TW201835052A - Photoacid generator and resin composition for photolithography - Google Patents

Abstract

The objective of the present invention is to provide a non-ionic photoacid generator having high photosensitivity to an i-line, and excellent heat-resistance stability, solubility in hydrophobic materials, and alkali developability. The present invention is a non-ionic photoacid generator (A) characterized by being represented by formula (1). [In formula (1), X is a monovalent organic group that is desorbed by the action of an acid and can be substituted by a hydrogen atom, and Rf is a C1-18 hydrocarbon group (all or part of the hydrogen may be replaced by fluorine)].

Description

Photoacid generator and resin composition for photolithography

The present invention relates to a photoacid generator and a resin composition for photolithography. More specifically, the present invention relates to a non-ionic photoacid generator suitable for generating strong acid by the action of ultraviolet rays (i-rays), and a resin composition for photolithography containing the same.

Previously, in the microfabrication field represented by the manufacture of semiconductors, photolithographic steps using i-rays with a wavelength of 365 nm have been widely used. As the resist material used in the photolithography step, for example, a resin composition containing a polymer having a third butyl ester group of a carboxylic acid or a third butyl carbonate group of phenol and a photoacid generator has been used. Thing. As photoacid generators, triarylsulfonium salts (Patent Document 1), benzamidine methylsulfonium salts having a naphthalene skeleton (Patent Document 2), and the like are known as ionic photoacid generators; Nonionic acid generators such as an acid generator (Patent Document 3) and an acid generator (Patent Document 4) having a sulfonyldiazomethane structure. Further, by performing post-exposure heating (Post-exposure-bake, PEB), the third butyl ester group or the third butyl carbonate gene in the polymer is dissociated to form a carboxylic acid or phenol. Hydroxyl, UV-irradiated parts become easily soluble in alkaline developer. This phenomenon is used for pattern formation.

However, as the photolithography step becomes finer processing, the effect of swelling in the pattern of the unexposed portion by the alkaline developer becomes larger, and it is necessary to suppress the swelling of the resist material. In order to solve these problems, a method has been proposed in which a polymer in a resist material contains an alicyclic skeleton or a fluorine-containing skeleton and is made hydrophobic to suppress swelling of the resist material.

Ionic photoacid generators have insufficient compatibility with hydrophobic materials containing these alicyclic skeletons and fluorine-containing skeletons. Therefore, due to phase separation in the resist material, sufficient resist performance cannot be exhibited. The problem that the pattern cannot be formed. On the other hand, although the nonionic photoacid generator has good compatibility with a hydrophobic material, there is a problem that scum is generated in the exposed portion in the alkaline development step. In addition, there is a problem of insufficient sensitivity to i-rays, and a problem of narrowing allowance due to decomposition in post-exposure heating (PEB) due to insufficient thermal stability. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open Publication No. 50-151997 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 9-118663 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 6-67433 [Patent Literature 4] Japanese Patent Japanese Patent Application Laid-Open No. 10-213889

[Problems to be Solved by the Invention] Therefore, an object is to provide a nonionic photoacid generator having high sensitivity to i-rays, excellent heat resistance stability, excellent solubility in a hydrophobic material, and excellent alkali developability. [Means for solving problems]

The present inventors have conducted studies in order to achieve the aforementioned object, and as a result, have completed the present invention. That is, the present invention is a nonionic photoacid generator (A) and a resin composition (Q) for photolithography. The nonionic photoacid generator (A) is characterized by the following general formula (1) ) Indicates that the resin composition (Q) for photolithography includes the non-ionic photoacid generator (A).

[Chemical 1]

[In the formula (1), X is a monovalent organic group which can be detached by an acid and substituted with a hydrogen atom, and Rf represents a hydrocarbon group having 1 to 18 carbon atoms (a part or all of hydrogen may be substituted with fluorine) [Effect of the invention]

The non-ionic photoacid generator (A) of the present invention is non-ionic, and therefore has better compatibility with a hydrophobic material than an ionic acid generator. In addition, since it has a naphthalenedimethylimide skeleton, it has excellent heat resistance and can be heated after exposure (PEB). In addition, since it has a substituent on the naphthalene dimethyl imine skeleton, it can have an effect on the electronic state of the naphthalene ring, thereby making the moire absorption coefficient for i-rays high. Thereby, by irradiating i-rays, the nonionic photoacid generator (A) is easily decomposed, and sulfonic acid as a strong acid can be generated. In addition, since X can be detached and replaced with a hydrogen atom by the action of an acid, only the exposed portion has excellent affinity for the alkaline developing solution, and the occurrence of scum in the exposed portion is small.

Therefore, the resin composition (Q) for photolithography containing the non-ionic photoacid generator (A) of the present invention has high sensitivity to i-rays and has a wide margin in post-exposure heating (PEB). Excellent sex. Furthermore, the resin composition (Q) for photolithography of the present invention has less scum generation in the alkaline development step, and a good resist pattern can be obtained.

The nonionic acid generator (A) of the present invention is represented by the following general formula (1).

[Chemical 2]

In formula (1), X is a monovalent organic group which can be detached by an acid and substituted with a hydrogen atom, and Rf represents a hydrocarbon group having 1 to 18 carbon atoms (a part or all of hydrogen may be substituted with fluorine).

Examples of the monovalent organic group of X which can be removed by an acid and substituted with a hydrogen atom include a 1-branched alkyl group, a silyl group, a fluorenyl group, an alkoxycarbonyl group, and a general formula ( 2) Representing the basis.

[Chemical 3]

In formula (2), R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² or R ³ may be bonded to each other to form a ring structure. .

Examples of the 1-branched alkyl group include isopropyl, second butyl, third butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 1,1-dimethylbutyl. Base etc.

Examples of the silyl group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, and methyldiisopropyl. Silyl, triisopropylsilyl, tert-butyldimethylsilyl, methyldi-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyl Tri-divalent carbon-based silane groups such as diphenyl silane groups and triphenyl silane groups.

Examples of the fluorenyl group include ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, heptyl fluorenyl, hexyl fluorenyl, pentyl fluorenyl, pentyl fluorenyl, isopentyl, lauryl fluorenyl, and myristoyl ), Palmitoyl, stearyl, ethylenediyl, malonyl, succinyl, glutaryl, hexamethylene, piperoyl, octyl , Nonafluorenyl, decanediyl, acrylfluorenyl, propynylfluorenyl, methacrylfluorenyl, butenylfluorenyl, oleyl, cisbutenylfluorenyl, transbutenylfluorenyl, medium Mesaconoyl, hydrazone, benzamidine, phthalate, m-xylylene, p-xylylene, naphthyl, tolyl, hydrazone Hydratropoyl, atropoyl, cinnamyl, furanomethyl, thenoyl, nicotinoyl, isonicotino, p-toluenesulfonyl and methanesulfonyl醯 基 et al.

Examples of the group represented by the general formula (2) include a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, and 1 -Ethoxypropyl, 1-propoxyethyl, 1-phenoxyethyl, 1-benzyloxyethyl, tetrahydropyranyl, tetrahydrofuranyl, and the like.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group represented by the following general formula (3), and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and 2-ethylmethylhexyl group. Oxycarbonyl, third butoxycarbonyl, and the like.

[Chemical 4]

In formula (3), R ⁴ , R ^5, and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a ring structure or a branched structure, or may be bonded to each other to form a ring structure.

Among these X's, from the standpoint of ease of detachment due to the action of an acid and by-products during detachment, a silane group, an alkoxycarbonyl group, and a group represented by the general formula (2) are further preferred. It is preferably an alkoxycarbonyl group, particularly preferably a third butoxycarbonyl group and a 2-ethylhexyloxycarbonyl group.

Rf is a hydrocarbon group having 1 to 18 carbons (a part or all of hydrogen may be substituted with fluorine). The hydrocarbon group having 1 to 18 carbons may have a substituent. Examples of the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an aryl group, and a heterocyclic hydrocarbon group.

Examples of the alkyl group include a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl , N-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, second butyl, third butyl, Isopentyl, neopentyl, third pentyl, isohexyl and isoctadecyl, etc.), and cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl and 10-camphoryl etc.).

Examples of the aryl group include an aryl group having 6 to 10 carbon atoms (such as a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, and a pentafluorophenyl group).

Examples of the heterocyclic hydrocarbon group include a heterocyclic hydrocarbon group having 4 to 18 carbon atoms (thienyl, furyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, and pyrazinyl) , Indolyl, benzofuranyl, benzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, morphazinyl , Xanthenyl, thienyl, phenoxazinyl, phenoxanyl, chromanyl, isochromanyl, dibenzothienyl , Xanthonyl, xanthonyl, dibenzofuranyl, etc.).

Examples of the group in which a part or all of the hydrogen of the hydrocarbon group having 1 to 18 carbon atoms are substituted with fluorine include a straight-chain alkyl group (Rf1), a branched-chain alkyl group (Rf2) having a hydrogen atom represented by CxFy substituted with a fluorine atom, Cycloalkyl (Rf3), and aryl (Rf4).

Examples of the linear alkyl group (Rf1) in which a hydrogen atom is substituted with a fluorine atom include trifluoromethyl (x = 1, y = 3), pentafluoroethyl (x = 2, y = 5), and heptafluoro Propyl (x = 3, y = 7), nonafluorobutyl (x = 4, y = 9), perfluorohexyl (x = 6, y = 13), and perfluorooctyl (x = 8, y = 17) Wait.

Examples of the branched alkyl group (Rf2) in which a hydrogen atom is substituted with a fluorine atom include perfluoroisopropyl (x = 3, y = 7) and perfluorothird butyl (x = 4, y = 9) , And perfluoro-2-ethylhexyl (x = 8, y = 17).

Examples of the cycloalkyl group (Rf3) in which a hydrogen atom is substituted with a fluorine atom include perfluorocyclobutyl (x = 4, y = 7), perfluorocyclopentyl (x = 5, y = 9), and all Fluorocyclohexyl (x = 6, y = 11), and perfluoro (1-cyclohexyl) methyl (x = 7, y = 13).

Examples of the aryl group (Rf4) in which a hydrogen atom is substituted with a fluorine atom include a pentafluorophenyl group (x = 6, y = 5) and a 3-trifluoromethyltetrafluorophenyl group (x = 7, y = 7) Wait.

Among Rf, from the viewpoints of the decomposability of the sulfonate moiety, the deprotection of the photoresist, and the ease of obtaining raw materials, a straight-chain alkyl group (Rf1) having a hydrogen atom substituted with a fluorine atom and branching are preferred. Alkyl alkyl (Rf2) and aryl (Rf4), further preferably linear alkyl (Rf1), and aryl (Rf4), particularly preferably trifluoromethyl (x = 1, y = 3), Fluoroethyl (x = 2, y = 5), heptafluoropropyl (x = 3, y = 7), nonafluorobutyl (x = 4, y = 9), and pentafluorophenyl (x = 6, y = 5).

Preferred specific examples of the non-ionic photoacid generator represented by the general formula (1) are shown below.

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

The method for synthesizing the nonionic photoacid generator (A) of the present invention is not particularly limited as long as it can synthesize the target substance. For example, 3-hydroxy-1,8-naphthalenedicarboxylic anhydride and chlorosilane, 3,4 -Dihydro-2H-pyran or di-third butyl dicarbonate is reacted to obtain a precursor (P1), and the precursor (P1) is reacted with a hydroxylamine. Then, by reacting with the corresponding sulfonic anhydride or sulfonyl chloride, a non-ionic photoacid generator (A) can be synthesized.

The reaction conditions of 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride with chlorosilane, 3,4-dihydro-2H-pyran or di-third butyl dicarbonate are at a temperature of -30 ° C to 80 The reaction is carried out at a temperature of 1 to 50 hours, and it is preferable to use a reaction solvent, an alkali catalyst, and an acid catalyst in order to complete the reaction quickly and with good yield. The reaction solvent is not particularly limited, and acetonitrile, tetrahydrofuran, dichloromethane, chloroform, and the like are preferable. Examples of the base catalyst include pyridine, methylmorpholine, dimethylaminopyridine, 2,6-dimethylpyridine, triethylamine, imidazole, 1,8-diazabicyclo [5.4.0] One-carbon-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene, DBU), sodium hydroxide, etc., as the acid catalyst, p-toluenesulfonic acid can be cited, usually relative to 3-hydroxy- 1,8-naphthalenedicarboxylic acid anhydride is added in an amount of 1 mol% to 100 mol%. The molar ratio of 3-hydroxy-1,8-naphthalenedicarboxylic anhydride to chlorosilane, 3,4-dihydro-2H-pyran, or di-third butyl dicarbonate is usually 1: 1 to 1: 2 proceed.

As for the nonionic photoacid generator (A) of the present invention obtained by reacting the precursor (P1) with hydroxylamine, and then with the corresponding sulfonic anhydride or sulfonyl chloride, an appropriate organic compound can be used if necessary. The solvent is recrystallized and purified.

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

Examples of the solvent include carbonates (propylene carbonate, ethylene carbonate, 1,2-butyl carbonate, dimethyl carbonate, and diethyl carbonate); and esters (ethyl acetate, ethyl lactate). , Β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol Monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol Monobutyl ether acetate, etc.).

When a solvent is used, the use ratio of the solvent is preferably 15 parts by weight to 1,000 parts by weight, and more preferably 30 parts by weight to 500 parts by weight, with respect to 100 parts by weight of the photoacid generator of the present invention.

The resin composition (Q) for photolithography of the present invention contains a non-ionic photoacid generator (A) as an essential component. Therefore, by exposing ultraviolet rays and post-exposure heating (PEB), exposed portions and unexposed portions are made. There is a difference in the solubility of the developer. The non-ionic photoacid generator (A) can be used alone or in combination of two or more. Examples of the resin composition (Q) for photolithography include a mixture of a negative chemically amplified resin (QN) and a non-ionic photoacid generator (A); and a positive-type chemically amplified resin (QP) and a non-ionic light. Mixture of acid generators (A).

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

The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl group-containing resin. For example, novolac resin, polyhydroxystyrene, a copolymer of hydroxystyrene, hydroxystyrene and benzene can be used. Copolymers of ethylene, copolymers of hydroxystyrene, styrene and (meth) acrylic acid derivatives, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyfluorene imide containing phenolic hydroxyl groups, Polyamino acids containing phenolic hydroxyl groups, phenol-dicyclopentadiene condensation resins, and the like. Among these, novolak resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene, and (meth) acrylic acid derivatives are preferred. , Phenol-benzenedimethanol condensation resin. In addition, these phenolic hydroxyl group-containing resins (QN1) may be used singly 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-phenol Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Phenol, 2,3,5-tricresol, 3,4,5-tricresol, catechol, resorcinol, catechol, α-naphthol, β-naphthol, etc. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

Specific examples of the novolak resin include phenol / formaldehyde condensation novolac resin, cresol / formaldehyde condensation novolac resin, phenol-naphthol / formaldehyde condensation novolac resin, and the like.

The phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low-molecular compound as a part of the component. Examples of the phenolic low-molecular compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, and 1,1 -Bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl ] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethyl Alkane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, 4,4 '-{1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] Phenyl] ethylidene} bisphenol and the like. These phenolic low-molecular compounds may be used alone or in combination of two or more.

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

From the viewpoints of the resolution, thermal shock resistance, heat resistance, and residual film rate of the obtained insulating film, the weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2,000 or more, and more preferably about 2,000 to 20,000. . In addition, when the entire solvent-removing composition is 100% by weight, the content ratio of the phenolic hydroxyl group-containing resin (QN1) in the negative chemically amplified resin (QN) is preferably 30% to 90%. % By weight, more preferably 40% by weight to 80% by weight. In the case where the content ratio of the phenolic hydroxyl-containing resin (QN1) is 30% to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability based on an alkaline aqueous solution, so it is more good.

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

Examples of the crosslinking agent (QN2) include a bisphenol A-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac resin-based epoxy compound, and a soluble phenol resin-based ring Oxygen compounds, poly (hydroxystyrene) -based epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea ( urea) compounds, methylol-containing phenol compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing compounds Phenol compounds containing carboxyl groups, melamine resins containing carboxymethyl groups, benzoguanamine resins containing carboxymethyl groups, urea resins containing carboxymethyl groups, phenol resins containing carboxymethyl groups, melamine compounds containing carboxymethyl groups, carboxyl groups containing carboxyl groups Methyl benzoguanamine compounds, carboxymethyl-containing urea compounds, carboxymethyl-containing phenol compounds, and the like.

Among these crosslinking agents (QN2), a methylol-containing phenol compound, a methoxymethyl-containing melamine compound, a methoxymethyl-containing phenol compound, and a methoxymethyl-containing glycoluril are preferable. Compounds, methoxymethyl-containing urea compounds, and ethoxymethyl-containing phenol compounds, and further preferably methoxymethyl-containing melamine compounds (such as hexamethoxymethylmelamine, etc.), and methoxy-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds. Melamine compounds containing methoxymethyl are marketed under the trade names of CYMEL 300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui cyanamide), and the glycoluril compounds containing methoxymethyl are CYMEL1174 (manufactured by Mitsui cyanamide) is commercially available, and methoxymethyl-containing urea (Urea) compounds are commercially available under the trade name of MX290 (manufactured by Sanwa Chemical Co., Ltd.).

From the viewpoint of reduction of the residual film rate, distortion or swelling of the pattern, and developability, the content of the cross-linking agent (QN2) is usually 5 with respect to all the acidic functional groups in the phenolic hydroxyl group-containing resin (QN1). Molar% to 60 Molar%, preferably 10 Molar% to 50 Molar%, more preferably 15 Molar% to 40 Molar%.

Examples of the positive chemically amplified resin (QP) include a part of hydrogen atoms of an acidic functional group in an alkali-soluble resin (QP1) containing one or more acidic functional groups such as a phenolic hydroxyl group, a carboxyl group, or a sulfofluorenyl group, or All protective groups substituted with acid-dissociable groups were introduced into the resin (QP2). The acid-dissociable group is a group that can be dissociated in the presence of a strong acid produced by a nonionic photoacid generator (A). The protective group introduction resin (QP2) itself is alkali-insoluble or alkali-insoluble.

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 as the hydroxyl group-containing resin (QN1) can be used.

The carboxyl group-containing resin (QP12) is not particularly limited as long as it is a carboxyl group-containing polymer. For example, a carboxyl group-containing vinyl monomer (Ba) and a hydrophobic group-containing vinyl group may be used. The body (Bb) is obtained by polymerizing a vinyl group.

Examples of the carboxyl group-containing vinyl monomer (Ba) include unsaturated monocarboxylic acids [(meth) acrylic acid, butenoic acid, and cinnamic acid], unsaturated polybasic (2- to 4-membered) carboxylic acids [ (Anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl groups of 1 to 10 carbon) esters [maleic acid mono Alkyl esters, fumarate monoalkyl esters, citraconic acid monoalkyl esters, etc.], and these salts [alkali metal salts (sodium and potassium salts, etc.), alkaline earth metal salts (calcium salts and magnesium Salt, etc.), amine and ammonium salts, etc.]. From the viewpoints of polymerizability and ease of acquisition, among these, unsaturated monocarboxylic acids are preferred, and (meth) acrylic acid is more preferred.

Examples of the hydrophobic group-containing vinyl monomer (Bb) include a (meth) acrylate (Bb1) and an aromatic hydrocarbon monomer (Bb2).

Examples of the (meth) acrylate (Bb1) include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group [for example, (meth) acrylate, (meth) acrylate , N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, etc.) And alicyclic group-containing (meth) acrylates [dicyclopentyl (meth) acrylate, dicyclopentene (meth) acrylate, isobornyl (meth) acrylate, etc.] and the like.

Examples of the aromatic hydrocarbon monomer (Bb2) include a hydrocarbon monomer having a styrene skeleton [for example, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, and benzylstyrene] and vinylnaphthalene.

In the carboxyl group-containing resin (QP12), the molar ratio of (Ba) / (Bb) added monomer is usually 10 to 100/0 to 90, and from the viewpoint of developability, it is preferably 10 to 80/20 to 90, more preferably 25 to 85/15 to 75.

The sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer containing a sulfonic acid group. For example, the sulfonic acid group-containing vinyl monomer (Bc) can be made hydrophobic if necessary. Is obtained by subjecting a vinyl monomer (Bb) of a base to vinyl polymerization. As the hydrophobic group-containing vinyl monomer (Bb), the same ones as described above can be used.

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

In the sulfonic acid group-containing resin (QP13), the molar ratio of (Bc) / (Bb) added monomer is usually 10 to 100/0 to 90, and from the viewpoint of developability, it is preferably 10 to 80 / 20 to 90, more preferably 25 to 85/15 to 75.

The hydrophilic-lipophile balance (HLB) value of the alkali-soluble resin (QP1) varies according to the resin skeleton of the alkali-soluble resin (QP1). The preferred range is 4-19, more preferably 5 ~ 18. Particularly preferred is 6-17. When the HLB value is 4 or more, the developability is better when development is performed. When the HLB value is 19 or less, the water resistance of the cured product is more favorable.

In addition, the HLB value in the present invention is an HLB value based on the Oda method, and refers to a hydrophilic-hydrophobic equilibrium value, and can be calculated from a ratio of an organic value to an inorganic value of an organic compound. HLB ≒ 10 × Inorganic / Organic In addition, the inorganic and organic values are described in detail in the document "Synthesis and Application of Surfactants" (published by the Bookstore, by Oda and Teramura); or "Introduction to Shinkansen Surfactants" (by Takehiko Fujimoto, issued by Sanyo Chemical Industry Co., Ltd.).

Examples of the acid-dissociable group introduced into the protective group introduction resin (QP2) include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silane group, a germanyl group, Alkoxycarbonyl, fluorenyl, and cyclic acid dissociative groups. These may be used alone or in combination of two or more.

Examples of the 1-substituted methyl group include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, and benzyloxymethyl. Methyl, benzylthiomethyl, benzamidinemethyl, bromobenzylmethyl, methoxybenzylmethyl, methylthiobenzylmethyl, α-methylbenzylmethyl, cyclic Propylmethyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthio Benzyl, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butyl Oxycarbonylmethyl and the like.

Examples of 1-substituted ethyl include 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, 1- Ethylthioethyl, 1,1-diethoxyethyl, 1-ethoxypropyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-phenoxyethyl, 1-phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1,1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1- N-butoxycarbonylethyl, 1-thirdbutoxycarbonylethyl, and the like.

Examples of the 1-branched alkyl group include isopropyl, second butyl, third butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 1,1-dimethylbutyl. Base etc.

Examples of the silyl group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, and methyldiisopropyl. Silyl, triisopropylsilyl, tert-butyldimethylsilyl, methyldi-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyl Tri-divalent carbon-based silyl groups such as diphenylsilyl and triphenylsilyl.

Examples of the germanyl group include trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, and isopropyldimethylgermanyl. , Methyldiisopropylgermanyl, triisopropylgermanyl, tert-butyldimethylgermanyl, methyldi-tert-butylgermanyl, tri-tert-butylgermane Tri-divalent carbon-based germanyl, such as phenyldimethyl, phenyldimethylgermanyl, methyldiphenylgermanyl, and triphenylgermanyl.

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

Examples of the fluorenyl group include ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, heptyl fluorenyl, hexyl fluorenyl, pentyl fluorenyl, pentyl fluorenyl, isopentyl fluorenyl, lauryl fluorenyl, and myristoyl ), Palmitoyl, stearyl, ethylenediyl, malonyl, succinyl, glutaryl, hexamethylene, piperoyl, octyl , Nonafluorenyl, decanediyl, acrylfluorenyl, propynylfluorenyl, methacrylfluorenyl, butenylfluorenyl, oleyl, cisbutenylfluorenyl, transbutenylfluorenyl, medium Mesaconoyl, hydrazone, benzamidine, phthalate, m-xylylene, p-xylylene, naphthyl, tolyl, hydrazone Hydratropoyl, atropoyl, cinnamyl, furanomethyl, thenoyl, nicotinoyl, isonicotino, p-toluenesulfonyl, methanesulfonyl醯 基 et al.

Examples of the cyclic acid-dissociative group include cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, and tetrahydrothioranyl. (Tetrahydrothiopyranyl), tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydrothiophene- 1,1-dioxide-based and the like.

Among these acid-dissociable groups, a third butyl group, a benzyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a trimethylsilyl group, a third butoxycarbonyl group, and a third group are preferred. Butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuryl, tetrahydrothioranyl, and tetrahydrothiofuranyl.

Introduction rate of acid-dissociable groups in the protective group-introducing resin (QP2) {the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protective-group-introducing resin (QP2)} Depending on the type of the acid-dissociable group or the alkali-soluble resin introduced into the group, it cannot be specified in general, but it is preferably 10% to 100%, and more preferably 15% to 100%.

The polystyrene-converted weight average molecular weight (hereinafter referred to as "Mw") measured by Gel Permeation Chromatography (GPC) of the protective group introduction resin (QP2) is preferably 1,000 to 150,000, and more preferably 3,000 to 100,000.

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

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

The resist using the photography resin composition (Q) of the present invention can be formed, for example, by a known method such as spin coating, curtain coating, roll coating, spray coating, and screen printing. A resin solution prepared by dissolving (in the case of containing inorganic fine particles, dissolving and dispersing) a predetermined organic solvent is coated on a substrate, and then the solvent is dried by heating or hot air blowing.

As the organic solvent that dissolves the resin composition (Q) for photography of the present invention, if the resin composition can be dissolved and the resin solution can be adjusted to physical properties (viscosity, etc.) applicable to spin coating, etc., There is no particular limitation. For example, N-methylpyrrolidone, N, N-dimethylformamidine, dimethylmethylene, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate can be used. Esters, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, xylene and other known solvents. From the viewpoint of drying temperature, 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, etc.) are preferred. , Propylene glycol monomethyl ether acetate, acetone and xylene), can be used alone or in combination of two or more. When an organic solvent is used, the amount of the solvent to be blended is not particularly limited, and it is usually preferably 30% to 1,000% by weight based on the weight of the solid content of the resin composition (Q) for photography, and more preferably 40% to 900% by weight, and particularly preferably 50% to 800% by weight.

The drying conditions of the resin solution after coating differ depending on the solvent used, and it is preferably carried out at 50 ° C to 2000 ° C within a range of 2 minutes to 30 minutes. The dried resin composition for photography The amount of residual solvent (Q) (% by weight) is determined as appropriate.

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

Examples of the method of light irradiation include a method of exposing a resist with actinic rays through a photomask having a wiring pattern. The actinic ray used for light irradiation is not particularly limited as long as it can decompose the nonionic photoacid generator (A) in the photography resin composition (Q) of the present invention. Actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, pigment lasers, and nitrogen lasers). , LED, helium-cadmium laser, etc.). Among these, a high-pressure mercury lamp and an ultra-high-pressure mercury lamp are preferable.

The post-exposure heating (PEB) temperature is usually 40 ° C to 200 ° C, preferably 50 ° C to 190 ° C, and still more preferably 60 ° C to 180 ° C. If the temperature is lower than 40 ° C, the deprotection reaction or cross-linking reaction cannot be sufficiently performed. Therefore, the difference in solubility between the ultraviolet irradiated portion and the ultraviolet unirradiated portion is insufficient to form a pattern. . As the heating time, if it is generally less than 0.5 minutes to 120 minutes, it is difficult to control the time and temperature; if it is more 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 into a wiring pattern shape using an alkaline developer. The alkaline developing solution is not particularly limited as long as the conditions are such that the solubility of the ultraviolet irradiated portion and the ultraviolet unirradiated portion of the resin composition (Q) for photography differs. Examples of the alkaline developer include an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium bicarbonate, and an aqueous solution of tetramethylammonium salt. These alkaline developing solutions may be added with a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, and N-methylpyrrolidone.

Examples of the development method include an immersion method, a shower method, and a spray method using an alkaline developer, and a spray method is preferred. The temperature of the developing solution is preferably used at 25 ° C to 40 ° C. The development time is appropriately determined depending on the thickness of the resist. [Example]

Hereinafter, the present invention will be further described with examples and comparative examples, but the present invention is not limited to these examples. In the following, unless otherwise specified,% means% by weight and parts means parts by weight.

<Production Example 1> <Manufacturing method of N-hydroxy-3-third butoxycarbonyloxy-1,8-naphthalenedimethylimine [intermediate (1)]> 3-hydroxy-1,8 -5.5 parts of naphthalenedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.9 parts of di-third butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dispersed in 32 parts of acetonitrile, 2.2 parts of pyridine was added and Stir at 50 ° C for 2 hours. After cooling to room temperature, it was poured into water and the precipitate was separated by filtration to obtain a white solid. The white solid was washed with water and dried to obtain 8.1 parts of 3-tert-butoxycarbonyloxy-1,8-naphthalenedicarboxylic anhydride. 8.1 parts of the obtained 3-third butoxycarbonyloxy-1,8-naphthalenedicarboxylic acid anhydride was dissolved in 137 parts of acetonitrile, and 2.0 parts of a hydroxylamine aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added. And stirred at room temperature for 2 hours. The reaction solution was poured into water, and the precipitate was separated by filtration to obtain a white solid. This white solid was washed with water and dried to obtain 8.0 parts of the title compound [Intermediate (1)].

<Production Example 2> <N-Hydroxy-3- (2-isopropyl-5-methyl-cyclohexyloxy) carbonyloxy-1,8-naphthalenedimethylimide [Intermediate (2)] Manufacturing Method ＞ 5.5 parts of 3-hydroxy-1,8-naphthalenedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.9 parts of menthyl chloroformate (manufactured by Tokyo Chemical Industry Co., Ltd.) are dispersed in To 47 parts of acetonitrile, 2.8 parts of triethylamine was added and stirred at 50 ° C for 2 hours. After cooling to room temperature, it was poured into water and the precipitate was separated by filtration to obtain a white solid. The white solid was washed with water and dried to obtain 8.0 parts of 3- (2-isopropyl-5-methyl-cyclohexyloxy) carbonyloxy-1,8-naphthalenedicarboxylic acid anhydride. 8.0 parts of the obtained 3- (2-isopropyl-5-methyl-cyclohexyloxy) carbonyloxy-1,8-naphthalenedicarboxylic acid anhydride was dissolved in 124 parts of acetonitrile, and an aqueous hydroxylamine solution (Tokyo Chemical Co. Industrial Co., Ltd., 50% aqueous solution) 1.5 parts and stirred at room temperature for 2 hours. The reaction solution was poured into water, and the precipitate was separated by filtration to obtain a white solid. This white solid was washed with water and dried to obtain 4.0 parts of the title compound [Intermediate (2)].

<Production Example 3> <Synthesis method of N-hydroxy-3- (2-tetrahydropyranyl) oxy-1,8-naphthalenedimethylimide [intermediate (3)]> 3-hydroxy- 5.5 parts of 1,8-naphthalenedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.3 parts of 3,4-dihydro-2H-pyran (manufactured by Tokyo Chemical Industry Co., Ltd.) were dispersed in 32 parts of acetonitrile and added 4.9 parts of p-toluenesulfonic acid was stirred at 50 ° C for 2 hours. After cooling to room temperature, it was poured into water, and the precipitate was separated by filtration to obtain a red-brown solid. The red-brown solid was washed with water and dried to obtain 7.6 parts of 3- (2-tetrahydropyranyl) oxy-1,8-naphthalenedicarboxylic acid anhydride. 7.6 parts of the obtained 3- (2-tetrahydropyranyl) oxy-1,8-naphthalenedicarboxylic acid anhydride was dissolved in 137 parts of acetonitrile, and an aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added. ) 2.0 parts and stirred at room temperature for 2 hours. The reaction solution was poured into water, and the precipitate was separated by filtration to obtain a red-brown solid. This red-brown solid was washed with water and dried to obtain 7.6 parts of the title compound [Intermediate (3)].

<Production Example 4> <Synthesis method of N-hydroxy-3-trimethylsilyloxy-1,8-naphthalenedimethylimide [intermediate (4)]> 3-hydroxy-1,8-naphthalene 5.5 parts of dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.9 parts of trimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dispersed in 32 parts of acetonitrile, and 2.8 parts of triethylamine was added and stirred at 50 ° C. 2 hours. After cooling to room temperature, it was poured into water, and the precipitate was separated by filtration to obtain a red-brown solid. The red-brown solid was washed with water and dried to obtain 7.3 parts of 3-trimethylsilyloxy-1,8-naphthalenedicarboxylic acid anhydride. 7.3 parts of the obtained 3-trimethylsilyloxy-1,8-naphthalenedicarboxylic acid anhydride was dissolved in 137 parts of acetonitrile, and 2.0 parts of an aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added to Stir at room temperature for 2 hours. The reaction solution was poured into water, and the precipitate was separated by filtration to obtain a red-brown solid. This red-brown solid was washed with water and dried to obtain 7.3 parts of the title compound [Intermediate (4)].

〈Example 1〉 〈3-Third-butoxycarbonyloxy-1,8-naphthalenedimethylimide trifluoromethanesulfonate [nonionic photoacid generator (A-1)] synthesis method ＞ 8.0 parts of N-hydroxy-3-third butoxycarbonyloxy-1,8-naphthalenedimethylimide [intermediate (1)] obtained in Production Example 1 was dispersed in 52 parts of methylene chloride After adding 3.8 parts of pyridine, while cooling to 0 ° C or lower, 10.2 parts of trifluoromethanesulfonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and stirred for 2 hours. The reaction solution was poured into water while maintaining the temperature at 0 ° C and washed with water four times, and then dichloromethane was distilled off under reduced pressure to obtain the title compound [nonionic photoacid generator (A-1)] 10.0 servings.

〈Example 2〉 〈3-Third-butoxycarbonyloxy-1,8-naphthalenedimethylimide pentafluoroethanesulfonate [nonionic photoacid generator (A-2)] Synthesis method ＞ In Example 1, except that 10.2 parts of trifluoromethanesulfonic anhydride was 7.9 parts of pentafluoroethanesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed to obtain 11.1 parts of the title compound [nonionic photoacid generator (A-2)].

〈Example 3〉 〈3-Third-butoxycarbonyloxy-1,8-naphthalenedimethylimide heptafluoropropanesulfonate [non-ionic photoacid generator (A-3)] ＞ In Example 1, except that 10.2 parts of trifluoromethanesulfonic anhydride was 9.7 parts of heptafluoropropanesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed to obtain 12.2 parts of the title compound [nonionic photoacid generator (A-3)].

〈Example 4〉 〈3-Third-butoxycarbonyloxy-1,8-naphthalenedimethylimine nonafluorobutanesulfonate [nonionic photoacid generator (A-4)] synthesis method ＞ In Example 1, except that 10.2 parts of trifluoromethanesulfonic anhydride was 11.6 parts of nonafluorobutanesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed to obtain 13.3 parts of the title compound [nonionic photoacid generator (A-4)].

〈Example 5〉 〈3-Third-butoxycarbonyloxy-1,8-naphthalenedimethylimide pentafluorobenzenesulfonate [nonionic photoacid generator (A-5)] synthesis method ＞ In Example 1, except that 10.2 parts of trifluoromethanesulfonic anhydride was 9.7 parts of pentafluorobenzenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed to obtain 12.2 parts of the title compound [nonionic photoacid generator (A-5)].

<Example 6> <3- (2-Isopropyl-5-methyl-cyclohexyloxy) carbonyloxy-1,8-naphthalenedimethylimide trifluoromethanesulfonate [non-ionic light Synthesis method of acid generator (A-6)]> The N-hydroxy-3- (2-isopropyl-5-methyl-cyclohexyloxy) carbonyloxy-1,8 obtained in Production Example 2 -After dispersing 4.0 parts of naphthalenedimethylimide [intermediate (2)] in 21 parts of dichloromethane and adding 1.5 parts of pyridine, while cooling to 0 ° C or lower, trifluoromethanesulfonic anhydride (Tokyo Chemical Industry Co., Ltd.) was added dropwise. Co., Ltd.) 4.1 parts, and stirred for 2 hours. The reaction solution was poured into water while maintaining the temperature at 0 ° C and washed with water four times, and then dichloromethane was distilled off under reduced pressure to obtain the title compound [nonionic photoacid generator (A-6)] 4.1 copies.

<Example 7> <3- (2-tetrahydropyranyl) oxy-1,8-naphthalenedimethylimide triflate [non-ionic photoacid generator (A-7)] Synthesis method> 7.6 parts of N-hydroxy-3- (2-tetrahydropyranyl) oxy-1,8-naphthalenedimethylimide [intermediate (3)] obtained in Production Example 3 was dispersed in After adding 3.8 parts of pyridine to 52 parts of methylene chloride, while cooling to 0 ° C or lower, 10.2 parts of trifluoromethanesulfonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred for 2 hours. The reaction solution was poured into water while being maintained at 0 ° C and washed four times with water, and then dichloromethane was distilled off under reduced pressure to obtain the title compound [non-ionic photoacid generator (A-7)] 9.7 servings.

〈Example 8〉 〈Synthesis method of 3-trimethylsilyloxy-1,8-naphthalenedimethylimide trifluoromethanesulfonate [nonionic photoacid generator (A-8)]> 7.3 parts of N-hydroxy-3-trimethylsilyloxy-1,8-naphthalenedimethylimide [intermediate (4)] obtained in Production Example 4 was dispersed in 52 parts of methylene chloride, and pyridine was added 3.8 After cooling the mixture to 0 ° C or lower, 10.2 parts of trifluoromethanesulfonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 2 hours. The reaction solution was poured into water while being maintained at 0 ° C and washed four times with water, and then dichloromethane was distilled off under reduced pressure to obtain the title compound [non-ionic photoacid generator (A-8)] 9.7 servings.

<Comparative Example 1> <1,8-Naphthalenedimethylimine trifluoromethanesulfonate [non-ionic photoacid generator (A'-1)] Synthesis method> The following formula (4) was used directly Indicated 1,8-naphthalenedimethylimide triflate (manufactured by Aldrich).

[Chemical 13]

<Comparative example 2> <Synthesis method of 3-hydroxy-1,8-naphthalenedimethylimide triflate [nonionic photoacid generator (A'-2)]> In Example 1, 10.0 parts of the obtained 3-tert-butoxycarbonyloxy-1,8-naphthalenedimethylimide triflate [nonionic photoacid generator (A-1)] was dissolved in dichloromethane Among 52 parts, 4.0 parts of trifluoromethanesulfonic acid was added dropwise and stirred at room temperature for 1 hour. The precipitate was filtered and separated from the reaction solution, and then washed with water and dried to obtain 7.9 parts of a non-ionic photoacid generator (A'-2) represented by the following formula (5).

[Chemical 14]

<Comparative Example 3> <Synthesis of (4-phenylthiophenyl) diphenylsulfonium triflate [ionic photoacid generator (A'-3)]> According to Japanese Patent Laid-Open No. 2007 -091628 Example 1 of the Gazette, (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate [ionic photoacid generator (A'-3 )].

[Chemical 15]

<Examples 1 to 8 and Comparative Examples 1 to 3> As the performance evaluation of the photoacid generator, the nonionic photoacid generator (A) obtained in Examples 1 to 8 was evaluated by the following method. -1) ～ Non-ionic photoacid generator (A-8), Non-ionic photoacid generator (A'-1), Non-ionic photoacid generator (A'-2) for comparison, and The Molar absorption coefficient, resist hardenability, thermal decomposition temperature, solvent solubility, and alkaline developability of the comparative ionic photoacid generator (A'-3) were evaluated. The results are shown in Table 1. in.

<Mole absorption coefficient> Dilute the synthesized photoacid generator to 0.25 mmol / L with acetonitrile and use an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550) in the range of 200 nm to 500 nm The absorbance at a unit length of 1 cm was measured. The molar absorption coefficient (ε ₃₆₅ ) of the i-ray (365 nm) was calculated from the following formula. ε ₃₆₅ (L ･ mol ^-1 ･ cm ^-1 ) = A ₃₆₅ /(0.00025 mol / L × 1 cm) [where A ₃₆₅ represents the absorbance at 365 nm]

<Resist Hardenability> 75 parts of a phenol resin (manufactured by DIC Corporation, "phenolite TD431") and a melamine hardener ( Resin manufactured by Mitsui Cyanamide Co., Ltd., 25 parts of "CYMEL 300"), 1 part of the synthesized photoacid generator, and 200 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) The solution was coated on a 10 cm square glass substrate. Then, vacuum drying was performed at 25 ° C for 5 minutes, and then drying was performed on a hot plate at 80 ° C for 3 minutes, thereby forming a resist having a film thickness of about 3 μm. Using an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd., HMW-661F-01), the L-34 (manufactured by Kenco Optical Co., Ltd.) was used in a predetermined amount, and the cutoff was less than 340 nm A light filter) filter defines the wavelength of ultraviolet light for full exposure of the resist. The cumulative exposure was measured at a wavelength of 365 nm. Then, after performing a 10-minute post-exposure heating (PEB) using a 120 ° C downwind dryer, and then developing by immersing in a 0.5% potassium hydroxide solution for 30 seconds, washing and drying were performed immediately. The thickness of this resist was measured using a shape measuring microscope (ultra-depth shape measuring microscope UK-8550, manufactured by KEYENCE Corporation). Here, from the change in the film thickness of the resist before and after development to the minimum exposure amount within 10%, the resist hardenability was evaluated in accordance with the following criteria. ○: The minimum exposure is 250 mJ / cm ² or less △: The minimum exposure is more than 250 mJ / cm ² and 500 mJ / cm ² or less ×: The minimum exposure is more than 500 mJ / cm ²

<Thermal decomposition temperature> Using a differential thermal and thermogravimetric simultaneous measurement device (TG / DTA 6200, manufactured by SII Corporation), the synthesized photoacid generator was measured at 30 ° C to 500 ° C under a nitrogen environment at a temperature rise of 10 ° C / min. For weight change up to ℃, the point of 5% weight reduction is taken as the thermal decomposition temperature.

<Solvent solubility> Take 0.1 g of the synthesized photoacid generator into a test tube, add propylene glycol monomethyl ether acetate (PGMEA) under the temperature adjustment of 25 ° C, and add to the photoacid generator The agent is completely dissolved. In addition, in the case where it did not completely dissolve even when 20 g was added, it was evaluated as insoluble.

<Alkali developability> After taking 0.5 part of the synthesized photoacid generator into a test tube, adding 2.38% tetramethylammonium hydroxide aqueous solution to make 100 parts, and using an ultrasonic cleaner in tetramethyl hydroxide Disperse in aqueous ammonium solution for 1 minute. The dispersion was prepared for each of the two photoacid generators, and only one of them was irradiated with an ultraviolet ray (Eggraphics, ECS-151U) at 100 mJ / cm ^{2 with a} cutoff of less than 340. A filter of nm light defines the wavelength of ultraviolet light. Based on the state of the dispersion after standing still for 24 hours under light shielding, the alkali developability was evaluated according to the following criteria. ○: Completely dissolved △: Not completely dissolved and turbid ×: Not completely dissolved, and the dissolution residue precipitated on the bottom of the test tube

[Table 1]

As clearly shown in Table 1, it can be seen that the non-ionic photoacid generator (A) of Examples 1 to 8 of the present invention has a molar absorption coefficient in the range of 500 to 10,000, has excellent resist hardenability, and When the acid dissociable groups are detached when irradiated with ultraviolet light, the polarity increases and the alkali developability is excellent, so the occurrence of scum is small. Moreover, it turned out that it has sufficient performance for use as a photoresist from a viewpoint of the solubility with respect to a solvent, and a thermal decomposition temperature. On the other hand, in Comparative Example 1 containing a naphthylfluorenimide skeleton having no substituent, it is understood that the naphthyl skeletons tend to undergo molecular alignment with each other and the crystallinity becomes high, so the solubility in a solvent is too low. In addition, in Comparative Example 2 in which the hydroxyl group was not protected by an acid dissociable group, it was found that the resist hardening property and the solvent solubility were insufficient. In addition, it is found that in Comparative Example 3, which is an ionic photoacid generator, the dispersibility of the acid generator in the resist is low, so that the resist hardenability is lowered. [Industrial availability]

The non-ionic photoacid generator (A) of the present invention has high sensitivity to i-rays and is excellent in alkali developability, and is therefore useful as a photolithographic material for micro-processing, typified by the production of semiconductors.

no

no

Claims (5)

A non-ionic photoacid generator (A), characterized by being represented by the following general formula (1); [In the formula (1), X is a monovalent organic group which can be detached by an acid and substituted with a hydrogen atom, and Rf represents a hydrocarbon group having 1 to 18 carbon atoms (a part or all of hydrogen may be substituted with fluorine) ]. The non-ionic photoacid generator (A) according to item 1 of the scope of patent application, wherein in the general formula (1), X is a silane group, an alkoxycarbonyl group, or is represented by the following general formula (2) Base [In formula (2), R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² or R ³ may be bonded to each other to form a ring structure]. The non-ionic photoacid generator (A) according to item 1 or 2 of the scope of patent application, wherein in the general formula (1), X is an alkoxy group represented by the following general formula (3) Carbonyl [In formula (3), R ⁴ , R ^5, and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a ring structure or a branched structure, or may be bonded to each other to form a ring structure]. The non-ionic photoacid generator (A) according to any one of claims 1 to 3 in the scope of patent application, wherein, in the general formula (1), Rf is CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , or C ₆ F ₅ . A resin composition (Q) for photolithography, which comprises the non-ionic photoacid generator (A) according to any one of claims 1 to 4 of the scope of patent application.