TW202206410A - Nonionic photoacid generator, and photolithography resin composition - Google Patents

Abstract

The purpose of the present invention is to provide: a photoacid generator containing a sulfonamide compound which has a high decomposition rate in response to near-ultraviolet rays, generates a superacid bis-sulfonamide, and is highly soluble in a resist solvent; and a photolithography resin composition which contains the photoacid generator and is highly sensitive to near-ultraviolet rays. The present invention pertains to: a nonionic photoacid generator (A) characterized by containing a sulfonamide compound represented by general formula (1); and a photolithography resin composition (Q) containing the nonionic photoacid generator (A).

Description

Nonionic photoacid generator and resin composition for photolithography

The present invention relates to a nonionic photoacid generator and a resin composition for photolithography. More specifically, it relates to a nonionic photoacid generator containing a sulfonamide compound suitable for acting on ultraviolet rays (i rays, KrF rays) to generate superacids, and a nonionic photoacid generator containing the same resin composition for photolithography.

Conventionally, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography step in which a desired pattern can be transferred to a resist using light of various wavelengths has been widely used. As the resist material, for example, a resin composition containing a polymer having a tertiary butyl ester group of a carboxylic acid or a tertiary butyl carbonate group of a phenol and a photoacid generator can be used. By dissolving the resist material in a solvent and coating it on a substrate and irradiating it with light, the photoacid generator is decomposed and a super acid such as trifluoromethanesulfonic acid is generated (showing higher than 100% sulfuric acid). acidity acid). Furthermore, by performing post-exposure heating (PEB), acid-reactive groups such as tertiary butyl ester groups or tertiary butyl carbonate groups in the polymer are dissociated by the generated acid to form carboxylic acid groups or phenolic groups. Hydroxyl group, the light-irradiated part becomes easily soluble in an alkaline developing solution. Since pattern formation is performed by utilizing this phenomenon, in order to realize energy saving and shortening of step time, it is desired to develop a high-sensitivity resist material that can obtain a desired pattern with a small exposure amount. Therefore, as a photoacid generator for realizing a high-sensitivity resist material, it is desirable that the photodecomposition rate is high and the generated acid has a higher acid strength.

For the above reasons, as photoacid generators suitable for the photolithography step, triaryl perionium salts (Patent Document 1), benzalylmethyl perionium salts having a naphthalene skeleton (Patent Document 2), and the like are disclosed A photoacid generator, and a nonionic photoacid generator having an oxime sulfonate structure (Patent Document 3), a naphthalimide structure (Patent Document 4, Patent Document 5), or the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 50-151997 [Patent Document 2] Japanese Patent Laid-Open No. 9-118663 [Patent Document 3] Japanese Patent Laid-Open No. 6-67433 [Patent Document 4] Japanese Patent Laid-Open No. 2004-217748 [Patent Document 5] Japanese Patent No. 5990447

[The problem to be solved by the invention] As a light source for the photolithography step for decomposing the photoacid generator in the resin composition for photolithography, in terms of availability and stability, near-infrared rays such as i-rays (365 nm) and KrF rays (248 nm) are widely used. As for ultraviolet rays, with the growth of the semiconductor market, there is an increasing demand for the development of photoacid generators with high sensitivity to these near-ultraviolet rays. In addition, with the diversification of photolithography steps, in order to prevent solid precipitation and phase separation even in high-concentration resin compositions for photolithography, there is a demand for resists contained in the resin composition for photolithography. The solvent is highly soluble.

However, ionic photoacid generators such as triaryl perionate or benzalkonium methyl perionate have a low photodecomposition rate with respect to i-rays and have low sensitivity, and since they are salts, there is a problem in that if they are contained in a high concentration in light In the resin composition for lithography, phase separation or precipitation occurs.

Nonionic photoacid generators having an oxime sulfonate structure and a naphthalimide structure have a high photodecomposition rate with respect to i-rays, but in practical use, the generation of acids is limited to sulfonic acids, and sufficient acidity cannot be obtained, and there are some problems. low sensitivity problem.

That is, the object of the present invention is to provide a photoacid generator containing a sulfonamide compound that has a high decomposition rate against near ultraviolet rays such as i-rays and KrF rays, and generates bissulfonamide as a super acid and is highly soluble in a resist solvent. agent, and a resin composition for photolithography containing the photoacid generator and having high sensitivity to near-ultraviolet rays. [Means of Solving Problems]

The present inventors have completed the present invention as a result of diligent studies in order to achieve the object. That is, the present invention is a nonionic photoacid generator (A); and a resin composition (Q) for photolithography comprising the nonionic photoacid generator (A), the nonionic photoacid generator (A) is characterized by containing a sulfonamide compound represented by the following general formula (1).

[hua 1]

[In the formula, R _f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, R ¹ is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, and R _f and R ¹ can be bonded to each other. Forming a ring, R ² is a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heteroatom-containing aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl R ³ is a cyclic alkyl group, an aryl group, or an aryl group containing a heteroatom, and R ² and R ³ may be bonded to each other to form a ring (which may contain a heteroatom). ] [Effect of invention]

The nonionic photoacid generator (A) of the present invention has a high decomposition rate with respect to near-ultraviolet rays, generates a super acid, and is excellent in solubility in a resist solvent. Moreover, the resin composition (Q) for photolithography containing this nonionic photoacid generator (A) has high sensitivity to near ultraviolet rays.

The sulfonamide compound contained in the nonionic photoacid generator (A) of the present invention is represented by the following general formula (1).

[hua 2]

[In the formula, R _f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, R ¹ is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, and R _f and R ¹ can be bonded to each other. Forming a ring, R ² is a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heteroatom-containing aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl R ³ is a cyclic alkyl group, an aryl group, or an aryl group containing a heteroatom, and R ² and R ³ may be bonded to each other to form a ring (which may contain a heteroatom). ]

In the general formula (1), R _f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, and may have a substituent. R _f and R ¹ may be bonded to form a ring.

The fluoroalkyl group is an alkyl group in which at least one hydrogen is substituted with fluorine, and examples thereof include fluoroalkyl groups having 1 to 10 carbon atoms (excluding substituents. The same applies to the following unless otherwise specified), and examples thereof include linear fluoroalkyl groups ( RF1), branched fluoroalkyl (RF2), or cyclic fluoroalkyl (RF3), etc.

Examples of linear fluoroalkyl groups (RF1) include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, and difluoro Methyl, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl, difluoro(methoxycarbonyl)methyl and 2-adamantylcarbonyloxy base-1,1-difluoroethyl, etc.

As a branched fluoroalkyl group (RF2), a hexafluoroisopropyl group, a nonafluoro-tert-butyl group, a perfluoro-2-ethylhexyl group, etc. are mentioned.

As a cyclic fluoroalkyl group (RF3), a heptafluorocyclobutyl group, a nonafluorocyclopentyl group, a perfluorocyclohexyl group, a perfluoro(1-cyclohexyl)methyl group, etc. are mentioned.

The fluoroaryl group is an aryl group in which at least one hydrogen is substituted with fluorine, and examples thereof include fluoroaryl groups (RF4) having 6 to 10 carbon atoms.

Examples of the fluoroaryl group (RF4) having 6 to 10 carbon atoms include 3,4,5-trifluorophenyl, pentafluorophenyl, perfluoronaphthyl, 3-trifluoromethyltetrafluorophenyl, and 3 , 5-bis-trifluoromethylphenyl, etc.

Among R _f , from the viewpoint of the deprotection ability of the photoresist and the easiness of obtaining raw materials, straight-chain fluoroalkyl groups (RF1), branched fluoroalkyl groups (RF2), and fluoroaryl groups (RF2) are preferred. RF4), more preferably straight-chain fluoroalkyl (RF1), and fluoroaryl (RF4), particularly preferably trifluoromethyl (CF ₃ ), pentafluoroethyl (C ₂ F ₅ ), heptafluoropropyl (C ₃ F ₇ ), nonafluorobutyl (C ₄ F ₉ ) and pentafluorophenyl (C ₆ F ₅ ).

In the general formula (1), R ¹ is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, and may have a substituent.

Examples of the alkyl group include a straight-chain alkyl group (RA1) having 1 to 18 carbon atoms, a branched alkyl group (RA2) having 1 to 18 carbon atoms, and a cyclic alkyl group (RA3) having 3 to 18 carbon atoms.

Examples of straight-chain alkyl groups (RA1) include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and benzyl , benzyloxymethyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 1-methoxyethyl, trimethylsiloxymethyl, triethylsiloxy methyl and tert-butyldimethylsiloxymethyl, etc.

Examples of branched alkyl groups (RA2) include isopropyl, isobutyl, 2-butyl, 3-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and 1-methylbutyl base, 2-ethylhexyl, 2-hexyldecyl, isodecyl and isooctadecyl, etc.

Examples of the cyclic alkyl group (RA3) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, 1-adamantyl, 2-adamantyl, menthyl, and 10-camphoryl , Octahydronaphthyl, tricyclodecyl, tetracyclododecyl and 4-dodecylcyclohexyl, etc.

As the fluoroalkyl group, the same ones as the above-mentioned linear fluoroalkyl group (RF1), branched fluoroalkyl group (RF2), or cyclic fluoroalkyl group (RF3) can be mentioned.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms (RA4), and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-azulene, 2-tolyl, 3-tolyl, 4-Tolyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-xylyl, 2,6-diphenyl Tolyl, 3,5-xylyl, 2,4-dinitrophenyl and 2,4,6-mesityl, etc.

As a fluoroaryl group, the same thing as the said fluoroaryl group (RF4) is mentioned.

Among these, from the viewpoint of availability of raw materials, a straight-chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, and a straight-chain fluoroalkyl group having 1 to 10 carbon atoms ( RF1), an aryl group having 6 to 8 carbon atoms and a fluoroaryl group having 6 to 8 carbon atoms, more preferably methyl, ethyl, propyl, butyl, octyl, 10-camphoryl, trifluoromethyl ( CF ₃ ), pentafluoroethyl (C ₂ F ₅ ), heptafluoropropyl (C ₃ F ₇ ), nonafluorobutyl (C ₄ F ₉ ), phenyl, 4-tolyl, 2-nitrobenzene phenyl, 4-nitrophenyl, 2,4-dinitrophenyl and pentafluorophenyl (C ₆ F ₅ ), particularly preferred are trifluoromethyl (CF ₃ ), pentafluoroethyl (C ₂ F ₅ ), heptafluoropropyl (C ₃ F ₇ ), nonafluorobutyl (C ₄ F ₉ ) and pentafluorophenyl (C ₆ F ₅ ).

In the general formula (1), R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryl group containing a heteroatom, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, The alkylsulfonyl group or the arylsulfonyl group may have a substituent. R ² and R ³ may be bonded to form a ring (which may contain heteroatoms).

As the alkyl group, the same as the above-mentioned linear alkyl group (RA1), branched alkyl group (RA2), and cyclic alkyl group (RA3) can be mentioned.

Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms (RE1), and the like, and examples include linear, branched, or cyclic alkenyl groups (vinyl, cyanovinyl, dicyanovinyl, phenylvinyl, etc.). base, 1-propenyl, 2-propenyl, 1-buten-1-yl, 2-buten-1-yl, 2-methyl-2-propenyl, 1-cyclopenten-1-yl, 1-cyclohexen-1-yl, 1-decen-1-yl and norbornenyl, etc.) and the like.

Examples of the alkynyl group include alkynyl groups having 2 to 10 carbon atoms (RY1) and the like, and examples include linear, branched, or cyclic alkynyl groups (ethynyl, 1-propyn-1-yl, 2-propyn- 1-yl, 1-butyn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 2-pentyn-1-yl, 3 -Pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 3-methyl-1-butyn-1-yl, 1-methyl-2-butyn- 1-yl, 1-methyl-3-butyn-1-yl, 1,1-dimethyl-2-propyn-1-yl, 1-cyclooctyn-1-yl and 2-phenylacetylene -1-base etc.) etc.

Examples of the aryl group include aryl groups having 6 to 14 carbon atoms (RA5), and examples thereof include phenyl, 4-cyanophenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, and 2-anthracene. base, 9-anthryl, 3-phenanthryl, 9-phenanthryl, 1-azulene, 2-fluorenyl, 9',9'-dimethyl-2-fluorenyl and 9',9'-bistri Fluoromethyl-2-fluorenyl, etc.

Examples of the heteroatom-containing aryl group include heteroatom-containing aryl groups (RA6) having 3 to 14 carbon atoms, and examples thereof include those containing one or more heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur. Furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, thiophenyl, benzofuranyl, isobenzofuranyl, benzopyranyl, benzothiazolyl, benzimidazolyl, Indolyl, indoleninyl group, naphthothiazolyl, naphthoxazolyl, xanthene, thiathanthyl, phenothiyl, dibenzo-p-iodobenzonitrile, thioxanthyl Anthracene group, xanthone group, thioxanthone group, anthraquinone group, dibenzofuran group, fluorenyl group, carbazole group and coumarin group, etc.

Examples of the alkylcarbonyl group include alkylcarbonyl groups (RC1) having 1 to 10 carbon atoms (excluding carbonyl carbons), and the like, and examples include straight-chain or branched alkylcarbonyl groups (acetyl, propionyl, butyryl, 2-methyl) propylpropionyl, pentamyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethylpropanoyl, octanoyl, 2-ethylhexyl and decanoyl, etc.) and the like.

Examples of the arylcarbonyl group include an arylcarbonyl group (RC2) having 6 to 10 carbon atoms (excluding carbonyl carbons), and the like, and examples thereof include a benzyl group, a naphtholinyl group, and a 4-tolylcarbyl group.

Examples of the alkoxycarbonyl group include alkoxycarbonyl groups (RC3) having 1 to 10 carbon atoms (excluding carbonyl carbons), and the like, and examples include linear or branched alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, third pentoxycarbonyl, octoxycarbonyl, 2- ethylhexyloxycarbonyl and benzyloxycarbonyl (Cbz, etc.), etc.

Examples of the aryloxycarbonyl group include aryloxycarbonyl (RC4) having 6 to 10 carbon atoms (excluding carbon on the carbonyl group), and the like, and examples thereof include phenoxycarbonyl, 2-tolyloxycarbonyl, and 4-tolyloxy ylcarbonyl, 4-methoxyphenoxycarbonyl, 4-chlorophenoxycarbonyl, 1-naphthoxycarbonyl, 2-naphthoxycarbonyl and the like.

Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 10 carbon atoms (RC5), and the like, and examples include straight-chain or branched alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, propylsulfonyl, etc.). Sulfonyl, Isopropyl Sulfonyl, Butyl Sulfonyl, Isobutyl Sulfonyl, Second Butyl Sulfonyl, Third Butyl Sulfonyl, Amyl Sulfonyl, Isopentyl Sulfonyl, neopentylsulfonyl, third pentylsulfonyl, octylsulfonyl, decylsulfonyl, trifluoromethanesulfonyl, pentafluoroethanesulfonyl, nonafluorobutane Sulfonyl and perfluorooctane sulfonyl, etc.), etc.

Examples of the arylsulfonyl group include arylsulfonyl groups (RC6) having 6 to 10 carbon atoms (benzenesulfonyl, 2-toluenesulfonyl, 4-toluenesulfonyl, 2-nitrobenzenesulfonyl) base, 4-nitrobenzenesulfonyl, 2,4-dinitrobenzenesulfonyl, 2-mesitylenesulfonyl, 4-butylbenzenesulfonyl, 4-tert-butylbenzenesulfonyl base, naphthylsulfonyl, pentafluorobenzenesulfonyl and 3,5-bis(trifluoromethyl)benzenesulfonyl, etc.) and the like.

In the general formula (1), R ³ is a cyclic alkyl group, an aryl group or a heteroatom-containing aryl group, and may have a substituent.

Examples of the cyclic alkyl group include cyclic alkyl groups having 3 to 12 carbon atoms (RA7), and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and 1-adamantane. base, 2-adamantyl, menthyl, 10-camphoryl, octahydronaphthyl, tricyclodecyl, tetracyclododecyl and 4-hexylcyclohexyl, etc.

As an aryl group, the same thing as the said aryl group (RA5) is mentioned.

Examples of the heteroatom-containing aryl group include the same ones as the above-mentioned heteroatom-containing aryl group (RA6).

As the substituents of the aryl group (RA5) and the heteroatom-containing aryl group (RA6), the same ones as those exemplified in the following (R ⁶ ) can be mentioned.

In the general formula (1), R ³ can be bonded to R ² at an appropriate position on the carbon of the cyclic alkyl group (RA7), aryl group (RA5) and heteroatom-containing aryl group (RA6) to form a ring structure, which may contain heteroatoms.

In the general formula (1), among the above R ² and R ³ , the following (a) and (b) are preferably used from the viewpoints of availability of raw materials, ease of synthesis, and stability.

(a): In the general formula (1), R ² is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heteroatom-containing aryl group having 3 to 14 carbon atoms, and R ³ is carbon A cyclic alkyl group with 3 to 12 carbon atoms, an aryl group with 6 to 14 carbon atoms, or a heteroatom-containing aryl group with 3 to 14 carbon atoms, R ² and R ³ are bonded to each other to form a 5- to 7-membered ring (may contain heteroatoms). Preferably, the following general formula (1)-1, general formula (1)-2, and general formula (2)-1 to general formula (2)-5 can be mentioned. Furthermore, general formula (1)-1 and general formula (2)-1 to general formula (2)-5 are preferable. In the general formula (1)-2, a plurality of R ¹ are independent of each other.

[hua 3]

[hua 4]

(b): In the general formula (1), R ² is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroatom-containing group having 3 to 14 carbon atoms. aryl group, arylcarbonyl group with carbon number 6-10 (excluding carbonyl carbon), alkoxycarbonyl group with carbon number 1-10 (excluding carbonyl carbon), or alkylsulfonyl group with carbon number 1-10, R ³ is a cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heteroatom-containing aryl group having 3 to 14 carbon atoms. Preferably, the following general formula (3)-1 to general formula (3)-4, general formula (4)-1, and general formula (4)-2 can be mentioned. Furthermore, general formula (3)-1, general formula (3)-2, general formula (3)-4, general formula (4)-1, and general formula (4)-2 are more preferable. Furthermore, R ² is a group selected from the above-mentioned groups.

[hua 5]

[hua 6]

In the general formula (1)-1, G ¹ is a group in which R ² and R ³ are bonded to form a ring, and examples include -CH ₂ -, -CH ₂ -CH ₂ -, -O-, -S-, or -NR ⁷ - etc., R ⁷ is an alkyl group having 1 to 4 carbon atoms, phenyl, acetyl, propionyl, butyryl, benzyl, methanesulfonyl, benzenesulfonyl, and tosylsulfonyl , or nitrobenzenesulfonyl group (nosyl), from the viewpoint of availability of raw materials and ease of synthesis, preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetyl group, and a benzyl group , and more preferably methyl and phenyl.

In general formula (2)-1 to general formula (2)-5, G ² is a group in which R ² and R ³ are bonded to form a ring, and examples thereof include -CH ₂ -, -O-, -S-, or -NR ⁸ - or the like (R ⁸ is the same as R ⁷ described above), and R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an acetyl group from the viewpoints of availability of raw materials and ease of synthesis. base, benzyl.

In general formula (2)-1 to general formula (2)-5, R ⁴ and R ⁵ are hydrogen atoms or substituents of the ring formed by R ² and R ³ bonded to each other, and each independently includes a hydrogen atom, An alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms (RA5), a halogen atom, etc., from the viewpoint of ease of synthesis, preferably a hydrogen atom, a straight chain alkane having 1 to 6 carbon atoms base, phenyl, halogen atom.

As the halogen atom, the same ones as those listed in (R ⁶ ) described later can be mentioned.

In the general formula (3)-4, G ³ and G ⁴ are groups constituting a condensed ring, and when the combination is represented as (G ³ , G ⁴ ), (-O-, -O-), (-O-, -O-), (- S-,-S-), (-C(O)-,-O-), (-C(O)-,-S-), (-C(O)-,-C(O)-), (-CH=CH-,single bond), (-O-,single bond), (-S-,single bond), (-CH ₂ -,single bond) or (-C(O)-,single bond) Wait.

In general formula (4)-1 and general formula (4)-2, G ⁵ is -CMe ₂ -, -O-, -S-, or -NR ⁹ - (Me represents a methyl group, R ⁹ is the same as the R ⁷ ), from the viewpoints of availability of raw materials and ease of synthesis, R ⁹ is preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetyl group, or a benzyl group, and more preferably a methyl group .

In the general formula, (R ⁶ ) _n is an independent n (n is an integer of 0-8) substituents at any position on the aryl group (RA5) or the heteroatom-containing aryl group (RA6) , can be bonded to each other to form a ring, such as: alkyl, fluoroalkyl, alkenyl, alkynyl, aryl, heteroatom-containing aryl, alkoxy, alkylthio, alkylcarbonyl, arylcarbonyl , alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkyl carbonate, aryl carbonate, alkylsulfonyl, arylsulfonyl, amine and halogen atoms, etc.

In the general formula (1)-1, the general formula (1)-2, and the general formula (2)-1 to the general formula (2)-5, the substitution position of (R ⁶ ) is to place R in the general formula (1). The structure formed by the bonding of ² and R ³ is determined as the parent skeleton, and is in the general formula (3)-1 to the general formula (3)-4, the general formula (4)-1 and the general formula (4)-2. , the substitution position of (R ⁶ ) is determined by setting R ³ as the parent skeleton in the general formula (1).

As the alkyl group in (R ⁶ ), the same as the above-mentioned straight-chain alkyl group (RA1), branched alkyl group (RA2), and cyclic alkyl group (RA3) can be mentioned, in terms of availability of raw materials and ease of synthesis From the viewpoint of , preferably a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a Tributyl, pentyl, hexyl, 2-ethylhexyl, cyclopentyl and cyclohexyl.

As the fluoroalkyl group in (R ⁶ ), the same ones as the above-mentioned straight-chain fluoroalkyl group (RF1), branched fluoroalkyl group (RF2), and cyclic fluoroalkyl group (RF3) can be mentioned. In terms of availability of raw materials, From the viewpoint of ease of synthesis, straight-chain, branched, or cyclic fluoroalkyl groups having 1 to 8 carbon atoms are preferred, and trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluoromethyl are more preferred. Fluorobutyl and hexafluoroisopropyl.

As the alkenyl group in (R ⁶ ), the same ones as those of the above-mentioned alkenyl group (RE1) can be mentioned.

Examples of the alkynyl group in (R ⁶ ) include the same ones as the alkynyl group (RY1) described above, and from the viewpoint of ease of synthesis, 1-propyn-1-yl, 1-butyn- 1-yl, 1-pentyn-1-yl, 2-phenylethyn-1-yl.

As the aryl group in (R ⁶ ), the same ones as the above-mentioned aryl group (RA5) can be mentioned.

As the heteroatom-containing aryl group in (R ⁶ ), the same ones as those of the above-mentioned heteroatom-containing aryl group (RA6) can be mentioned.

Examples of the alkoxy group in (R ⁶ ) include alkoxy groups having 1 to 10 carbon atoms (RC7) and the like, and are linear, branched or cyclic alkoxy groups (methoxy, ethoxy, propoxy) , isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, hexyloxy, cyclohexyloxy, phenoxy, tolyloxy, benzyloxy, decyloxy base, naphthoxy, methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, benzyloxymethoxy, trimethylsiloxy methoxy, triethylsiloxy, triisopropylsiloxy, t-butyldimethylsiloxy, etc.), from the viewpoint of ease of synthesis, methoxy, ethoxy group, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, benzyloxy and tert-butyldimethylsilyloxy.

Examples of the alkylthio group in (R ⁶ ) include alkylthio groups having 1 to 10 carbon atoms (RC8) and the like, and are linear, branched or cyclic alkylthio groups (methylthio, ethylthio, propylthio) , isopropylthio, butylthio, isobutylthio, second butylthio, third butylthio, pentylthio, isopentylthio, neopentylthio, third pentylthio, phenylthio (phenylthio), tolylthio, benzylthio, octylthio, decylthio, naphthylthio, etc.), from the viewpoint of ease of synthesis, methylthio, ethylthio, propylthio base, isopropylthio, butylthio, benzylthio, octylthio, phenylthio.

Examples of the alkylcarbonyl group in (R ⁶ ) include the same ones as the above-mentioned alkylcarbonyl group (RC1), and from the viewpoint of ease of synthesis, acetyl, propionyl, butyryl, 2- Methylbutyryl and 2,2-dimethylpropionyl.

As the arylcarbonyl group in (R ⁶ ), the same ones as those of the above-mentioned arylcarbonyl group (RC2) can be mentioned.

Examples of the alkoxycarbonyl group in (R ⁶ ) include the same ones as the alkoxycarbonyl group (RC3) described above, and from the viewpoint of ease of synthesis, methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, third pentoxycarbonyl, and 2-ethylhexyloxycarbonyl.

As the aryloxycarbonyl group in (R ⁶ ), the same ones as the above-mentioned aryloxycarbonyl group (RC4) can be mentioned.

Examples of the alkylcarbonyloxy group in (R ⁶ ) include an alkylcarbonyloxy group (RC9) having 1 to 10 carbon atoms (excluding carbonyl carbon), and the like, and a linear or branched alkylcarbonyloxy group (acetyl Oxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, 2-butylcarbonyloxy, 3-butylcarbonyloxy , pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy, decylcarbonyloxy, benzylcarbonyloxy, etc.), etc., from the viewpoint of availability of raw materials In other words, preferred are acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, 2-butylcarbonyloxy, tert-butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy and 2-ethylhexylcarbonyloxy.

Examples of the arylcarbonyloxy group in (R ⁶ ) include arylcarbonyloxy groups (RC10) having 6 to 10 carbon atoms (excluding carbonyl carbons), and the like, and examples thereof include phenylcarbonyloxy and 1-naphthyl. Carbonyloxy, 2-naphthylcarbonyloxy, 1-azulenecarbonyloxy, 2-tolylcarbonyloxy, 3-tolylcarbonyloxy, 4-tolylcarbonyloxy, 2-chlorophenylcarbonyl oxy, 3-chlorophenylcarbonyloxy, 4-chlorophenylcarbonyloxy, 2,4-xylylcarbonyloxy, 2,6-xylylcarbonyloxy, 3,5-xylyl Carbonyloxy, 2,4,6-mesitylcarbonyloxy, 3,5-bis-trifluoromethylphenylcarbonyloxy, pentafluorophenylcarbonyloxy and the like.

Examples of the alkyl carbonate group in (R ⁶ ) include an alkyl carbonate group (RC11) having 1 to 10 carbon atoms (excluding carbonyl carbon), and the like, such as methyl carbonate group, ethyl carbonate group, propylene carbonate group, and the like. Ester group, 2-propyl carbonate group, butyl carbonate group, 2-butyl carbonate group, isobutyl carbonate group, 3-butyl carbonate group, 3-amyl carbonate group, benzyl carbonate group, 2-carbonate group From the viewpoint of availability of raw materials, such as ethylhexyl carbonate, menthyl carbonate, methyl carbonate, ethyl carbonate, propyl carbonate, isopropyl carbonate, and butyl carbonate are preferred. , isobutyl carbonate, 3-butyl carbonate, 3-amyl carbonate, 2-ethylhexyl carbonate.

Examples of the aryl carbonate group in (R ⁶ ) include aryl carbonate groups (RC12) having 6 to 10 carbon atoms (excluding carbonyl carbon), and examples thereof include phenyl carbonate groups and 1-naphthyl carbonate groups. base, 2-naphthyl carbonate, 1-azulene carbonate, 2-cresyl carbonate, 3-cresyl carbonate, 4-cresyl carbonate, 2-chlorophenyl carbonate, 3-chlorobenzene carbonate Ester, 4-chlorophenyl carbonate, 2,4-dimethyl carbonate, 2,6-dimethyl carbonate, 3,5-dimethyl carbonate, 2,4,6-methylcarbonate Cresyl, 3,5-bis-trifluoromethyl phenyl carbonate and pentafluorophenyl carbonate.

Examples of the alkylsulfonyl group in (R ⁶ ) include the same ones as the above-mentioned alkylsulfonyl group (RC5), and from the viewpoint of availability of raw materials, methylsulfonyl group and ethyl group are preferred. Sulfonyl, butylsulfonyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl and perfluorooctanesulfonyl.

Examples of the arylsulfonyl group in (R ⁶ ) include the same ones as those of the above-mentioned arylsulfonyl group (RC6), and from the viewpoint of availability of raw materials, benzenesulfonyl group and 4-toluene are preferred. Sulfonyl, 2-nitrobenzenesulfonyl and pentafluorobenzenesulfonyl.

Examples of the halogen atom in (R ⁶ ) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and from the viewpoints of availability of raw materials and ease of synthesis, a fluorine atom, a chlorine atom and Bromine atom.

In the compound, the three-dimensional structure (E, Z) may be any one or a mixture thereof.

The method for synthesizing the sulfonamide compound contained in the nonionic photoacid generator (A) of the present invention is not particularly limited as long as the target product can be synthesized. For example, the compound of the general formula (1) can be obtained by the method described below. manufacture.

[hua 7]

In the above reaction formula, R ¹ to R ³ and R _f are as defined in the general formula (1). The first stage reaction is carried out in organic solvents (toluene, butyl acetate, acetonitrile, dimethyl formamide (DMF), dimethyl acetamide (DMAc), dichloromethane, chloroform, benzotrifluoride, etc.) or water, under -78℃～reflux conditions, make precursor (PR1), sulfonic acid halide equivalent represented by R ¹ SO ₂ X, base (sodium bicarbonate, potassium carbonate, Sodium hydroxide, potassium hydroxide, pyridine, chloropyridine, dichloropyridine, lutidine, 2,6-di-tert-butylpyridine, triethylamine, ethyldiisopropylamine, diazabicyclodeca Monoene (DBU), tetramethyl piperidine (TMP), tetramethyl guanidine (TMG), hexamethyl disilazane (HMDS), potassium tertiary butoxide, dimethine Lithium isopropylamide, sodium hexamethyldisilazane, etc.) react for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent, thereby obtaining the precursor (PR2). (PR2) may be purified by recrystallization or washing with a solvent as necessary. The reaction can also be continued in an unpurified state depending on the situation.

The second stage of the reaction is to make the precursor (PR2) in an organic solvent (toluene, butyl acetate, acetonitrile, DMF, DMAc, dichloromethane, chloroform, benzotrifluoride, etc.) ), sulfonic acid halide equivalents represented by R _f SO ₂ X, bases (sodium bicarbonate, potassium carbonate, pyridine, chloropyridine, dichloropyridine, 2,6-di-tert-butylpyridine, triethylpyridine amine, ethyldiisopropylamine, TMP, TMG, HMDS, potassium tert-butoxide, lithium diisopropylamide, sodium bishexamethyldisilazane, etc.) for 5 minutes to 3 hours. After the completion of the reaction, the precipitated solid is filtered or extracted with an appropriate solvent, and volatile components are distilled off to obtain the sulfonamide compound of the general formula (1) as a solid. The obtained solid can be purified by column chromatography, washing with an organic solvent, recrystallization, and the like, if necessary.

The nonionic photoacid generator (A) of the present invention generates a superacid by light irradiation, and is therefore suitable for use as a resin composition (resist) for photolithography.

In order to easily dissolve in a resist material, the nonionic photoacid generator (A) of the present invention may be dissolved in a solvent that does not inhibit the reaction in advance.

Examples of solvents that are easily dissolved in the resist material include carbonates (propylene carbonate, ethylidene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.), ethers (ethylene glycol monomethyl ether, Propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.), and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, etc.) Acetate and diethylene glycol monobutyl ether acetate, etc.), etc.

When a solvent is used, the use ratio of the solvent is preferably 15 parts by weight to 1000 parts by weight, more preferably 30 parts by weight to 500 parts by weight, relative to 100 parts by weight of the nonionic photoacid generator (A) of the present invention. share.

Since the resin composition (Q) for photolithography of the present invention contains a nonionic photoacid generator (A) as an essential component, by performing ultraviolet irradiation and post-exposure heating (PEB), the exposed part and the unexposed part are developed. The solubility of the liquid varies. The nonionic photoacid generator (A) may be used alone or in combination of two or more, or may be used in combination with ionic photoacid generators such as periconium salts. Examples of the resin composition (Q) for photolithography include a mixture of a negative-type chemically amplified resin (QN) and a nonionic photoacid generator (A); and a positive-type chemically amplified resin (QP) and a nonionic photoacid generator. Mixture of acid generators (A).

As a negative type chemically amplified resin (QN), it includes a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl group-containing resin, and for example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, hydroxystyrene and Styrene copolymer, hydroxystyrene, copolymer of styrene and (meth)acrylic acid derivatives, phenol/xylylene glycol condensation resin, cresol/xylylene glycol condensation resin, polyimide containing phenolic hydroxyl group , Polyamide acid containing phenolic hydroxyl group, phenol-dicyclopentadiene condensation resin. Among these, preferred are novolak resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic derivatives , Phenol/benzenedimethanol condensation resin. In addition, these phenolic hydroxyl group containing resin (QN1) may be used individually by 1 type, and may be used in mixture of 2 or more types.

The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, gallic phenol, 1-naphthol, 2-naphthol. Moreover, as said aldehyde, formaldehyde, p-formaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned.

As said novolak resin, a phenol/formaldehyde condensed novolak resin, a cresol/formaldehyde condensed novolak resin, and a phenol/naphthol/formaldehyde condensed novolak resin are mentioned, for example.

Moreover, you may contain a phenolic low molecular weight compound as a part of components in the said phenolic hydroxyl group containing resin (QN1). As the phenolic low molecular compound, for example, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1 -Bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl ]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl] ]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethyl Alkane, 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl] Phenyl]ethylene}bisphenol. These phenolic low molecular weight compounds may be used alone or in combination of two or more.

When the phenolic hydroxyl group-containing resin (QN1) is 100% by weight, the content of the phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less, and more preferably It is 1% by weight to 30% by weight.

The weight-average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2,000 or more, and more preferably 2,000 to 20000. Moreover, when making the whole composition except a solvent into 100 weight%, it is preferable that the content rate of the phenolic hydroxyl group-containing resin (QN1) in the negative type chemically amplified resin (QN) is 30 weight% - 90% by weight, more preferably 40% by weight to 80% by weight. When the content ratio of the phenolic hydroxyl group-containing resin (QN1) is 30% by weight to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability by an alkaline aqueous solution, So better.

The crosslinking agent (QN2) is not particularly limited as long as it is a compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with a strong acid generated from the nonionic photoacid generator (A).

As a crosslinking agent (QN2), for example, a bisphenol A-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolak resin-based epoxy compound, and a resol-based epoxy compound can be mentioned. Oxygen compound, poly(hydroxystyrene)-based epoxy compound, oxetane compound, methylol-containing melamine compound, methylol-containing benzoguanamine compound, methylol-containing urea compound, hydroxyl group-containing Methyl phenolic compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenolic compounds, Carboxymethyl-containing melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, carboxymethyl-containing phenol resin, carboxymethyl-containing melamine compound, carboxymethyl-containing benzoguanamine Amine compounds, carboxymethyl-containing urea compounds, and carboxymethyl-containing phenolic compounds.

Among these crosslinking agents (QN2), preferred are methylol-containing phenolic compounds, methoxymethyl-containing melamine compounds, methoxymethyl-containing phenolic compounds, and methoxymethyl-containing glycerol compounds. Urea compounds, methoxymethyl-containing urea compounds, and acetoxymethyl-containing phenolic compounds, more preferably methoxymethyl-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds, etc. Methoxymethyl-containing melamine compounds are CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 305 (Mitsui Cyanamid) ( Co., Ltd.) and other trade names are commercially available, and methoxymethyl-containing glycoluril compounds are commercially available under such trade names as CYMEL 1174 (Mitsui Cyanamid Co., Ltd.), and methyl-containing Oxymethyl urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

The content of the crosslinking agent (QN2) is usually 5 mol with respect to all the acidic functional groups in the phenolic hydroxyl group-containing resin (QN1) from the viewpoint of the reduction of the residual film ratio, the warpage or swelling of the pattern, and the developability. % to 60 mol %, preferably 10 mol % to 50 mol %, more preferably 15 mol % to 40 mol %.

Examples of positive-type chemically amplified resin (QP) include alkali-soluble resin (QP1) containing one or more acidic functional groups such as phenolic hydroxyl group, carboxyl group, or sulfonyl group, and hydrogen of acidic functional group in (QP1). A protective group in which a part or all of the atoms are substituted with an acid dissociable group is introduced into the resin (QP2). The protective group-introducing resin (QP2) itself is alkali-insoluble or alkali-hardly soluble. In addition, an acid dissociable group is a group which can be dissociated in the presence of the superacid generated from the nonionic photoacid generator (A).

As alkali-soluble resin (QP1), a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), a sulfonic acid group-containing resin (QP13), etc. are mentioned, for example. As the phenolic hydroxyl group-containing resin (QP11), the same thing as the above-mentioned hydroxyl group-containing resin (QN1) can be used.

The carboxyl group-containing resin (QP12) is not particularly limited as long as it is a polymer having a carboxyl group. For example, the carboxyl group-containing vinyl monomer (Va) can be mixed with an optional hydrophobic group-containing vinyl monomer (Vb) is obtained by vinyl polymerization.

Examples of the carboxyl group-containing vinyl monomer (Va) include unsaturated monocarboxylic acids [(meth)acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated polyvalent (divalent to tetravalent) carboxylic acids [ (anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl with 1 to 10 carbon) esters [monoalkyl maleate, fumaric acid, etc.] Acid monoalkyl esters and citraconic acid monoalkyl esters, etc.], and their salts [alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), amine salts, and ammonium salts salt, etc.]. Among these, from the viewpoint of polymerizability and easiness of acquisition, unsaturated monocarboxylic acid is preferable, and (meth)acrylic acid is more preferable.

As the hydrophobic group-containing vinyl monomer (Vb), a (meth)acrylate (Vb1), an aromatic hydrocarbon monomer (Vb2), etc. are mentioned.

Examples of the (meth)acrylate (Vb1) include alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group [methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate] base) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, etc.] and alicyclic (meth)acrylate [(meth)acrylate dicyclopentenyl, (meth)acrylate dicyclopentenyl and (meth)acrylate isobornyl, etc.] and the like.

Examples of the aromatic hydrocarbon monomer (Vb2) include hydrocarbon monomers having a styrene skeleton [styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylbenzene Ethylene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene and benzyl styrene, etc.] and vinyl naphthalene.

The molar ratio of the input monomers (Va)/(Vb) in the carboxyl group-containing resin (QP12) is usually 10 to 100/0 to 90, and preferably 10 to 80/20 to 10 from the viewpoint of developability. 90, more preferably 25 to 85/15 to 75.

The sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer having a sulfonic acid group. Based on vinyl monomer (Vb) to obtain vinyl polymerization. As the hydrophobic group-containing vinyl monomer (Vb), the same ones as described above can be used.

Examples of the sulfonic acid group-containing vinyl monomer (Vc) include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, 2-( Meth)acryloamide-2-methylpropanesulfonic acid and salts of these. Examples of the salt include alkali metal (sodium, potassium, etc.) salts, alkaline earth metal (calcium, magnesium, etc.) salts, primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

The molar ratio of the charged monomers (Vc)/(Vb) in the sulfonic acid group-containing resin (QP13) is usually 10 to 100/0 to 90, preferably 10 to 80/ from the viewpoint of developability 20 to 90, more preferably 25 to 85/15 to 75.

The preferred range of the HLB value of the alkali-soluble resin (QP1) varies depending on the resin skeleton of the alkali-soluble resin (QP1). When the HLB value is 4 or more, the developability at the time of image development is more favorable, and when it is 19 or less, the water resistance of the cured product is more favorable.

The HLB value in the present invention is an HLB value obtained by the Oda method, is a hydrophilic-hydrophobic balance value, and can be calculated from the ratio of the organic value and the inorganic value of the organic compound. ＜Evaluation method of HLB＞ HLB≒10×inorganic/organic In addition, the values of inorganic and organic properties can be found on page 501 of the document "Synthesis and Application of Surfactants" (published by Maki Shoten, written by Oda and Teramura), or "New-Introduction to Surfactants" (Takehiko Fujimoto). Published by Sanyo Chemical Industry Co., Ltd.) on page 198.

Examples of acid dissociable groups to be introduced into the resin (QP2) as protecting groups include substituted methyl groups, 1-substituted ethyl groups, 1-branched alkyl groups, silyl groups, germyl groups, alkoxycarbonyl groups, Acyl group and cyclic acid dissociable group, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the substituted methyl group include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzyl Sulfanylmethyl, benzylmethyl, bromobenzylmethyl, methoxybenzylmethyl, methylthiobenzylmethyl, α-methylbenzylmethyl, cyclopropyl Methyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl group, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, tert-butoxycarbonylmethyl.

Examples of 1-substituted ethyl groups include 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, and 1-ethylthio ethyl, 1,1-diethoxyethyl, 1-ethoxypropyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-phenoxyethyl, 1- Phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1 ,1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxy ylcarbonylethyl, 1-tert-butoxycarbonylethyl.

Examples of the 1-branched alkyl group include isopropyl, 2-butyl, 3-butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 1,1-dimethylbutyl base.

As a silyl group, a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group are mentioned, for example. Silyl, triisopropylsilyl, tert-butyldimethylsilyl, di-tert-butylmethylsilyl, tri-tert-butylsilyl, dimethylphenylsilyl, methylbis Tri-carbyl silyl groups such as phenylsilyl, triphenylsilyl, etc.

As the germanyl group, for example, trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, isopropyldimethylgermanyl, etc. may be mentioned. Methylgermanyl, methyldiisopropylgermanyl, triisopropylgermanyl, tert-butyldimethylgermyl, di-tert-butylmethylgermanyl, Tri-carbonylgermanyl such as tri-tert-butylgermanyl, dimethylphenylgermanyl, methyldiphenylgermanyl, triphenylgermanyl and the like.

As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tertiary butoxycarbonyl group are mentioned, for example.

Examples of the acyl group include an acetyl group, a propionyl group, a butyl group, a heptyl group, a hexyl group, a pentamyl group, a trimethyl acetyl group, an isopentyl group, a lauryl group, and a myristyl group. , palmityl, stearyl, ethylene glycol, malonyl, succinyl, glutaryl, adipyl, heptadiyl, caprylyl, azela, decyl Dialyl, acrylyl, propynyl, methacryloyl, butenyl, oleoyl, maleic, fumaric, mesacanoyl, camphordiyl, benzyl, ortho Phthaloyl, isophthaloyl, terephthaloyl, naphthyl, tolyl, hydroatoryl, atoryl, cinnamyl, furocarbyl, Thienocarbyl, nicotinyl, isonicotinyl, p-toluenesulfonyl, methanesulfonyl.

Examples of cyclic acid dissociable groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, and tetrahydrothiopyranyl (thiopyranyl), tetrahydrothiofuranyl (thiofuranyl), 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydro Thiophene-1,1-dioxide group.

Among these acid dissociable groups, tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, Tributoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl and tetrahydrothiofuranyl.

Rate of introduction of acid dissociable groups in protective group-introduced resin (QP2) {acid dissociable groups relative to the total number of unprotected acidic functional groups and acid dissociable groups in protective group-introduced resin (QP2) The ratio of the number of these groups} cannot be uniformly defined according to the acid dissociable group or the type of the alkali-soluble resin into which the group is introduced, but is preferably 10% to 100%, more preferably 15% to 100%.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the protecting group-introducing resin (QP2) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000 .

In addition, the ratio (Mw/Mn) of the Mw of the protecting group-introducing resin (QP2) to the number average molecular weight in terms of polystyrene (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1-10, preferably 1-5.

The content of the nonionic photoacid generator (A) based on the weight of the solid content of the resin composition for photolithography (Q) is preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight , particularly preferably 0.05% by weight to 7% by weight. When it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be more favorably exhibited, and when it is 20% by weight or less, the physical properties of the portion insoluble in the alkaline developer can be more favorably exhibited.

The resist using the resin composition (Q) for photolithography of the present invention may contain a quencher (acid diffusion control agent) for the purpose of improving the shape of a pattern after exposure, change with time, and the like. The quencher is not particularly limited as long as it is a compound having a basic site having a larger pKa than the acid generated by the nonionic photoacid generator (A). For example, known amines (triamylamine, triisopropanolamine, dicyclohexylamine, N,N-dicyclohexylmethylamine, etc.), known pyridines (pyridine, 2,6-dicyclohexylamine, etc.) picoline, 2,6-di-tert-butylpyridine, 2,6-diphenylpyridine, etc.), well-known anilines (2,6-diisopropylaniline, etc.), well-known imidazoles (2,6-diisopropylaniline, etc.) 4,5-triphenylimidazole, 4,5-diphenylimidazole, 2-phenylimidazole, etc.), and well-known salts of onium and weak acid anion (triphenyl benzoate) that decompose during exposure to generate weak acid salicylate, triphenyl salicylate, triphenyl salicylate, 3,5-bistrifluoromethylbenzoate, diphenyl iodopentafluorobenzoate, 4-fluorobenzoic acid-4-isobutyl-4'- Tolyl iodonium, etc.). The content of the quencher depends on the content of the nonionic photoacid generator (A), but is 5% by weight or less, preferably 3% by weight with respect to the total solid content of the resin composition for photolithography (Q) the following. When it exceeds 5 weight%, the effective density|concentration of the acid which generate|occur|produces at the time of exposure will fall, and there exists a problem that a pattern cannot be obtained after image development.

The resist using the resin composition (Q) for photolithography of the present invention can be formed, for example, by using known methods such as spin coating, curtain coating, roll coating, spray coating, and screen printing. In the method, after applying a resin solution dissolved (dissolving and dispersing in the case of including inorganic fine particles) in a predetermined organic solvent on a substrate, the solvent is dried by heating or blowing with hot air.

As an organic solvent (resist solvent) for dissolving the resin composition (Q) for photolithography, if the resin composition can be dissolved, the resin solution can be adjusted to have physical properties (viscosity, etc.) suitable for spin coating or the like The organic solvent is not particularly limited. For example, N-methylpyrrolidone, DMF, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, γ-butyl can be used Known solvents such as lactone, propylene glycol monomethyl ether acetate, acetone, and xylene. Among these solvents, from the viewpoint of drying temperature and the like, those having a boiling point of 200° C. or lower (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate) are preferred. , propylene glycol monomethyl ether acetate, acetone and xylene), can also be used alone or in combination of two or more. When an organic solvent is used, the compounding amount of the solvent is not particularly limited, but based on the weight of the solid content of the resin composition for photolithography (Q), it is usually preferably 30% by weight to 1,000% by weight, and more preferably 40% by weight to 900% by weight, particularly preferably 50% by weight to 800% by weight.

The drying conditions of the applied resin solution vary depending on the solvent used, but it is preferably carried out in the range of 50° C. to 200° C. for 1 minute to 30 minutes, and the resin composition for photolithography after drying is performed. The residual solvent amount (% by weight) of (Q) is appropriately determined.

After the resist is formed on the substrate, light irradiation in the shape of the wiring pattern is performed. Then, after performing post-exposure heating (PEB), alkali development is performed to form a wiring pattern.

As a method of performing light irradiation, a method of exposing a resist with actinic rays through a photomask having a wiring pattern is exemplified. The actinic ray used for light irradiation is not particularly limited as long as the nonionic photoacid generator (A) in the resin composition (Q) for photolithography of the present invention can be decomposed. As the actinic rays, there are low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, extra high pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, argon-fluorine (ArF) Excimer laser, krypton-fluorine (KrF) excimer laser, pigment laser, nitrogen laser, LED, helium-cadmium laser, etc.), etc. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, LEDs, and krypton-fluorine (KrF) excimer lasers are preferred.

The temperature of post-exposure heating (PEB) is usually 40°C to 200°C, preferably 50°C to 190°C, and more preferably 60°C to 180°C. When the temperature is lower than 40°C, the deprotection reaction or the crosslinking reaction cannot sufficiently proceed, so the difference in solubility between the UV-irradiated portion and the UV-unirradiated portion is insufficient to form a pattern, and when the temperature is higher than 200°C, the productivity decreases. The problem. The heating time is usually 0.5 minutes to 120 minutes, and when it is less than 0.5 minutes, it is difficult to control the time and temperature, and when it exceeds 120 minutes, there is a problem that the productivity decreases.

As a method of performing alkali development, the method of dissolving and removing in the shape of a wiring pattern using an alkali developing solution is mentioned. The alkaline developer is not particularly limited as long as it is a condition that the solubility of the ultraviolet-irradiated part and the ultraviolet-unirradiated part of the resin composition for photolithography (Q) is poor. As an alkaline developing solution, there exist a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium hydrogencarbonate, a tetramethylammonium salt aqueous solution, etc.. Water-soluble organic solvents can also be added to these alkaline developing solutions. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, THF, N-methylpyrrolidone, and the like.

As a developing method, there exist a dipping method using an alkaline developer, a shower method, and a spray method, but the spray method is preferable. The temperature of the developer is preferably used at 25°C to 40°C. The development time is appropriately determined according to the thickness of the resist. [Example]

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, % refers to % by weight, and parts refers to parts by weight.

<Production Example 1> <Synthesis of 9-fluorenone hydrazone [precursor (P1)]> Using 9-fluorenone as a raw material, the precursor (P1) was obtained according to the method described in the literature ("Angew. Chem., Int. Ed.", 2019, 58, 8762.).

<Production Example 2> <Synthesis of 2-butyl-9-fluorenone hydrazone [precursor (P2)]> Using 2-bromo-9-fluorenone as a raw material, an alkylated product was obtained in the same manner as the method described in Japanese Patent No. 2014/084269. Next, according to the method described in Production Example 1, a precursor (P2) was obtained using the obtained alkylate.

<Production Example 3> <Synthesis of 9(10H)-anthrone hydrazone [precursor (P3)]> Using anthrone as a raw material, a precursor (P3) was obtained in the same manner as the method described in the literature ("Chem. Sci.", 2011, 2, 2029.).

<Production Example 4> ＜Synthesis of thioxanthone hydrazone [precursor (P4)]＞ Using thioxanthone as a raw material, the precursor (P4) was synthesized according to the synthesis method described in the literature ("Angew. Chem., Int. Ed.", 2010, 49, 6580.).

<Production Example 5> <Synthesis of precursor (P5)> Triethylamine was added dropwise to the slurry obtained by dispersing the precursor (P4) synthesized in Production Example 4 in dichloromethane and cooled to -78°C, followed by stirring for 5 minutes. Then, pentafluorobenzenesulfonyl chloride was added dropwise and stirred for 1 hour, and then the temperature was raised to 0°C. After putting into deionized water to stop the reaction, the precipitated solid was filtered and dried under reduced pressure to obtain a precursor (P5) of the following formula.

[hua 8]

<Production Example 6> <Synthesis of precursor (P6)> Using 4-hydroxycarbazole as a raw material, a ketone body was synthesized according to the method described in the literature ("J. Photopolym. Sci. Technol.", 2018, 31, 37.). Next, according to the method described in Production Example 1, a precursor (P6) of the following formula was obtained using the obtained ketone body.

[Chemical 9]

<Production Example 7> <Synthesis of precursor (P7)> The corresponding ketone bodies were synthesized according to the method described in Japanese Patent Laid-Open No. 2010-024290. Next, according to the method described in Production Example 1, a precursor (P7) of the following formula was obtained using the obtained ketone body.

[Chemical 10]

<Production Example 8> <Synthesis of precursor (P8)> The same procedure as Production Example 1 and Production Example 5 was carried out, except that 6,7-dimethyl-1-tetralone was used as a raw material and pentafluorobenzenesulfonic acid chloride was used as 2-nitrobenzenesulfonic acid chloride. , thereby obtaining the precursor (P8) of the following formula.

[Chemical 11]

<Production Example 9> <Synthesis of precursor (P9)> Using 6-methoxy-2-naphthoic acid as a raw material, according to the method described in the literature ("Synthesis", 2005, 1789.), 2,3-dihydro-7-methane as a ketone body was synthesized Oxy-1H-benzo[e]inden-1-one. Next, according to the method described in Production Example 1, a precursor (P9) of the following formula was obtained using the obtained ketone body.

[Chemical 12]

<Production Example 10> <Synthesis of precursor (P10)> Using 2-naphthol and ethyl 2-bromooctanoate as raw materials, according to the method described in Japanese Patent Laid-Open No. 2011-209719, 2-hexylnaphtho[2,1-b]furan-1(2H) was synthesized as a ketone body )-ketone. Next, according to the method described in Production Example 1, a precursor (P10) of the following formula was obtained using the obtained ketone body.

[Chemical 13]

<Production Example 11> <Synthesis of precursor (P11)> Using methyl 1-hydroxy-2-naphthoate and methyl 2-bromopropionate as raw materials, according to the method described in the literature ("Synthetic Communications.", 2012, 42, 989.), they were synthesized as ketones 2-methylnaphtho[1,2-b]furan-3(2H)-one. Next, according to the method described in Production Example 1, a precursor (P11) of the following formula was obtained using the obtained ketone body.

[Chemical 14]

<Production Example 12> <Synthesis of precursor (P12)> Using diphenyl sulfide and heptyl chloride as raw materials, and using dichloromethane as a solvent, 1-[4-(phenylthio) as a ketone body was synthesized according to the method described in Japanese Patent Laid-Open No. 2009-242469. ) phenyl]-1-heptanone. Next, according to the method described in Production Example 1, a precursor (P12) of the following formula was obtained using the obtained ketone body.

[Chemical 15]

<Production Example 13> <Synthesis of precursor (P13)> Using 9-ethylcarbazole as a raw material, the corresponding ketone body was synthesized according to the method described in Japanese Patent Laid-Open No. 2009-242469. Next, according to the method described in Production Example 1, a precursor (P13) of the following formula was obtained using the obtained ketone body.

[Chemical 16]

<Production Example 14> <Synthesis of precursor (P14)> According to the method described in Japanese Patent Laid-Open No. 2016-113504, 2-benzyl-3,3-dimethyl-3H-indole was synthesized, and further according to the literature ("Chem. Sci.", 2016, 7 346.) to synthesize the corresponding ketone body. Next, according to the method described in Production Example 1, a precursor (P14) of the following formula was obtained using the obtained ketone body.

[Chemical 17]

<Production Example 15> <Synthesis of precursor (P15)> Using 2-amino-4-methoxyphenol and 2,2-dibromoacetophenone (synthesized according to the literature "Asian Journal of Chemistry (Chem. Asian J.)", 2012, 7, 2240.) as raw materials, according to The method described in the literature ("J. Org. Chem.", 2016, 81. 51.) synthesized 2-benzyl-5-methoxy-1,3- ketone body benzoxazole. Next, according to the method described in Production Example 1, a precursor (P15) of the following formula was obtained using the obtained ketone body.

[Chemical 18]

<Production Example 16> <Synthesis of precursor (P16)> Using benzothiazole and ethyl chloroglyoxylate as raw materials, according to the method described in the literature ("Synthesis", 2011, 1633.), the corresponding ketone body was synthesized, and then according to the method described in Production Example 1 Synthesize the corresponding hydrazone. Next, except that pentafluorobenzenesulfonyl chloride was used as p-toluenesulfonyl chloride, it was carried out in the same manner as in Production Example 5, whereby a precursor (P16) of the following formula was obtained.

[Chemical 19]

<Production Example 17> <Synthesis of precursor (P17)> Using benzothiazole and 4-cyanobenzyl chloride as raw materials, according to the method described in the literature ("Synlett", 2013, 24, 2233.), 4-(2-benzene as a ketone body was synthesized) thiazolylcarbonyl)benzonitrile. Next, according to the method described in Production Example 1, a precursor (P17) of the following formula was obtained using the obtained ketone body.

[hua 20]

<Production Example 18> <Synthesis of precursor (P18)> Using 2-aminobenzenethiol and 3-(dimethylamino)-1-phenyl-2-propan-1-one as raw materials, according to the literature ("Green Chem.", 2016, 18 , 402.) to synthesize 1-(2-benzothiazolyl)-2-phenyl-1,2-ethanedione as a ketone body. Next, according to the method described in Production Example 1, a precursor (P18) of the following formula was obtained using the obtained ketone body.

[Chemical 21]

<Production Example 19> <Synthesis of precursor (P19)> Using 3-amino-2-naphthalenethiol as a raw material, according to the method described in WO2015/087094, 2-acetylnaphtho[2,3-d]thiazole as a ketone body was synthesized. Next, according to the method described in Production Example 1, a precursor (P19) of the following formula was obtained using the obtained ketone body.

[Chemical 22]

<Example 1> <Synthesis of Compound (A1)> 30 parts of 2,6-di-tert-butylpyridine was added dropwise to the slurry obtained by dispersing 10 parts of the precursor (P1) synthesized in Production Example 1 in 350 parts of methylene chloride and cooled to 0° C., followed by stirring. 5 minutes. Next, 35 parts of trifluoromethanesulfonic anhydride was added dropwise, followed by stirring for 1 hour. Deionized water was added to the reaction solution to stop the reaction, and the organic layer was washed three times with deionized water. By concentrating the organic layer, 18 parts of compound (A1) were obtained as a yellow solid.

<Example 2> <Synthesis of Compound (A2)> Compound (A2) 23 was obtained in the same manner as in Example 1, except that the precursor (P1) synthesized in Production Example 1 was used as a raw material and the trifluoromethanesulfonic anhydride was used as 72 parts of nonafluorobutanesulfonic anhydride. share.

<Example 3> <Synthesis of Compound (A3)> Using the precursor (P1) synthesized in Production Example 1 as a raw material, except that trifluoromethanesulfonic anhydride was used as 30 parts of pentafluorobenzenesulfonic acid chloride, it was carried out in the same manner as in Example 1 to obtain a compound (A3) 20 servings.

<Example 4> <Synthesis of Compound (A4)> Using the precursor (P1) synthesized in Production Example 1 as a raw material, and using trifluoromethanesulfonic anhydride as 36 parts of perfluoropropane-1,3-disulfonyl difluoride, it was the same as Example 1. By doing so, 15 parts of compound (A4) were obtained.

<Example 5> <Synthesis of Compound (A5)> Using the precursor (P2) synthesized in Production Example 2 as a raw material, it was carried out in the same manner as in Example 1, whereby 14 parts of compound (A5) were obtained.

<Example 6> <Synthesis of Compound (A6)> Using 11H-benzo[b]fluoren-11-one as a raw material and using the precursor synthesized according to the method described in Production Example 1, it was carried out in the same manner as in Example 1, thereby obtaining a compound of the following formula ( A6) 14 servings.

[Chemical 23]

<Example 7> <Synthesis of Compound (A7)> 19 parts of N-ethyldiisopropylamine was added dropwise to the slurry obtained by dispersing 10 parts of the precursor (P3) synthesized in Production Example 3 in 320 parts of methylene chloride and cooled to 0°C, followed by stirring for 5 minutes. . Next, 33 parts of trifluoromethanesulfonic anhydride was added dropwise, followed by stirring for 1 hour. Deionized water was added to the reaction solution to stop the reaction, and the organic layer was washed three times with deionized water. By concentrating the organic layer, 16 parts of compound (A7) were obtained as a tan solid.

<Example 8 to Example 10> <Synthesis of Compound (A8) to Compound (A10)> Compounds (A8) to (A10) were synthesized in the same manner as in the synthesis method described in Example 7, except that the precursor synthesized from the corresponding raw materials according to the method described in Production Example 1 or Production Example 3 was used. .

<Example 11> <Synthesis of Compound (A11)> Using the precursor (P4) synthesized in Production Example 4 as a raw material, it was carried out in the same manner as in Example 7, whereby 14 parts of compound (A11) were obtained.

<Example 12> <Synthesis of Compound (A12)> The precursor (P5) synthesized in Production Example 5 was set to 10 parts, dichloromethane was set to 150 parts, N-ethyldiisopropylamine was set to 4.2 parts, and trifluoromethanesulfonic anhydride was set to 7.4 parts, except Other than that, it carried out similarly to Example 7, and obtained 10 parts of compound (A12) by carrying out.

<Example 13 and Example 14> <Synthesis of Compound (A13) and Compound (A14)> Compound (A13) and compound (A14) were synthesized in the same manner as in the synthesis method described in Example 7, except that the precursor synthesized from the corresponding raw materials according to the method described in Production Example 4 was used.

<Example 15> <Synthesis of Compound (A15)> Using the corresponding raw material (synthesized according to the method described in Production Example 4) with pentafluorobenzenesulfonyl chloride as methanesulfonyl chloride, and synthesized in the same manner as in the method described in Production Example 5. Example 7 was carried out in the same manner, whereby 10 parts of compound (A15) were obtained.

<Example 16 to Example 22> <Synthesis of Compound (A16) to Compound (A22)> Compounds (A16) through Compound (A22).

<Example 23> <Synthesis of Compound (A23)> Using the precursor (P6) synthesized in Production Example 6 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, thereby obtaining 10 parts of a compound (A23) of the following formula.

[Chemical 24]

<Example 24> <Synthesis of Compound (A24)> Using the precursor (P7) synthesized in Production Example 7 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, whereby 16 parts of compound (A24) were obtained.

<Example 25> <Synthesis of Compound (A25)> As the precursor (P1), 10 parts of the precursor (P8) synthesized in Production Example 8, 180 parts of dichloromethane, 7.7 parts of 2,6-di-tert-butylpyridine, and 7.7 parts of trifluoromethanesulfonic acid were used. Except having used the acid anhydride as 9.1 parts, it carried out similarly to Example 1, and obtained 11 parts of compound (A25).

<Example 26 and Example 27> <Synthesis of Compound (A26) and Compound (A27)> The compound (A26) and the compound (A27) were synthesized in the same manner as in Example 1, except that the precursor synthesized from the corresponding raw material according to the method described in Production Example 1 was used.

<Example 28 and Example 29> <Synthesis of Compound (A28) and Compound (A29)> Compound (A28) and compound (A29) were synthesized in the same manner as in Example 24, except that the precursor synthesized from the corresponding raw materials according to the method described in Production Example 7 was used.

<Example 30> <Synthesis of Compound (A30)> Using the precursor (P9) synthesized in Production Example 9 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, thereby obtaining 15 parts of compound (A30).

<Example 31> <Synthesis of Compound (A31)> The same procedure as in Example 1 was carried out, except that the precursor synthesized from the corresponding raw material according to the method described in Production Example 7 was used as the raw material, and the trifluoromethanesulfonic anhydride was used as 61 parts of heptadecafluorooctanesulfonic acid fluoride. This obtained 35 parts of compound (A31).

<Example 32> <Synthesis of Compound (A32)> Using the precursor (P10) synthesized in Production Example 10 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, thereby obtaining 14 parts of compound (A32).

<Example 33> <Synthesis of Compound (A33)> 16 parts of compound (A33) were obtained in the same manner as in Example 32, except that the precursor synthesized by the method described in Production Example 10 using 2-naphthol and 2-chloropropane chloride was used as a raw material.

<Example 34 to Example 36> <Synthesis of Compound (A34) to Compound (A36)> Compounds (A34 to A36) were synthesized in the same manner as in Example 24, except that the precursor synthesized from the corresponding raw materials according to the method described in Production Example 7 was used.

<Example 37> <Synthesis of Compound (A37)> Using the precursor (P11) synthesized in Production Example 11 as a raw material, it was carried out in the same manner as the synthesis method described in Example 2, whereby 22 parts of compound (A37) were obtained.

<Example 38> <Synthesis of Compound (A38)> A compound (A38 ) 12 servings.

<Example 39> <Synthesis of Compound (A39)> Except having used the precursor (P1) as a benzophenone hydrazone, it carried out similarly to Example 1, and obtained 18 parts of compound (A39).

<Example 40> <Synthesis of Compound (A40)> Using the precursor (P12) synthesized in Production Example 12 as a raw material, it was carried out in the same manner as in the synthesis method described in Example 1, whereby 12 parts of compound (A40) were obtained.

<Example 41> <Synthesis of Compound (A41)> Using the precursor (P13) synthesized in Production Example 13 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, thereby obtaining 10 parts of a compound (A41) of the following formula.

[Chemical 25]

<Example 42 to Example 44> <Synthesis of Compound (A42) to Compound (A44)> Compounds (A42 to A44) were synthesized in the same manner as in the synthesis method described in Example 1 or Example 2 using the precursor synthesized from the corresponding raw materials according to the method described in Production Example 1.

<Example 45 and Example 46> <Synthesis of Compound (A45) and Compound (A46)> The compound (A45) and the compound (A46) were synthesized in the same manner as in Example 1, except that the precursor synthesized from the corresponding raw materials according to the method described in Production Example 12 was used.

<Example 47> <Synthesis of Compound (A47)> Using the precursor (P14) synthesized in Production Example 14 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, whereby 12 parts of compound (A47) were obtained.

<Example 48> <Synthesis of Compound (A48)> Using the precursor (P15) synthesized in Production Example 15 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, whereby 13 parts of compound (A48) were obtained.

<Example 49> <Synthesis of Compound (A49)> As the precursor (P1), 10 parts of the precursor (P16) synthesized in Production Example 16, 170 parts of dichloromethane, 7.1 parts of 2,6-di-tert-butylpyridine, and 7.1 parts of trifluoromethanesulfonic acid were used. Except having used acid anhydride as 8.4 parts, it carried out similarly to Example 1, and obtained 11 parts of compound (A49).

<Example 50> <Synthesis of Compound (A50)> Using the precursor (P17) synthesized in Production Example 17 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, whereby 14 parts of compound (A50) were obtained.

<Example 51> <Synthesis of Compound (A51)> Using the precursor (P18) synthesized in Production Example 18 as a raw material, it was carried out in the same manner as the synthesis method described in Example 2, whereby 18 parts of compound (A51) were obtained.

<Example 52> <Synthesis of Compound (A52)> The compound ( A52) 15 copies.

<Example 53> <Synthesis of Compound (A53)> The same procedure as in Example 1 was carried out, except that 2-amino-4-methoxyphenol was used as 3-amino-2-naphthol and the precursor synthesized in the same manner as in Production Example 15 was used. , thereby obtaining 12 parts of compound (A53).

<Example 54> <Synthesis of Compound (A54)> Using the precursor (P19) synthesized in Production Example 19 as a raw material, it was carried out in the same manner as the synthesis method described in Example 1, whereby 13 parts of compound (A54) were obtained.

The structures and properties of Compound (A1) to Compound (A54) are described in Tables 1 to 4.

[Table 1] Example general formula R _f R ¹ (R ⁶ ) _n G ¹ compound traits Example 1 (1)-1 _{CF3 CF3} (without) single bond A1 yellow solid Example 2 (1)-1 C ₄ F ₉ C ₄ F ₉ (without) single bond A2 yellow solid Example 3 (1)-1 _{C6F5 _ C6F5 _} (without) single bond A3 yellow solid Example 4 (1)-1 -(CF ₂ ) ₃ - (without) single bond A4 yellow solid Example 5 (1)-1 _{CF3 CF3} 2- ⁿ Bu single bond A5 yellow solid Example 6 (1)-1 _{CF3 CF3} Reference compound A6 single bond A6 orange solid Example 7 (1)-1 _{CF3 CF3} (without) -CH ₂ - A7 tan solid Example 8 (1)-1 _{CF3 CF3} (without) -CH ₂ -CH ₂ - A8 tan solid Example 9 (1)-1 _{CF3 CF3} (without) -O- A9 yellow solid Example 10 (1)-1 _{CF3 CF3} 3-MeO -O- A10 tan solid Example 11 (1)-1 _{CF3 CF3} (without) -S- A11 yellow solid Example 12 (1)-1 _{CF3 C6F5 _} (without) -S- A12 yellow solid Example 13 (1)-1 _{CF3 CF3} 2- ^iPr -S- A13 tan solid Example 14 (1)-1 F F 2,4-Et ₂ -S- A14 tan solid Example 15 (1)-1 _CF3 Me 2- _CF3 -S- A15 yellow solid Example 16 (1)-1 _{CF3 CF3} (without) -NMe- A16 yellow solid Example 17 (1)-1 C ₄ F ₉ C ₄ F ₉ (without) -NPh- A17 yellow-red solid Example 18 (1)-2 _{CF3 CF3} (without) (without) A18 tan solid Example 19 (1)-2 _{CF3 CF3} 2- ^t Bu (without) A19 tan solid

[Table 2] Example general formula R _f R ¹ (R ⁶ ) _n ^R4 R ⁵ G ² compound traits Example 20 (2)-1 _{CF3 CF3} (without) H H -CH ₂ - A20 white solid Example 21 (2)-1 _{CF3 CF3} (without) ⁿ Bu H -CH ₂ - A21 white solid Example 22 (2)-1 C ₄ F ₉ C ₄ F ₉ (without) H H -O- A22 light yellow solid Example 23 (2)-1 _{CF3 CF3} Reference compound A23 H H -O- A23 orange solid Example 24 (2)-1 _{CF3 CF3} 5-Cl Me H -S- A24 light yellow solid Example 25 (2)-2 _CF3 2-NO ₂ -Ph 6,7-Me ₂ H H -CH ₂ - A25 Milky white solid Example 26 (2)-2 _{CF3 CF3} 7-MeS H H -CH ₂ - A26 light brown solid Example 27 (2)-2 _{CF3 CF3} 6-MeO H Ph -O- A27 yellow solid Example 28 (2)-2 _{CF3 CF3} 7-MeO H H -S- A28 light yellow solid Example 29 (2)-2 _{CF3 CF3} 7-Cl Me H -NMe- A29 light brown solid Example 30 (2)-3 _{CF3 CF3} 7-MeO H H -CH ₂ - A30 light brown solid Example 31 (2)-3 C ₈ F ₁₇ C ₈ F ₁₇ (without) H H -O- A31 yellow solid Example 32 (2)-3 _{CF3 CF3} (without) ⁿ Hex H -O- A32 yellow solid Example 33 (2)-3 _{CF3 CF3} (without) Me H -O- A33 tan solid Example 34 (2)-3 _{CF3 CF3} (without) H H -S- A34 yellow solid Example 35 (2)-4 _{CF3 CF3} (without) Me Me -S- A35 brown solid Example 36 (2)-5 _{CF3 CF3} (without) H H -O- A36 yellow solid Example 37 (2)-5 C ₄ F ₉ C ₄ F ₉ (without) Me H -O- A37 yellow solid Example 38 (2)-5 _{CF3 CF3} (without) ⁿ Hex H -O- A38 yellow solid

[table 3] Example general formula R _f R ¹ (R ⁶ ) _n R ² G ³ ,G ⁴ R ³ bond position compound traits Example 39 (3)-1 _{CF3 CF3} (without) Ph (without) 1 person A39 white solid Example 40 (3)-1 _{CF3 CF3} 4-C ₆ H ₄ S ⁿ Hex (without) 1 person A40 Milky white solid Example 41 (3)-1 _{CF3 CF3} Reference compound A41 Me (without) 3 digits A41 yellow-orange solid Example 42 (3)-2 _{CF3 CF3} 6-MeO Me (without) 2 digits A42 light brown solid Example 43 (3)-2 C ₄ F ₉ C ₄ F ₉ (without) Ph (without) 2 digits A43 Milky white solid Example 44 (3)-3 _{CF3 CF3} (without) ⁿ C ₁₂ H ₂₅ (without) 1 person A44 tan solid Example 45 (3)-4 _{CF3 CF3} (without) Ph -O-, single key 2 digits A45 yellow solid Example 46 (3)-4 _{CF3 CF3} (without) 4-CNC ₆ H ₄ -CH ₂ -, single key 2 digits A46 yellow solid

[In Table 3, the R ³ bonding position is represented by the bonding position of the carbon to which R ³ is bonded to R ³ -CR ² =N in the general formula (1). ]

[Table 4] Example general formula R _f R ¹ (R ⁶ ) _n R ² G ⁵ compound traits Example 47 (4)-1 _{CF3 CF3} (without) Ph -CMe ₂ - A47 light yellow solid Example 48 (4)-1 _{CF3 CF3} 5-MeO Ph -O- A48 light yellow solid Example 49 (4)-1 _CF3 4-Me-Ph (without) CO ₂ Et -S- A49 light brown solid Example 50 (4)-1 _{CF3 CF3} (without) 4-CNC ₆ H ₄ -S- A50 light yellow solid Example 51 (4)-1 C ₄ F ₉ C ₄ F ₉ (without) Bz -S- A51 tan solid Example 52 (4)-1 _{CF3 CF3} (without) CO ₂ Et -NMe- A52 light yellow solid Example 53 (4)-2 _{CF3 CF3} (without) Ph -O- A53 tan solid Example 54 (4)-2 _{CF3 CF3} (without) Me -S- A54 light brown solid

In Tables 1 to 4, H represents a hydrogen atom, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Hex represents a hexyl group, Ph represents a phenyl group, and Bz represents a benzyl group.

<Comparative Example 1> <Synthesis of ionic photoacid generator [compound (A'1)]> 10 parts of triphenyl perium bromide were dispersed in 109 parts of chloroform, and 9.3 parts of sodium bis-trifluoromethanesulfonamide and 109 parts of deionized water were added. After stirring vigorously for 1 hour, it was left to stand, the separated aqueous layer was removed, and the organic layer was further washed with water twice. The organic layer was concentrated and dried with a vacuum dryer to obtain 13 parts of an ionic photoacid generator [compound (A'1)] of a comparative example.

<Comparative Example 2> <Synthesis of nonionic photoacid generator [compound (A'2)]> Imide 1,8-naphthalenedicarboxylate triflate (A'2) (manufactured by Aldrich) was used as it was.

[Chemical 26]

<Example 1 to Example 54, Comparative Example 1 and Comparative Example 2> For the nonionic photoacid generator (A1) to the nonionic photoacid generator (A54) obtained in Examples 1 to 54, the ionic photoacid generator (A'1) for comparison, and the nonionic photoacid generator (A'1) The i-ray sensitivity and resist solvent solubility of the ionic photoacid generator (A'2) were evaluated by the following methods, and the results are described in Tables 5 and 6.

<i-ray decomposition rate> 0.3 parts of the synthesized compounds of Examples and Comparative Examples and 0.1 part of perfluorobenzene as a standard substance were dissolved in 100 parts of heavy acetonitrile, 0.6 mL was injected into an NMR tube, and ¹⁹ F-NMR was performed. analyze. Next, this NMR tube was exposed to 500 mJ·cm ² of L-34 (Kenko Optical ( Kenko Kougaku) Co., Ltd., a filter that cuts off light below 340 nm) The filter has a limited wavelength of ultraviolet light. In addition, about the accumulated exposure amount, the wavelength of 365 nm was measured. The NMR tube after exposure was analyzed by ¹⁹ F-NMR again, and the i-ray decomposition rate was calculated from the integrated value of ¹⁹ F-NMR signals of the compounds before and after exposure (based on a reference material). Since the decomposition rate is high at the same exposure amount, it is excellent as a photoacid generator. Therefore, the i-ray decomposition rate was evaluated as follows, and the results are described in Tables 5 and 6. i-ray decomposition rate = (integrated value of compound signal before exposure - integrated value of compound signal after exposure) / (integrated value of compound signal before exposure)

＜Solubility＞ The compounds of Examples and Comparative Examples were added to propylene glycol monomethyl ether acetate as a general-purpose resist solvent so as to have a concentration of 50%, stirred with a turbo mixer for one minute, and then immersed in a constant temperature bath at 25°C. It was left to stand for one hour, and it was visually confirmed whether it was uniformly dissolved. In the case of unevenness, propylene glycol monomethyl ether acetate was added so that the concentration was gradually decreased by 5%, and the operation was repeated. Repeat in 1% units when the concentration is below 5%. The first uniform concentration was taken as the solubility of the compound in the resist solvent. When the solubility is high, precipitation or phase separation is less likely to occur when the resin composition for photolithography is used, and thus it is excellent. The results are described in Table 5 and Table 6.

<Evaluation of resin composition for positive photolithography> <Preparation of resin composition for positive photolithography (QP-1)> 40 parts of resins represented by the following formula, 60 parts of novolak resins obtained by addition-condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst, and 1 part of compounds of Examples and Comparative Examples were dissolved in 152 parts of propylene glycol monomethyl ether acetate was filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare a resin composition for positive photolithography (QP-1).

[Chemical 27]

<Minimum exposure amount> The prepared resin composition for positive photolithography (QP-1) was spin-coated on a silicon wafer substrate, and then dried to obtain a photoresist layer having a film thickness of about 20 μm. The resist layer was pre-baked at 130° C. for 6 minutes by means of a hot plate. Then, pattern exposure (i-ray) was performed using TME-150RSC-12 (made by Topcon), and post-exposure heating (PEB) was performed at 75° C. for 5 minutes using a hot plate. After that, a development treatment was performed for 5 minutes by an immersion method using a 2.38 wt % aqueous tetramethyl ammonium hydroxide solution, followed by washing with running water, and purging with nitrogen gas to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount [mJ/cm ² ] required to form a resist pattern was measured. The minimum exposure amount corresponds to the i-ray sensitivity and is excellent when it is small. The results are described in Tables 5 and 6.

<Evaluation of Resin Composition for Negative Photolithography> <Preparation of resin composition for negative photolithography> Dissolved in 75 parts of phenol resin (manufactured by DIC, "Phenolite TD431"), melamine hardener (manufactured by Mitsui Cyanamid Co., Ltd., "Cymel 300") ") 25 parts, 1 part of the compounds of the synthesized examples and comparative examples, and 100 parts of propylene glycol monomethyl ether acetate, were filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare the respective negative types Resin composition for photolithography.

<Exposure part curability> Each resin composition for negative photolithography prepared above was applied on a 10 cm square glass substrate under the conditions of 200 rpm and 10 seconds using a spin coater. Next, after vacuum drying at 25 degreeC for 5 minutes, it dried for 5 minutes on the hotplate of 100 degreeC, and the resist with a film thickness of about 40 micrometers was formed. This resist was exposed to a predetermined amount of L-34 (Kenco Optical ( Kenko Kougaku) Co., Ltd., 340 nm low-pass filter) wavelength-limited ultraviolet light. In addition, about the accumulated exposure amount, the wavelength of 365 nm was measured. Then, after performing post-exposure heating (PEB) in a downwind dryer at 150° C. for 10 minutes, it was developed by immersing in a 0.5% potassium hydroxide solution for 60 seconds, and immediately washed with water and dried. The film thickness of the resist was measured using a profile measuring microscope (Ultra-depth profile measuring microscope UK-8550, manufactured by Keyence Co., Ltd.). Here, the minimum exposure amount [mJ/cm ² ] in which the film thickness change of the resist before and after the development is within 10% is defined as the exposure part curability. The exposure part hardening property corresponds to the i-ray sensitivity, and the lower the minimum exposure amount, the more excellent the i-ray sensitivity. The results are described in Tables 5 and 6.

[table 5] compound i-ray resolution Solubility Minimum exposure Curability of exposed parts Example 1 A1 40% 10% 250 250 Example 2 A2 40% 15% 200 200 Example 3 A3 30% 10% 250 300 Example 4 A4 25% 5% 250 400 Example 5 A5 45% 25% 200 200 Example 6 A6 30% 5% 200 250 Example 7 A7 35% 10% 300 350 Example 8 A8 30% 15% 350 350 Example 9 A9 40% 10% 300 300 Example 10 A10 45% 10% 250 250 Example 11 A11 45% 10% 250 300 Example 12 A12 25% 15% 350 400 Example 13 A13 50% 20% 200 250 Example 14 A14 50% 20% 250 300 Example 15 A15 35% 5% 500 500 Example 16 A16 35% 10% 350 450 Example 17 A17 35% 10% 350 450 Example 18 A18 30% 15% 400 450 Example 19 A19 35% 15% 350 450 Example 20 A20 15% 25% 450 500 Example 21 A21 20% 30% 400 400 Example 22 A22 25% 20% 350 350 Example 23 A23 50% 10% 150 200

[Table 6] Example 24 A24 20% 15% 400 450 Example 25 A25 20% 20% 450 500 Example 26 A26 25% 20% 400 400 Example 27 A27 30% 15% 250 250 Example 28 A28 25% 20% 350 350 Example 29 A29 20% 20% 450 500 Example 30 A30 30% 15% 250 300 Example 31 A31 25% 15% 300 350 Example 32 A32 30% 25% 250 250 Example 33 A33 40% 15% 200 200 Example 34 A34 30% 15% 300 350 Example 35 A35 30% 10% 250 250 Example 36 A36 30% 10% 250 300 Example 37 A37 35% 15% 300 350 Example 38 A38 40% 25% 250 250 Example 39 A39 15% 20% 450 450 Example 40 A40 30% 30% 250 300 Example 41 A41 45% 10% 200 250 Example 42 A42 30% 10% 350 400 Example 43 A43 25% 15% 350 350 Example 44 A44 20% 20% 350 400 Example 45 A45 25% 10% 300 350 Example 46 A46 30% 10% 250 250 Example 47 A47 20% 15% 400 450 Example 48 A48 30% 15% 300 300 Example 49 A49 20% 20% 350 350 Example 50 A50 35% 15% 250 250 Example 51 A51 30% 15% 300 350 Example 52 A52 20% 20% 450 450 Example 53 A53 35% 5% 250 250 Example 54 A54 35% 10% 300 350 Comparative Example 1 A'1 3% 1% 1000 1500 Comparative Example 2 A'2 10% 3% ＞2000 600

<Example 55 to Example 72, Comparative Example 3 to Comparative Example 8> For nonionic photoacid generators (A5, A13, A23, A33, A40 and A50), ionic photoacid generators (A'1) and nonionic photoacid generators (A'2) for comparison The i-ray sensitivity and KrF ray sensitivity of the resin composition for positive photolithography (QP-2) to the resin composition for positive photolithography (QP-4) were evaluated by the following methods, and the results were recorded in Table 7 and Table 8.

<Evaluation of resin composition for positive photolithography> <Preparation of resin composition for positive photolithography (QP-2)> 43 parts of tertiary butyl methacrylate, 30 parts of methoxy polyethylene glycol methacrylate, 45 parts of methoxydiethylene glycol methacrylate, and 0.4 parts of azobisisobutyronitrile were reacted under dioxane 10 parts of resins having the following structural units (m≒9) and 20 parts of novolak resins (co-condensates formed by condensing m-cresol and p-cresol with formaldehyde (m-cresol/p-cresol= 40/60 (mass ratio), Mw=7,000)), 1 part of the compounds of Examples and Comparative Examples, 0.03 parts of N,N-dicyclohexylmethylamine and 87 parts of propylene glycol monomethyl ether acetate were mixed and dissolved , and filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare a resin composition for positive photolithography (QP-2).

[Chemical 28]

<Minimum exposure amount> The resin composition for positive photolithography (QP-2) prepared above was spin-coated on a substrate on which copper was vapor-deposited on a silicon wafer, and then dried to obtain a photoresist layer. The resist layer was pre-baked at 110° C. for 3 minutes by a hot plate to obtain a coating film with a film thickness of about 5 μm. Next, pattern exposure (i-ray) was performed using TME-150RSC-12 (made by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 60 seconds with a hot plate. After that, a development treatment was performed for 5 minutes by an immersion method using a 2.38 wt % aqueous tetramethyl ammonium hydroxide solution, followed by washing with running water, and purging with nitrogen gas to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount [mJ/cm ² ] required to form a resist pattern was measured. The minimum exposure amount corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 7.

<Preparation of resin composition for positive photolithography (QP-3)> 35 parts of resins having the following structural units (the numbers in the lower right of the parentheses in the structural formula indicate the content by weight of the structural units in the resin), 10 parts of polyhydroxystyrene resin (copolymer of p-hydroxystyrene:styrene:tert-butyl acrylate=12:3:5, Mw=1.0×10 ⁴ ), 27.5 parts of novolak resin (m-formaldehyde A co-condensate of phenol and p-cresol condensed (m-cresol/p-cresol = 40/60 (mass ratio), Mw = 5,000)) and 27.5 parts of novolak resin (m-cresol and p-cresol are made of formaldehyde Co-condensate formed by condensation of phenol (m-cresol/p-cresol = 40/60 (mass ratio), Mw = 7,000)), surfactant (BYK310, manufactured by BYK-Chemie) 0.05 part , 1 part of the compounds of Examples and Comparative Examples were mixed in a mixed solvent (methoxybutyl acetate/propylene glycol monomethyl ether acetate=60/40 (mass ratio)) so that the solid content concentration was 40% by weight and After dissolving, the resin composition for positive photolithography (QP-3) was prepared by filtering through a membrane filter (pore size 0.45 μm, PTFE membrane).

[Chemical 29]

<Minimum exposure amount> After spin-coating the resin composition for positive photolithography (QP-3) prepared above on a copper substrate, it was dried to obtain a photoresist layer with a film thickness of about 11 μm. The resist layer was pre-baked at 130° C. for 5 minutes by means of a hot plate. Next, pattern exposure (i-ray) was performed using TME-150RSC-12 (made by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 90 seconds with a hot plate. After that, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was dropped onto the substrate, and it was left to stand at 23° C. for 30 seconds. The operation was carried out twice, and then washed with running water and purged with nitrogen gas. A 10 μm line-and-space (L&S) pattern was obtained. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount [mJ/cm ² ] required to form a resist pattern was measured. The minimum exposure amount corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 7.

[Table 7] compound resin composition Minimum exposure Example 55 A5 QP-2 1000 Example 56 A13 QP-2 1500 Example 57 A23 QP-2 1000 Example 58 A33 QP-2 1000 Example 59 A40 QP-2 1500 Example 60 A50 QP-2 1500 Example 61 A5 QP-3 1000 Example 62 A13 QP-3 1500 Example 63 A23 QP-3 1000 Example 64 A33 QP-3 1000 Example 65 A40 QP-3 1000 Example 66 A50 QP-3 1000 Comparative Example 3 A'1 QP-2 not resolved Comparative Example 4 A'2 QP-2 4000 Comparative Example 5 A'1 QP-3 ＞5000 Comparative Example 6 A'2 QP-3 3000

<Preparation of resin composition for positive photolithography (QP-4)> 100 parts of resins having the following structural units (the numbers in the lower right of the parentheses in the structural formula represent the % by weight of the structural units in the resin), 1 part of the compounds of Examples and Comparative Examples, and 0.2 2-phenylbenzimidazole 0.1 part of surfactant (Ftergent FTX-218, manufactured by NEOS Co., Ltd.) was mixed with 230 parts of propylene glycol monomethyl ether acetate and dissolved, and then passed through a membrane filter (pore size 0.45 μm, PTFE membrane) was filtered to prepare a resin composition for positive photolithography (QP-4).

[Chemical 30]

<Minimum exposure amount> The resin composition for positive photolithography (QP-4) prepared above was spin-coated on a substrate on which copper was vapor-deposited on a silicon wafer, and then dried to obtain a photoresist layer. The resist layer was prebaked at 110° C. for 1 minute with a hot plate to obtain a coating film with a film thickness of 6 μm. Next, pattern exposure (i-ray) was performed using TME-150RSC-12 (made by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 1 minute with a hot plate. Then, by the dipping method using 2.38 wt % tetramethylammonium hydroxide aqueous solution, developing treatment was performed for 80 seconds, and washing with running water was performed, and purging with nitrogen gas was performed to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount (i-ray) [mJ/cm ² ] required to form a resist pattern was measured. The minimum exposure amount corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 8.

<Minimum exposure dose (KrF rays)> The resin composition for positive photolithography (QP-4) prepared as described above was spin-coated on a substrate on which copper was vapor-deposited on a silicon wafer, and then dried to obtain a photoresist Floor. The resist layer was prebaked at 110° C. for 1 minute with a hot plate to obtain a coating film with a film thickness of 6 μm. Next, pattern exposure (KrF rays) was performed using FPA-5000ES3 (manufactured by Canon), and post-exposure heating (PEB) was performed at 90° C. with a hot plate for 1 minute. Then, by the dipping method using 2.38 wt % tetramethylammonium hydroxide aqueous solution, developing treatment was performed for 80 seconds, and washing with running water was performed, and purging with nitrogen gas was performed to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount (KrF rays) [mJ/cm ² ] required to form a resist pattern was measured. The minimum exposure amount corresponds to the KrF ray sensitivity and is excellent when it is small. The results are shown in Table 8.

[Table 8] compound resin composition Minimum exposure Minimum exposure (KrF rays) Example 67 A5 QP-4 200 100 Example 68 A13 QP-4 200 100 Example 69 A23 QP-4 100 100 Example 70 A33 QP-4 200 100 Example 71 A40 QP-4 300 100 Example 72 A50 QP-4 200 100 Comparative Example 7 A'1 QP-4 not resolved 500 Comparative Example 8 A'2 QP-4 600 800

As is clear from Tables 5 to 8, it can be seen that the nonionic photoacid generators (A) of Examples 1 to 72 of the present invention are efficiently decomposed by i-ray irradiation, and the resin compositions for photolithography are Since propylene glycol monomethyl ether acetate, which is commonly used in China, exhibits high solubility, the nonionic photoacid generator (A) of the present invention is a photoacid generator excellent in i-ray sensitivity and solubility in resist solvents. agent. In addition, since the compound of the present invention efficiently generates bissulfonamide as a super acid by i-ray irradiation, the minimum exposure amount of the resin composition for positive photolithography containing it is small, and negative photolithography is achieved. The resin composition has good curability in the exposed area and excellent i-ray sensitivity. In addition, it is clear from Table 8 that the nonionic photoacid generator (A) of the present invention is efficiently decomposed by KrF ray irradiation, and generates bissulfonamide as a super acid, so positive photolithography containing it Since the minimum exposure amount with the resin composition is small and the KrF ray sensitivity is excellent, it can be said that the near-ultraviolet sensitivity is excellent. On the other hand, in Comparative Examples (1, 3, 5, and 7) as the ionic photoacid generator, the generated acid was bissulfonamide, but due to its poor i-ray decomposition rate and solubility, photolithography containing it The i-ray sensitivity and KrF ray sensitivity of the resin composition are poor. In addition, it can be seen that the i-ray decomposition rate is the same in the comparative examples (2, 4, 6, and 8) as the nonionic photoacid generator, but since the generated acid is trifluoromethanesulfonic acid, the resin for photolithography containing it is found The i-ray sensitivity and KrF-ray sensitivity of the composition were low, and the near-ultraviolet sensitivity was poor. [Industrial Availability]

The nonionic photoacid generator (A) of the present invention decomposes with high sensitivity to near-ultraviolet rays (i-rays, KrF rays) to generate superacids, so that it can be effectively used as a photomicrograph for microfabrication represented by the manufacture of semiconductors film material.

without

Claims (5)

A nonionic photoacid generator (A), characterized in that it contains a sulfonamide compound represented by the following general formula (1),

[In the formula, R _f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, R ¹ is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, and R _f and R ¹ can be bonded to each other. Forming a ring, R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryl group containing a heteroatom, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group group, or arylsulfonyl group, R ³ is a cyclic alkyl group, an aryl group, or an aryl group containing a heteroatom, and R ² and R ³ can be bonded to each other to form a ring (which may contain a heteroatom)]. The nonionic photoacid generator (A) according to claim 1, wherein in the general formula (1), R ² is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aryl group having a carbon number of 6 to 14. A heteroatom-containing aryl group of 3-14, R ³ is a cyclic alkyl group with a carbon number of 3-12, an aryl group with a carbon number of 6-14, or a heteroatom-containing aryl group with a carbon number of 3-14, R ² It bonds with R ³ to form a 5- to 7-membered ring (which may contain heteroatoms). The nonionic photoacid generator (A) according to claim 1, wherein in the general formula (1), R ² is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 6 carbon atoms. Aryl group of ~14, aryl group of carbon number 3 to 14 containing heteroatom, arylcarbonyl group of carbon number of 6 to 10 (excluding carbonyl carbon), alkoxy group of carbon number of 1 to 10 (excluding carbonyl carbon) Carbonyl, or alkylsulfonyl with 1 to 10 carbons, R ³ is a cyclic alkyl group with 3 to 12 carbons, an aryl group with 6 to 14 carbons, or a heteroatom-containing aryl group with 3 to 14 carbons base. The nonionic photoacid generator (A) according to any one of claim 1 to claim 3, wherein in the general formula (1), R _f and R ¹ are independently CF ₃ and C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , or C ₆ F ₅ . A resin composition (Q) for photolithography, comprising the nonionic photoacid generator (A) according to any one of Claims 1 to 4.