure as in Example 24 was carried out, except that 4.7 g of 3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorosulfanylmethyl)-propanesulfonyl chloride was used instead of 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride, and 1.8 g of 4-methoxybenzoyl cyanide oxime was used instead of 1.7 g of N-hydroxyphthalimide, to give N-[3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorosulfanylmethyl)-propanesulfonyloxy]phthalimide as a pale yellow solid (3.5 g; yield 57%).

[0273] Example 38 The same procedure as in Example 24 was carried out, except that 4.5 g of 3-(1-adamantanecarbonyloxy)-2-(pentafluorosulfanyl)-1-propenesulfonyl chloride was changed to 5.2 g of 1-{4-(1-adamantanemethyloxycarbonyl)phenyl}-2-(pentafluorosulfanyl)-ethanesulfonyl chloride and 1.7 g of N-hydroxyphthalimide was changed to 2.5 g of compound (G-2) obtained in Example 28, to give N-methyl-N-[1-{4-(1-adamantanemethyloxycarbonyl)phenyl}-2-(pentafluorosulfanyl)-ethanesulfonyloxy]-8-methoxycoumarin-3-carbonylamide as a pale yellow solid (4.5 g; yield 61%).

[0274] Example 39 The same procedure as in Example 33 was carried out except that 5.5 g of compound (G-6) was used instead of 4.8 g of compound (G-3), to give triphenylsulfonium 3-(1-adamantanemethyloxycarbonyl)-1-(4-fluorophenyltetrafluorosulfanylmethyl)-propanesulfonate as a white solid (6.1 g; yield 77%).

[0275] Example 40 The same procedure as in Example 33 was carried out except that 6.3 g of compound (G-7) was used instead of 4.8 g of compound (G-3), to give triphenylsulfonium 3-(1-adamantanemethyloxycarbonyl)-1-(pentafluorophenyltetrafluorosulfanylmethyl)-propanesulfonate as a white solid (6.4 g; yield 74%).

[0276] Example 41 The same procedure as in Example 33 was carried out except that 4.4 g of compound (G-8) was used instead of 4.8 g of compound (G-3), to give triphenylsulfonium 3-{2-(methacryloyloxy)ethoxycarbonyl}-1-(pentafluorosulfanylmethyl)-propanesulfonate as a white solid (4.7 g; yield 69%).

[0277] Photoresists were prepared by the following method using the compounds obtained in the Examples or the compounds shown in the Tables as Comparative Examples as acid generators, and the optimum exposure dose, resolution, and pattern shape were measured using the obtained photoresists.

[0278] (Preparation of Photoresist) 80 parts by weight of the acid-reactive compound obtained in Preparation Example 1 was mixed with 7.4 parts by weight of a compound of an Example or Comparative Example, 1.1 parts by weight of tris[2-(methoxymethoxy)ethyl]amine, 896 parts by weight of propylene glycol monomethyl ether acetate, and 364 parts by weight of cyclohexanone to obtain a mixture, and the obtained mixture was filtered through a 0.2 μm Teflon (registered trademark) filter to prepare a photoresist.

[0279] (Exposure and Development) An antireflective coating solution (ARC-29A, manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon substrate and baked at 200°C for 60 seconds to produce an antireflective coating (78 nm thick). The photoresist prepared above was spin-coated onto the substrate with the antireflective coating and baked at 120°C for 60 seconds using a hot plate to produce a resist film with a thickness of 160 nm. The resulting resist film was exposed using an ArF excimer laser microstepper (NSR-S307E, manufactured by Nikon Corporation, NA=0.85, 4 / 5 annular illumination, Cr mask), baked at 100°C for 60 seconds, and then developed by immersion in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds.

[0280] (Evaluation of optimal exposure dose, resolution, and pattern shape) The exposure dose required to resolve 80 nm lines and spaces at 1:1 was determined as the optimal exposure dose (Eop, mJ / cm ２ The minimum line width (nm) of the separated lines and spaces at this exposure dose was taken as the resolution. The cross-section of the resist pattern was observed using a scanning electron microscope.

[0281] (Gas Phase Acidity Evaluation) The gas phase acidity ΔG (kcal / mol) of sulfonic acid generated from the compound of each Example or Comparative Example was calculated by DFT calculation (B3LYP / 6-311+G(d,p)) using quantum chemistry calculation software (Gaussian16 program).

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] From the above table, it can be seen that the compounds of the present invention can generate sulfonic acids with higher acid strength and can form patterns with higher resolution than the conventional acid generators described in the comparative examples. Therefore, it can be seen that the use of the compounds of the present invention makes it possible to manufacture semiconductor devices with high-resolution wiring patterns and circuit patterns with good yield.

Claims

1. A compound which is a salt of an anion represented by the following formula (a-1) or (a-2) and a cation: (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

2. A compound represented by the following formula (b-1) or (b-2): (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ２ , R ３ are the same or different and represent an organic group. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

3. A compound represented by the following formula (c-1) or (c-2): (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ４ , R ５ R may be the same or different and represent a hydrocarbon group which may have a substituent. ４ , R ５ may be bonded to each other to form a ring together with the adjacent carbon atoms. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group is bonded to a linking group. L represents a single bond or a linking group. n represents 0 or 1.

4. A compound represented by the following formula (d-1) or (d-2): (In the formula, R １ R represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group in which two or more of the above groups are bonded via a linking group. ６ , R ７ R may be the same or different and represent a hydrocarbon group which may have a substituent. １０ represents a fluorine atom, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ２０ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a group having a group in which the above group and a linking group are bonded together; and n represents 0 or 1.

5. An acid generator comprising the compound according to any one of claims 1 to 4.

6. A photoresist comprising the acid generator of claim 5 and an acid-reactive compound.

7. A method for manufacturing an electronic device or an optical device, comprising the step of forming a pattern by photolithography using the photoresist according to claim 6.

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