WO2022030107A1

WO2022030107A1 - Nonionic photoacid generator, and photolithography resin composition

Info

Publication number: WO2022030107A1
Application number: PCT/JP2021/022438
Authority: WO
Inventors: 竜輔高橋; 智仁木津
Original assignee: サンアプロ株式会社
Priority date: 2020-08-06
Filing date: 2021-06-14
Publication date: 2022-02-10
Also published as: JPWO2022030107A1; TW202206410A

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 contains a nonionic photoacid generator containing a sulfonamide compound suitable for generating a superstrong acid by acting with ultraviolet rays (i-ray, KrF-ray), and the nonionic photoacid generator. The present invention relates to a resin composition for photolithography.

Conventionally, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography process obtained by transferring a desired pattern to a resist using light of various wavelengths has been widely used.
As the resist material, for example, a tert-butyl ester of a carboxylic acid or a resin composition containing a polymer having a tert-butyl carbonate of phenol and a photoacid generator is used. When this resist material is dissolved in a solvent and applied on a substrate and irradiated with light, the photoacid generator decomposes and a super strong acid such as trifluoromethanesulfonic acid (an acid showing higher acidity than 100% sulfuric acid). Occurs. Further, by heating after exposure (PEB), acid-reactive groups such as tert-butyl ester group or tert-butyl carbonate group in the polymer are dissociated by the generated acid, and carboxylic acid or phenolic hydroxyl group is generated. It is formed and the light-irradiated portion becomes easily soluble in the alkaline developing solution. Since pattern formation is performed using this phenomenon, the development of a highly sensitive resist material that can obtain a desired pattern with a small exposure amount is eagerly desired for energy saving and shortening of process time.
Therefore, as a photoacid generator that realizes a highly sensitive resist material, it is desirable that the photodecomposition rate and the generated acid have higher acid strength.

For the above reasons, ionic photoacid generators such as triarylsulfonium salt (Patent Document 1), phenacylsulfonium salt having a naphthalene skeleton (Patent Document 2), and oxime are preferable photoacid generators for the photolithography step. A nonionic photoacid generator having a sulfonate structure (Patent Document 3), a naphthalimide structure (Patent Document 4, Patent Document 5) and the like is disclosed.

Japanese Unexamined Patent Publication No. 50-151997 Japanese Unexamined Patent Publication No. 9-118663 Japanese Unexamined Patent Publication No. 6-67433 Japanese Unexamined Patent Publication No. 2004-217748 Japanese Patent No. 5990447

Near ultraviolet rays such as i-line (365 nm) and KrF line (248 nm) are widely used as a light source for a photolithography process that decomposes a photoacid generator in a resin composition for photolithography because of its availability and stability. As the semiconductor market grows, there is an increasing demand for the development of photoacid generators that are highly sensitive to these near-ultraviolet rays. Further, in the present day when the photolithography process is diversified, the resist solvent contained in the photolithography resin composition is contained so that the solid does not precipitate or phase separate even in the high-concentration photolithography resin composition. Is required to be highly soluble.

However, ionic photoacid generators such as triarylsulfonium salt and phenacylsulfonium salt have a low photodecomposition rate for i-rays and low sensitivity, and because they are salts, they have a high concentration in the resin composition for photolithography. There was a problem that phase separation or precipitation occurred when it was contained.

A nonionic photoacid generator having an oxime sulfonate structure and a naphthalimide structure has a high photodecomposition rate for i-rays, but practically the generated acid is limited to sulfonic acid, and sufficient acidity cannot be obtained with low sensitivity. There was a problem.

That is, an object of the present invention is a photoacid generator containing a sulfonamide compound that generates a bissulfonamide that has a high decomposition rate and is a super-strong acid with respect to near-ultraviolet rays such as i-rays and KrF rays and is highly soluble in a resist solvent. And a resin composition for photolithography having high sensitivity to near-ultraviolet rays containing the same.

The present inventors have reached the present invention as a result of diligent studies to achieve the above object.
That is, the present invention comprises a nonionic photoacid generator (A) and the nonionic photoacid generator (A), which are characterized by containing a sulfonamide compound represented by the following general formula (1). It is a resin composition (Q) for photolithography including.

[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 are. R2 may be bonded to each other to form a ring, and R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatomic aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryl. It is an oxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, R ³ is a cyclic alkyl group, an aryl group, or a heteroatomic aryl group, and ^R2 and R3 ^are bonded to each other to form a ring (containing a heteroatom). It may be formed). ]

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

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 may be combined with R ¹ 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 hereinafter unless otherwise specified), and linear fluoro. Examples thereof include an alkyl group (RF1), a branched fluoroalkyl group (RF2), a cyclic fluoroalkyl group (RF3) and the like.

The linear fluoroalkyl group (RF1) includes a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorodecanyl group, and a difluoromethyl group. , 1,1,2,2,3,3,4,5,5,6,6-dodecafluorohexyl group, difluoro (methoxycarbonyl) methyl group and 2-adamantyl carbonyloxy-1,1-difluoro Examples thereof include an ethyl group.

Examples of the branched fluoroalkyl group (RF2) include a hexafluoroisopropyl group, a nonafluoro-tert-butyl group and a perfluoro-2-ethylhexyl group.

Examples of the cyclic fluoroalkyl group (RF3) include a heptafluorocyclobutyl group, a nonafluorocyclopentyl group, a perfluorocyclohexyl group and a perfluoro (1-cyclohexyl) methyl group.

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

Fluoroaryl groups (RF4) having 6 to 10 carbon atoms include 3,4,5-trifluorophenyl group, pentafluorophenyl group, perfluoronaphthyl group, 3-trifluoromethyltetrafluorophenyl group and 3,5-. Examples thereof include a bistrifluoromethylphenyl group.

Of the R _fs , a linear fluoroalkyl group (RF1), a branched fluoroalkyl group (RF2), and a fluoroaryl group (RF4) are preferable from the viewpoint of the deprotective ability of the photoresist and the availability of raw materials. , Linear fluoroalkyl group (RF1), and fluoroaryl group (RF4) are more preferred, trifluoromethyl group (CF ₃ ), pentafluoroethyl group (C ₂ F ₅ ), heptafluoropropyl group (C ₃ F ₇ ). ), Nonafluorobutyl group (C ₄ F ₉ ) and pentafluorophenyl group (C ₆ F ₅ ) are particularly preferred.

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 linear alkyl group having 1 to 18 carbon atoms (RA1), a branched alkyl group having 1 to 18 carbon atoms (RA2), a cyclic alkyl group having 3 to 18 carbon atoms (RA3), and the like. ..

The linear alkyl group (RA1) includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group and a benzyloxymethyl group. , Methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 1-methoxyethyl group, trimethylsiloxymethyl group, triethylsiloxymethyl group, tert-butyldimethylsiloxymethyl group and the like.

Branched alkyl groups (RA2) include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 1-methylbutyl group and 2-ethylhexyl. Examples thereof include a group, a 2-hexyldecyl group, an isodecyl group and an isooctadecyl group.

Examples of the cyclic alkyl group (RA3) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a 1-adamantyl group, a 2-adamantyl group, a menthyl group, a 10-campayl group, an octahydronaphthyl group, and a tri. Cyclodecanyl group, tetracyclododecanyl group, 4-dodecylcyclohexyl group and the like can be mentioned.

Examples of the fluoroalkyl group include the same as the above-mentioned linear fluoroalkyl group (RF1), branched fluoroalkyl group (RF2) or cyclic fluoroalkyl group (RF3).

Examples of the aryl group include an aryl group (RA4) having 6 to 10 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azurenyl group, a 2-tolyl group, a 3-tolyl group, and 4-. Tolyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-nitrophenyl group, 4-nitrophenyl group, 2,4-kisilyl group, 2,6-xysilyl group, 3,5-xysilyl group , 2,4-Dinitrophenyl group, 2,4,6-mesityl group and the like.

Examples of the fluoroaryl group include the same group as the above-mentioned fluoroaryl group (RF4).

Of these, from the viewpoint of availability of raw materials, a linear alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a linear fluoroalkyl group having 1 to 10 carbon atoms (RF1), and a carbon number of carbon atoms are preferable. It is an aryl group of 6 to 8 and a fluoroaryl group having 6 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a 10-campayl group, or a trifluoromethyl group (CF ₃ ). ), Pentafluoroethyl group (C ₂ F ₅ ), heptafluoropropyl group (C ₃ F ₇ ), nonafluorobutyl group (C ₄ F ₉ ), phenyl group, 4-tolyl group, 2-nitrophenyl group, 4 -Nitrophenyl group, 2,4-dinitrophenyl group and pentafluorophenyl group (C ₆ F ₅ ), particularly preferably trifluoromethyl group (CF ₃ ), pentafluoroethyl group (C ₂ F ₅ ), hepta. Fluoropropyl group (C ₃ F ₇ ), nonafluorobutyl group (C ₄ F ₉ ) and pentafluorophenyl group (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, a heteroatomic aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an alkylsulfonyl. It is a group or an arylsulfonyl group and may have a substituent. R ² may be combined with R ³ to form a ring (which may contain a heteroatom).

Examples of the alkyl group include the same as the linear alkyl group (RA1), the branched alkyl group (RA2) and the cyclic alkyl group (RA3).

Examples of the alkenyl group include an alkenyl group (RE1) having 2 to 10 carbon atoms, and a linear, branched or cyclic alkenyl group (ethenyl, cyanoethenyl, dicyanoethenyl, phenylethenyl, 1-propenyl, 2-propenyl). , 1-butene-1-yl, 2-butene-1-yl, 2-methyl-2-propenyl, 1-cyclopentene-1-yl, 1-cyclohexene-1-yl, 1-decene-1-yl and norbornenyl Etc.) etc.

Examples of the alkynyl group include an alkynyl group (RY1) having 2 to 10 carbon atoms, and a linear, branched, or cyclic alkynyl group (ethynyl, 1-propyne-1-yl, 2-propyne-1-yl). , 1-butyne-1-yl, 2-butyne-1-yl, 3-butyne-1-yl, 1-pentyne-1-yl, 2-pentyne-1-yl, 3-pentyne-1-yl, 4 -Pentin-1-yl, 1-hexin-1-yl, 3-methyl-1-butyne-1-yl, 1-methyl-2-butyne-1-yl, 1-methyl-3-butyne-1-yl , 1,1-dimethyl-2-propin-1-yl, 1-cyclooctyne-1-yl, 2-phenylethin-1-yl, etc.) and the like.

Examples of the aryl group include an aryl group (RA5) having 6 to 14 carbon atoms, such as a phenyl group, a 4-cyanophenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group, a 2-anthrasenyl group, and 9 -Anthrasenyl group, 3-phenanthrenyl, 9-phenanthrenyl, 1-azulenyl group, 2-fluorenyl group, 9', 9'-dimethyl-2-fluorenyl group and 9', 9'-bistrifluoromethyl-2-fluorenyl group, etc. Can be mentioned.

Examples of the heteroatom-containing aryl group include a heteroatom-containing aryl group (RA6) having 3 to 14 carbon atoms, and a furanyl group and a thienyl group containing one or more heteroatoms from the group consisting of oxygen, nitrogen and sulfur. , Pyrrolyl group, oxazolyl group, thiazolyl group, thiophenyl group, benzofuranyl group, isobenzofuranyl group, benzopyranyl group, benzothiazolyl group, benzoimidazolyl group, indolyl group, indoleninyl group, naphthothiazolyl group, naphthoxazolyl group, xanthenyl group, thioxanthenyl. Examples thereof include a group, a phenoxatyynyl group, a dibenzo-p-dioxynyl group, a thianthrenyl group, a xanthonyl group, a thioxanthonyl group, an anthraquinonyl group, a dibenzofuranyl group, a fluorenyl group, a carbazolyl group and a coumarinyl group.

Examples of the alkylcarbonyl group include an alkylcarbonyl group (RC1) having 1 to 10 carbon atoms (not containing carbonyl carbon), and a linear or branched alkylcarbonyl group (acetyl, propionyl, butanoyl, 2-methylpropionyl, etc.). Pentanoyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethylpropanoyl, octanoyl, 2-ethylhexanoyl, decanoyl, etc.) and the like.

Examples of the arylcarbonyl group include an arylcarbonyl group (RC2) having 6 to 10 carbon atoms (without carbonyl carbon), and examples thereof include a benzoyl group, a naphthoyl group, and a 4-toluyl group.

Examples of the alkoxycarbonyl group include an alkoxycarbonyl group (RC3) having 1 to 10 carbon atoms (not containing carbonyl carbon), and a linear or branched alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxy). Examples thereof include carbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, tert-amyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl and benzyloxycarbonyl (Cbz)).

Examples of the aryloxycarbonyl group include an aryloxycarbonyl group (RC4) having 6 to 10 carbon atoms (not including carbon on the carbonyl), such as a phenoxycarbonyl group, a 2-triloxycarbonyl group, and a 4-triloxycarbonyl group. Examples thereof include a group, a 4-methoxyphenoxycarbonyl group, a 4-chlorophenoxycarbonyl group, a 1-naphthoxycarbonyl group, a 2-naphthoxycarbonyl group and the like.

Examples of the alkylsulfonyl group include an alkylsulfonyl group (RC5) having 1 to 10 carbon atoms, and a linear or branched alkylsulfonyl group (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, etc. sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, decylsulfonyl, tolfluoromethanesulfonyl, pentafluoroethanesulfonyl, nonafluorobutanesulfonyl and perfluorooctane (Sulfonyl, etc.)) and the like.

Examples of the aryl sulfonyl group include an aryl sulfonyl group (RC6) having 6 to 10 carbon atoms (benzenesulfonyl, 2-toluenesulfonyl, 4-toluenesulfonyl, 2-nitrobenzenesulfonyl, 4-nitrobenzenesulfonyl, 2,4-dinitrobenzenesulfonyl, 2-Mesitylene sulfonyl, 4-butylbenzene sulfonyl, 4-tert-butyl benzene sulfonyl, naphthyl sulfonyl, pentafluoro benzene sulfonyl and 3,5-bis (trifluoromethyl) benzene sulfonyl, 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 a cyclic alkyl group (RA7) having 3 to 12 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a 1-adamantyl group, a 2-adamantyl group, and the like. Examples thereof include a mentyl group, a 10-campayl group, an octahydronaphthyl group, a tricyclodecanyl group, a tetracyclododecanyl group and a 4-hexylcyclohexyl group.

Examples of the aryl group include the same aryl group as the above-mentioned aryl group (RA5).

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

Examples of the substituent of the aryl group (RA5) and the heteroatom-containing aryl group (RA6) include the ^same groups as those listed in (R6) described later.

In the general formula (1), R ³ is 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 cyclic structure. And may contain heteroatoms.

Among the above ^- mentioned ^R2 and R3 in the general formula (1), the following (a) and (b) are preferably mentioned from the viewpoint 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 aryl group having 3 to 14 carbon atoms, and R ³ is. It is a cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heteroatom aryl group having 3 to 14 carbon atoms, and R ² and R ³ are bonded to each other to form a 5- to 7-membered ring (5 to 7-membered ring). It may contain heteroatoms).
Preferably, the following general formulas (1) -1, (1) -2, and (2) -1 to (2) -5 are mentioned. More preferably, the general formulas (1) -1 and (2) -1 to (2) -5.
In the general formula (1) -2, a plurality of R ^1s are independent of each other.

(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 3 to 14 carbon atoms. An aryl group, an arylcarbonyl group having 6 to 10 carbon atoms (without carbonyl carbon), an alkoxycarbonyl group having 1 to 10 carbon atoms (without carbonyl carbon), or an alkylsulfonyl group having 1 to 10 carbon atoms. R ³ is a cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heteroatomic aryl group having 3 to 14 carbon atoms.
The following general formulas (3) -1 to (3) -4, (4) -1 and (4) -2 are preferably mentioned. More preferably, the general formulas (3) -1, (3) -2, (3) -4, (4) -1 and (4) -2. R ² is a group selected from the above groups.

In the general formula (1) -1, G ¹ is a group in which R ² and R ³ are combined to form a ring, and is -CH _2- , -CH ₂ -CH _2- , -O-, -S-. , Or -NR ^7- , etc., and R ⁷ is an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetyl group, a propionyl group, a butanoyl group, a benzoyl group, a mesyl group, a benzenesulfonyl group, a tosyl group, or a nosyl group. The group is preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetyl group or a benzoyl group, and more preferably a methyl group or a phenyl group from the viewpoint of availability of raw materials and ease of synthesis.

In the general formulas (2) -1 to (2) -5, G ² is a group in which R ² and R ³ are bonded to form a ring, and is -CH _2- , -O-, -S-, or. -NR ⁸ -etc. (R ⁸ is the same as R ⁷ above), and R ⁸ is preferably an alkyl group or phenyl group having 1 to 4 carbon atoms from the viewpoint of availability of raw materials and ease of synthesis. It is an acetyl group and a benzoyl group.

In the general formulas (2) -1 to (2) -5, R ⁴ and R ⁵ are hydrogen atoms or substituents of a ring formed by bonding R ² and R ³ , and each of them is an independent hydrogen atom. Examples thereof include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms (RA5), a halogen atom and the like, preferably a hydrogen atom and a linear alkyl group having 1 to 6 carbon atoms from the viewpoint of easiness of synthesis. , Phenyl group, hydrogen atom.

Examples of the halogen atom include those similar to those listed in (R ⁶ ) described later.

In the general formula (3) -4, G ³ and G ⁴ are groups constituting a fused ring, and when the combination thereof is expressed as (G ³ , G ⁴ ), (-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) And so on.

In the general formulas (4) -1 and (4) -2, G ⁵ is -CMe _2- , -O-, -S-, or -NR ^9- (Me represents a methyl group, and R ⁹ is the above. (Similar to R ⁷ ), R ⁹ is preferably an alkyl group, a phenyl group, an acetyl group, a benzoyl group having 1 to 4 carbon atoms, and more preferably a methyl group, from the viewpoint of availability of raw materials and ease of synthesis. Is.

In the above general formula, (R ⁶ ) _n is an mutually independent n substituents (n is an integer of 0 to 8) at arbitrary positions on the above aryl group (RA5) or heteroatomic aryl group (RA6). Alkyl group, fluoroalkyl group, alkenyl group, alkynyl group, aryl group, heteroatomic aryl group including alkoxy group, alkylthio group, alkylcarbonyl group, arylcarbonyl group, which may be bonded to each other to form a ring. Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyl carbonate group, an arylcarbonate group, an alkylsulfonyl group, an arylsulfonyl group, an amino group and a halogen atom.

In the general formulas (1) -1, (1) -2 and (2) -1 to (2) -5, the substitution position of (R ⁶ ) is the combination of R ² and R ³ in the general formula (1). The structure formed by the above is regarded as the mother skeleton and determined, and the substitution positions of (R ⁶ ) in the general formulas (3) -1 to (3) -4, (4) -1 and (4) -2 are general. In equation (1), R ³ is regarded as the mother skeleton and determined.

Examples of the alkyl group of (R ⁶ ) include those similar to the above-mentioned linear alkyl group (RA1), branched alkyl group (RA2) and cyclic alkyl group (RA3), and availability of raw materials and easy synthesis. From the viewpoint of sex, it is preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-. It is a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a cyclopentyl group and a cyclohexyl group.

Examples of the fluoroalkyl group of (R ⁶ ) include those similar to the above-mentioned linear fluoroalkyl group (RF1), branched fluoroalkyl group (RF2), and cyclic fluoroalkyl group (RF3), and availability of raw materials can be mentioned. From the viewpoint of ease of synthesis, a linear, branched or cyclic fluoroalkyl group having 1 to 8 carbon atoms is preferable, and a trifluoromethyl group, a pentafluoroethyl group or a heptafluoropropyl group is more preferable. It is a nonafluorobutyl group and a hexafluoroisopropyl group.

Examples of the alkenyl group of (R ⁶ ) include the same as the above-mentioned alkenyl group (RE1).

Examples of the alkynyl group of (R6) include the ^same as the above-mentioned alkynyl group (RY1), and from the viewpoint of easiness of synthesis, 1-propyne-1-yl group and 1-butyne-1-yl group. , 1-Pentyne-1-yl group and 2-phenylethin-1-yl group are preferable.

Examples of the aryl group of (R ⁶ ) include the same aryl group as the above-mentioned aryl group (RA5).

Examples of the heteroatom-containing aryl group of (R6) include the ^same as the heteroatom-containing aryl group (RA6).

Examples of the alkoxy group of (R ⁶ ) include an alkoxy group (RC7) having 1 to 10 carbon atoms, and a linear, branched or cyclic alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc.). sec-butoxy, tert-butoxy, hexyloxy, cyclohexyloxy, phenoxy, triloxy, benzyloxy, decyloxy, naphthoxy, methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, benzyloxymethoxy, trimethylsiloxy, triethylsiloxy, (Triisopropylsiloxy, tert-butyldimethylsiloxy, etc.), etc., preferably from the viewpoint of ease of synthesis, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyroxy, hexyloxy, benzyloxy and tert-butyl. It is dimethylsiloxy.

Examples of the alkylthio group of (R6) include an alkylthio group having ¹ to 10 carbon atoms (RC8), and a linear, branched or cyclic alkylthio group (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio). , St-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, phenylthio, trilthio, benzylthio, octylthio, decylthio, naphthylthio, etc.), and methylthio is preferable from the viewpoint of ease of synthesis. , Ethylthio, propylthio, isopropylthio, butylthio, benzylthio, octylthio, phenylthio.

Examples of the alkylcarbonyl group of (R ⁶ ) include the same group as the above-mentioned alkylcarbonyl group (RC1), preferably acetyl, propionyl, butanoyl, 2-methylbutanoyl and 2, from the viewpoint of ease of synthesis. 2-Dimethylpropanoyl.

Examples of the arylcarbonyl group of (R6) include the ^same arylcarbonyl group as the above-mentioned arylcarbonyl group (RC2).

Examples of the alkoxycarbonyl group of (R ⁶ ) include the same as the alkoxycarbonyl group (RC3) described above, and from the viewpoint of ease of synthesis, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl and butoxy are preferable. Carbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, tert-amyloxycarbonyl, and 2-ethylhexyloxycarbonyl.

Examples of the aryloxycarbonyl group of (R6) include the ^same aryloxycarbonyl group as the above-mentioned aryloxycarbonyl group (RC4).

Examples of the alkylcarbonyloxy group of (R6) include an alkylcarbonyloxy group ( ^RC9 ) having 1 to 10 carbon atoms (not containing carbonyl carbon), and a linear or branched alkylcarbonyloxy group. (Acetoxy, Ethyl Carbonyloxy, Propyl Carbonyloxy, Isopropyl Carbonyloxy, Butyl Carbonyloxy, Isobutyl Carbonyloxy, sec-Butyl Carbonyloxy, tert-Butyl Carbonyloxy, Pentyl Carbonyloxy, Hexyl Carbony Roxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy, decylcarbonyloxy, benzylcarbonyloxy, etc.), etc., preferably acetoxy, ethylcarboniloxy, propylcarbonyloxy, etc. Isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, pentylcarboniloxy, hexylcarbonyloxy and 2-ethylhexylcarbonyloxy.

Examples of the arylcarbonyloxy group of (R6) include an arylcarbonyloxy group (RC10) having ⁶ to 10 carbon atoms (without carbonyl carbon), such as a phenylcarbonyloxy group and 1-naphthylcarbo. Nyloxy group, 2-naphthylcarbonyloxy group, 1-azurenylcarbonyloxy group, 2-tolylcarbonyloxy group, 3-tolylcarbonyloxy group, 4-tolylcarbonyloxy group, 2-chlorophenylcarboni Loxy group, 3-chlorophenylcarbonyloxy group, 4-chlorophenylcarbonyloxy group, 2,4-xysilylcarbonyloxy group, 2,6-xysilylcarbonyloxy group, 3,5-xysilylcarbonyloxy Examples thereof include a group, a 2,4,6-mesitylcarbonyloxy group, a 3,5-bistrifluoromethylphenylcarbonyloxy group and a pentafluorophenylcarbonyloxy group.

Examples of the alkyl carbonate group of (R ⁶ ) include an alkyl carbonate group (RC11) having 1 to 10 carbon atoms (not containing carbonyl carbon), a methyl carbonate group, an ethyl carbonate group, a propyl carbonate group, and 2-. Obtaining raw materials for propyl carbonate group, butyl carbonate group, 2-butyl carbonate group, isobutyl carbonate group, tert-butyl carbonate group, tert-amyl carbonate group, benzyl carbonate group, 2-ethylhexyl carbonate group, mentyl carbonate group and the like. From the viewpoint of properties, a methyl carbonate group, an ethyl carbonate group, a propyl carbonate group, an isopropyl carbonate group, a butyl carbonate group, an isobutyl carbonate group, a tert-butyl carbonate group, a tert-amyl carbonate group and a 2-ethylhexyl carbonate group are preferable.

Examples of the aryl carbonate group of (R ⁶ ) include an aryl carbonate group (RC12) having 6 to 10 carbon atoms (without carbonyl carbon), such as a phenyl carbonate group, a 1-naphthyl carbonate group and a 2-naphthyl carbonate. Group, 1-azurenyl carbonate group, 2-tolyl carbonate group, 3-tolyl carbonate group, 4-tolyl carbonate group, 2-chlorophenyl carbonate group, 3-chlorophenyl carbonate group, 4-chlorophenyl carbonate group, 2,4-chi Cyril carbonate group, 2,6-xysilyl carbonate group, 3,5-kisilyl carbonate group, 2,4,6-mesityl carbonate group, 3,5-bistrifluoromethylphenyl carbonate group, pentafluorophenyl carbonate group, etc. Can be mentioned.

Examples of the alkylsulfonyl group of (R6) include the ^same as the above-mentioned alkylsulfonyl group (RC5), and from the viewpoint of availability of raw materials, methylsulfonyl, ethylsulfonyl, butylsulfonyl, trifluoromethanesulfonyl, and nona are preferable. Fluorobutanesulfonyl and perfluorooctanesulfonyl.

Examples of the aryl sulfonyl group of (R ⁶ ) include the same aryl sulfonyl group as the above-mentioned aryl sulfonyl group (RC6), and from the viewpoint of availability of raw materials, benzenesulfonyl, 4-toluenesulfonyl, 2-nitrobenzenesulfonyl and penta are preferable. Fluorobenzenesulfonyl.

Examples of the halogen atom in ( ^R6 ) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and from the viewpoint of availability of raw materials and ease of synthesis, fluorine atoms, chlorine atoms and bromine atoms are preferable. be.

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

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 desired product can be synthesized, but for example, the compound of the general formula (1) is described below. Can be manufactured.

In the above reaction formula, R ¹ to R ³ and R _f are the same as the definitions in the general formula (1).
The first-stage reaction consists of a precursor (PR1), a sulfonic acid halide equivalent represented by R ¹ SO ₂ X, and a base (sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, pyridine, chloro). Pyridine, dichloropyrididine, rutidin, 2,6-ditercious butylpyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene (DBU), tetramethylpiperidin (TMP), tetramethylguanidine (TMG), hexamethyldisilazane ( HMDS), potassium tertiary butoxide, lithium diisopropylamide, sodium hexamethyldisilazane, etc.) in organic solvents (toluene, butyl acetate, acetonitrile, dimethylformamide (DMF), dimethylacetamide (DMAc), dichloromethane, chloroform, benztrifluoride, etc.) ) Or in water at −78 ° C. to reflux conditions for 5 minutes to 3 hours. After the reaction is completed, the precursor (PR2) can be obtained by filtering the precipitated solid or extracting it with an appropriate solvent. (PR2) can be purified by recrystallization or washing with a solvent, if necessary. In some cases, a subsequent reaction can be carried out in an unpurified state.

The second-stage reaction consists of a precursor (PR2), a sulfonic acid halide equivalent represented by R _f SO ₂ X, and a base (sodium hydrogen carbonate, potassium carbonate, pyridine, chloropyridine, dichloropyridine, 2, 6). -Ditertial butyl pyridine, triethylamine, ethyl diisopropylamine, TMP, TMG, HMDS, potassium tertiary butoxide, lithium diisopropylamide, sodium bishexamethyl disilazane, etc.) in organic solvents (toluene, butyl acetate, acetonitrile, DMF, DMAc, etc.) In dichloromethane, chloroform, benztrifluoride, etc.), react at −78 to 30 ° C. for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent and the volatile components are distilled off to obtain a solid sulfonamide compound of the general formula (1). The obtained solid can be purified by column chromatography, washing with an organic solvent, recrystallization or the like, if necessary.

The non-ionic photoacid generator (A) of the present invention is suitable for use as a resin composition (resist) for photolithography because a super strong acid is generated by light irradiation.

The nonionic photoacid generator (A) of the present invention may be previously dissolved in a solvent that does not inhibit the reaction in order to facilitate dissolution in the resist material.

Examples of the solvent that facilitates dissolution in the resist material include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, β-propiolactone, etc.). β-butyrolactone, γ-butyrolactone, δ-valerolactone, 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.), ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.) and the like.

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

Since the resin composition for photolithography (Q) of the present invention contains a nonionic photoacid generator (A) as an essential component, it is exposed to an exposed portion and unexposed by performing ultraviolet irradiation and post-exposure heating (PEB). There is a difference in the solubility of the part in the developer. The non-ionic photoacid generator (A) may be used alone or in combination of two or more, or may be used in combination with an ionic photoacid generator such as a sulfonium salt.
The resin composition (Q) for photolithography includes a mixture of a negative chemical amplification resin (QN) and a nonionic photoacid generator (A); and a positive chemical amplification resin (QP) and a nonionic photoacid. A mixture with the generator (A) can be mentioned.

The negative chemical amplification resin (QN) is composed of a phenolic hydroxyl group-containing resin (QN1) and a cross-linking agent (QN2).

The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a resin containing a phenolic hydroxyl group. Combined, hydroxystyrene, styrene and (meth) acrylic acid derivative copolymer, phenol / xylylene glycol condensed resin, cresol / xylylene glycol condensed resin, polyimide containing phenolic hydroxyl group, polyamic acid containing phenolic hydroxyl group , Phenolic-dicyclopentadiene condensation resin is used. Among these, novolak resin, polyhydroxystyrene, hydroxystyrene copolymer, hydroxystyrene and styrene copolymer, hydroxystyrene, styrene and (meth) acrylic acid derivative copolymer, phenol / xylylene glycol condensation. Resin is preferred. These phenolic hydroxyl group-containing resins (QN1) may be used alone or in combination of two or more.

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, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, catechol, resorcinol, pyrogallol, 1-naphthol and 2-naphthol.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, and phenol / naphthol / formaldehyde condensed novolak resin.

Further, the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic small molecule compound as a part of the component.
Examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) -1-. Phenyl ethane, 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] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, 4,4'-{1- [4- [1] -(4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene} bisphenol. These phenolic small molecule compounds may be used alone or in admixture of two or more.

The content ratio of this phenolic small molecule compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less when the phenolic hydroxyl group-containing resin (QN1) is 100% by weight, preferably 1 to 30%. % By weight is even more preferred.

The weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, preferably 2000 to 20000, from the viewpoints of resolution, thermal shock resistance, thermal stability, residual film ratio, etc. of the obtained insulating film. Is even more preferable.
Further, the content ratio of the phenolic hydroxyl group-containing resin (QN1) in the negative chemical amplification resin (QN) is 30 to 90% by weight when the whole composition excluding the solvent is 100% by weight. Is preferable, and 40 to 80% by weight is more preferable. When the content ratio of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90% by weight, the film formed by using the photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution. Therefore, it is preferable.

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

Examples of the cross-linking agent (QN2) include bisphenol A-based epoxy compound, bisphenol F-based epoxy compound, bisphenol S-based epoxy compound, novolak resin-based epoxy compound, resole resin-based epoxy compound, poly (hydroxystyrene) -based epoxy compound, and oxetane. Compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl groups Phenolic compound contained, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing Examples thereof include urea compounds and carboxymethyl group-containing phenol compounds.

Among these cross-linking agents (QN2), methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycol uryl compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compounds. Is preferable, and methoxymethyl group-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl group-containing glycol uryl compounds, methoxymethyl group-containing urea compounds, and the like are even more preferable. The methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Sianamid Co., Ltd.), and the methoxymethyl group-containing glycoluril compound is a trade name such as CYMEL1174 (manufactured by Mitsui Sianamid Co., Ltd.). Further, the methoxymethyl group-containing urea compound is commercially available under a trade name such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

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

The positive chemical amplification resin (QP) includes an alkali-soluble resin (QP1) containing one or more acidic functional groups such as a phenolic hydroxyl group, a carboxyl group, or a sulfonyl group, and an acidic functional group in (QP1). Examples thereof include a protective group-introduced resin (QP2) in which a part or all of the hydrogen atom is replaced with an acid dissociative group.
The protecting group-introduced resin (QP2) is itself alkali-insoluble or sparingly soluble in alkali.
The acid dissociable group is a group that can be dissociated in the presence of a super strong acid generated from the nonionic photoacid generator (A).

Examples of the alkali-soluble resin (QP1) include a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), and a sulfonic acid group-containing resin (QP13).
As the phenolic hydroxyl group-containing resin (QP11), the same one 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, a carboxyl group-containing vinyl monomer (Va) and, if necessary, a hydrophobic group-containing vinyl monomer (Vb) are vinyl-polymerized. It can be obtained by.

Examples of the carboxyl group-containing vinyl monomer (Va) include unsaturated monocarboxylic acids [(meth) acrylic acid, crotonic acid, cinnamic acid, etc.] and unsaturated polyvalent (2- to tetravalent) carboxylic acids [(anhydrous) malein. Acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polyvalent carboxylic acid alkyl (alkyl group having 1 to 10 carbon atoms) ester [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, etc.] ], And these salts [alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), amine salts, ammonium salts, etc.].
Of these, unsaturated monocarboxylic acids are preferable, and (meth) acrylic acid is more preferable, from the viewpoint of polymerizability and availability.

Examples of the hydrophobic group-containing vinyl monomer (Vb) include (meth) acrylic acid ester (Vb1) and an aromatic hydrocarbon monomer (Vb2).

Examples of the (meth) acrylic acid ester (Vb1) include alkyl (meth) acrylates having 1 to 20 carbon atoms of the alkyl group [methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). ) Acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.] and alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, sidiclopentenyl (Meta) acrylate, isobornyl (meth) acrylate, 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, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, Cyclocarbon styrene, benzyl styrene, etc.] and vinyl naphthalene.

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

The sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer having a sulfonic acid group. For example, a sulfonic acid group-containing vinyl monomer (Vc) and, if necessary, a hydrophobic group-containing vinyl monomer (Vb) can be used. Obtained by 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 vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, and 2- (meth) acryloylamide-2-methylpropanesulfonic acid. And these salts. Examples of the salt include alkali metal (sodium and potassium etc.) salts, alkaline earth metal (calcium and magnesium etc.) salts, primary to tertiary amine salts, ammonium salts and quaternary ammonium salts.

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

The HLB value of the alkali-soluble resin (QP1) varies in a preferable range depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17.
When the HLB value is 4 or more, the developability is further good when developing, and when the HLB value is 19 or less, the water resistance of the cured product is further good.

The HLB value in the present invention is an HLB value obtained by the Oda method, which 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. ..
<HLB evaluation method>
HLB ≈ 10 × Inorganic / Organic For the values of inorganic and organic, refer to page 501 of the document "Synthesis of Surfactants and Their Applications" (published by Maki Shoten, Oda, Teramura); or " It is described in detail on page 198 of "Introduction to New Surfactants" (written by Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).

The acid dissociable group in the protective group-introduced resin (QP2) includes a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a gelmil group, an alkoxycarbonyl group, an acyl group and a cyclic acid dissociation. Sexual groups and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, and a methoxyphenacil group. , Methylthiophenacil group, α-methylphenacil group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, Examples thereof include ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, butoxycarbonylmethyl group and tert-butoxycarbonylmethyl group.

Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group and 1,1-diethoxyethyl group. Group, 1-ethoxypropyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-propoxycarbonylethyl group, 1 -Isopropoxycarbonylethyl group, 1-butoxycarbonylethyl group, 1-tert-butoxycarbonylethyl group can be mentioned.

Examples of the 1-branched alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group and a 1,1-dimethylbutyl group.

Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group and a di-tert-. Examples thereof include a tricarbylsilyl group such as a butylmethylsilyl group, a tri-tert-butylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group and a triphenylsilyl group.

Examples of the gel mill group include a trimethyl gel mill group, an ethyl dimethyl gel mill group, a methyl diethyl gel mill group, a triethyl gel mill group, an isopropyl dimethyl gel mill group, a methyl diisopropyl gel mill group, a triisopropyl gel mill group and tert-butyl. Examples thereof include a tricarbylgelmill group such as a dimethylgelmill group, a di-tert-butylmethylgelmill group, a tri-tert-butylgelmill group, a dimethylphenylgelmill group, a methyldiphenylgelmill group and a triphenylgelmill group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyle group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauroyl group, a myritoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group and a succinyl group. Group, glutalyl group, adipoil group, piperoyl group, suberoyl group, azella oil group, sebacyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyle group, oleoyl group, male oil group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group. , Phthalloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoil group, hydroatropoil group, atropoil group, cinnamoyl group, floyl group, tenoyl group, nicotinoyle group, isonicotinoyl group, p-toluenesulfonyl group, mesyl group. Be done.

Examples of the cyclic acid dissociative group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuranyl. Examples thereof include a group, a 3-bromotetrahydropyranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group and a 3-tetrahydrothiophene-1,1-dioxide group.

Among these acid dissociative groups, tert-butyl group, benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tetrahydropyranyl group, A tetrahydrofuranyl group, a tetrahydrothiopyranyl group and a tetrahydrothiofuranyl group are preferable.

Introduction rate of acid dissociative groups in the protective group-introduced resin (QP2) {Ratio of the number of acid dissociative groups to the total number of unprotected acidic functional groups and acid dissociative groups in the protective group-introduced resin (QP2) } Can not be unconditionally specified depending on the type of acid dissociable group or 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”) measured by gel permeation chromatography (GPC) of the protecting group-introduced resin (QP2) is preferably 1,000 to 150,000, preferably 3,000 to 100, 000 is more preferable.

The ratio (Mw / Mn) of the Mw of the protecting group-introduced resin (QP2) to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 1. It is 10, preferably 1 to 5.

The content of the nonionic photoacid generator (A) based on the weight of the solid content of the photolithography resin composition (Q) is preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight. It is preferable, and 0.05 to 7% by weight is particularly preferable.
If it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be exhibited more satisfactorily, and if it is 20% by weight or less, the physical properties of the insoluble portion with respect to the alkaline developer can be further exhibited.

The resist using the resin composition for photolithography (Q) of the present invention may contain a quencher (acid diffusion control agent) for the purpose of improving the shape of the pattern after exposure, changes over time, and the like. The quencher is not particularly limited as long as it is a compound having _a basic site showing pKa larger than the acid generated by the nonionic photoacid generator (A). For example, known amines (tripentylamine, triisopropanolamine, dicyclohexylamine, N, N-dicyclohexylmethylamine, etc.), known pyridines (pyridine, 2,6-lutidine, 2,6-di-tert-butyl). Pyridine, 2,6-diphenylpyridine, etc.), known anilins (2,6-diisopropylaniline, etc.), known imidazoles (2,4,5-triphenylimidazole, 4,5-diphenylimidazole, 2-phenyl) (Imidazole, etc.), and salts of known onium and weak acid anion that decompose during exposure to generate weak acid (triphenylsulfonium benzoate, triphenylsulfonium salicylate, 3,5-bistrifluoromethyltriphenylsulfonium benzoate, pentafluoro). (Diphenyliodonium benzoate, -4-isobutyl-4'-tolyliodonium 4-fluorobenzoate, etc.) can be mentioned. The content of the quencher depends on the content of the nonionic photoacid generator (A), but is 5% by weight or less, preferably 5% by weight or less, based on the total solid content of the photolithography resin composition (Q). It is 3% by weight or less. If it exceeds 5% by weight, the effective concentration of the acid generated during exposure decreases, and there is a problem that a pattern cannot be obtained after development.

The resist using the photolithography resin composition (Q) of the present invention is prepared by, for example, spin-coating, curtain-coating, or rolling a resin solution dissolved in a predetermined organic solvent (dissolving and dispersing when inorganic fine particles are contained). It can be formed by applying to a substrate using a known method such as coating, spray coating, screen printing, and then drying the solvent by heating or hot air blowing.

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

The drying conditions of the resin solution after coating vary depending on the solvent used, but are preferably carried out at 50 to 200 ° C. for 1 to 30 minutes, and the residual solvent amount of the resin composition (Q) for photolithography after drying (Q). Weight%) etc. will be determined as appropriate.

After forming a resist on the substrate, light irradiation in the shape of a wiring pattern is performed. Then, after exposure and heating (PEB), alkaline development is performed to form a wiring pattern.

Examples of the method of irradiating light include a method of exposing a resist with an active ray through a photomask having a wiring pattern. The active light beam used for light irradiation is not particularly limited as long as the nonionic photoacid generator (A) in the photolithography resin composition (Q) of the present invention can be decomposed.
As active light, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halogen lamp, electron beam irradiator, X-ray irradiator, laser (argon laser, argon / fluorine (ArF) excimer laser, Crypton / fluorine (KrF) excimer laser, dye laser, nitrogen laser, LED, helium cadmium laser, etc.). Of these, high pressure mercury lamps, ultrahigh pressure mercury lamps, LEDs and krypton-fluorine (KrF) excimer lasers are preferable.

The temperature of the post-exposure heating (PEB) is usually 40 to 200 ° C., preferably 50 to 190 ° C., more preferably 60 to 180 ° C. If the temperature is lower than 40 ° C, the deprotection reaction or the cross-linking reaction cannot be sufficiently performed, so that the difference in solubility between the UV-irradiated portion and the UV-non-irradiated portion is insufficient and a pattern cannot be formed. There is.
The heating time is usually 0.5 to 120 minutes, and if it is less than 0.5 minutes, it is difficult to control the time and temperature, and if it is longer than 120 minutes, there is a problem that productivity is lowered.

Examples of the method of alkaline development include a method of dissolving and removing the wiring pattern shape using an alkaline developer. The alkaline developer is not particularly limited as long as the solubility of the ultraviolet-irradiated portion and the non-ultraviolet-irradiated portion of the photolithography resin composition (Q) can be different.
Examples of the alkaline developer include an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydrogencarbonate and an aqueous solution of tetramethylammonium salt.
A water-soluble organic solvent may be added to these alkaline developers. Examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, THF, N-methylpyrrolidone and the like.

As a developing method, there are a dip 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 25-40 ° C. The development time is appropriately determined according to the thickness of the resist.

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

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

<Manufacturing 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 in the method shown in Table 2014/084269.
Then, the obtained alkylated product was used to obtain a precursor (P2) according to the method described in Production Example 1.

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

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

<Manufacturing example 5>
<Synthesis of precursor (P5)>
The precursor (P4) synthesized in Production Example 4 was dispersed in dichloromethane, triethylamine was added dropwise to the slurry cooled to −78 ° C., and the mixture was stirred for 5 minutes. Then, pentafluorobenzenesulfonic acid chloride was added dropwise, and the mixture was stirred for 1 hour and then heated to 0 ° C. After the reaction was stopped by adding deionized water, the precipitated solid was filtered and dried under reduced pressure to obtain a precursor (P5) of the following formula.

<Manufacturing 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.).
Then, using the obtained ketone body, a precursor (P6) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 7>
<Synthesis of precursor (P7)>
The corresponding ketone bodies were synthesized according to the method described in JP-A-2010-024290.
Then, using the obtained ketone body, a precursor (P7) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 8>
<Synthesis of precursor (P8)>
The precursor of the following formula (P8) was obtained in the same manner as in Production Example 1 and then in Production Example 5 except that the pentafluorobenzenesulfonic acid chloride was changed to 2-nitrobenzenesulfonyl chloride using 6,7-dimethyl-1-tetralone as a raw material. ) Was obtained.

<Manufacturing example 9>
<Synthesis of precursor (P9)>
Using 6-methoxy-2-naphthalene propionic acid as a raw material and following the method described in the literature (Synthesis, 2005, 1789.), The ketone body 2,3-dihydro-7-methoxy-1H-benz [e] indene- 1-on was synthesized.
Then, using the obtained ketone body, a precursor (P9) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 10>
<Synthesis of precursor (P10)>
Using 2-naphthol and ethyl 2-bromooctanoate as raw materials, 2-hexylnaphtho [2,1-b] furan-1 (2H) -one, which is a ketone body, is synthesized according to the method described in JP-A-2011-209719. did.
Then, using the obtained ketone body, a precursor (P10) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 11>
<Synthesis of precursor (P11)>
2-Methylnaphtho [1, 2] which is a ketone body according to the method described in the literature (Synthetic Communications., 2012, 42, 989.) Using methyl 1-hydroxy-2-naphthoate and methyl 2-bromopropionate as raw materials. -B] Fran-3 (2H) -on was synthesized.
Then, using the obtained ketone body, a precursor (P11) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 12>
<Synthesis of precursor (P12)>
1- [4- (Phenylthio) phenyl] -1-heptanone, which is a ketone body, was synthesized according to the method described in JP-A-2009-242469, except that diphenylsulfide and heptanoyl chloride were used as raw materials and the solvent was dichloromethane. ..
Then, using the obtained ketone body, a precursor (P12) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing 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 JP-A-2009-24469.
Then, using the obtained ketone body, a precursor (P13) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 14>
<Synthesis of precursor (P14)>
2-Benzyl-3,3-dimethyl-3H-indole is synthesized according to the method described in JP-A-2016-11354, and further corresponds to the method described in the literature (Chem. Sci., 2016, 7.346.). Ketone bodies were synthesized.
Then, using the obtained ketone body, a precursor (P14) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 15>
<Synthesis of precursor (P15)>
Using 2-amino-4-methoxyphenol and 2,2-dibromoacetophenone (synthesized according to the literature Chem. Asian J., 2012, 7, 2240.) As raw materials, the literature (J. Org. Chem., 2016, 81.51. The ketone form 2-benzoyl-5-methoxy-1,3-benzoxazole was synthesized according to the method described in (.).
Then, using the obtained ketone body, a precursor (P15) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 16>
<Synthesis of precursor (P16)>
Using benzothiazole and ethyl chloroglycyoxylate as raw materials, the corresponding ketone bodies were synthesized according to the method described in the literature (Synthesis, 2011, 1633.), And the corresponding hydrazone bodies were further synthesized according to the method described in Production Example 1.
Next, the precursor (P16) of the following formula was obtained in the same manner as in Production Example 5 except that the pentafluorobenzenesulfonic acid chloride was changed to p-toluenesulfonic acid chloride.

<Manufacturing example 17>
<Synthesis of precursor (P17)>
4- (2-Benzothiazolylcarbonyl) benzonitrile, which is a ketone body, was synthesized from benzothiazole and 4-cyanobenzoyl chloride as raw materials according to the method described in the literature (Synlett, 2013, 24, 2233.).
Then, using the obtained ketone body, a precursor (P17) of the following formula was obtained according to the method described in Production Example 1.

<Manufacturing example 18>
<Synthesis of precursor (P18)>
Using 2-aminobenzenethiol and 3- (dimethylamino) -1-phenyl-2-propen-1-one as raw materials, in a ketone form according to the method described in the literature (Green Chem., 2016, 18, 402.). A certain 1- (2-benzothiazoyl) -2-phenyl-1,2-ethandione was synthesized.
Then, using the obtained ketone body, a precursor (P18) of the following formula was obtained according to the method described in Production Example 1.

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

<Example 1>
<Synthesis of compound (A1)>
10 parts of the precursor (P1) synthesized in Production Example 1 was dispersed in 350 parts of dichloromethane, 30 parts of 2,6-di-tert-butylpyridine was added dropwise to the slurry cooled to 0 ° C., and the mixture was stirred for 5 minutes. Then, 35 parts of trifluoromethanesulfonic anhydride was added dropwise and stirred for 1 hour. Deionized water was added to the reaction solution to stop the reaction, and the organic layer was washed with deionized water three times. By concentrating the organic layer, 18 parts of the yellow solid compound (A1) was obtained.

<Example 2>
<Synthesis of compound (A2)>
Using the precursor (P1) synthesized in Production Example 1 as a raw material, 23 parts of compound (A2) were prepared in the same manner as in Example 1 except that the trifluoromethanesulfonic anhydride was 72 parts of nonafluorobutanesulfonic anhydride. Got

<Example 3>
<Synthesis of compound (A3)>
Using the precursor (P1) synthesized in Production Example 1 as a raw material, 20 parts of compound (A3) was prepared in the same manner as in Example 1 except that the trifluoromethanesulfonic anhydride was made into 30 parts of pentafluorobenzenesulfonic acid chloride. Got

<Example 4>
<Synthesis of compound (A4)>
The same 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 made into 36 parts of perfluoropropane-1,3-disulfonyldifluoride. 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, 14 parts of compound (A5) was obtained in the same manner as in Example 1.

<Example 6>
<Synthesis of compound (A6)>
The compound (A6) 14 of the following formula was prepared in the same manner as in Example 1 except that a precursor synthesized from 11H-benzo [b] fluorene-11-one as a raw material according to the method described in Production Example 1 was used. I got a part.

<Example 7>
<Synthesis of compound (A7)>
10 parts of the precursor (P3) synthesized in Production Example 3 was dispersed in 320 parts of dichloromethane, and 19 parts of N-ethyldiisopropylamine was added dropwise to the slurry cooled to 0 ° C., and the mixture was stirred for 5 minutes. Then, 33 parts of trifluoromethanesulfonic anhydride was added dropwise and stirred for 1 hour. Deionized water was added to the reaction solution to stop the reaction, and the organic layer was washed with deionized water three times. By concentrating the organic layer, 16 parts of a yellowish brown solid compound (A7) was obtained.

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

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

<Example 12>
<Synthesis of compound (A12)>
Example 7 except that the precursor (P5) synthesized in Production Example 5 was 10 parts, dichloromethane was 150 parts, N-ethyldiisopropylamine was 4.2 parts, and trifluoromethanesulfonic anhydride was 7.4 parts. By doing the same, 10 parts of compound (A12) was obtained.

<Examples 13 and 14>
<Synthesis of compounds (A13) and (A14)>
Compounds (A13) and (A14) were synthesized in the same manner as in Example 7 except that the precursor synthesized from the corresponding raw material according to the method described in Production Example 4 was used.

<Example 15>
<Synthesis of compound (A15)>
Example 7 except that a precursor synthesized in the same manner as in Production Example 5 by converting pentafluorobenzenesulfonic acid chloride into methanesulfonyl chloride from the corresponding raw material (synthesized according to the method described in Production Example 4) was used. By doing the same, 10 parts of compound (A15) was obtained.

<Examples 16 to 22>
<Synthesis of compounds (A16) to (A22)>
Compounds (A16) to (A22) were prepared in the same manner as in Example 1 or 7 except that the precursor synthesized from the corresponding raw material according to the method described in Production Example 1 or 4 was used. Synthesized.

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

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

<Example 25>
<Synthesis of compound (A25)>
9. 10 parts of the precursor (P8) synthesized in Production Example 8 of the precursor (P1), 180 parts of dichloromethane, 7.7 parts of 2,6-di-tert-butylpyridine, and 9. of trifluoromethanesulfonic anhydride. 11 parts of compound (A25) were obtained in the same manner as in Example 1 except that 1 part was used.

<Examples 26 and 27>
<Synthesis of compounds (A26) and (A27)>
Compounds (A26) and (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.

<Examples 28 and 29>
<Synthesis of compounds (A28) and (A29)>
Compounds (A28) and (A29) were synthesized in the same manner as in Example 24 except that the precursor synthesized from the corresponding raw material 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, 15 parts of compound (A30) was obtained in the same manner as in the synthesis method described in Example 1.

<Example 31>
<Synthesis of compound (A31)>
By using the precursor synthesized from the corresponding raw material according to the method described in Production Example 7 as a raw material and using 61 parts of heptadecafluorooctanesulfonic acid fluoride as the trifluoromethanesulfonic anhydride in the same manner as in Example 1. 35 parts of compound (A31) was obtained.

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

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

<Examples 34 to 36>
<Synthesis of compounds (A34) to (A36)>
Compounds (A34 to A36) were synthesized in the same manner as in Example 24 except that the precursor synthesized from the corresponding raw material 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, 22 parts of compound (A37) was obtained in the same manner as in the synthesis method described in Example 2.

<Example 38>
<Synthesis of compound (A38)>
12 parts of compound (A38) were prepared in the same manner as in Example 37 except that a precursor synthesized by converting methyl 2-bromopropionate to methyl 2-bromooctanoate in the same manner as in Production Example 11 was used. Obtained.

<Example 39>
<Synthesis of compound (A39)>
18 parts of compound (A39) was obtained in the same manner as in Example 1 except that the precursor (P1) was changed to benzophenone hydrazone.

<Example 40>
<Synthesis of compound (A40)>
Using the precursor (P12) synthesized in Production Example 12 as a raw material, 12 parts of compound (A40) was obtained by the same procedure as in the synthesis method described in Example 1.

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

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

<Examples 45 and 46>
<Synthesis of compounds (A45) and (A46)>
Compounds (A45) and (A46) 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 12 was used.

<Example 47>
<Synthesis of compound (A47)>
Using the precursor (P14) synthesized in Production Example 14 as a raw material, 12 parts of compound (A47) was obtained by the same procedure as in the synthesis method described in Example 1.

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

<Example 49>
<Synthesis of compound (A49)>
8. 10 parts of the precursor (P16) synthesized in Production Example 16 of the precursor (P1), 170 parts of dichloromethane, 7.1 parts of 2,6-di-tert-butylpyridine, and 8. trifluoromethanesulfonic anhydride. 11 parts of compound (A49) were obtained in the same manner as in Example 1 except that 4 parts were used.

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

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

<Example 52>
<Synthesis of compound (A52)>
15 parts of compound (A52) was obtained in the same manner as in Example 1 except that a hydrazone compound (precursor) synthesized in the same manner as in Production Example 16 was used by converting benzothiazole to 1-methylbenzimidazole. rice field.

<Example 53>
<Synthesis of compound (A53)>
Compound (A53) was prepared in the same manner as in Example 1 except that a precursor synthesized by converting 2-amino-4-methoxyphenol to 3-amino-2-naphthol in the same manner as in Production Example 15 was used. I got 12 copies.

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

The structures and properties of the compounds (A1) to (A54) are shown in Tables 1 to 4.

[ ^In Table ³ , the R3 bond position represents the bond position of the carbon bonded to R3 represented by R3 ^- CR2 ⁼ N in the general formula (1). ]

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

<Comparative Example 1>
<Synthesis of ionic photoacid generator [Compound (A'1)]>
10 parts of triphenylsulfonium bromide was dispersed in 109 parts of chloroform, and 9.3 parts of sodium bistrifluoromethanesulfonamide and 109 parts of deionized water were added. After stirring vigorously for 1 hour, the mixture was allowed to stand to remove the separated aqueous layer, and the organic layer was washed with water twice. By concentrating the organic layer and drying it in a vacuum dryer, 13 parts of the ionic photoacid generator [Compound (A'1)] of Comparative Example was obtained.

<Comparative Example 2>
<Synthesis of nonionic photoacid generator [Compound (A'2)]>
1,8-Naphthalic acid imide trifluoromethanesulfonate (A'2) (manufactured by Aldrich) was used as it was.

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

<I-line decomposition rate>
0.3 parts of the compounds of Examples and Comparative Examples synthesized in 100 parts of heavy acetonitrile and 0.1 part of perfluorobenzene as a standard substance were dissolved and 0.6 mL was injected into an NMR tube, and ¹⁹ F-NMR analysis was performed. gone. Next, the wavelength of this NMR tube is limited by an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd., HMW-661F-01) and an L-34 (filter manufactured by Kenko Optics Co., Ltd. that cuts light less than 340 nm). The ultraviolet light was exposed to 500 mJ · cm ² . The integrated exposure amount was measured at a wavelength of 365 nm. The NMR tube after exposure was analyzed again by ¹⁹ F-NMR, and the i-ray resolution rate was calculated from the integrated value of the ¹⁹ F-NMR signals of the compounds before and after exposure (based on the standard substance). Since the high decomposition rate is excellent as a photoacid generator at the same exposure amount, the i-ray decomposition rate was evaluated as follows, and the results are shown in Tables 5 and 6.
i-ray decomposition rate = (integral value of compound signal before exposure-integral value of compound signal after exposure) / (integral 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 vortex mixer for 1 minute, and then immersed in a constant temperature bath at 25 ° C. and allowed to stand for 1 hour. It was visually confirmed whether the mixture was uniformly dissolved. In the case of non-uniformity, propylene glycol monomethyl ether acetate was added so that the concentration decreased by 5%, and the operation was repeated. The concentration of 5% or less was repeated in 1% increments. The first uniform concentration was defined as the solubility of the compound in the resist solvent. The higher the solubility, the more difficult it is to precipitate or phase-separate when the resin composition for photolithography is obtained. The results are shown in Tables 5 and 6.

<Evaluation of resin composition for positive photolithography>
<Preparation of resin composition for positive photolithography (QP-1)>
40 parts of the resin represented by the following formula, 60 parts of the novolak resin obtained by polycondensing m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst, and 1 part of the compounds of Examples and Comparative Examples are propylene glycol. A resin composition for positive photolithography (QP-1) was prepared by dissolving in 152 parts of monomethyl ether acetate and filtering through a membrane filter (pore size 0.45 μm, PTFE film).

<Minimum exposure>
The resin composition for positive photolithography (QP-1) prepared above was spin-coated on a silicon wafer substrate and then dried to obtain a photoresist layer having a film thickness of about 20 μm. This resist layer was prebaked on a hot plate at 130 ° C. for 6 minutes. Next, pattern exposure (i-line) was performed using TME-150RSC-12 (manufactured by Topcon), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 5 minutes, washed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L & S) pattern. Further, below that, the minimum exposure amount at which the residue of this pattern was not recognized, that is, the minimum exposure amount [mJ / cm ² ] required to form the resist pattern was measured. It is better that the minimum exposure amount corresponds to the i-line sensitivity and is small. The results are shown in Tables 5 and 6.

<Evaluation of resin composition for negative photolithography>
<Preparation of resin composition for negative photolithography>
75 parts of phenol resin ("Phenolite TD431" manufactured by DIC), 25 parts of melamine curing agent ("Simel 300" manufactured by Mitsui Sianamid Co., Ltd.), 1 part of the synthesized compound of Examples and Comparative Examples, and propylene glycol monomethyl. Each resin composition for negative photolysis was prepared by dissolving it in 100 parts of ether acetate and filtering it through a membrane filter (pore diameter 0.45 μm, PTFE film).

<Currability of exposed part>
Each of the negative photolithography resin compositions prepared above was applied onto a 10 cm square glass substrate at 200 rpm for 10 seconds using a spin coater. Then, it was vacuum dried at 25 ° C. for 5 minutes and then dried on a hot plate at 100 ° C. for 5 minutes to form a resist having a film thickness of about 40 μm. Using an ultraviolet irradiation device (HMW-661F-01 manufactured by ORC Manufacturing Co., Ltd.) for this resist, ultraviolet light whose wavelength is limited by L-34 (340 nm low pass filter manufactured by Kenko Optical Co., Ltd.) is applied to the entire surface of a predetermined amount. Exposed. The integrated exposure amount was measured at a wavelength of 365 nm. Then, after exposure for 10 minutes in a normal wind dryer at 150 ° C., heating (PEB) was performed, and then the mixture was developed by immersing it in a 0.5% potassium hydroxide solution for 60 seconds, and immediately washed with water and dried. The film thickness of this resist was measured using a shape measuring microscope (ultra-depth shape measuring microscope UK-8550, manufactured by KEYENCE CORPORATION). Here, the minimum exposure amount [mJ / cm ² ] at which the change in the film thickness of the resist before and after development is within 10% was defined as the curability of the exposed portion. The curability of the exposed portion corresponds to the i-line sensitivity, and the smaller the minimum exposure amount, the better the i-line sensitivity. The results are shown in Tables 5 and 6.

<Examples 55 to 72, Comparative Examples 3 to 8>
Non-ionic photoacid generators (A5, A13, A23, A33, A40 and A50), ionic photoacid generators (A'1) and non-ionic photoacid generators (A'2) for comparison. The i-line sensitivity and KrF line sensitivity of the positive photolithography resin compositions (QP-2) to (QP-4) were evaluated by the following methods, and the results are shown in Tables 7 and 8.

<Evaluation of resin composition for positive photolithography>
<Preparation of resin composition for positive photolithography (QP-2)>
The following structural unit (m≈9) obtained by reacting 43 parts of tert-butyl methacrylate, 30 parts of methoxypolyethylene glycol methacrylate, 45 parts of methoxydiethylene glycol methacrylate, and 0.4 part of azobisisobutyronitrile under dioxane. ) And 20 parts of novolak resin (m-cresol / p-cresol = 40/60 (mass ratio), Mw = 7 by condensing m-cresol and p-cresol with formaldehyde). , 000)), 1 part of the compounds of Examples and Comparative Examples, and 0.03 part of N, N-dicyclohexymethylamine were mixed and dissolved in 87 parts of propylene glycol monomethyl ether acetate, and then a membrane filter. A resin composition for positive photolithography (QP-2) was prepared by filtering through (pore diameter 0.45 μm, PTFE film).

<Minimum exposure>
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. This resist layer was prebaked on a hot plate at 110 ° C. for 3 minutes to obtain a coating film having a film thickness of about 5 μm. Next, pattern exposure (i-line) was performed using TME-150RSC-12 (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90 ° C. for 60 seconds using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 5 minutes, washed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L & S) pattern. Further, below that, the minimum exposure amount at which the residue of this pattern was not recognized, that is, the minimum exposure amount [mJ / cm ² ] required to form the resist pattern was measured. It is better that the minimum exposure amount corresponds to the i-line sensitivity and is small. The results are shown in Table 7.

<Preparation of resin composition for positive photolithography (QP-3)>
35 parts of the resin having the following structural units (the number in the lower right of the parentheses in the structural formula represents the content weight% of the structural units in the resin) and 10 parts of the polyhydroxystyrene resin (p-hydroxystyrene: styrene: tert). -Butyl acrylate = 12: 3: 5 copolymer, Mw = 1.0 x 10 ⁴ ) and 27.5 parts of novolak resin (m-cresol and p-cresol) fused with formaldehyde (cocondensate) m-cresol / p-cresol = 40/60 (mass ratio), Mw = 5,000)) and 27.5 parts of novolak resin (m-cresol and p-cresol) condensate with formaldehyde (m) -Cresol / p-cresol = 40/60 (mass ratio), Mw = 7,000)), 0.05 part of surfactant (BYK310, manufactured by Big Chemie), and 1 part of the compound of Examples and Comparative Examples. Was mixed and dissolved in a mixed solvent (methoxybutyl acetate / propylene glycol monomethyl ether acetate = 60/40 (mass ratio)) so that the solid content concentration became 40% by weight, and then a membrane filter (pore size 0.45 μm) was dissolved. , PTFE film) to prepare a resin composition for positive photolithography (QP-3).

<Minimum exposure>
The resin composition for positive photolithography (QP-3) prepared above was spin-coated on a copper substrate and then dried to obtain a photoresist layer having a film thickness of about 11 μm. This resist layer was prebaked on a hot plate at 130 ° C. for 5 minutes. Next, pattern exposure (i-line) was performed using TME-150RSC-12 (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90 ° C. for 90 seconds using a hot plate. Then, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was dropped onto the substrate and allowed to stand at 23 ° C. for 30 seconds twice, washed with running water, blown with nitrogen, and line-and-space (10 μm). L & S) pattern was obtained. Further, below that, the minimum exposure amount at which the residue of this pattern was not recognized, that is, the minimum exposure amount [mJ / cm ² ] required to form the resist pattern was measured. It is better that the minimum exposure amount corresponds to the i-line sensitivity and is small. The results are shown in Table 7.

<Preparation of resin composition for positive photolithography (QP-4)>
100 parts of the resin having the following structural units (the number in the lower right of the parentheses in the structural formula represents the content weight% of the structural units in the resin), 1 part of the compounds of Examples and Comparative Examples, and 2-phenylbenz. 0.2 parts of imidazole and 0.1 part of a surfactant (Futergent FTX-218, manufactured by Neos Co., Ltd.) were mixed and dissolved in 230 parts of propylene glycol monomethyl ether acetate, and then a membrane filter (pore size 0). A resin composition for positive photolithography (QP-4) was prepared by filtering through a (.45 μm, PTFE film).

<Minimum exposure>
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. This resist layer was prebaked on a hot plate at 110 ° C. for 1 minute to obtain a coating film having a film thickness of 6 μm. Next, pattern exposure (i-line) was performed using TME-150RSC-12 (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90 ° C. for 1 minute using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 80 seconds, washed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L & S) pattern. Further, below that, the minimum exposure amount at which the residue of this pattern was not recognized, that is, the minimum exposure amount (i-line) [mJ / cm ² ] required to form the resist pattern was measured. It is better that the minimum exposure amount corresponds to the i-line sensitivity and is small. The results are shown in Table 8.

<Minimum exposure (KrF line)>
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. This resist layer was prebaked on a hot plate at 110 ° C. for 1 minute to obtain a coating film having a film thickness of 6 μm. Next, pattern exposure (KrF line) was performed using FPA-5000ES3 (manufactured by Canon Inc.), and post-exposure heating (PEB) was performed at 90 ° C. for 1 minute using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 80 seconds, washed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L & S) pattern. Further, below that, the minimum exposure amount at which the residue of this pattern was not recognized, that is, the minimum exposure amount (KrF line) [mJ / cm ² ] required to form the resist pattern was measured. The minimum exposure amount corresponds to the KrF line sensitivity, and the smaller the exposure amount, the better. The results are shown in Table 8.

As is clear from Tables 5 to 8, the nonionic photoacid generators (A) of Examples 1 to 72 of the present invention are efficiently decomposed by i-ray irradiation, and are widely used in resin compositions for photolithography. Since it is known that the nonionic photoacid generator (A) of the present invention exhibits high solubility in the propylene glycol monomethyl ether acetate produced, the photoacid generator (A) of the present invention has excellent i-ray sensitivity and solubility in a resist solvent. Is. Further, since the compound of the present invention efficiently generates bissulfonamide, which is a superacid, by i-ray irradiation, the minimum exposure amount of the resin composition for positive photolithography containing this is small, and the resin for negative photolithography. The curability of the exposed portion of the composition is good, and the i-ray sensitivity is excellent.
Further, as is clear from Table 8, the nonionic photoacid generator (A) of the present invention is efficiently decomposed by irradiation with KrF rays to generate bissulfonamide, which is a super strong acid. Since the minimum exposure amount of the resin composition for type photolithography is small and the KrF line sensitivity is excellent, it can be said that the resin composition is excellent in near-ultraviolet sensitivity.
On the other hand, in Comparative Example (1, 3, 5, 7), which is an ionic photoacid generator, the generated acid is bissulfonamide, but the i-ray decomposition rate and solubility are poor, so that it is contained in the photolithography. The resin composition has poor i-line sensitivity and KrF line sensitivity. Further, in the comparative example (2, 4, 6, 8) which is a nonionic photoacid generator, the i-ray decomposition rate is the same, but since the generated acid is trifluoromethanesulfonic acid, a photo containing it. It can be seen that the resin composition for lithography has low i-line and KrF line sensitivity and poor near-ultraviolet sensitivity.

Since the nonionic photoacid generator (A) of the present invention decomposes with high sensitivity to near ultraviolet rays (i-ray, KrF-ray) to generate superstrong acid, photolithography for microfabrication represented by semiconductor production It is useful as a material.

Claims

A nonionic photoacid generator (A) containing 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 are. R2 may be bonded to each other to form a ring, and R 2 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatomic aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryl. It is an oxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, R 3 is a cyclic alkyl group, an aryl group, or a heteroatomic aryl group, and R2 and R3 are bonded to each other to form a ring (containing a heteroatom). It may be formed). ]
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 aryl group having 3 to 14 carbon atoms, and R 3 has 3 to 14 carbon atoms. It is a cyclic alkyl group of 12, an aryl group having 6 to 14 carbon atoms, or a heteroatom-containing aryl group having 3 to 14 carbon atoms, and R2 and R3 are bonded to each other to form a 5- to 7-membered ring (containing a heteroatom). The nonionic photoacid generator (A) according to claim 1, which forms (may be).
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, a heteroatomic aryl group having 3 to 14 carbon atoms, and carbon. It is an arylcarbonyl group having 6 to 10 (without carbonyl carbon), an alkoxycarbonyl group having 1 to 10 carbons (without carbonyl carbon), or an alkylsulfonyl group having 1 to 10 carbon atoms , and R3 is carbon. The nonionic photoacid generator (A) according to claim 1, which is a cyclic alkyl group having 3 to 12, an aryl group having 6 to 14 carbon atoms, or a heteroatomic aryl group having 3 to 14 carbon atoms.
In any of claims 1 to 3, wherein R f and R 1 are independently CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , or C 6 F 5 in the general formula (1). The non-ionic photoacid generator (A) according to the above.
A resin composition for photolithography (Q) containing the nonionic photoacid generator (A) according to any one of claims 1 to 4.