JP7022006B2 - Photoacid generator and resin composition for photolithography - Google Patents

Description

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

Conventionally, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography process using an i-line having a wavelength of 365 nm as a light source has been widely used.
As the resist material used in the photolithography step, for example, a resin composition containing a polymer having a tert-butyl ester of a carboxylic acid or a tert-butyl carbonate of a phenol and a photoacid generator is used. By irradiating this resist material with light, the photoacid generator decomposes to generate a strong acid such as trifluoromethanesulfonic acid. 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 ultraviolet irradiation part becomes easily soluble in the alkaline developing solution. Since pattern formation is performed using this phenomenon, there is a demand for an i-line highly sensitive photoacid generator that has a high photodecomposition rate and can realize energy saving and shortening of process time.
In order to realize a higher-definition photolithography process, a method for solving a new problem caused by high-definition has been proposed. For example, since it becomes necessary to limit the diffusion length of a strong acid generated by the decomposition of a photoacid generator, it is generally proposed to add organic amines to a resist material as a quencher component for solving this problem. .. Further, since the influence of the alkaline developer on the swelling of the unexposed portion of the pattern becomes large, it becomes necessary to suppress the swelling of the resist material. In order to solve this problem, a method has been proposed in which the polymer in the resist material contains an alicyclic skeleton, a fluorine-containing skeleton, or the like to increase the hydrophobicity to suppress the swelling of the resist material.

Examples of the photoacid generator that generates a strong acid in the resist material used in these photolithography steps include an ionic system such as a triarylsulfonium salt (Patent Document 1) and a phenacylsulfonium salt having a naphthalene skeleton (Patent Document 2). A photoacid generator and a non-ion having an oxime sulfonate structure (Patent Document 3), a sulfonyldiazomethane structure (Patent Document 4), a phthalimide structure (Patent Document 5), a naphthalimide structure (Patent Document 6, Patent Document 7) and the like. A system photoacid generator is known.

However, ionic photoacid generators such as triarylsulfonium salt and phenacylsulfonium salt are compatible with hydrophobic materials containing an alicyclic skeleton, a fluorine-containing skeleton, etc. in a resist material that realizes high definition. There is a problem that sufficient resist performance cannot be exhibited and a pattern cannot be formed because the phase is separated in the resist material.

A nonionic acid generator having an oxime sulfonate structure and a sulfonyldiazomethane structure has sufficient compatibility, but has poor thermal stability, and is decomposed by PEB to generate an acid, so that the unexposed part becomes alkali-soluble. There is a problem that the allowable width is small.

Nonionic photoacid generators having a phthalimide structure and a naphthalimide structure are excellent in compatibility and thermal stability, but poor in basic resistance, and because they react with quenchers in a resist material, the resin composition for a resist changes over time. There is a problem that the change is large and the pattern of the desired shape cannot be obtained with the passage of time after compounding.

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. 10-21389 Japanese Patent No. 5126873 Japanese Unexamined Patent Publication No. 2004-217748 Japanese Patent No. 5990447

That is, an object of the present invention is a nonionic photoacid having a naphthalimide structure having all the properties of compatibility, high sensitivity, thermal stability, and basic resistance required for a high-definition photolithography resist material for i-line. It is in the provision of generators.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention has a nonionic photoacid generator (A) represented by the following general formula (1); and a resin composition for photolithography containing the nonionic photoacid generator (A). It is a thing (Q).

[In the formula (1), R1 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to One of R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms. , Rf is a hydrocarbon atom, or a hydrocarbon group having 1 to 18 carbon atoms in which at least one or more hydrogens are substituted with fluorine. ]

The nonionic photoacid generator (A) of the present invention is nucleophilic to a carbonyl group by a base leading to degradation due to the steric effect of the substituent introduced into R1 adjacent to the imidecarbonyl group of the naphthalimide structure. Inhibit the attack. Further, the steric effect of R1 destabilizes the transition state of decomposition through ring opening, so that the nonionic photoacid generator (A) has high basic resistance. Further, since it has a substituent in any of R2 to R6, it can act on the electronic state on the naphthalene ring and has high sensitivity to i-rays. As a result, the nonionic photoacid generator (A) can be easily decomposed by irradiating with i-rays to generate sulfonic acid, which is a strong acid. In addition, because it has a nonionic naphthalimide structure, it has excellent compatibility with hydrophobic resist materials and excellent thermal stability, and can be heated after exposure (PEB).

Therefore, the resin composition for photolithography (Q) containing the nonionic photoacid generator (A) of the present invention has high sensitivity to i-rays, good compatibility with resist materials, and basic resistance. Since the thermal stability is good, there is little change over time, and the permissible range for post-exposure heating (PEB) is wide, so workability is excellent.

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

[In the formula (1), R1 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to One of R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms. , Rf is a hydrocarbon atom, or a hydrocarbon group having 1 to 18 carbon atoms in which at least one or more hydrogens are substituted with fluorine. ]

R1 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, preferably a carbide having 1 to 12 carbon atoms. It is a hydrogen group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group or an alkylcarbonate group.

Hydrocarbon groups having 1 to 12 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, and carbon atoms. 6-12 aryl groups are mentioned.

Alkyl groups having 1 to 12 carbon atoms include linear, branched, or cyclic alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert. -Pentyl, 1-methylbutyl, cyclopentyl, cyclohexyl, octyl, decanyl, dodecanyl, decalynyl, menthyl, norbornanyl, adamantyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 1-methoxyethyl, benzyloxymethyl, trimethylsiloxymethyl, trie Kirsiloxymethyl, triisopropylsiloxymethyl, tert-butyldimethylsiloxymethyl, tert-butyldiphenylsiloxymethyl, etc.) and the like, preferably linear and branched having 1 to 6 carbon atoms from the viewpoint of availability of raw materials. Alternatively, it is a cyclic alkyl group, and particularly preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl and cyclohexyl.

Examples of alkenyl groups having 2 to 12 carbon atoms include linear, branched, or cyclic alkenyl groups (ethenyl, 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, 1-dodecene-1-yl, norbornenyl, etc.) and the like.

Examples of the alkynyl group having 2 to 12 carbon atoms include linear, branched, or cyclic alkynyl groups (ethynyl, 1-propyne-1-yl, 2-propyne-1-yl, 1-butyne-1-yl, 2). -Butin-1-yl, 3-butyne-1-yl, 1-pentin-1-yl, 2-pentin-1-yl, 3-pentin-1-yl, 4-pentin-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-decine -1-yl, 1-cyclooctyne-1-yl, etc.) and the like can be mentioned.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azulenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, and a 2-chlorophenyl group. -Chlorophenyl group, 4-chlorophenyl group, 2,4-xylyl group, 2,6-xylyl group, 3,5-xylyl group, 2,4,6-mesityl group, 3,5-bistrifluoromethylphenyl group and penta Fluorophenyl group and the like can be mentioned.

Examples of the alkoxy group include an alkoxy group having 1 to 12 carbon atoms, and a linear or branched alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, phenoxy). , Triloxy, benzyloxy, decyloxy, dodecyloxy, naphthoxy, methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, benzyloxymethoxy, trimethylsiloxy, triequilloxy, triisopropylsiloxy, tert-butyldimethylsiloxy and tert -Butyldiphenylsiloxy, etc.), and preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyroxy, hexyloxy, benzyloxy and tert-butyldimethylsiloxy from the viewpoint of ease of synthesis.

Examples of the alkylthio group include an alkylthio group having 1 to 12 carbon atoms, and a linear or branched alkylthio group (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, iso). Pentilthio, neopentylthio, tert-pentylthio, phenylthio, tosylthio, benzylthio, octylthio, decylthio, dodecylthio, etc.), etc., preferably methylthio, ethylthio, propylthio, isopropylthio, butylthio, benzylthio, etc. from the viewpoint of ease of synthesis. Octylthio and dodecylthio.

Examples of the alkylcarbonyl group include an alkylcarbonyl group having 1 to 12 carbon atoms (including carbon on the carbonyl), which may be linear or branched alkylcarbonyl groups (acetyl, propionyl, butanoyl, 2-methylpropionyl). , Pentanoyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethylpropanoyl, octanoyl, 2-ethylhexanoyl, decanoyl, undecanoyl, etc.), etc., and is preferably acetyl from the viewpoint of ease of synthesis. , Propionyl, butanoyl, 2-methylbutanoyl and 2,2-dimethylpropanoyl.

Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 12 carbon atoms (including carbon on the carbonyl), and a linear or branched alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy). Carbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, tert-amyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, mentoxycarbonyl, undecanoxycarbonyl, etc.) and easy to synthesize. From the viewpoint of sex, it is preferably a branched alkoxycarbonyl group, and particularly preferably isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, tert-amyloxycarbonyl, 2-ethylhexyloxycarbonyl and mentoxycarbonyl.

Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 12 carbon atoms (including carbon on the carbonyl), and a linear or branched alkylcarbonyloxy group (acetoxy, ethylcarbonyloxy, propyl). Carbonyloxy, Isopropyl Carbonyloxy, Butyl Carbonyloxy, Isobutyl Carbonyloxy, sec-Butyl Carbonyloxy, tert-Butyl Carbonyloxy, Octyl Carboniloxy, 2-Ethylhexyl Carbonyloxy, Undecyl Carbonyloxy And benzylcarbonyloxy, etc.), and are preferable from the viewpoint of availability of raw materials, such as acetoxy, ethylcarboniloxy, propylcarboniloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butyl. Carbonyloxy, tert-butylcarbonyloxy, pentylcarboniloxy, hexylcarbonyloxy and 2-ethylhexylcarbonyloxy.

Examples of the alkyl carbonate group include an alkyl carbonate group having 2 to 12 carbon atoms, such as methyl carbonate, ethyl carbonate, propyl carbonate, 2-propyl carbonate, butyl carbonate, 2-butyl carbonate, isobutyl carbonate, tert-butyl carbonate and tert. -Amil carbonate, benzyl carbonate, 2-ethylhexyl carbonate, mentyl carbonate and the like, preferably methyl carbonate, ethyl carbonate, propyl carbonate, isopropyl carbonate, butyl carbonate, isobutyl carbonate, tert-butyl carbonate, etc. from the viewpoint of availability of raw materials. tert-amyl carbonate, 2-ethylhexyl carbonate and mentyl carbonate.

Of these, as R1, from the viewpoint of availability of raw materials, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkylcarbonyloxy group and an alkylcarbonate group are preferable, and an alkyl group having 1 to 12 carbon atoms and an alkoxy group are further used. preferable.

One of R2 to R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms. Is.
The hydrocarbon group, hydroxy group, alkoxy group, alkylthio group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkylcarbonate group having 1 to 12 carbon atoms are the same as those mentioned above.
Of these, the following cases (1) to (4) are preferable from the viewpoint of acting on the electronic state on the naphthalene ring to increase the i-line sensitivity.

(1) R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to R5 are hydrogen atoms. Is.
Of R6, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group or an alkylcarbonate group is preferable, and an alkyl group or an alkoxy group having 1 to 12 carbon atoms is particularly preferable. , Alkoxy carbonate group.
(2) R5 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to R4 and R6 are. It is a hydrogen atom.
Of R5, a hydrocarbon group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.
(3) R2 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R3 to R6 are hydrogen atoms. Is.
Of R2, a hydrocarbon group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.
(4) R4 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2, R3, R5 and R6 is a hydrogen atom.
Of R4, a hydrocarbon group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 12 carbon atoms is particularly preferable.

Rf is a fluorine atom or a hydrocarbon group having 1 to 18 carbon atoms in which at least one or more of hydrogen is substituted with a fluorine atom, and controls compatibility with a resist solution, photodegradability, and the strength of the generated acid. Has the effect of
Examples of the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an aryl group and a heterocyclic hydrocarbon group.

Hydrocarbon groups in which at least one hydrogen having 1 to 18 carbon atoms is substituted with fluorine include a linear fluoroalkyl group (RF1) in which a hydrogen atom is substituted with a fluorine atom, a branched fluoroalkyl group (RF2), and the like. Cyclic fluoroalkyl groups (RF3), fluoroaryl groups (RF4) and the like can be mentioned.

Examples of the linear fluoroalkyl group (RF1) in which the hydrogen atom is replaced with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluorohexyl group and a perfluorooctyl group. Can be mentioned.

Examples of the branched alkyl group (RF2) in which a hydrogen atom is substituted with a fluorine atom include a hexafluoroisopropyl group, a nonafluoro-tert-butyl group and a perfluoro-2-ethylhexyl group.

Examples of the cyclic alkyl group (RF3) in which a hydrogen atom is substituted with a fluorine atom include a heptafluorocyclobutyl group, a nonafluorocyclopentyl group, a perfluorocyclohexyl group and a perfluoro (1-cyclohexyl) methyl group.

Examples of the aryl group (RF4) in which a hydrogen atom is replaced with a fluorine atom include a pentafluorophenyl group, a 3-trifluoromethyltetrafluorophenyl group and a 3,5-bistrifluoromethylphenyl group.

Of Rf, linear alkyl groups (RF1) and branched alkyl groups (RF2) in which hydrogen atoms are substituted with fluorine atoms from the viewpoints of photodegradability, photoresist deprotection ability, and availability of raw materials. , And an aryl group (RF4) are preferred, a linear alkyl group (RF1) and an aryl group (RF4) are even more preferred, a trifluoromethyl group (CF ₃ ), a pentafluoroethyl group (C ₂ F ₅ ), a heptafluoro. Propyl groups (C ₃ F ₇ ), nonafluorobutyl groups (C ₄ F ₉ ) and pentafluorophenyl groups (C ₆ F ₅ ) are particularly preferred.

The method for synthesizing the nonionic photoacid generator (A) of the present invention is not particularly limited as long as the target product can be synthesized, but for example, it can be produced by the production method described below.

In the above reaction formula, R1 to R6 and Rf are the same as the definitions in the formula (1).
In the first-stage reaction, the precursor (P1) and the peroxide are refluxed in an organic solvent (acetonitrile, methanol, ethanol, isopropanol, chloroform, etc.) for 6 to 48 hours to react. After the reaction is completed, the reaction solution is poured into water, the precipitated solid is filtered and washed with an appropriate organic solvent to obtain a precursor (P2).

The peroxide is not particularly limited as long as it is generally used for the Bayer-Villiger oxidation reaction, but known organic peroxides (peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, etc.) are not particularly limited. ) And inorganic peroxides (hydrogen peroxide, potassium peroxymonosulfate, potassium peroxymonosulfate, potassium hydrogen sulfate, potassium sulfate triple salt, etc.) can be used, and acids (acetic acid, phosphoric acid, etc.) can be used as needed. (Sulfuric acid, etc.) and alkalis (sodium hydroxide, sodium hydrogen peroxide, potassium carbonate, etc.) can be used in combination.

In the second-stage reaction, the precursor (P2) and an organic solvent (acetonitrile, dioxane, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), etc.) are mixed and stirred, and this mixture is mixed with hydroxylamine. React. The reaction time is 10 minutes to 48 hours, and the reaction temperature is 0 to 50 ° C. After the reaction is completed, the reaction solution is neutralized with a dilute acid. The precursor (P3) is obtained by filtering the precipitated solid or extracting the oil to be separated with an organic solvent and then distilling off the volatile components. The precursor (P3) can be washed with a suitable organic solvent or purified by a recrystallization method, if necessary.

In the reaction of the third stage, a precursor (P3), a base (imidazole, pyridine, dimethylaminopyridine, triethylamine, methylmorpholine, etc.), a sulfonic acid halide represented by RfSO ₂ X, etc. are used as an organic solvent (acetoyl, chloroform, etc.). , Dichloromethane, DMF, ethyl acetate, etc.). The reaction temperature is −20 to 30 ° C., and the reaction time is 1 to 6 hours. After the reaction is completed, the present invention is represented by the general formula (1) by neutralizing with a dilute acid and filtering the precipitated solid, or extracting the separated oil with an organic solvent and then distilling off the volatile matter. The nonionic photoacid generator (A) is obtained as a solid. The obtained solid can be purified by washing with a suitable organic solvent or recrystallization, if necessary.

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.

As the solvent, carbonate (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), ester (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 (, etc.), and ether esters ( Examples thereof include ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate).

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 photoacid generator 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 nonionic photoacid generator (A) can be used alone or in combination of two or more.
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, phenol-containing hydroxyl group-containing polyimide, phenolic hydroxyl group-containing polyamic Acid and phenol-dicyclopentadiene condensation resins are 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.

Specific 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) is a part of the hydrogen atom of the acidic functional group in the alkali-soluble resin (QP1) containing one or more acidic functional groups such as a phenolic hydroxyl group, a carboxyl group, or a sulfonyl group. Alternatively, a protective group-introduced resin (QP2) in which the whole is substituted with an acid dissociative group can be mentioned.
The acid dissociable group is a group that can be dissociated in the presence of a strong acid generated from the nonionic photoacid generator (A).
The protecting group-introduced resin (QP2) is itself alkali-insoluble or sparingly soluble in alkali.

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 (Ba) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb) are vinyl-polymerized. It can be obtained by.

Examples of the carboxyl group-containing vinyl monomer (Ba) 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 (Bb) include (meth) acrylic acid ester (Bb1) and an aromatic hydrocarbon monomer (Bb2).

Examples of the (meth) acrylic acid ester (Bb1) include alkyl (meth) acrylates having 1 to 20 carbon atoms in 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 (Bb2) 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 (Ba) / (Bb) 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 (Bc) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb) can be used. Obtained by 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 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 (Bc) / (Bb) 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 The values of inorganic and organic are described in the literature “Synthesis of Surfactants and Their Applications” (published by Maki Shoten, Oda, Teramura), page 501; 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, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-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-n-propoxycarbonylethyl group , 1-Isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-tert-butoxycarbonylethyl group.

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 tricarbylsilyl groups such as butylmethylsilyl group, tri-tert-butylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and 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 resin composition for photography (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 photography (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 it to a substrate using a known method such as coating, spray coating, screen printing, and then drying the solvent by heating or blowing hot air.

The organic solvent for dissolving the resin composition (Q) for photography is particularly limited as long as it can dissolve the resin composition and can adjust the resin solution to physical properties (viscosity, etc.) applicable to spin coating and the like. Not done. For example, known solvents such as N-methylpyrrolidone, DMF, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methylethylketone, ethyl acetate, butyl acetate, ethyl lactate, 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 resin composition for photography (Q). The% by weight is more preferable, and 50 to 800% by weight is particularly preferable.

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 2 to 30 minutes, and the amount of residual solvent in the resin composition (Q) for photography 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 resin composition (Q) for photography of the present invention can be decomposed.
Active light includes 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, dye laser, nitrogen laser, LED, helium). Cadmium laser etc.) etc. Of these, high-pressure mercury lamps and ultra-high-pressure mercury lamps 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. 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 resin composition for photography (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 2,7-dimethyl-1,8-naphthalic anhydride [precursor (P2-1)]>
Disperse 1.6 parts of 3,8-dimethylacenaftenquinone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 195 parts of methanol, and add 10 parts of potassium peroxymonosulfate (double salt) and 2.5 parts of sodium hydrogen carbonate at a time. rice field. This dispersion was refluxed for one day and then poured into water to precipitate a solid. The solid was separated by filtration and dried under reduced pressure to obtain 0.91 part of the precursor (P2-1).

<Manufacturing example 2>
<Synthesis of N-hydroxy-2,7-dimethyl-1,8-naphthalic acidimide [precursor (P3-1)]>
1.1 parts of the precursor (P2-1) obtained in Production Example 1 was dispersed in 20 parts of acetonitrile, and 2.0 parts of a hydroxylamine aqueous solution (manufactured by Tokyo Kasei Kogyo Co., Ltd., 50% aqueous solution) was added at 50 ° C. Stirred for a day. The reaction solution was put into a dilute aqueous hydrochloric acid solution, the precipitate was separated by filtration, washed with water, and dried to obtain 1.1 parts of the precursor (P3-1).

<Manufacturing example 3>
<Synthesis of 2,7-dimethoxy-1,8-naphthalic anhydride [precursor (P2-2)]>
1.8 parts of 3,8-dimethoxyacenaftenquinone synthesized according to the method described in the literature (Helv. Chem. Acta, 1921, 342.) Using 2,7-dimethoxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material. 10 parts of potassium peroxymonosulfate (double salt) was added at once to 29 parts of methanol dispersion under a nitrogen atmosphere. The dispersion was refluxed for one day with strong stirring. After completion of the reaction, the mixture was cooled to room temperature and poured into a large amount of water. The obtained solid was filtered and dried under reduced pressure to obtain 1.5 parts of a precursor (P2-2).

<Manufacturing example 4>
<Synthesis of N-hydroxy-2,7-dimethoxy-1,8-naphthalateimide [precursor (P3-2)]>
1.2 parts of the precursor (P3-2) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 1.3 parts of the precursor (P2-2). ..

<Manufacturing example 5>
<Synthesis of 2,7-dimethylthio-1,8-naphthalic anhydride [precursor (P2-3)]>
Changed 2,7-dimethoxynaphthalene to 2,7-dimethylthionaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) and changed 1.8 parts of 3,8-dimethoxyacenaphthenicone to 2.0 parts of 3,8-dimethylthioacenaphthenicone. 1.7 parts of the precursor (P2-3) was obtained in the same manner as in Production Example 3 except for the above.

<Manufacturing example 6>
<Synthesis of N-hydroxy-2,7-dimethylthio-1,8-naphthalic acidimide [precursor (P3-3)]>
1.4 parts of the precursor (P3-3) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 1.5 parts of the precursor (P2-3). ..

<Manufacturing example 7>
<Synthesis of 2,7-dihydroxy-1,8-naphthalic anhydride [precursor (P2-4)]>
2.6 parts of the precursor (P2-2) synthesized in Production Example 3 was stirred and dispersed in 83 parts of dichloromethane, cooled to −78 ° C., and then 10 parts of boron tribromide was added dropwise and stirred for 1 hour. The cold bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. After the reaction was completed, the mixture was poured into a large amount of saturated aqueous sodium hydrogen carbonate solution, and the obtained solid was filtered off. The obtained solid was dispersed in dilute hydrochloric acid, stirred for 1 hour, filtered again, and washed thoroughly with water. The obtained yellow solid was dried to obtain 2.0 parts of a precursor (P2-4).

<Manufacturing example 8>
<Synthesis of 2,7-di-tert-butoxycarbonyloxy-1,8-naphthalic anhydride [precursor (P2-5)]>
4.4 parts of the precursor (P2-4) synthesized in Production Example 7 was dispersed in 75 parts of acetonitrile, and 0.3 parts of pyridine and then 10 parts of di-tert-butyl dicarbonate were added dropwise. After the temperature was raised to 40 ° C. to complete the reaction, water was added to precipitate a solid. This was filtered off and dried to obtain 7.8 parts of a precursor (P2-5).

<Manufacturing example 9>
<Synthesis of N-hydroxy-2,7-di-tert-butoxycarbonyloxy-1,8-naphthalateimide [precursor (P3-4)]>
2.0 parts of the precursor (P3-4) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 2.2 parts of the precursor (P2-5). ..

<Manufacturing example 10>
<Synthesis of 2,7-di-tert-butoxycarbonyl-1,8-naphthalic anhydride [precursor (P2-6)]>
5.9 parts of the precursor (P2-1) synthesized in Production Example 1 was dispersed in 262 parts of deionized water, 21 parts of potassium permanganate was added, and the mixture was stirred for 6 hours while refluxing. After the reaction was completed, an aqueous sodium hydroxide solution was added, the mixture was stirred, and the solid was filtered off. The filtrate was cooled in an ice bath, acidified by adding hydrochloric acid, and then stirred for 1 hour. The solid obtained by filtering this was thoroughly washed with water and dried under reduced pressure in a flask. Subsequently, 116 parts of dichloromethane was added to and dispersed in this dry solid, and 0.1 part of DMF was added. The dispersion was cooled in an ice bath, and 10 parts of oxalyl dichloride was slowly added dropwise. After stirring for 3 hours while maintaining the ice bath, all volatile substances were removed under reduced pressure. 78 parts of dehydrated THF was added to the residue, and 63 parts of a 10% THF solution of lithium tert-butoxide was slowly added dropwise while stirring under an ice bath. A solid was obtained by putting it in water to stop the reaction and then filtering it. Purification by column chromatography gave 3.6 parts of the precursor (P2-6).

<Manufacturing example 11>
<Synthesis of N-hydroxy-2,7-di-tert-butoxycarbonyl-1,8-naphthylimide [precursor (P3-5)]>
1.7 parts of the precursor (P3-5) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 2.0 parts of the precursor (P2-6). ..

<Manufacturing example 12>
<Synthesis of 2,3-dimethyl-1,8-naphthalic anhydride [precursor (P2-7)]>
Changed 2,7-dimethoxynaphthalene to 2,3-dimethylnaphthalene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and changed 1.8 parts of 3,8-dimethoxyacenaphthenicone to 1.6 parts of 3,4-dimethylacenaphthenicone. 1.3 parts of the precursor (P2-7) was obtained in the same manner as in Production Example 3 except for the above.

<Manufacturing example 13>
<Synthesis of N-hydroxy-2,3-dimethyl-1,8-naphthalic acidimide [precursor (P3-6)]>
1.2 parts of the precursor (P3-6) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 1.1 parts of the precursor (P2-7). ..

<Manufacturing example 14>
<Synthesis of 2,6-diisopropyl-1,8-naphthalic anhydride [precursor (P2-8)]>
Changed 2,7-dimethoxynaphthalene to 2,6-diisopropylnaphthalene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and changed 1.8-parts of 3,8-dimethoxyacenaftenquinone to 2.0 parts of 3,7-diisopropylacenaftenquinone. 1.7 parts of the precursor (P2-8) was obtained in the same manner as in Production Example 3 except for the above.

<Manufacturing example 15>
<Synthesis of N-Hydroxy-2,6-diisopropyl-1,8-naphthalateimide [precursor (P3-7)]>
1.4 parts of the precursor (P3-7) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 1.4 parts of the precursor (P2-8). ..

<Manufacturing example 16>
<Synthesis of 2,5-dimethyl-1,8-naphthalic anhydride [precursor (P2-9)]>
Changed 2,7-dimethoxynaphthalene to 2,5-dimethylnaphthalene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and changed 1.8 parts of 3,8-dimethoxyacenaphthenicone to 1.6 parts of 3,6-dimethylacenaphthenicone. 1.3 parts of the precursor (P2-9) was obtained in the same manner as in Production Example 3 except for the above.

<Manufacturing example 17>
<Synthesis of N-hydroxy-2,5-dimethyl-1,8-naphthalic acidimide [precursor (P3-8)]>
1.2 parts of the precursor (P3-8) was obtained in the same manner as in Production Example 2 except that 1.1 parts of the precursor (P2-1) was changed to 1.1 parts of the precursor (P2-9). ..

<Example 1>
<Synthesis of 2,7-dimethyl-1,8-naphthalic acid imidetrifluoromethanesulfonate [nonionic photoacid generator (A-1)]>
2.5 parts of the precursor (P3-1) synthesized in Production Example 2 was dispersed in 70 parts of dichloromethane, 1.0 part of pyridine was added, and then the mixture was cooled in an ice bath to obtain a trifluoromethanesulfonated product (Tokyo Chemical Industry). (Manufactured by Kogyo Co., Ltd.) 2.0 parts were dropped and reacted. After stirring for 1 hour, the reaction solution was put into ice-cooled dilute hydrochloric acid, washed with water three times, and the extract was concentrated to obtain a light brown solid. This solid was washed with isopropanol and dried to obtain 3.8 parts of a nonionic photoacid generator (A-1).

<Example 2>
<Synthesis of 2,7-dimethoxy-1,8-naphthanoimidenonafluorobutanesulfonate [nonionic photoacid generator (A-2)]>
Precursor (P3-1) is 2.9 parts of precursor (P3-2), 70 parts of dichloromethane is 47 parts, and 2.0 parts of trifluoromethanesulfonated product is nonafluorobutane sulfonated product (manufactured by Aldrich) 3. 5.6 parts of the nonionic photoacid generator (A-2) was obtained in the same manner as in Example 1 except that 7 parts and the reaction time were changed to 3 hours.

<Example 3>
<Synthesis of 2,7-dimethylthio-1,8-naphthalic acid imidetrifluoromethanesulfonate [nonionic photoacid generator (A-3)]>
The nonionic photoacid generator (A-3) was the same as in Example 1 except that the precursor (P3-1) was changed to 3.2 parts of the precursor (P3-3) and 70 parts of dichloromethane was changed to 47 parts. ) 4.4 copies were obtained.

<Example 4>
<Synthesis of 2,7-di-tert-butoxycarbonyloxy-1,8-naphthylimidepentafluorobenzenesulfonate [nonionic photoacid generator (A-4)]>
The precursor (P3-1) is 4.7 parts of the precursor (P3-4), 70 parts of dichloromethane is 47 parts, and 2.0 parts of trifluoromethanesulfonated is pentafluorobenzenesulfonated (manufactured by Aldrich) 3. 6.8 parts of the nonionic photoacid generator (A-4) was obtained in the same manner as in Example 1 except that 1 part and the reaction time were changed to 3 hours.

<Example 5>
<Synthesis of 2,7-di-tert-butoxycarbonyl-1,8-naphthylimidetrifluoromethanesulfonate [nonionic photoacid generator (A-5)]>
The nonionic photoacid generator (A-5) was the same as in Example 1 except that the precursor (P3-1) was changed to 4.4 parts of the precursor (P3-5) and 70 parts of dichloromethane was changed to 47 parts. ) 5.2 copies were obtained.

<Example 6>
<Synthesis of 2,7-diethylcarbonyloxy-1,8-naphthalic acidimide trifluoromethanesulfonate [nonionic photoacid generator (A-6)]>
A solution of 47 parts of dichloromethane of the nonionic photoacid generator (A-4) was cooled and stirred in an ice bath, and 0.5 part of trifluoromethanesulfonic acid was carefully added dropwise. After the generation of gas following the progress of the reaction had subsided, the mixture was further stirred for 30 minutes. The precipitated solid was filtered and washed with dichloromethane. Subsequently, 47 parts of dichloromethane was added to this solid, and 1.0 part of pyridine was added dropwise to the dispersion liquid bathed in ice. Further, 1.1 parts of propionic acid chloride was added, and the mixture was stirred for 3 hours. After completion of the reaction, the reaction solution was washed with water three times, concentrated, and washed with isopropanol to obtain 4.6 parts of a solid nonionic photoacid generator (A-6).

<Example 7>
<Synthesis of 2,3-dimethyl-1,8-naphthalic acid imidetrifluoromethanesulfonate [nonionic photoacid generator (A-7)]>
Nonionic photoacid generator (A-7) 3.7 in the same manner as in Example 1 except that the precursor (P3-1) was changed to the precursor (P3-6) and 70 parts of dichloromethane was changed to 47 parts. I got a part.

<Example 8>
<Synthesis of 2,6-diisopropyl-1,8-naphthalic acid imidetrifluoromethanesulfonate [nonionic photoacid generator (A-8)]>
The nonionic photoacid generator (A-8) was the same as in Example 1 except that the precursor (P3-1) was changed to 3.1 parts of the precursor (P3-7) and 70 parts of dichloromethane to 47 parts. ) 4.1 copies were obtained.

<Example 9>
<Synthesis of 2,5-dimethyl-1,8-naphthoimide trifluoromethanesulfonate [nonionic photoacid generator (A-9)]>
Nonionic photoacid generator (A-9) 3.7 in the same manner as in Example 1 except that the precursor (P3-1) was changed to the precursor (P3-8) and 70 parts of dichloromethane was changed to 47 parts. I got a part.

The structures of the nonionic photoacid generators (A-1) to (A-9) obtained in Examples 1 to 9 are described below.

<Comparative Example 1>
<Synthesis of nonionic surfactant (A'-1)>
1,8-Naphthalic acid imide trifluoromethanesulfonate (A'-1) (manufactured by Aldrich) was used as it was.

<Manufacturing example 18>
<Synthesis of 4-butylthio-1,8-naphthalic anhydride [precursor (P2'-1)]>
2.8 parts of 4-bromo-1,8-naphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dispersed in 9.5 parts of dimethylacetamide, and 1.0 part of 1-butanethiol was added. The container was immersed in a water bath, and 1.7 parts of DBU was added dropwise to this dispersion. After the dropping was completed, the dispersion was stirred at 70 ° C. for one day. After cooling to room temperature, the reaction solution was poured into a large amount of water, the precipitated solid was filtered, and the mixture was thoroughly washed with water. The obtained solid was dried to obtain 2.3 parts of a precursor (P2'-1).

<Comparative Example 2>
<Synthesis of nonionic surfactant (A'-2)>
Precursor (P3'-1) in the same manner as in Production Example 2 except that 2.6 parts of the precursor (P2-1) was changed to 3.1 parts of the precursor (P2'-1) synthesized in Production Example 18. ) 2.8 copies were obtained. Subsequently, a non-ionic photoacid generator (similar to Example 1) except that 2.9 parts of the precursor (P3-1) was changed to 3.4 parts of the precursor (P3'-1) synthesized. A'-2) 4.3 copies were obtained.

<Comparative Example 3>
<Synthesis of nonionic surfactant (A'-3)>
1,8-Naphthalic acid imide paratoluene sulfonate (A'-3) (manufactured by Aldrich) was used as it was.

The structures of the nonionic photoacid generators (A'-1) to (A'-3) obtained in Comparative Examples 1 to 3 are described below.

<Examples 1 to 9, Comparative Examples 1 to 3>
As a performance evaluation of the photoacid generator, the nonionic photoacid generators (A-1) to (A-9) obtained in Examples 1 to 9 and the nonionic photoacid generator (A) for comparison. The i-ray sensitivity and basic resistance of'-1) to (A'-3) were evaluated by the following methods, and the results are shown in Table 1.

<Evaluation method of i-line sensitivity>
<Currability of exposed part>
75 parts of phenol resin (DIC, "Phenolite TD431"), 25 parts of melamine curing agent (Mitsui Sianamid Co., Ltd., "Simel 300"), 1 part of synthesized photoacid generator, and propylene glycol monomethyl ether acetate ( Hereinafter, it is abbreviated as PGMEA.) 100 parts of the resin solution 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. Ultraviolet rays whose wavelength is limited by an L-34 (filter that cuts light less than 340 nm, manufactured by Kenko Optical Co., Ltd.) using an ultraviolet irradiation device (HMW-661F-01, manufactured by ORC Manufacturing Co., Ltd.) for this resist. A predetermined amount of light was exposed on the entire surface. 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 at which the change in the film thickness of the resist before and after development is within 10% is defined as the curability of the exposed portion. Since the i-line sensitivity is good enough to show sufficient curability of the exposed portion with a small exposure amount, the i-line sensitivity of the photoacid generator was evaluated according to the following criteria.
◯: Minimum exposure is 500 mJ / cm ² or less ×: Minimum exposure is more than 500 mJ / cm ²

<Evaluation method of basic resistance>
Two parts of triethylamine were weighed in a screw tube with a cap, and 200 parts of deuterated chloroform was added and mixed. Subsequently, 3 parts of the synthesized nonionic photoacid generator was added and stirred quickly to obtain a uniform photoacid generator solution. After allowing this solution to stand at room temperature for 24 hours, the decomposition rate D [%] was measured by fluorine 19NMR. The decomposition rate D was determined as follows.
Decomposition rate D [%]: D = Integral ratio of decomposition product / (Integral ratio of photoacid generator + Integral ratio of decomposition product) × 100
Here, the basic resistance of the photoacid generator was evaluated from the decomposition rate D [%] as follows.
◯: Decomposition rate D [%] is 20% or less ×: Decomposition rate D [%] is more than 20%

As is clear from Table 1, the nonionic photoacid generator (A) having the naphthalimide structure of Examples 1 to 9 of the present invention has excellent basic resistance because it has a substituent on R1, and is a quencher. Since it does not react with, the resist resin composition does not change with time, and a pattern having a desired shape can be obtained. In addition, since the second substituent acts on the electronic state on the naphthalene ring and one or more of the hydrogens on the hydrocarbon of Rf are substituted with fluorine, it decomposes with high i-ray sensitivity and produces a strong acid. Can be generated. Further, since it has a naphthalimide structure and is excellent in thermal stability, it is not decomposed by PEB and has an excellent allowable range. On the other hand, Comparative Examples 1 and 2, which are nonionic photoacid generators having a naphthalimide structure and no substituent on R1, are easy because they do not have a substituent having a steric hindrance in the vicinity of the imidecarbonyl group. Reacts with the basic component and decomposes. As a result, the resist resin composition changes significantly with time because it reacts with the quencher in the resist material, and a pattern having a desired shape cannot be obtained with the passage of time after blending. Further, in Comparative Example 3, which is a photoacid generator having a hydrocarbon group not substituted with fluorine in Rf, it can be seen that the pattern cannot be formed because the i-ray sensitivity is inferior.

Since the nonionic photoacid generator (A) of the present invention has high sensitivity to i-rays, required basic resistance and thermal stability, photolithography for microfabrication represented by semiconductor manufacturing is performed. It is useful as a material.

Claims (7)

A nonionic photoacid generator (A) represented by the following general formula (1).

[In the formula (1), R1 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to One of R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms. , Rf is a hydrocarbon atom, or a hydrocarbon group having 1 to 18 carbon atoms in which at least one or more hydrogens are substituted with fluorine. ] In the general formula (1), R6 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to The nonionic photoacid generator (A) according to claim 1, wherein R5 is a hydrogen atom. In the general formula (1), R5 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to The nonionic photoacid generator (A) according to claim 1, wherein R4 and R6 are hydrogen atoms. In the general formula (1), R2 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R3 to The nonionic photoacid generator (A) according to claim 1, wherein R6 is a hydrogen atom. In the general formula (1), R4 is a hydrocarbon group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2. The nonionic photoacid generator (A) according to claim 1, wherein R3, R5 and R6 are hydrogen atoms. The nonionic photoacid according to any one of claims 1 to 5, 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 . Generating agent (A). A resin composition for photolithography (Q) containing the nonionic photoacid generator (A) according to any one of claims 1 to 6.