TW594383B - Positive resist composition for electron beam - Google Patents

Abstract

Provided is chemically amplified positive resist composition for electron beam, which may improve the resist pattern profile thereof and the line width variation during the pulling and placing in a vacuum chamber. A chemically amplified positive resist composition for electron beam comprises a resin having an specifically structured acid-decomposable group and being decomposable by the action of an acid and thereby whose solubility in an alkali developing solution is increased, and a compound which generates an acid when exposed to active light or radiation.

Description

594383 V. Description of the Invention (1) Technical Field The present invention relates to a positive-electron wire photoresist composition used in a semiconductor integrated circuit element, a photomask for manufacturing integrated circuits, etc. The compounds are chemically amplified photoresist compositions described in US Pat. No. 4,491,628, European Patent No. 29, 139, and the like. The chemically amplified positive photoresist composition is radiation by far ultraviolet light or the like. Irradiation, generation of an acid in the exposed part, and reaction using the acid as a catalyst, the solubility of the irradiated part and the non-irradiated part of the developing solution in the developing solution is changed. Pattern forming material for forming a pattern on the substrate. 0 The above chemical amplification is a positive type. The photoresist composition can be classified into an alkali-soluble resin, a compound that generates an acid by radiation exposure (photoacid generator), and an alkali-soluble tree having an acid-decomposable group. The dissolution prevents the combination! The three-component system is formed by the reaction with the acid and the resin and the photoacid generator are decomposed into the base-soluble group by the reaction with the acid, and the two-component system is decomposed by the reaction with the acid. A mixed system of an alkali-soluble resin, a low-molecular dissolution preventing compound having an acid-decomposable group, and a photoacid generator. In Japanese Patent Application Laid-Open No. 9-3 1 9092, it is disclosed that a resin having an acetal group introduced with an oxygen bond has a fixed wave reduction effect such as /, Π3, and the like. Effect: Result 0 and Yukai Hei 1 0- 22 1 Publication No. 854 discloses that a resin having a substituted acetal group unit 妖妖 J \ \\ When these resins having an acetal group are used as an electron beam photoresist, the rear electron beam exhibits a strong effect of back scattering and the resulting light is -3- Resist pattern is inverse cone

594383 V. Description of the invention (2) The outline of the shape. In addition, it is desired to improve the line width variation in the vacuum chamber of the electron beam irradiation device due to the time during which it is placed. The object of the present invention is to provide a chemically amplified positive electron beam photoresist with an excellent pattern profile obtained by using a photoresist for electron beam irradiation, and an improvement in line width variation due to standing time in a vacuum chamber of an electron beam irradiation apparatus.剂 组合 物。 Composition. The invention shows that the present inventors have intensively studied the present situation in view of the current situation, and found that the use of a positive electron beam photoresist composition having a compound having an acid-decomposable group having a specific structure can achieve the above-mentioned object, and thus completed the present invention . In other words, the positive-electron-ray photoresist composition of the present invention has the following structure: (1) A positive-electron-ray photoresist composition is characterized in that it comprises (a) a compound containing the following general formula (X) Resin is a structural unit of the base, and is decomposed by an acid to increase the solubility of the alkali developing solution, and (b) a compound that generates an acid by irradiation with an electron beam.

(Wherein R1 and R2 represent the same or different hydrogen atoms, 594383 of carbon number 1 to 4 5. Description of the invention (3) alkyl group, R3 and R4 represent the same or different hydrogen atoms, straight chain which may have a substituent, Branched and cyclic radicals R 5 represents a linear, branched, cyclic alkyl, aryl, and aryl alkyl group which may have a substituent, and m represents 1 to 20 The integer '0 represents an integer from 0 to 5). (2) A positive electron beam photoresist composition comprising (a) a structural unit represented by the following general formula (I), general formula (Π), and general formula (III); Resin that decomposes and increases solubility in alkali imaging solution, (b) Compound that generates acid by electron beam irradiation, R21

R21 ~ (CH2— 〇

R21 — < CH2-Cf

OH (where 'R21 represents a hydrogen atom or a methyl group, and R22 represents a group that does not decompose by the action of an acid' R23 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, 594383 V. Description of the invention (4) Alkoxy group, A fluorenyl group or a fluorenyl group 'η represents an integer of 1 to 3, and w represents a group represented by the general formula (X)). (3) The positive electron beam photoresist composition according to the above (1) or (2), wherein the ratio of the structural unit represented by the general formula (I), the general formula (I1), and the general formula (III) may be The following conditions (1) to (4) are satisfied: ① 0. 10 < (I) / (I) + (Π) + (III) < 0.25 ② 0 · 01 < (ΙΙ) / (Ι) + ( ΙΙ) + (ΙΙΙ) < 0.15 ③ (1) > (11) ④0.5 < (I) / (I) + (II) < 0.85 (wherein (I), (II), ( III) are Mohr fractions each representing a structural unit represented by the general formula (I), the general formula (II), and the general formula (I 11)). (4) The positive-electron-ray photoresist composition according to any one of (1) to (3) above, wherein (b) the compound that generates an acid by irradiation with electron rays is at least one kind of compound irradiated with electron rays The following general formulae (A-1), (A-2), (A-3), (A-4), (A-5), (A-6), and (A-7) produce sulfonic acids Show compounds,

(A-1) 594383 V. Description of the invention (5) R4O-*-〇R5 'x-(Α · 2) (wherein I to R5 represent the same or different hydrogen atom, alkyl group, cycloalkyl group, And a radical, a radical, a halogen atom, or -S- R ^ 'Rs represents a radical, or an aryl radical, and X-represents at least one radical having a carbon number of 8 or more selected from a branched or cyclic carbon, and Alkoxy, or at least 2 linear, branched or cyclic carbons with 4 to 7 alkyl and alkoxy groups, or at least 3 selected from linear or branched carbons 1 Benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid, of ~ 3 alkyl and alkoxy groups, or 丄 ~ 5 halogen atoms, or straight or branched acetic acid groups having 1 to 10 carbon atoms Anion of acid)

(Where 'R? ~ R1Q's each represent the same or different hydrogen atom, radical, radical, alkoxy, meridian, or halogen atom' and the above m, n, p, and Q each represent, 1 ~ Integer of 3) 594383 V. Description of the invention (6)

(Wherein, 'Rn to R13 represent the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, halogen atom or -S-R6 group, R6 and X_ are synonymous with the above, 1, m and η may be the same or different integers from 1 to 3. When l, m, and η are each 2 or 3, 2 of 3 to 3 Ru ~ each are bonded to each other to form a carbon-containing ring, heterocyclic ring, or aromatic ring. 5 to 8 rings)

(Wherein R14 to R16 represent the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, halogen atom or -S-R6 group, R6 and X- are synonymous with the above, l, m and η Can be the same or different integers from 1 to 3. When l, m, and η are 2 or 3 each, 2 to 3 of R14 to R16 each have 2 bonds to each other to form a carbon-containing ring, heterocyclic ring, or aromatic ring. 5 to 8 rings) 594383 V. Description of the invention (7)

N——〇S〇2Y (A-6) (where γ represents a linear, branched, cyclic alkyl, or aralkyl group which may be substituted,

The radicals shown (R31 ~ R51 represent the same or different hydrogen atoms, linear, branched, cyclic alkyl, alkoxy, alkoxy, fluorenyl, fluorenylamino, sulfonamido, and aryl groups which may have substituents) , Fluorenyl, aralkyl, or alkoxycarbonyl, or methylsulfonyl, nitro, chlorine, bromine, iodine, hydroxyl, or cyano, R31 to 594383 V. Description of the invention (8) R 3 5 , R 3 6 to R 4 2 and R 4 3 to R 5 1 each have two bonds to form a 5 to 8 carbocyclic ring formed by a hydrogen atom and / or a hetero atom, and γ may be bonded to other groups With the residue of the imide sulfonate compound being bonded, X represents a linear, branched alkylene group which may have a substituent, a heteroatom-containing monocyclic or polycyclic cyclic alkylene group which may have a substituent, may Substituted straight chain, branched alkenyl, heteroatom-containing monocyclic or polycyclic cyclic alkenyl, substituted alkenyl, substituted alkenyl, and χ Can also be bonded to other sulfonium imine sulfonate residues)

Ar1-S02-S02-Ar2 (A-7) (where A r i and A r 2 represent the same or different, substituted or unsubstituted aryl groups). (5) The positive-electron-ray photoresist composition according to any one of (1) to (4), further comprising a cyclic amine compound. (6) The positive electron beam photoresist composition according to any one of (1) to (5), further comprising a fluorine-based surfactant or a silicon-based surfactant or both. (7) Such as ( 1) The positive-electron-ray photoresist composition according to any one of (1) to (6), further comprising a compound that is decomposed by an acid to increase solubility in an alkali image solution. Embodiments of the invention The present invention will be described in detail below. (a) -1: Resin having a group represented by the general formula (X) above, which is decomposed by the action of an acid, and has increased solubility in an alkali developing solution. -10- 594383 V. Description of the invention (9) General The alkyl group of R1 and R2 in the formula (X) is a methyl group, an ethyl group, a propyl group, an n-butyl group, a second butyl group, or a third butyl group having 1 to 4 carbon atoms. R3 and R4 represent different or different hydrogen atoms, linear, branched, and cyclic alkyl groups which may have a substituent. The linear alkyl group is preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, etc. The branched fluorenyl group is preferably 1 to 30 carbons, more preferably 1 to 20, such as isopropyl, isobutyl, 3-butyl, isopentyl, 3-pentyl, and isohexyl , 3-hexyl, isoheptyl, 3-heptyl, isooctyl, 3-octyl, isononyl, 3-nonyl, 3-decyl, and the like. Cycloalkyl is preferably 3 to 30 carbons, more preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl Wait. R5 represents a linear, branched, cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. The linear or branched alkyl group of R5 is preferably 1 to 30 carbon atoms, more preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. , 3 -butyl, n-pentyl, isopentyl, 3 -pentyl, n-hexyl, isohexyl, 3 -hexyl, n-heptyl, iso-heptyl, 3 -heptyl, n-octyl, Isooctyl, 3rd-octyl, n-nonyl, isononyl, 3rd-nonyl, n-decyl, isodecyl, 3rd-decyl, n-decyl ~ isodecyl, N-dodecyl, isododecyl, n-tridecyl, isotridecyl, -11-594383 V. Description of the invention (10) N-tetradecyl, iso-tetradecyl, n-decyl Pentyl, isopentyl, n-hexadecyl, isohexadecyl, n-heptadecyl, isoctadecyl, n-octadecyl, isoctadecyl, n-nonadecane Group, isodecadecyl and the like. The cyclic alkyl group of R5 preferably has a carbon number of 1 to 30, more preferably 1 to 20, and may also be a cyclic alkyl group having a substituent when forming a ring with a number of 20, such as cyclopropyl and cyclobutyl. , Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloalkyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecane , Cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl, 4-cyclohexylcyclohexyl, 4-n-hexylcyclohexyl, pentenylcyclohexyl, hexyloxy ring Hexyl, pentenyloxycyclohexyl and the like. Any other substituted cyclic alkyl group may be used as long as it is within the above range. The aryl group of R5 is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, such as phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4- Ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl , 3-isopropylphenyl, 2-isopropylphenyl, 4-cyclopropylphenyl, 3-cyclopropylphenyl, 2-cyclopropylphenyl, 4-n-butylphenyl, 3 -N-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3iso-n-butylphenyl, 2-isobutylphenyl, 4-th-butylphenyl, 3 -3-Butylphenyl, 2-3-Butylphenyl, 4-cyclobutylphenyl, 3-cyclobutylphenyl, 2-cyclobutylphenyl, 4-cyclopentylphenyl , 4-cyclohexylphenyl, 4-cycloheptylphenyl, 4-cyclooctylphenyl, 2-cyclopentylphenyl, 2-cyclohexylphenyl, 2-cycloheptylphenyl, 2-cyclohexylphenyl Octylphenyl, 3-cyclopentylphenyl, 3-cyclohexylphenyl, 3-cycloheptylphenyl, 3-cyclooctylphenyl

• 12-594383 V. Description of the invention (11), 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cycloheptyloxyphenyl, 4-cyclooctyloxyphenyl, 2- Cyclopentyloxyphenyl, 2-cyclohexyloxyphenyl, 2-cycloheptyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclohexyloxybenzene , 3-cycloheptyloxyphenyl, 3-cyclooctyloxyphenyl, 4-n-pentylphenyl, 4-n-hexylphenyl, 4-n-heptylphenyl, 4-n-octylphenyl , 2-n-pentylphenyl, 2-n-hexylphenyl, 2-n-heptylphenyl, 2-n-octylphenyl, 3-n-pentylphenyl, 3-n-hexylphenyl, 3-n Heptylphenyl, 3-n-octylphenyl, 2,6-diisopropylphenyl, 2,3diisopropylphenyl, 2,4-diisopropylphenyl, 3,4-di Isopropylphenyl, 3,6-diisobutylphenyl, 2,3-di-third-butylphenyl, 2,4-di-third-butylphenyl, 3,4-di -3-butylphenyl, 2,6-di-n-butylphenyl, 2,3-di-n-butylphenyl, 2,4-di-n-butylphenyl, 3,4-di -N-butylphenyl, 2, 6-di-isobutylphenyl, 2, 3-di-isobutylphenyl, 2,4-di-isobutylphenyl, 3,4-di- Butylphenyl, 2,6-di-3-pentylphenyl, 2,3-di-3-pentylphenyl, 2,4-di-3-pentylphenyl, 3,4 -Di-three-pentylphenyl, 2,6-di-isopentylphenyl, 2,3-di-isopentylphenyl, 2,4-di-isopentylphenyl, 3,4 -Di-isopentylphenyl, 2,6-di-n-pentylphenyl, 2,3-di-n-pentylphenyl, 2,4-di-n-pentylphenyl, 3,4-di -N-pentylphenyl, 4-adamantylphenyl, 2-adamantylphenyl, 4-isobornylphenyl, 3-isobornylphenyl, 2-isobornylphenyl, 4-ring Pentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cycloheptyloxyphenyl, 4-cyclooctyloxyphenyl, 2-cyclopentyloxyphenyl, 2-cyclohexyloxyphenyl , 2-cycloheptyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclohexyl

-13- 594383 V. Statement (12) Oxyphenyl, 3-cycloheptyloxyphenyl, 3-cyclooctyloxyphenyl, 4-n-pentyloxyphenyl, 4-n-hexyloxy Phenyl, 4-n-heptyloxyphenyl, 4-n-octyloxyphenyl, 2-n-pentyloxyphenyl, 2-n-hexyloxyphenyl, 2-n-heptyloxyphenyl > 2- N-octyloxyphenyl, 3-n-pentyloxyphenyl, 3-n-hexyloxyphenyl > 3-n-heptyloxyphenyl, 3-n-octyloxyphenyl, 2,6-di-iso Propoxyphenyl, 2,3-di-isopropoxyphenyl, 2,4-di-isopropoxyphenyl > 3,4-di-isopropoxyphenyl, 2,6- Di-three-butoxyphenyl, 2, 3-mono-three-butoxyphenyl, 2, 4-di-three-butoxyphenyl, 3,4-di-three- Butoxyphenyl, 2,6- — *-n-butoxyphenyl, 2,3-di-n-butoxyphenyl-2,4-di-n-butoxyphenyl, 3,4- Di-n-butoxyphenyl 2,6-di-isobutoxyphenyl, 2,3-di-isobutoxyphenyl, 2,4-di-isobutoxyphenyl, 3,4 -Di-isobutoxyphenyl, 2,6-di-third-pentyloxy Phenyl, 2,3-di-three-pentyloxyphenyl, 2,4-di-three-pentyloxyphenyl, 3,4-di-three-pentyloxyphenyl, 2, 6-di-isopentyloxyphenyl, 2, 3-mono-isopentyloxyphenyl, 2,4-di-isopentyloxyphenyl, 3,4-di-isopentyloxyphenyl, 2,6-di-n-pentyloxyphenyl, 2,3-di-n-pentyloxyphenyl, 2,4-di-n-pentyloxyphenyl, 3,4-di-n-pentyloxybenzene Base, 4-adamantyloxyphenyl, 3-adamantyloxyphenyl, 2-adamantyloxyphenyl 4-isobornyloxyphenyl, 3-isobornyloxyphenyl, 2-isobornyl Oxyphenyl, and the like may be additionally substituted as long as they are within the above range, and are not limited to substituents other than the above examples. The aralkyl group of R5 is preferably carbon number Ί ~ 30, and more preferably 7 20 carbon number, such as phenethyl, 4-methylphenethyl, 3-methylphenethyl, 2-methylphenethyl -14-594383 V. Description of the invention (13), 4-ethylphenethyl, 3-ethylphenethyl, 2-ethylphenethyl, 4-n-propylphenethyl, 3-n-propyl Phenylphenethyl, 2-n-propylbenzylethyl, 4-isopropylphenethyl, 3-isopropylphenethyl, 2-isopropylphenethyl, 4-cyclopropylphenethyl, 3 -Cyclopropylphenethyl, 2-cyclopropylphenethyl, 4-n-butylphenethyl, 3-n-butylphenethyl, 2-n-butylphenethyl, 4-isobutylbenzene Ethyl, 3-isobutylphenethyl, 2-isobutylphenethyl, 4-th 3-butylphenethyl, 3-th 3-butylphenethyl, 2-th 3-butyl Phenethyl, 4-cyclobutylphenethyl, 3-cyclobutylphenethyl, 2-cyclobutylphenethyl, 4-cyclopentylphenethyl, 4-cyclohexylphenethyl, 4- Cycloheptylphenethyl, 4-cyclooctylphenethyl, 2-cyclopentylphenethyl, 2-cyclohexylphenethyl, 2-cycloheptylphenethyl, 2-cyclooctylphenethyl , 3 -cyclopentylphenethyl, 3 -cyclo Phenethyl, 3-cycloheptylphenethyl, 3-cyclooctylphenethyl, 4-cyclopentyloxyphenethyl, 4-cyclohexyloxyphenethyl, 4-cycloheptyloxybenzene Ethyl, 4-cyclooctyloxyphenethyl, 2-cyclopentyloxyphenethyl, 2-cyclohexyloxyphenethyl, 2-cycloheptyloxyphenethyl, 2-cyclooctyloxybenzene Ethyl, 3-cyclopentyloxyphenethyl, 3-cyclohexyloxyphenethyl, 3-cycloheptyloxyphenethyl, 3-cyclooctyloxyphenethyl, 4-n-pentylphenethyl , 4-n-hexylphenethyl, [n-heptylphenethyl, 4-n-octylphenethyl, 2-n-pentylphenethyl, 2-n-hexylphenethyl, 2-n-heptylphenethyl , 2-n-octylphenethyl, 3-n-pentylphenethyl, 3-n-hexylphenethyl, 3-n-heptylphenethyl, 3-n-octylphenethyl, 2,6- Diisopropylphenethyl, 2,3 diisopropylphenethyl, 2,4-diisopropylphenethyl, 3,4-diisopropylphenethyl, 3,6-diisobutyl Phenylphenethyl, 2,3-di-thi-butylphenethyl, 2,4-di-thi-butylphenethyl, 3,4-di-thi-3--1 5-

594383 V. Description of the invention (14) Butylphenethyl, 2,6-di-n-butylphenethyl, 2,3-di-n-butylphenethyl, 2,4-di-n-butylbenzene Ethyl, 3,4-di-n-butylphenethyl, 2,6-di-isobutylphenethyl, 2,3-di-isobutylphenethyl, 2,4-di-isobutyl Phenethyl, 3,4-di-isobutylphenethyl, 2, 6-di-three-pentylphenethyl, 2,3-di-three-pentylphenethyl, 2, Rendi-3-pentylphenethyl, 3,4-di-3-pentylphenethyl, 2,6-di-isopentylphenethyl, 2,3-

Di-isopentylphenethyl, 2,4-di-isopentylphenethyl, 3,4-di-isopentylphenethyl, 2,6-di-n-pentylphenethyl, 2, 3-di-n-pentylphenethyl, 2 4-di-n-pentylphenethyl, 3,4-di-n-pentylphenethyl, 4_adamantylphenethyl, 2-adamantyl Phenethyl, 4-isobornylphenethyl, 3-isobornylphenethyl, 2-isobornylphenethyl, 4-cyclopentyloxyphenethyl 4 cyclohexyloxyphenethyl, 4 -Cycloheptyloxyphenethyl, 4-cyclooctyloxyphenethyl, 2-cyclopentyloxyphenethyl, 2-cyclohexyloxyphenethyl, 2-cycloheptyloxy ~ 7β, cyclooctyl Oxyphenethyl, 3-cyclopentyloxyphenethyl, 3-cyclophenylphenethyl ^ oxyphenethyl, 3-cycloheptyloxyphenethyl, 3-cyclooctyloxyphenethyl,

4-n-pentyloxyphenethyl, 4-n-hexyloxyphenethyl, 4-n-heptyloxyphenylethyl 4-n-octyloxyphenethyl, 2-n-pentyloxyphenethyl, 2-n-hexyloxy Methyl, 2-n-heptyloxyphenethyl, 2-n-octyloxyphenethyl, 3-n-pentylacetophenidinyl 7-yl, 3-n-hexyloxyphenethyl, 3-n-heptyloxy Phenylphenethyl, 3-oxybenzidine n-octyloxyphenethyl, 2,6-di-isopropoxyphenethyl, 2,3-di-isopropylpyridyl, 2,4- Di-isopropoxyphenethyl, 3,4-di-isopropoxyoxybenzylphenethyl, 2,6-di-th-butoxyphenethyl, 2,3-di- 3-butoxy its phenethyl, 2,4-di-th 3-butoxyphenethyl, 3,4-di-th 3-but-16- 594383 V. Description of the invention (15) oxybenzene Ethyl, 2,6-mono-n-butoxyphenethyl, 2,3-di-n-butoxyphenethyl, 2,1-mono-n-butoxyphenethyl, 3,4-di- N-butoxyphenethyl, 2,6-di-isobutoxyphenethyl, 2,3-di-isobutoxyphenethyl, 2.4-di-isobutoxyphenethyl, 3, 4-di-isobutoxyphenethyl, 2, 6-di-three-pentoxyphenethyl, 2,3-di-three-pentyloxyphenethyl

2.4 -Di-thi-pentyloxyphenethyl, 3,4-di-th-pentyloxyphenethyl, 2,6-di-isopentyloxyphenethyl, 2,3-di- Isoamyloxyphenethyl, 2,4-di-isoamyloxyphenethyl, 3,4-di-amyloxyphenethyl, 2,6-di-n-amyloxyphenethyl, 2 , 3-di-n-pentyloxyphenethyl, 2,4-di-n-pentyloxyphenethyl, 3,4-di-n-pentyloxyphenethyl, Ren Konggang Oxyphenethyl, 3-adamantyloxyphenethyl, 2-adamantyloxyphenethyl, 4-isobornyloxyphenethyl, 3-isobornyloxyphenethyl, 2-isobornyloxyphenethyl, Alternatively, the alkyl group may be substituted with methyl, propyl, butyl, or the like.

Further, the other substituents of the above group include, for example, a hydroxyl group, a halogen atom (chlorine, chlorine, bromine, iodine), a nitro group, a cyano group, a fluorenylamino group, the above-mentioned alkyl group, a methoxy group, an ethoxy group, and a hydroxyethoxy group. , Propoxy, hydroxypropoxy, n-butoxy, isobutoxy, 2-butoxy, 3-butoxy, etc., alkoxy, methoxycarbonyl, ethoxycarbonyl, etc. Alkoxycarbonyl, benzyl, phenethyl, cumyl and other aralkyl groups, aralkyloxy, formamyl, ethyl fluorenyl, butyl fluorenyl, benzyl fluorenyl and pentyl fluorenyl groups, the alkenyl groups , Ethoxy, vinyloxy, allyloxy, allyloxy, butenyloxy, etc., aryloxycarbonyl groups such as the above-mentioned aryl, phenoxy »pentyloxy'benzyloxy, and the like. The substituent of the above R5 is an alkyl group with a carbon number of 1 to 2 and a carbon number of -17 to 594383. 5. Description of the invention (16) An aryl group or an aralkyl group with a carbon number of 7 to 20 is preferred. These substituents may further have a substituent. Specific examples of the group represented by the general formula (X) are shown below, but are not limited by these # # -18- V. Description of the invention (17) Η -〇 + 〇 ^ ~ ^ ~ 〇 > — Η

—〇 一一 οΛ / ^ 一 · < 〇) -〇 Η Η

-Η — 〇 Η —οΛλ ^ _ < 〇 Η ° -f ° ^ 〇- \ Η OCH3 Η

Η, CO

o ^^ O ^ ocH3

-19- 594383 V. Description of the Invention (is)

The resin having a group represented by the general formula (X), which is decomposed by an acid to increase solubility in an alkali developing solution (hereinafter referred to as having a general formula (X) -20-594383) Description of the invention (19) -based resin) refers to a compound having a molecular weight distribution obtained by polymerizing a monomer having a structure in which an acid-decomposable group represented by the general formula (X) is introduced, and alkali-soluble by the action of acid. Compounds. The resin having a group represented by the general formula (X) is a resin having a group represented by the general formula (X) on the main chain or side chain of the resin, or on both the main chain and the side chain. Among them, a resin having a group represented by the general formula (X) in a side chain is more preferable. Next, the base resin when the group represented by the general formula (X) is used as a side chain bond is an alkali-soluble resin having a -0H or -COOH, preferably -R, COOH, or Al-OΗ group on the side chain. . For example, the following alkali-soluble resin containing no acid-decomposable group. Among them, it represents a divalent or more aliphatic or aromatic hydrocarbon which may have a substituent, and -A r-represents a divalent or more aromatic group having a monocyclic or polycyclic substituent. The preferred base resin in the present invention is an alkali-soluble resin having a phenolic hydroxyl group. The alkali-soluble resin having a phenolic hydroxyl group used in the present invention contains at least 30 mole% o-, m- or p-hydroxystyrene (these are collectively referred to as hydroxyphenylethyl; (H)), or o-, m- Or a repeating unit of para-acyl-α-methylstyrene (these are collectively referred to as hydroxy-α-methylstyrene), preferably a 50 mol% copolymer or a homopolymer thereof, or the unit The benzene core is a partially hydrogenated resin, more preferably a p-hydroxystyrene homopolymer. It is a monomer other than hydroxystyrene and hydroxy-α-methylstyrene when the copolymer is prepared by copolymerization. Acrylates, methacrylates, acrylamines, methacrylamides, propionates, methacrylonitrile, maleic anhydride, styrene, α-methylstyrene, Acetyloxybenzene

-21-594383 V. Description of the invention (20) Ethylene and alkoxystyrene are preferred, more preferred are styrene, ethoxylated styrene, and 3-butoxystyrene. In the present invention, the content of the repeating unit (structural unit) having a group represented by the general formula (X) in the resin is preferably 5 mol% to 50 mol%, and more preferably 5 for all repeating units. ~ 30 mole%. The resin having a group represented by the general formula (X) in the present invention may contain other acid-decomposable groups in addition to the group represented by the general formula (X). A resin containing a group represented by the general formula (X) is prepared by reacting a corresponding vinyl ether with a phenolic hydroxyl-containing alkali-soluble resin dissolved in a suitable solvent such as tetrahydrofuran by a conventional method. The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, or hydrochloric acid, p-toluenesulfonic acid, or a salt such as pyridinium toluate. Corresponding vinyl ethers can be synthesized from active materials such as chloroethyl ethyl ether by nucleation substitution reaction and other methods, and synthesized using mercury or palladium catalysts. In addition, other methods can be synthesized by acetal exchange using the corresponding alcohol or vinyl ether. At this time, a vinyl ether having a substituent to be introduced in the alcohol is mixed with a less stable vinyl ether such as a 3-butyl vinyl ether, and it is carried out in the presence of an acid of p-toluenesulfonic acid or pyridinium toluate. . The weight average molecular weight of the resin containing the group represented by the general formula (X) is preferably 3,000 to 80,000, and more preferably 5,000 to 50,000. The molecular weight distribution (Mw / Mn) ranges from 1.01 to 4.0, and preferably 1.05 to 3.0. In order to obtain the molecular weight distribution polymer, a method using anionic polymerization, radical polymerization, or the like is preferred. -22- 594383 V. Description of the invention (21) The specific structure of the resin containing a group represented by the general formula (X) is shown below, but the present invention is not limited thereto. -23- 594383 V. Description of the Invention (22)

0H

-24- 594383

-25- 594383 V. Description of the Invention (24)

-26- 594383 V. Description of the Invention (25)

0H

-27- 594383 V. Description of the Invention (26)

28- 594383 V. Description of the invention (27)

The resin used in the present invention (a resin containing a group represented by the general formula (X) and a resin having a structural unit represented by the general formula (I), the general formula (II), and the general formula (III)),

-29- 594383 V. Description of the invention (28) In order to adjust the dissolution rate of alkali and improve the heat resistance, a polyhydroxy compound is added in the synthesis stage to make the polymer main chain cross-linked with polyfunctional acetal groups. The added amount of the polyhydroxy compound is from 0.01 to 1 mole%, preferably from 0.05 to 8 mole%, and more preferably from 0.1 to 5 mole% to the number of hydroxyl groups of the resin. In the case of 2 to 6 phenolic or alcoholic hydroxyl groups, the number of hydroxyl groups is preferably 2 to 4, and the number of hydroxyl groups is more preferably 2 or 3. The following are specific examples, but the present invention is not limited by these. -30- 594383 V. Description of the Invention (29)

(a) -2: It has the structural unit represented by the general formula (I), general formula (II) and general formula (III), and is decomposed by the action of acid to increase the solubility in an alkali developing solution. -31- 594383 V. Resin R21 of the invention description (30) represents a hydrogen atom or a methyl group.

R22 represents a group that is not decomposed by the action of an acid (called an acid stabilizer), such as a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an alkoxy group (except for -0-3 level (Alkyl), fluorenyl, cycloalkoxy, alkenyloxy, aryloxy, alkylcarbonyloxy, alkylfluorenylmethoxy, alkylfluorenylamino, arylfluorenylmethyl, aromatic Hydrazone and the like. The acid stabilizer is preferably amidino, alkylcarbonyloxy, alkoxy, cycloalkoxy, aryloxy, alkylamidooxyalkylamidoamino, and more preferably fluorenyl, alkylcarbonyl Oxy, alkoxy, cycloalkoxy, aryloxy.

The alkyl group in the acid stabilizer of R22 is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-butyl group, or a 3-butyl group having 1 to 4 carbon atoms. Cyclopropyl, cyclobutyl, cyclohexyl, adamantyl have 3 to 10 carbons, and alkenyl has 2 to 4 carbons such as vinyl, propenyl, allyl, and butenyl. Among them, aryl is preferably 6 to 14 carbon atoms such as phenyl, xylyl, tolyl, cumenyl, naphthyl, and anthracenyl. The alkoxy group has 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, and 2-butoxy groups. Alkoxy is preferred. The halogen atom of R23 is preferably fluorine, chlorine, bromine and iodine, and the alkyl group is methyl, ethyl, propyl, n-butyl, 2-butyl, 3-butyl, hexyl 'octyl, etc. The number of carbon atoms is preferably 1 to 8, and the number of aryl groups such as phenyl, xylyl, tolyl, cumenyl, naphthyl, and anthracenyl is preferably 6 to 14. Alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxy-32-594383 V. Description of the invention (31) propylpropoxy, n-butoxy, isobutoxy, 2 carbon atoms such as 1 to 4 carbon atoms are preferred. Carbonyl groups such as fluorenyl, propionyl, butylfluorenyl, benzamyl, and the like are ethoxyl, propylfluorenyl, and butylsulfonyl. A carbon number of 2 to 7 is preferred. The substituent W of the general formula (I) is the same as the general formula (X). The specific structure of the structural unit represented by the general formula (I) is not limited by these. -Butoxy and 3-butane are preferably 1 to 7, such as formamyl and ethenyl, and oxy, benzamyloxy and the general formula (X) and the above-mentioned buckle are shown. 33- 594383

Mon 34- 594383

= 35- 594383 V. Description of the invention (34)

-36- 594383

-37-594383 V. Description of the Invention (36)

-38 594383 V. Description of the Invention (37)

-39- 594383 V. Description of the invention (38) By containing the structural unit of the general formula (I I) in the resin, the resin can be decomposed by the action of acid and its solubility in the alkali developing solution. In addition, by introducing this structural unit, a contour with excellent rectangularity can be achieved. In addition, the amount of the structural unit represented by the general formula (I) can be effectively adjusted. Specific examples of the polymerizable monomer having a structural unit represented by the general formula (I I) are shown in τ, but the present invention is not limited thereto. # # -40- 594383 V. Description of the Invention (39)

-41-594383 V. Description of the Invention (40)

〇-42- 594383 V. Description of the invention (41) These resins containing a structural unit represented by the general formula (II) or the general formula (III) can be obtained by using a phenol resin or by making the monomer in the presence of a base. It is prepared by reacting with acid anhydride or by reacting with the corresponding halide in the presence of a base. In the present invention, the resin having a base which is decomposed by the action of an acid and increases the solubility in an alkali developing solution may be in addition to a structural unit represented by the general formula (I), the general formula (II), or the general formula (π I). It also contains other monomer units. In the present invention, the ratio of the structural units represented by the general formula (I), the general formula (II), and the general formula (III) is preferably to satisfy the following conditions (1) to (4). ① 0.10 < (I) / (I) + (11) + (IΠ) < 〇.25 ② 0.01 < (II) / (I) Ten (II) + (III) < 〇. 1 5 ® (Ι) χΠ) ④0.5 < (Ι) / (Ι) + (ΙΙ) < 0.85 (wherein (I), (Π), and (III) each represent a general formula (I), a general formula (II) ) And the mole fraction of the structural unit represented by the general formula (III)). By satisfying the above-mentioned conditions, the resin of the present invention can improve the rectangularity of the contour, and in particular, can improve the development defects. The repeating structural unit represented by the general formula (I), the general formula (II) or the general formula (III), or the repeating unit formed of other polymerizable monomers may be present in the resin individually or in combination of two or more. In addition, the resin contained in the positive-type photosensitive composition of the present invention can be appropriately polymerized with an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group to maintain good developability in an alkali developing solution.体 聚聚。 Body copolymerization. Have the general formula (I), the general formula (II), or the general formula synthesized by the above method

-43- 594383 V. Description of the invention (42) (III) The resin molecular weight of the repeating structural unit is 2,000 or more by weight average (Mw: polystyrene standard), preferably 3,000,000 to 200,000, more The best is 5,000 ~ 70,000. In addition, the degree of dispersion (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 3.5, and most preferably 1.0 to 3.0. The smaller the degree of dispersion, the heat resistance, and the formability (pattern outline) , Defocusing range, etc.) the better. A specific example of the resin having a repeating structural unit of the general formula (I), the general formula (I Π, and the general formula (I I I) is shown below. 'However, the present invention is not limited to these. -44- 594383

-45-594383 V. Description of the Invention (44)

-46- 594383

-47- 594383 V. Description of the Invention (46)

-48- 594383 V. Description of the Invention (47)

-49- 594383 V. Description of the Invention (48)

Ya ~ O oh

-50- 594383

-51-594383

-52- 594383 V. Description of the Invention (51)

OH

0

OH -53- 594383

-54- 594383 V. Description of the Invention (53)

och3

0CH3

-55- 594383 V. Description of the Invention (54)

0H

0 CH3

〇

〇

OH

〇, ch3

-56- 594383

57- 594383 V. Description of the invention (56)

In the positive photosensitive composition of the resin having a group represented by the general formula (X) (including a resin having a repeating structural unit of the general formula (I), the general formula (II), or the general formula (III)) (except for coating) The content of the coating solvent is preferably 50 to 99% by weight, and more preferably 70 to 97% by weight. Further, a resin having another acid-decomposable group can be used in the present invention. The resin used in the chemically amplified photoresist of the present invention and having a dissociative group which is decomposed by other acids and increases the solubility of the alkali developing solution is the main chain or side chain, or both the main chain and the side chain of the resin. The resin has a base decomposed by acid. Among them, a resin having a group decomposed by an acid on a side chain is more preferable. A preferred group for the acid-decomposed group is -COOA ^, and a group containing these more preferably is, for example, a group represented by -RG-COOA ^ or -Ar_0-B °. Where AG stands for-CiRWMRMMR. 3) ,, or-[(RWKR ^ -O-RQ6 group. B ° represents -A ° or -C0-0-A ° group (R °, R01 to R136 and Ar are synonymous with the following). -58- 594383 V. Description of the invention (57) The acid-decomposable group is silyl ether group, cumyl group, acetal group, tetrahydropyranyl ether group, ethanol ether group, ethanol ester group, tertiary alkyl ether group, tertiary alkyl group Ester groups, tertiary alkyl carbonate groups, etc. are preferred. More preferred are tertiary alkyl ester groups, tertiary alkyl carbonate groups, cumyl groups, acid ester groups, and tetrahydrosoranyl ether groups. The base resin when these groups obtained by acid decomposition are bonded at a side chain is an alkali-soluble resin having -0Η or-COOH on the side chain, preferably-RQ-COOH, or -A r-0H group. For example, the following alkali-soluble resins. The alkali-dissolving speed of these alkali-soluble resins is more preferably 170A / second or more under the measurement of 0.21 N tetramethylammonium hydroxide (TMAH) (23t). It is more than 3 3 0A / sec (A is Angstrom). Furthermore, in terms of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferred. A 1 μm film is more preferred. Thickness with 248nm transmittance From this viewpoint, more preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or Alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), ortho-alkylated or o-alkylated compound, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer And hydrogenated phenolic lacquer resin. The resin having a base obtained by acid decomposition used in the present invention is a base-soluble resin unit in which an acid-decomposable base is reacted with a precursor in an alkali-soluble resin or an acid-decomposed base is bonded. It can be obtained by copolymerization of various monomers. The above-mentioned acid generator, a resin having a group obtained by acid decomposition, and the following acid-decomposable low-molecular-weight dissolution preventing compound may be mixed.

-59- 594383 V. Description of the Invention (58) The acid-decomposable dissolution preventing compound used in the present invention has at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups is the farthest. A compound having at least 8 atoms bonded to it via sites other than acid-decomposable groups. The acid-decomposable low-molecular-weight dissolution preventing compound used in the present invention may contain at least one acid-decomposable group represented by the general formula (X). In the present invention, a preferred acid-decomposable dissolution preventing agent has at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups is at least 10 via the furthest position ( 11 is preferred, and 12 is more preferred. A compound having an atom other than an acid-decomposable group, or having at least three acid-decomposable groups in its structure, and the acid-decomposable group. The distance between them is at least 9 (preferably 10, more preferably 11) compounds bonded to an atom other than an acid-decomposable group at the furthest position. In addition, the upper limit of the above bonding atoms is preferably 50, more preferably 30. In the present invention, when the acid-decomposable group dissolves and prevents the acid-decomposable group in the compound from having three or more, preferably four or more, or when the acid-decomposable group is two, the acid-decomposable groups have a certain distance from each other. The above can significantly improve the dissolution preventing property of the alkali-soluble resin. The distance between the acid-decomposable groups is expressed by the number of bonded atoms except for the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonded atoms each, and the compound (3) is 12 bonded atoms.

-60- 594383 V. Description of the invention (59) 2 3 Βθ.0 ^ 0 ^ 0-Β ° (1) Α °-00C-2CH2-3CH2-1 COO-A0 ⑵

In addition, the acid-decomposable dissolution preventing compound of the present invention may have several acid-decomposable groups on one benzene ring, and is preferably a compound formed by a structure having i acid-decomposable groups on one benzene ring. . The molecular weight of the acid-decomposable dissolution preventing compound of the present invention is 3,000 or less, preferably 300 to 3000, and more preferably 1,000 to 2500. In a preferred embodiment of the present invention, the group decomposed by an acid includes a group represented by _COOA0 and -0-βϋ, for example, a group represented by -RQ-C00AG, or -Ar-0-BQ. Where A ° means-[(R.1) (R ° 2) (R ° 3), R ° 2) (R03 or -C (R ° 4) (R ° 5) -〇- R ° ^ B ° Represents A ° or -C-0-0- A. R. R, R02, r03, and r05 each represent the same or different hydrogen atom, alkyl, cycloalkyl, alkenyl, or aryl. R () 6 represents an alkyl group or an aryl group. However, at least two of Roi ~ RW are groups other than a hydrogen atom, and two of ~ r03 and R04 ~ RQ6 may be bonded to form a ring. RG represents a A bivalent or higher aliphatic or aromatic hydrocarbon group having a substituent, -A I- means that it may have a monocyclic or polycyclic substitution -61- 594383 5. A description of the invention (60) A bivalent or higher aromatic group. Here As the alkyl group, a methyl group, an ethyl group, a propyl group, a n-butyl group, a 2-butyl group, or a 3-butyl group having 1 to 4 carbon atoms is preferred, and the cycloalkyl group is a cyclopropyl group or a cyclobutyl group. 3, 10 carbon atoms are preferred for cyclohexyl, adamantine, and 2 to 4 carbon atoms for vinyl, acrylic, allyl, and butenyl are preferred for storage, and benzene is aryl for aryl. Carbonyl, tolyl, diphenyl, cumyl, naphthyl, and anthracenyl are preferably 6 to 14. The substituents include, for example, a hydroxyl group, a halogen atom (fluorine, (Chlorine, bromine, iodine), nitro, cyano, alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, Alkoxy groups such as 2-butoxy and 3-butoxy, alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, aralkyl groups such as benzyl, phenethyl, and cumyl, aralkyloxy Methyl, methylamyl, ethylamyl, butylamyl, benzamyl, cyano, pentamyl and other fluorenyl groups, fluorenyl such as butylamyloxy, the above fluorenyl, vinyloxy, acryloxy, alkenyl Alkenyloxy groups such as propoxy and butenyloxy, aryloxy groups such as the above-mentioned aryl groups and phenoxy groups, and aryloxycarbonyl groups such as benzamyloxy groups. The acid-decomposable groups include silyl ether groups, cumyl groups, and condensation groups. Aldehyde, tetrahydropyranyl, ethanol ether, ethanol ester, tertiary alkyl ether, tertiary alkyl ester, tertiary alkyl carbonate and the like are more preferred. Tertiary alkyl esters, Tertiary alkyl carbonate group, cumyl ester group, tetrahydropyranyl ether group. Acid-decomposable dissolution preventing compounds are disclosed in JP-A No. 1-289946, JP-A No. 1-289947, JP-A No. 2-2560, and JP-A No. 3 -1 28959, special Flat 3--15885 No. 5, Laid Open 3--17935 No. 3, JP-3-

-62- 594383 V. Description of the Invention (61) No. 191351, JP-A-3-20025 No. 1, JP-A-3-20025 No. 2, JP-A-3-2002 5 No. 3, JP-A-3-2002 5 No. 4, JP-A 3-2002 5 No. 5, JP Hei 3-25 9 1 49, JP No. 3-27 9 9 5 8, JP No. 3-2799 59, JP No. 4-1 650, JP No. 4-1651 JP 4-1 1 260, JP 4-1 23 56, JP 4-1 23 57, JP 3-3 3 229, JP 3-2 307 90, JP Hei 3-3 2043 8, No. 4 Heping 4-2 5 1 5 7, No. 4 Heping 4-5 2 7 3 2, No. 4 Heping 4-1 03 2 1 No. 5, No. Heping 4-1 No. 04542, No. 4-1 0788 No. 5, No. 4-1 07 889, Same as No. 4-1 5 2 1 9 5 and other phenolic OHs that make some or all of the polyhydroxy compounds described in the specification The compound is preferably bonded to the above-mentioned group, -R ^ COOA ^ or W group, and contains a protected compound. Even better are JP-A 1-289946, JP-A 3- 1 28959, JP-A 3- 1 5885 5, JP-A 3- 1 7 9 3 5 3, JP-A 3-20025 1 and JP-A 3-200252, JP 3-200255, JP 3-259 1 49, JP 3-279958, JP 4-1 650, JP 4-1 1 2 6 0, JP 4 -No. 1 2 3 5 No. 6, JP 4-No. 1 2 3 5 No. 7 No. 4, No. 4 No. Heping, No. 4 No. 4-No. 1 No. 3, No. 4 No. Heping, No. 4 Those using polyhydroxy compounds as described in the specifications such as 04542, JP 4-1 07885, JP 4-1 07889, and the same as 4-1 52 1 9 5. More specifically, for example, compounds represented by the general formulae [I] to [XV I]. -63- 594383

594383 V. Description of the Invention (63)

Rioi, R102, R108, r130 can be the same or different, hydrogen atom, -RLCOOKRMHR. 2) (R ° 3) or -c〇-〇-c (rq1) (rQ2) (rG3), but the definitions of rg, rg1, rG2, and rQ3 are the same as above, 1 ο ο; -C〇-, -C 〇〇-, -NHCONH-, -NHC〇〇-, -〇-, -S-, -SO-, -S02, -S〇3-, or

-65- 594383 V. Description of the invention (64) Where G = 2 ~ 6, but when G = 2, at least one of R15 () and R151 is an alkyl group R150, R151: may be the same or different hydrogen atom, alkyl group , Alkoxy, -OH, -COOH, -CN, halogen atom, -R152-CO〇R153 or -R154-OH, R152, R154: alkylene R " 3: hydrogen atom, alkyl, aryl, Or aralkyl, R99, R103 to R107, R109, Rill to RH8, R131 to R134: can be the same or different hydrogen atom, hydroxyl, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryl Oxy, aralkyl, aralkoxy, halogen atom, nitro, carboxyl, cyano, or -N (R155) (R156) (where R155, R156: hydrazone, alkyl, or aryl), R110 : Single bond, alkylene, or _Rl57 _ ^^ RlS9_ r158 r157, r159 ·· may be the same or different single bond, alkylene, -ο-,-S-,-CO-, or carboxyl,

-66- 594383 V. Description of the invention (65) Chlorine atom, alkyl group, alkoxy group, fluorenyl group, fluorenyloxy group, aryl group, nitro group, ^^ 'cyano group, or carboxyl group, but the hydroxyl group can be acid-decomposable group (For example, 3-butoxycarbonylmethyl, tetrahydropyranyl, 丨 _ethoxy_ 丨 _ethyl, 丨 _3-butoxy-1 -ethyl). R 1 1 9 and R 1 2 0 ·· M are the same or different methyl groups, methyl groups substituted with lower alkyl groups, halogen methyl groups, or halogenated alkyl groups, but the lower alkyl groups of the present invention are Refers to an alkyl group having 1 to 4 carbon atoms, A: a methyl group, a methyl group substituted with a lower alkyl group, a halogenated methyl group, or a halogenated alkyl group, a ~ v 'gl ~ nl: when plural, () The internal base may be the same or different, a ~ q, s, t, v, gl ~ il, kl ~ ml: integers of 0 or 1 ~ 5, r, u: integers of 0 or 1 ~ 4, Jlnl: 〇 or an integer from 1 to 3, (a + b), (e + f + g), (k + 1 + m), (q + r + s), (gl + hl + il + j " $ 2, ( j l + nl) $ 3, (r + u) g 4, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n) , (1 + 0) (m + p), (q + t), (s + v), (gl + kl), (hl + 11), (il + ml) $ 5 -67- 594383 V. Description of the invention (66) R 163 R 163

(VI) 〇 R161: hydrogen atom, monovalent organic group or R163

Among them, R162 ~ R166: may be the same or different hydrogen atom, hydroxyl group, halogen atom, alkyl group, alkoxy group, alkenyl group, -C〇-0-C (RQ1) (R ° 2) (R ° 3) , But at least two are -RQ-C〇〇- 匸 (feet ° 1) (!? ° 2) (1 ^ 3) or-(: 0-0- (: (1 ^ 1) (1 ^ 2) (Foot () 3), or 4 or 6 substituents of the same symbol may be different groups, -68- 594383 V. Description of the invention (67) X: divalent organic group, e2: 0 or 1, R173

Among them, R1 67 ~ R1W: may be the same or different hydrogen atom, hydroxyl group, halogen atom, alkyl group, alkoxy group, or alkenyl group, and each of the substituents having 4 or 6 same symbols may be different groups R171, R172: hydrogen atom, alkyl or R167 R168 R173

Ri7〇it 'R173: At least two are -RLCOO-CUWKRMKRG3) or -CO-OC (RQ1) (RG2) (RQ3), others are hydroxyl, f2, h2: 0 or 1, g2: 0 or 1 ~ 4 Integer, -69- 594383 V. Description of the invention (68)

Among them, R174 ~ R18 (): may be the same or different hydrogen atom, hydroxyl group, halogen atom, alkyl group, alkoxy group, nitro group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group , Alkoxy, alkenyl, aralkoxy or aryloxy are each 6 substituents of the same symbol may be different groups, Ri8i: at least 2 are _R () _ c〇〇_c (R〇i ) (R〇2) (R (n) or _c〇_〇_ C (RQ1) (RQ2) (R ° 3), others are hydroxyl groups. Specific examples of preferred compound structures are described below.)

-70- 594383 V. Description of the Invention (69) R0

-71-594383 V. Description of the Invention (70)

(8)

t # -72- 594383 V. Description of the invention (71) CH, CH3

(10)

(12)

-73- 594383 V. Description of the invention (72 CH, CH3

OR

OR 〇R ORRO, 丄 / OR

14)

clcior ^ (15)

4 7 594383 V. Description of the invention (73

OR OR

(16)

OR OR H3C

h3c

OR

OR -75- 594383 V. Description of the invention (74)

-76- 594383 V. Description of the Invention (75)

ch3 (22)

-77- 594383 V. Description of the Invention (76)

\) / 5 (2

Ro

g f 6 (2

(2 # -78- 594383 V. Description of the invention (77)

OR

OR

CH,

ch3 OR -79- 594383 V. Description of the Invention (78)

OR

OR

-80- 594383 V. Description of the Invention (79)

-81-594383

594383

594383 V. Description of the invention (82 R〇 -ο-

OR

OR

C —CH〇 —CH? —— C

general

OR

t · -84- 594383 V. Description of the invention (83) In the compounds (1) to (43), R represents a hydrogen atom, -CH2-C〇〇-C (CH3) 2C6H5, -CH2--〇〇-c4h9w- c〇〇 一 c4h9⑴

. However, at least two or three depending on the structure are groups other than a hydrogen atom, and each substituent 'R may be a different group. At this time, the content of the dissolution preventing compound is 3 to 45% by weight, preferably 5 to 30% by weight, and more preferably 10 to 20% by weight based on the total weight of the photosensitive composition (excluding the solvent). %. In addition, in order to adjust the alkali solubility, an alkali-soluble resin having no base obtained by acid decomposition may be mixed. Examples of the alkali-soluble resin include phenolic varnish resin, hydrogenated phenolic varnish resin, acetone-pyrophenol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, and hydrogenated polyhydroxystyrene. , Halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-substituted maleimide copolymers' o- / p- and m / p-hydroxystyrene copolymers, and partially-p-o- Alkyl (for example, 5 to 30 mole% o-methylate, o- (1-methoxy) ethylate, o- (丨 _ethoxy)) ethylate, o-2 -tetra Hydropyranyl, ortho- (3-butoxycarboxy) methylate, etc.) or ortho-fluorenyl (eg, 5 to 30 mole% of ortho-fluorenyl, ortho- (3-butoxy Group) fluorenyl compounds, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer

-85- 594383 V. Description of the Invention (84) Polymers, carboxyl-containing methacrylic resins and derivatives thereof, but not limited to these. More preferred alkali-soluble resins are phenolic resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-hydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially polyhydroxy Styrene ortho-alkylated, or alpha-methylstyrene-hydroxystyrene copolymer. This phenolic lacquer resin is obtained by adding and condensing aldehydes in the presence of an acidic catalyst, which is composed mainly of the monomers specified below. The specified monomers can be used alone or in combination of two or more phenols such as phenol, m-cresol, p-cresol, ortho-cresol, 2,5-xylitol, 3,5-xylol, Xylols such as 3,4-xylol, 2,3-xylol, m-ethylphenol, p-ethylphenol, o-ethylphenol, p-third-butylphenol, p- Alkyl phenols such as octylphenol, 2,3, 5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3, 5-dimethoxyphenol, 2-methoxy- Alkoxyphenols such as 4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-butoxyphenol, and p-butoxyphenol, 2-methyl-4 -isopropyl Dialkylphenols such as phenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, naphthol , But not limited by these. Examples of the aldehydes include formaldehyde, para-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p- Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde,

-86- 594383 V. Description of the invention (85) p-nitrobenzaldehyde, o-methylbenzaldehyde 'm-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n- Butylbenzaldehyde, furfural, acetaldehyde chloride, etc., among these, formaldehyde is preferably used. These aldehydes can be used alone or in combination of two or more. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, and oxalic acid. The weight-average molecular weight of the phenol enamel resin thus obtained is preferably from 1,000 to 30,000. If it is less than 1,000, the unexposed portion will decrease after the development, and if it is more than 30,000, the development speed will become small. More preferred is 2,000 to 20,000. In addition, the weight average molecular weight of the above polyhydroxystyrene, its derivatives, and copolymers other than the phenolic lacquer resin is 2,000 or more, preferably 5,000 to 20,000, and more preferably 5,000 to 100,000. Furthermore, in order to improve the heat resistance of the photoresist film, it is preferably 25,000 or more. Here, the weight-average molecular weight is defined in terms of polystyrene conversion by gel permeation chromatography. These alkali-soluble resins of the present invention may be used in combination of two or more. The amount of these alkali-soluble resins of the present invention added to the composition is preferably 5 to 30% by weight. The acid generator (b) used in the present invention is a compound that generates an acid by irradiation with electron rays. The compound used in the present invention to generate an acid by irradiation with electron rays can be used as long as it is decomposed to generate an acid by irradiation with electron rays, but it can be started from a photoinitiator photo-polymerization photoinitiator and a photo-radical polymerization photo-initiator. Agents, pigments

-87- 594383 V. Description of the invention (86) Conventional light (400 ~ 200 nm ultraviolet light, especially g-line, h-line, i-line) used in light decolorizer, photochromic agent, or microphotoresist, etc. , KrF excimer laser light), ArF excimer laser light, electron rays, X-rays, molecular rays, or ion beam-producing compounds and these mixtures, those who produce acids by decomposition by electron beam irradiation are appropriately selected and used. In addition, other photoacid generators used in the present invention include iron salts such as diazo iron salts, ammonium salts, rust salts, iodonium salts, sulphate salts, iron selenium salts, and arsenic salts, and organometallic / organic halogenation Compounds, photoacid generators with ortho-nitrobenzyl-type protective groups, sulfamates, and other typical photodecomposition compounds to produce sulfonic acids, dimill compounds, etc. Further, a compound which causes these groups to generate an acid by electron beam irradiation, or a compound which is introduced into the main chain or side chain of the polymer can be used. In addition, VNRPillai, Synthesis, (1), 1 (1980) 'A. Abad et al? Tetrahedron Lett. J (47) 4555 (1971), DHR Barton et al, J. Chem. Soc., ( C), a compound which generates an acid by light, as described in 3 29 (1 9 70), U.S. Patent No. 3,799,7 78, and European Patent No. 1,26,7 1 2. Among the above-mentioned compounds that are decomposed by electron beam irradiation to generate an acid, the compounds represented by the above-mentioned general formulae (A-1) to (A-7) are preferably used to generate a sulfonic acid compound by electron beam irradiation. The compounds represented by the general formulae (A-1) to (A-7) will be described in detail below. Acid generators represented by the general formulae (A-1) to (A-3): 1 ^ ~ 1 ^ 6 and the general formulae (A-1) to (A-3). Alkyl

-88- 594383 V. Description of the invention (87) A methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-butyl group, and a butyl group having 1 to 4 carbon atoms, which may have a substituent. Examples of the cycloalkyl group include an alkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent. The oxy group includes, for example, methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, 2-butoxy, and 3-butoxy carbons 1 to Four of them. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group include a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group having 6 to 14 carbon atoms. Examples of the substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, and a hydroxyl group. , Carboxyl, alkoxycarbonyl, nitro, etc. In the present invention, compounds of general formulae (A-1) to (A-3) are used, and the anion X_ has at least one branched or cyclic carbon number of 8 or more, preferably 10 or more alkyl or alkoxy groups, or at least two branched or cyclic carbons of 4 to 7 alkyl or alkoxy groups, or at least three branched or cyclic carbons of 1 to 3 alkyl or alkoxy groups, or benzenesulfonic acid, naphthalenesulfonic acid or anthracene having 1 to 5 halogen atoms, or having linear, branched, or cyclic carbon ester groups of 1 to 10 Anion of sulfonic acid. As a result, the diffusibility of the acid (benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having the above-mentioned group) generated after exposure is reduced, and the solvent solubility of the iodine and iodine compound is improved. In particular, in terms of reducing the diffusivity, the above-mentioned group is preferably a branched or cyclic alkyl group or an alkoxy group rather than a straight-chain type or a group. When the above-mentioned group is one, the difference between the diffusivity of the straight chain and the branched chain or the ring is more significant.

-89- 594383 V. Description of the Invention (88) Alkyl group having 8 or more carbon atoms, preferably 8-12 carbon atoms, for example, branched or cyclic octyl, nonyl, decyl, undecane Alkyl, dodecyl, tridecyl, tetradecyl, octadecyl and the like. Alkoxy groups having 8 or more carbon atoms, preferably 8 to 12 carbon atoms, for example, branched or cyclic octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy Tridecyloxy, tetradecyloxy, stearyloxy and the like. Examples of the alkyl group having 4 to 7 carbon atoms include linear, branched or cyclic butyl, pentyl, hexyl, and heptyl. Examples of the alkoxy group having 4 to 7 carbon atoms include linear, branched, or cyclic butoxy, pentyloxy, hexyloxy, and heptyloxy. Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, n-propoxy, and isopropoxy. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a more preferable one is an iodine atom. Examples of linear, branched, or cyclic carbon esters having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and 3-Butyl, n-hexyl, isohexyl, 3rd-hexyl, n-heptyl, isoheptyl, 3-heptyl, n-octyl, isooctyl, 3rd -Octyl ester, n-nonyl ester, isononyl ester, 3rd-nonyl ester, n-decyl ester, isodecyl ester, 3rd-decyl ester, cyclopropyl ester, cyclobutyl ester, cyclic Amyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. -90- 594383 V. Description of the invention (89) In addition to the above-mentioned specific substituents, the aromatic sulfonic acid shown by X · may contain a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carbon Numbers of 6 to 10 aryl groups, cyano groups, thioether groups, hydroxyl groups, pendant groups, nitro groups and the like are used as substituents. Specific examples of these compounds in the following (Al -1) to (A-1 -66), (A-2-1) to (A-2-5 9), (A-3-1) to (A-3-3 5), but not limited by these. -91-594383 V. Description of the Invention (90)

OH

(A-1-7) C1

-92- 594383 V. Description of the Invention (91)

-93- 594383 V. Description of the Invention (92) CH,

S " Gu 17 (: 8-〇, 〇 so; 〇-ch3

〇-f! Η ^ β-〇-〇- S〇3

-94- 594383 V. Description of the Invention (93) C1

(A-1 -18)

-95- 594383 V. Description of the Invention (94) 0 — CH3

SO3-H〇

OH

(A-1-24)

SO3

-96- 594383 V. Description of the Invention (95)

(A ten 30)

nHgC4-0 S〇3

-97- 594383 V. Description of the Invention

0H

(A-1-33)

(A-1-34)

-98- 594383 V. Description of the Invention (97)

s〇3

0H

SO;

lH9C4. ._. .so, r = \ / 3 (A-l-43) H9C4 \

-99- 594383 V. Description of the Invention (98)

(A-1-45) S〇3

ch3

〇-C4Hen -10 0- 594383 V. Description of the invention (99)

0H

(A-1-49)

(A -1-50)

-101-594383 V. Description of the Invention (100)

OH

iC3H7

α- OCH,

(Α Ten 57) S ΐ3Η7

(A-Bu 6〇) S〇3_

F-102- 594383 V. Description of the invention (101)

〇c4h9

h9c4〇

-103 594383

594383 V. Description of the invention (1〇3 0 " ι + ~ 0 ^ 17 ^ 8 〇-ι + -Ό 1h21c10

'3 so

'3 so (A-2-1) Ή ^. (A- 2-2) ^ 25 ^ 12 CHq

SO;

SO '3 (A-2-3) (A- 2-4) ci ^ 25 ^ 12,

SO 3 ^ 25 ^ 12

S〇3 一 (A-2-5) (A_2-δ)

U7C 0 " i + _H0 3 jh ^ c O ^ KD-(A-2-8) (A-2-7)

H- along 25〇12-〇 (A-2-9) iHi7cs-〇 ~ y ~~ s〇3 (A-2-10) -105- 594383 V. Description of the invention (104) C4H9t, H21Cl0- ° O ^ s〇3 " (A-2-11) Η, Θ 一 〇Ό ^ ί + — {D ^ ° — CH3 (A ~ 2-12) t 0 ~ i + _0

'3 (A-2-13) so 〇 · ι + ~ 0

(A-2-17) ch ~ o sh17c8 s Λ- / s〇i sH17C8 (A-2-14) h3〇o〇- ch3 7 9. 4 v ^ r ^ rr ^^ A > s〇3_ (A -2-16) QH / Cl Cl C4iV% c4— ^ ~ Vs〇3 (A-2-18) ⑽9 f -106- 594383

594383

594383 V. Description of the invention (1〇7 step 0_〇 ^ 1! _〇 " 0-CH3 ο3 ·. ^ 17〇8-〇-) H17c8-0

(A-2-35)

〇-ι + Ό so3- Post 4

(A-2-37) (A-2-36)

Ό ~ ι + ~ 〇- CH, t 0 ~ ι + _0 h3c S0〇

0 a CgH 17 so,

O-C ^ t -109- 594383 V. Description of the invention (108) -ch3

(A-2-41) S03 " nlkC4-〇 / 0— ηΗ ^ 4-〇 S03

〇 a C4Hgn (A-2-42> so3 "

(A-2-43) 0-0, ¾0

h3c-o < y < 〇 O-CH, SO,

(A-2-45) 'H17C8-〇- \ > -0-csh -110- 594383 V. Description of the invention (109) 0 ~ ι + Ό

HA 乂) -r-(^ c; X

h3co-^^ i +-< (^-〇ch3

CH ~ Q

CKO

(A-2-52) 〇 ^ 2 ^ 5

(A-2-53) -111- 594383 V. Description of the invention (11〇-Qr ^ Or

so3- F, 丄 J

Ah 1 F (A_2_54)

S〇3_ Fk 丄 / F

Ah F F (A-2-55)

Or heart so3- F, 丄

F— Ah, F F (A-2-56)

F (A-2-58) ΌγΆ so3 " F, 丄

F, Ah, F F (A-2-57)

(A-2-59) -112- 594383 V. Description of the invention (111)

(A-3-1)

(A-3-2) (A-3-3) (A-3-4)

(A-3-5) -113 594383 V. Description of the invention (112) c4h〇c

-114- 594383

594383

594383

594383 V. Description of the invention (116)

(h9c4 (A-3-24) (A-3-25) (A-3-26) (A-3-27) (A-3-28) -118- 594383

594383 V. Description of the Invention (118)

(A-3-34)

(A-3-35) In the specific example, η represents a straight chain, s represents a second order, t represents a third order, and i represents a branch. The compounds represented by the general formulae (A-1) to (A-3) correspond to, for example, c 1 · salts (wherein the general formulae (A-1) to (A-3) are X · compounds substituted with C1 ·), χ · Γ + (X-is the same as in the general formulae (A-1) to (A-3), γ + represents cations such as H +, Na +, K +, NH4 +, N (CH3) 4 +) in aqueous solution It is synthesized by salt exchange. Alkyl groups, cycloalkyl groups, and alkoxy groups of Rn to R13 and R14 to R16 in the general formulae (A-4) and (A-5) of the acid generators represented by the general formulae (A-4) and (A-5) And halogen atoms are the same as those of R1 to R5 described above as specific examples. R6, X · are synonymous with the above. In addition, when l, m, and η are each 2 or 3, 2 or 3 of each of Rh to R13 or R14 to 16 may be bonded to each other to form 5 to 8 containing carbocyclic, heterocyclic, or aromatic rings. Elements made of rings.

-120- 594383 V. Description of the invention (119) In the following, specific examples of the compound represented by the general formula (A-4) (A-4-1) to (A-4-28), general formula (A -5) Specific examples (A-5-1) to (A-5-30) of the compounds shown are not limited thereto.

-121-594383 V. Description of the Invention (12〇)

^ 25 ^ 12

2

2

2

-122- 594383

-123- 594383

-124- 594383

-125- 594383

V. Invention Description (125)

-127- 594383

-128- 594383

594383

594383

594383 V. Description of the invention (13〇)

CsH17n

-132- five 131

Invention description

It indicates the second order. In the specific example, η indicates a straight chain, level, and 1 indicates a branched chain. When the compound represented by the general formula < A 4) and (A -5) corresponds to, for example, C 1) (A 5) is a compound in which x is substituted with C Γ), an X · γι compound (X · 系 和 通, Λ c ^ (A-4) and (A-5) are the same, and γ + represents a cation such as H + N < ^ 3) 4 +) in an aqueous solution and synthesized from a salt. Acid generator represented by general formula (A-6) The linear and branched chain of the above general formula (A-6) and R31 to R51, for example, methyl, ethyl, propyl, isopropyl, and n-butyl 2nd represents the 3rd salt (the compound shown by the general formula, Na +, K + is exchanged for a cyclic alkylbutyl group, No. 133-594383) V. Description of the invention (132) 3-butyl, hexyl, sheep A linear or branched alkyl group having 1 to 20 carbon atoms, and a cyclic alkyl group such as fluorenyl, cyclopentyl, or cyclohexyl. Examples of the aralkyl group of Y include benzyl or phenethyl The carbon number is 7 to 12 aralkyl groups. Preferred substituents of the aromatic group are, for example, a lower alkane group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, and an ethylamino group. And halogen atoms. Examples of the alkoxy group of r31 to R5i include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, and Alkoxy groups having 1 to 20 carbon atoms, such as 3-butoxy, octyloxy, and dodecyloxy, or alkoxy groups having substituents, such as ethoxyethoxy. The fluorenyl group includes, for example, ethenyl , Propionyl, benzamidine and the like. Examples of the fluorenyl group include acetamido and propylamino , Benzamidine, etc. Sulfonamido groups include, for example, methanesulfonamido, ethanesulfonamido, and carbon atoms of 1 to 4 sulfonamido, p-toluenesulfonamido, substituted or unsubstituted. , Substituted benzenesulfonylamino, aryl such as phenyl, tolyl, naphthyl, etc. oxycarbonyl groups such as fluorenyloxycarbonyl, ethoxycarbonyl, ethoxyethenylcarbonyl, octyloxy Alkylcarbonyl, dodecylcarbonyl, and the like have 2 to 20 alkanoylcarbonyl groups. Examples of the alkoxy group are propionyloxy, octyloxy, and benzyloxy. Aralkyls, such as substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, etc., have 7 to 15 carbon atoms. Preferred substituents of aralkyl are, for example, the same as those described above. The same applies to each group. R31 to R35, r36 to r42, and R43 to R51 in R31 to r51 may have 2 -134- 594383. 5. Description of the invention (133) Bond formation is made of carbon and / or heteroatoms. 5 to 8 carbocycles, such as cyclohexane, pyridine, furan, or batches. Moreover, X and Y may be bonded to residues of other sulfonium imine sulfonate compounds to form two Polymer, Terpolymer. Other sulfonium imine sulfonate is, for example, a compound represented by the general formula (A-6), and X or Y is a monovalent group. The alkyl group of X is, for example, linear or branched carbon number 1 to 10 alkylene groups or monocyclic or polycyclic cyclic alkylene groups which may contain heteroatoms. Linear or branched alkylene groups such as methyl, ethyl, propyl, or octyl, etc. Preferred substituents of the alkyl group are, for example, alkoxy, fluorenyl, methylamidino, nitro, fluorenylamino, sulfonamido, halogen atom, aryl, and alkoxycarbonyl. The alkane exemplified here An oxygen group, a nitro group, a nitro group, an acid group, an aryl group, an aryl group, and an oxo group are synonymous with those exemplified by R31 to R5i. A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, Iodine atom. Examples of the cyclic alkylene group include 4 to 8 carbon atoms such as cyclopentyl and cyclohexyl, and monocyclic cycloalkylene groups such as 7-carbonyl bicyclic [2. 2. 1] 5 to 1 carbon atoms such as heptyl. 5 polycyclic ethylene radicals, preferred substituents of the cycloalkylene radicals such as 1 to 4 carbons, alkyl, alkoxy, fluorenyl, methylamidino, nitro, fluorenylamino, sulfonamido, Halogen atom, aryl, alkoxycarbonyl. The alkoxy, fluorenyl, nitro, fluorenyl, sulfonamido, aryl, and ethoxy curtain groups exemplified herein are synonymous with those exemplified herein. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the arylene group include a phenylene group and a naphthyl group. Examples of preferred substituents for aryl groups such as noctyl, nodicyloxy, fluorenyl, formamyl, nitro, fluorenylamino, and sulfonamide

-135- 594383 V. Description of the invention (134) group, halogen atom, aryl group, alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, fluorenyl group, nitro group, fluorenylamino group, sulfonylamino group, and aryl fetoxyfluorenyl group exemplified herein are synonymous with those exemplified herein. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The alkenyl group is, for example, 2 to 4 carbon atoms. For example, the preferred substituents of the alkenyl group such as vinylene group and butylene group are alkyl group, alkoxy group, fluorenyl group, formamyl group, nitrate, etc. Group, sulfonylamino group, sulfonylamino group, halogen atom, aryl group, and oxocarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, fluorenylnitro group, fluorenylamino group, sulfonylamino group, aryl group, and oxocarbonyl group exemplified herein have the same meanings as those exemplified herein. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Cyclic alkenyl groups include, for example, cyclopentenyl, cyclohexenyl, and the like. The number of carbon atoms is 4 to 8 monocyclic cycloalkenyl, 7-carbonyl bicyclic [2 2. " Polycyclic cycloalkenyl having 5 to 15 carbon atoms such as alkenyl. The aralkyl group is, for example, a tolyl group, an xylylene group, or the like, and the substituent is, for example, an arylene group. Specific examples (A-6-1) to (A-6-49) of the compounds represented by these general formulae (A-6) are described below, but the present invention is not limited thereto. -136- 594383 V. Description of the Invention (135)

〇

NO,

-137- 594383 V. Description of the Invention (136) 〇

NHAc

(A-6-7) 〇

Γ

Ph

N-OS〇2-Me (A-6-9)

N ~ OSO9 — Et (A-6-10) -138- 594383 V. Description of the invention (137

〇 OHC

0

COMe

〇 NHS02Me

〇

OMe-139- 594383 V. Description of the invention (138 〇

Me

Hair OMe

J〇T NHAc α

NO〇 (A-6-20) -140- 594383 V. Description of the invention (139 〇

~ Όγ OMe 〇

Me

N-0S02Me 0 (A-6-24) 〇

Me -141-594383 V. Description of the invention (14.0)

Η I N- OS〇2 n-CgH ^ y b (A-6-26)

Me〇

NO, 〇

OMe 0: N-OS〇: 〇 ~ " 0 ^ N〇2 (A-6-29) 〇: N-〇S〇 0

Cl (A-6-30) 〇

OMe -142- 594383

594383 V. Description of the invention (142 〇 n-C8H17

N—0S02 0

(A-6-37) 〇 C

-〇-Me ο

Me,

Me〆

Ph.

Ph〆 n-oso2 OMe

O (A-6-39) 〇 n-oso2

Me 0 (A-6-40) -144- 594383 V. Description of the invention (143) 〇 MeO 0 COOMe

〇

-145- 594383 V. Description of the invention (144) The compound represented by the general formula (A-6) can be prepared by G_F.] Aubert, Ber. 28, 360 (1895), DE Ames et al., J. Chem. Soc .. 3518 (1955) method, or MAStolberg et al., 1.800 (1: 111.300 :: 79, 26 1 5 (1 9 5 7) method, etc. synthesized | ^ The hydroxyammonium imine compound and the sulfonic acid chloride are synthesized under basic conditions by, for example, L. Bauer et al.] Or g. Chem. 24, 1294 (1959). The general formula (7) Ar, Ah in the general formula (7) of the acid generator may be the same or different, substituted or unsubstituted aryl groups. Here, the aryl group includes, for example, phenyl, tolyl, naphthyl, etc. Substitution of aryl Examples of the group include an alkyl group, a cycloalkyl group, an alkoxy group, a fluorenyl group, a methylfluorenyl group, a nitro group, a fluorenylamino group, a sulfonylamino group, a halogen atom, an aryl group, an alkoxycarbonyl group, and the like. Nominal, cyclic, molybdenum, oxo, fluorenyl, formamidine, nitro, fluorenylamino, fluorenylamino, halogen atom, aryl, fluorenyloxy group are synonymous with those exemplified above. Halogen atom Examples include fluorine, chlorine, bromine, and iodine. Specific examples of the acid generator represented by the general formula (A-7) are, for example, the compounds (A_7-1) to (A-7-14) shown below. However, the present invention is not limited thereto. -594383 V. Description of the invention (145 C1 (A-7-1)

Cl h3c—S〇2— S02— (A-7-2) CH, h3co ~ ^^-so2—so2 (A-7-3)

och3 H3C S〇2- S02 ~ ^^^ ~ *-· (A-7 -4) f3c ~ {3 ~ s〇2_ S〇2 ~ C ^

Hb ^ O

S02 —SO ·: (A-7-5) S〇2—S02 (A-7-6) S02—S02_ (A-7-7)

a

Cl CF3

'ο S〇2—S02 — (\ /) — Cl (A-7-8) -147- 594383 V. Description of the invention (146 οα S〇2— S〇2 ο CH, (A-7-9) OCH ,

Cl

S02—S〇2— ^ (A-7-10)

och3-^^ S0-S02-^^

HC h3c (A-7-12) F F 'J so2- so2-^^-f f ^ f F F (A—7-13)

The synthesis of the acid generator represented by the above general formula (A-7) is, for example, GCDenser, Jr., etc., "Journal of Organic Chemistry", 31, 3418 ~ 3419 (1966) Documented method, Di · 148-594383 V. Description of the invention (147) T. P. Η 1 1 di tch by "J 〇U rna 1 0 fthe Chemical Society" 93, 1524 ~ 1527 (1908), or the method described in "Berich te der Deutschen Chenιs chen Gese1 1schaft" by O. Hinsberg 49.2 5 9 3 ~ 2 5 94 (1 9 1 8) And so on. In other words, a method using a cobalt sulfate in an aqueous sulfuric acid solution, a method using a sulfinic acid represented by the general formula (a), a method using ethyl gutoxonate, and a method using a sulfonic acid chloride represented by the general formula (b). Or a method of synthesizing a sulfenic acid represented by the general formula (a) and a sulfonic acid chloride represented by the general formula (b) under basic conditions. A r}-S 02H (a) Ar2-S〇2C1 (b) (wherein Ar! And Bay 1 * 2 are the same as defined by the general formula (A-7)) Among the acid generators represented by the formulae (A-1) to (A-7), the acid generators represented by the general formulae (A-1) to (A-5) are preferable, and the more preferable one is (A-1) ~ (A-4) An acid generator as shown in FIG. This can make the resolution and sensitivity more excellent. In the present invention, the acid generator (preferably, the content of the compound represented by the general formulae (A-1) to (A-7) in the composition) is 0.1 for the solid content of the entire composition. ∼25% by weight is preferable, 1∼15% by weight is more preferable, and 2∼10% by weight is most preferable. An organic basic compound can be used in the composition of the present invention. This can improve the stability during storage and reduce the line width variation by using PED. The preferred organic basic compounds used in the present invention are those which are more experimental than phenol. -149- 594383 5. Explanation of the invention (148). Among them, nitrogen-containing basic compounds are preferred. A preferable chemical environment has, for example, the structures shown in the following (A) to (E). R251 R250—A —R252 ... (A) Among them, R25 (), R251 and R252 may be the same or different hydrogen atom, alkyl group having 1 to 6 carbon atoms, amino alkyl group having 1 to 6 carbon atoms, A hydroxyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R251 and R 2 5 2 may be bonded to each other to form a ring. One N — C = N—… (B) 1 1 = C——N = C—— (C) 1 1 = C—N —... (D) R254 r255 ... (E) | j. „R256 'wherein R253, R254, R255, and R 2 5 6 may be the same or different alkyl groups having 1 to 6 carbon atoms. More preferred compounds are nitrogen-containing cyclic compounds (referred to as cyclic amine compounds), or Nitrogen-containing basic compounds having more than two nitrogen atoms in different chemical environments in one molecule. Cyclic amine compounds are more preferably polycyclic. The preferred cyclic amine compounds are -150- 594383 V. Description of the invention (149 ) Form is, for example, a compound represented by the following general formula (F).

(Wherein, γ and z each represent a substituted straight chain, branched chain, or cyclic alkylene group which may contain a halogen atom.) Here, the hetero atom is, for example, a nitrogen atom, a sulfur atom, or an oxygen atom. As the alkylene group, 2 to 10 carbons are preferable, and 2 to 5 are more preferable. Examples of the alkylene substituent include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Specific examples of the compound represented by the general formula (F) include compounds shown below.

Among the above, 1,8-diazobicyclo [54, 〇] undecane-7-ene, and 5-5-diazobicyclo [4.3 · 〇] nonene are more preferred. Nitrogen-containing basic compounds having two nitrogen atoms of different chemical environments in one molecule are more preferably compounds containing both substituted or unsubstituted amine groups and nitrogen atom-containing ring structures or compounds having alkylamine groups. . Preferred specific -151-V. Description of the invention (15) For example, substituted or un-Frwr steep, substituted or unL, substituted or unsubstituted amine strong amine, hepatic amine Pyridine, substituted or unselected one, ^ D k, substituted or unsubstituted imidazole, substituted or substituted, sitting, substituted or unsubstituted, coercion, substituted: , Substituted or unsubstituted purha, substituted or unsubstituted: Midazoline, substituted or unsubstituted orally, or substituted or unterminally substituted piperazine, substituted or unsubstituted Substituted aminomorpholine, substituted or substituted aminokylmorpholine, and the like. Preferred substituents are amine, amine alkyl, alkyl amine, amine aryl, aryl amine, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryloxy, nitrate Group, hydroxy, cyano. More preferred compounds are, for example, guanidine, 丨, dimethyl guanidine, 1, ^,% tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethyl Hydrazidine, 4-monomethylaminolatidine, 2-diethylaminolatidine, 2aminomethyl) pyridine, 2-amino-3 -methylpyridine, 2 -Amine-4 -methylradine, 2 -Fee-5 -methyl (¾dine, 2-amino-6 -methylttDine, 3-aminoethylpyridine, 4-amine Ethylpyridine, 3-aminopyrrolidine, piperin, N- (L-aminoethyl) piperidine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6 , 6-tetramethylpiperidine, 4-piperidinylpiperidine, 2-iminopyrimidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyridine Azole, 5-amino-3 -methyl-1 -p-tripyrazole, pyridine, 2- (aminomethyl) -5 -methylpyridine, pyrimidine, 2, 4-diaminopyrimidine, 4, 6-dihydroxypyrimidine, 2-pyrazoline, 3-pyroxyline, N-amino molybdenum, N- (2-i-feminylethyl) morphine, dimethyl odor, triphenyl Butimidazole, methyldiphenylimidazole, etc. are not limited to these. -152- ---- 594383 V. Description of the invention (151) These nitrogen-containing basic compounds can be used alone or in combination of two or more. The amount of nitrogen-containing basic compounds used is based on the solid content of the composition. It is usually from 0. 00 1 to 10% by weight, and more preferably from 0. 0 1 to 5% by weight. If it is less than 0.001% by weight, the above-mentioned addition effect of the nitrogen-containing basic compound cannot be obtained. At 10% by weight, the sensitivity tends to decrease or the developability of the non-exposed portion tends to deteriorate. The chemically amplified positive-type photoresist composition of the present invention may further contain a surfactant, a dye, and a pigment as required. , A plasticizer, a photosensitizer, and a compound having two or more phenolic groups that promote solubility in a developing solution. The photosensitive resin composition of the present invention preferably contains a surfactant. Specific examples include Polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, polyethylene oxide oleyl ether, etc., polyethylene oxide alkyl ethers, polyethylene oxide Poly (ethylene oxide) alkyl octyl phenol ether, polyethylene oxide nonyl phenol ether, etc. Ethers, polyethylene oxide • polypropylene oxide block copolymers, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate Acid esters, sorbitol trioleate, sorbitol monostearate, etc. sorbitol fatty acid esters, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol mono Polyepoxy groups of palmitate, polyethylene oxide sorbitol monostearate, polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, etc. Non-ionic surfactants such as sorbitol fatty acid esters, Yebu Dunpu EF 3 0 1, EF 3 0 3, EF 3 5 2 (made by Shin Akita Kasei Co., Ltd.), Meka

-153- 594383 V. Description of the invention (152) FAK F171, F173, F176, F189, R0 8 (made by Dainippon Ink (stock)), Floraton FC430, FC431 (made by Sumitomo Shriyem (stock)) , Safron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, polysiloxane polymer KP -341 (Shin-Etsu Chemical Industry Co., Ltd.) (Manufactured), or acrylic or methacrylic (co) polymerized polyfluorolon No. 75, No. 95 (made by Kyoeisha Oil Chemical Industry Co., Ltd.), Dunlong Yilulu S- 3 66 (ton Longyi Chemical (stock) system) and so on. Among these surfactants, fluorine-based or silicon-based surfactants are preferred in terms of coating properties and reduction of development defects. The compounding amount of the surfactant is usually 0.1 to 2% by weight, preferably 0.01 to 1% by weight based on the solid content of all the components in the composition of the present invention. These surfactants can be used alone or in combination of two or more. In addition, the chemically amplified positive photoresist of the present invention can be added by adding the following spectroscopic sensitizers, and the acid generator used does not have absorption and is sensitized in the long wavelength range of far ultraviolet light. The i or g line has sensitivity. Suitable spectroscopic sensitizers, such as benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p, _tetraethyldiaminobenzophenone, 2- Thiothanone chloride, anthrone, 9-ethoxyanthracene, i, stilbene, perylene, phenothiagen, benzyl acridine tangerine, benzoflavin, sedoflavin-T, 9,10- Diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitropyrene, 5-nitronaphthalene, pentane, p-benzoquinone, 2-chloro-4-nitroaniline, N-acetamidine P-nitroaniline, p-nitro

-154 · 594383 V. Description of the Invention (153) Aniline, N-Ethyl-4, nitro-1, naphthylamine, bitteramine, anthraquinone, 2-ethylanthraquinone, 2- 3rd-butyl Anthraquinone, 1,2-benzoanthraquinone, 3-methyl-1,3-diaza-1,9-benzoanthrone, diphenylmethylanthracene, 1,2-naphthoquinone, 3,3, -Carbonyl-bis (5, 7-dimethoxycarbonylcoumarin), coronabenzene and the like, but not limited to these. Compounds having two or more phenolic OH groups that promote solubility in the developing solution, such as polyhydroxy compounds, and preferred polyhydroxy compounds are phenol, resorcinol, fluorinated saccharin, 2,3,4-trihydroxy Benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 〇6, 〇6 ', 〇〇 "-ginseng (4-hydroxyphenyl) -1,3,5-triisopropyl Base benzene, ginseno (4-hydroxyphenyl) methane, ginseno (4-hydroxyphenyl) ethane, 1,1, bis (4-hydroxyphenyl) cyclohexane. The chemically amplified positive photoresist of the present invention The agent composition is prepared by dissolving each of the above components in a solvent and coating the carrier with a solvent. The available solvents are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, and formazan. Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Ν, Ν-di Methylformamide, diamine Methyl arylene, N-methylpyrrolidone, tetrahydrofuran, etc. are preferred, and these can be used alone or in combination. The substrate for the above-mentioned chemically amplified positive photoresist composition used in the manufacture of precision integrated circuit components ( For example, silicon / silicon dioxide coating) (as required, on the substrate provided with the above-mentioned antireflection film), it is coated by a suitable coating method such as a spinner, a roller-155-594383 V. Description of the Invention (154). After coating, it is exposed and fired through a predetermined hood, and a good photoresist pattern is obtained by development. The chemically amplified positive photoresist composition of the present invention can use, for example, sodium hydroxide or hydroxide Inorganic bases such as potassium, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-propylamine, triethylamine and methyldiamine Tertiary amines such as ethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, ammonium amines such as formamidine or acetamide, tetramethylammonium hydroxide, and trimethyl (2-hydroxyethyl) ammonium Hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide Compounds, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide Compounds, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and other quaternary ammonium salts, cyclic amines such as pyrrole and piperidine, and other alkaline aqueous solutions. However, the present invention is not limited to these. (Resins, acid generators, organic bases, and surfactants used in the examples) The synthesis of the resin of the present invention is a method using acetalized vinyl ether, using alcohol and Synthesis of alkyl vinyl ether by any of the acetal exchange methods. [Synthesis Example 1-1 Synthesis of vinyl ether] Ethyl vinyl ether was mixed with phenethylphenol alcohol, and mercury acetate was added to the solution at room temperature. Stir for 12 hours. After ethyl acetate, water extraction and water washing, the target acetophen vinyl ether (X ") was obtained by distillation under reduced pressure.

-156- 594383 V. Description of the Invention (155) [Synthesis Example 1-2 Synthesis of Vinyl Ether] Ethyl vinyl ether was mixed with phenethyl alcohol, and phenanthroline complex was added to it at room temperature. Stir for 20 hours. Extracted with vinegar water, washed with water, and distilled under reduced pressure to obtain the desired phenyl ether (X-1) ◦ [Synthesis Example I-3 Synthesis of vinyl ether] THF in phenylmagnesium bromide or phenyllithium In the solution, Kun # 2 _ chloroene ether, heated under reflux for 16 hours. Ethyl acetic acid, acetic acid after the water, 'the target acetophenacetic acid is obtained by steam-saturation under reduced pressure ^ [Synthesis Example I-4 ~ 6] The same knife / same as the synthesis example is appropriately selected. , Each made of vinyl ether. Palladium-1,10-acid ethyl ester, ethyl ethoxylated ethylethyl, taken and washed -1) 〇 X-2 ~ X-6-157- 594383 V. Description of the invention (156)

X-1

X-2 X-3 X-4 OCH, X- 5 X- 6 [Synthesis Example Π-1] Dissolve 32.4 g (0.2 mol) of p-ethoxybenzylbenzene in 120 ml of butyl acetate Suspected, under nitrogen gas flow and stirring, at 80 ° C, 0.03 3 g of azobisisobutyronitrile (AIBN) was added in 3 times in 2.5 hours, and finally the stirring was continued for 5 hours to carry out the polymerization reaction. The reaction solution was poured into 120 ml of hexane to precipitate a white resin. The obtained resin was dried, and then dissolved in 50 m of methanol. To this was added 7.7 g (0.19 mol sodium hydroxide) / 50m 1 of water-soluble solution -158- 594383 V. Description of the invention (157) The liquid ’was dehydrated by heating under reflux for 3 hours. Then, it was diluted by adding 200 m 1 of water, and neutralized with hydrochloric acid to precipitate a white resin. This resin was filtered, washed with water, and dried. In addition, it was dissolved in 200 m 1 of tetrahydrofuran, stirred vigorously in 5 L of ultrapure water, and then dripped and re-settled. This re-sinking operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at i 2 0 ° C for 12 hours to obtain a poly (p-hydroxystyrene) alkali-soluble resin R-1 0. The weight average molecular weight of the obtained resin was 15,000. [Synthesis Example II-2] 3 5.2 g (0.2 mol) of de-p-3-butoxy monomer and 5.21 g (0.05 mol) of 3-butylbenzene were dehydrated and distilled and purified by a conventional method. The ethylene monomer was dissolved in 100 ml of tetrahydrofuran. Under nitrogen flow and stirring, at 80 ° C, 0.03 3 g of azobisisobutyronitrile (AI BN) was added in 3 times in 2.5 hours. Finally, the stirring was continued for 5 hours to carry out the polymerization reaction. The reaction solution was poured into 1,200 ml of hexane to precipitate a white resin. The obtained resin was dried and then dissolved in 150 m 1 of tetrahydrofuran. 4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating under reflux for 6 hours, and then re-sinked in 5L of ultrapure water, and the resin was filtered, washed with water, and dried. It was dissolved in 200 ml of tetrahydrofuran, stirred vigorously in 5 L of ultrapure water, and then dripped and re-settled. This re-sinking operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / 3rd-butylstyrene) copolymer alkali-soluble resin R-159- 594383. 5. Description of the invention (158) The weight average molecular weight of the obtained resin was 1 2 0 0 0. [Synthesis Example II-3] Poly (p-hydroxystyrene) (VP80 00) manufactured by Japan Soda Co., Ltd. was used as the alkali-soluble resin R_3. The weight-average molecular weight was 9800 ° [Synthesis Example III-1] 80 ml of the alkali-soluble resin r_ 3 2 obtained in Synthesis Example II-3 was dissolved in 80 ml of propylene glycol monomethyl ether acetate (PGMEA) and distilled under reduced pressure , Azeotropic removal of water and PGMEA. After confirming that the water content was extremely low, 7.0 g of vinyl ether X-1 obtained in Synthesis Example 1-1 and 50 mg of p-toluenesulfonic acid were added, and after stirring at room temperature for 1 hour, triethylamine was added to terminate the reaction. Ethyl acetate was added to the reaction solution and washed with water, and then ethyl acetate and water 'azeotropic component PGMEA' were left under reduced pressure to obtain the alkali-soluble resin B-1 having a substituent of the present invention. The weight average molecular weight of the obtained resin was 1 1 000 ° [Synthesis Example II 1-2] Alkali-soluble resin R-3 obtained in Synthesis Example II-3 20 g of propylene glycol monomethyl ether acetate (PGMEA) 80 ml was dissolved in a flask Under reduced pressure distillation, azeotropic removal of water and PGMEA. After confirming that the water content was extremely low, 7.0 g of acetophenol and 6.5 g of 3-butyl vinyl ether and 50 mg of p-toluenesulfonic acid were added. After stirring at room temperature for 1 hour, triethylamine was added to Stop the reaction. -160-

594383 V. Description of the invention (159) After adding ethyl acetate to the reaction solution and washing it with water, ethyl acetate, water and azeotrope-containing PGMEA 'are distilled off under reduced pressure to obtain an alkali-soluble resin having a substituent according to the present invention. B-1. The weight average molecular weight of the obtained resin was 11,000.

Similarly, by using the alkali-soluble resin and vinyl ether shown in Table 1 below, the resin B-2 to B-1 of the present invention having substituents can be prepared. Similarly, the alkali-soluble resin shown in Table 1 below and Vinyl ether, the same resin as above was synthesized, and 1.5 g of pyridine and 1.5 g of acetic anhydride were added and stirred at room temperature for 1 hour to obtain the alkali-soluble resin B-13 ~ B of the present invention having substituents. -twenty four

-161-594383 V. Description of the invention (16〇) Table 1 Acid anhydride B-1 X-1 R-3 Μ ^ \ \\ B-2 X-2 R-3 sister B -3 X-3 R-3 Μ j \\\ B-4 X-4 R-3 Μ y \ \ ν B-5 X-5 R-3 Μ ^ \\\ B-6 X-6 R-3 B-7 X-1 R-2 Μ B-8 X-2 R-2 sister B-9 X-3 R-2 Μ j \\\ B-10 X-4 R-2 Μ j \ \\ B- 11 X-5 R-2 M \\ B-12 X-6 R-2 and B-13 X-1 R-3 acetic anhydride B-14 X-2 R-3 acetic anhydride B-15 X-3 R- 3 Acetic anhydride B-16 X-4 R-3 Acetic anhydride B-17 X-5 R-3 Acetic anhydride B-18 X-6 R-3 Acetic anhydride B-19 X-1 R-1 Acetic anhydride B-20 X-2 R-1 Acetic anhydride B-21 X-3 R-1 Acetic anhydride B-22 X-4 R-1 Acetic anhydride B-23 X-5 R-1 Acetic anhydride B-24 X-6 R-1 Acetic anhydride-162- 594383 V. Description of the invention (invention) In addition, 'B-24 was prepared from the corresponding alcohol and the third butyl ethyl ether using the above acetal exchange method. [Synthesis Example I-1] A resin C-1 was obtained by using an alkali-soluble resin shown in Table 2 below and ethyl vinyl ether (Y-1) represented by the following formula. Table 2 Vinyl ether dry polymer C-1 Y-1 R-3 used for resin In addition, resin C-2 uses poly (p--1-benzyloxy-1-) described in JP-A No. 8-1 23032. Methylethoxystyrene / p-hydroxystyrene / p-third-butoxystyrene). [Synthesis Example V-1] (Synthesis of D-1) 19.9 g (0.030 mol) of commercially available triaryl C1 salt (50% aqueous solution of triphenylsulfonium chloride produced by Fluk a), triphenylsulfonium, An aqueous solution of a mixture of 4,4'-bis (diphenylsulphenyl) diphenyl sulfide and the like was dissolved in 200 ml of ion-exchanged water. 400 ml of ion-exchanged water of 10.5 g (0.030 mol) of a hard type (branched type) dodecylbenzenesulfonic acid Na salt having the following structure was added under stirring at room temperature and dissolved in the solution. The precipitated viscous solid was separated with a decanter and washed with 1 L of ion-exchanged water. -163- 594383 V. Description of the invention (162) The viscous solid obtained was dissolved in 100 ml of acetone, and recrystallized in 500 ml of ion-exchanged water with stirring. The precipitate was dried under vacuum at 50 ° C. 15.5 g of a glassy solid was obtained. An acid generator (D_ 丨) was confirmed by NMR measurement to confirm that the solid was the object.

[Synthesis Example V-2] (Synthesis of D-2) 68 g (0.174 mol) of triphenylmanganese iodide and 42.5 g (0.1 83 mol) of silver oxide were dissolved in 5000 m 1 of methanol. Stir for 5 hours at room temperature. The insoluble component was filtered, and 59.4 g (0.209 mol) of triisopropylbenzenesulfonic acid was added. After stirring at room temperature for 3 hours, it was concentrated to a powder and washed with water. The obtained powder was recrystallized at ethyl acetate / acetone = 6/4 to obtain 50 g of the desired acid generator (D-2). The structure was confirmed by NMR. [Synthesis example V-3] (Synthesis of D-3) 7 g of phosphorus pentoxide and 70 g of methanesulfonic acid were stirred and mixed, dissolved, and stirred at room temperature. Add 25 grams (0.124 moles) of diphenyl sulfene and 20.4 grams (0.136 moles) of n-butoxybenzene and stir. Stir at 501: 4 hours. The obtained reaction solution was poured into 5000 m 1 of ice water, washed twice with 150 m 1 of toluene, and weakly basic with tetramethylammonium hydroxide to obtain butoxyphenyldiphenylmethane. Aqueous solution of sulfonate. After adding 1,000 ml of ethyl acetate to the mixture and stirring, 26 g (0.14 mol) of 2-sulfobenzoic anhydride was added to the solution with butanol during the period, and -164- 594383 V. Description of the invention (163 ) Stirring. Since the organic phase and water phase are separated, it is washed twice with 500 ml of a 10% tetramethylammonium hydroxide aqueous solution, and washed with water three times to dry the organic phase. Concentrate to obtain the desired acid generator (D-3). [Synthesis example V-4] (Synthesis of D-4) 1) Synthesis of tetramethylammonium pentafluorobenzenesulfonate dissolved in 25 g of pentafluorobenzenesulfonyl chloride in 100 ml of methanol under ice-cooling, and slowly added thereto 100 g of 25% tetramethylammonium hydroxide. After stirring at room temperature for 3 hours, a tetramethylammonium pentafluorobenzenesulfonate solution was prepared. This solution was exchanged with a salt of a salt of iron and iodonium. 2) The synthesis of bis (4-th-3-pentylphenyl) iodofluorene pentafluorobenzenesulfonate (D-4) makes 60 g of 3-pentylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice-cooling. After stirring under ice-cooling for 2 hours, it was stirred at room temperature for 10 hours. 500 ml of water was added to the reaction solution under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water, and then concentrated to obtain bis (4-th-3-pentylphenyl) iodine. Sulfate. This sulfate was added to an excess of tetramethylammonium pentafluorobenzenesulfonate solution. 500 m of water was added to the solution, and the solution was extracted with dichloromethane, and the organic phase was washed with 5% tetramethylammonium hydroxide aqueous solution, washed with water, and concentrated to obtain di (4-thi-pentylphenyl). ) Iodopentafluorobenzoate (D-4). [Synthesis Example V-5] (Synthesis of D-5) 50 g of diphenylimine was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. Slowly pour the reaction solution into 2L of ice.

-165- 594383 V. Description of the Invention (164) 400 ml of concentrated hydrochloric acid was added thereto, and heated at 70 ° C for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, and after filtration, 400 ml of 200 g of ammonium iodide was added. The precipitated powder was filtered, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenyl ether. Iodide. 30.5 g of triphenylphosphonium iodide was dissolved in 1,000 ml of methanol, 19.1 g of silver oxide was added to the solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered, and an excessive solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto, the reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was adjusted to 5% tetramethylammonium hydroxide Wash with water and water. The organic phase was dried over anhydrous sodium sulfate and then concentrated to obtain triphenylchloropentafluorobenzenesulfonate (D-5). [Synthesis Example V-6] (Synthesis of D-6) 50 g of triaryl chlorochloride (triphenyl chlorochloride manufactured by Fluka) was dissolved in 5000 ml of water, and an excessive amount of tetramethyl pentafluorobenzenesulfonic acid was added thereto. An ammonium salt solution can precipitate an oily substance. The upper layer of clarifying solution was removed by a decanter, and the obtained oily substance was washed with water and dried to obtain triaryl pentafluorobenzene sulfonate (D-6). Furthermore, as the acid generator D-7, JP 8- 1-diazo-1-methylsulfonyl-4-phenylbutane-2-one described in JP 1 2 3 0 3 2. For the organic base, the following structures (E-1), (E-2), and (E-3) were used. -166- 594383

As the surfactant (F-1), Mekafak R08 (manufactured by Dainippon Ink Co., Ltd.) was used. As the surfactant (F-2), Dunlong Yiluolu s-3 6 6 (made by Dunlong Yilu Chemical Co., Ltd.) was used. [Examples 1-2 2. Comparative Examples 1 to 3] [Preparation and evaluation of photosensitive composition] Each raw material represented by the following Table 3 was dissolved in 8 g of PGMEA (propylene glycol monomethyl ether acetate), and Filter through a 0.2 μm filter to make a photoresist solution. Moreover, the amount of the surfactant used was 0.035 g. Each photoresist solution was coated on a silicon wafer with a spin coater, and dried at 130 ° C. for 60 seconds with a vacuum adsorption hot plate to obtain a photoresist film having a film thickness of 0.3 μm. -167- 594383 V. Description of the invention (166) Table 3 Resin resin amount (g) acid generator acid generation dose (g) organic test organic base (g) surfactant Example 1 B-1 2.0 D-1 0.1 E-2 0.002 F-2 Example 2 B-2 2.0 D-1 0.1 E-2 0.002 F-1 Example 3 B-3 2.0 D-1 0.1 E-3 0.002 F-1 Example 4 B-4 2.0 D-1 0.1 E-2 0.002 F-1 Example 5 B-5 2.0 D-2 0.1 E-1 0.002 F-2 Example 6 B-6 2.0 D-3 0.1 E-2 0.002 F-1 Example 7 B-1 2.0 D-2 / D-3 0.1 E-2 0.002 F-2 Example 8 B-2 2.0 D-2 / D-3 0.1 E-2 0.002 F-1 Example 9 B-3 2.0 D- 2 / D-3 0.1 E-2 0.002 F-1 Example 10 B-4 2.0 D-2 / D-3 0.1 E-2 0.002 F-2 Example 11 B-5 2.0 D-2 / D-3 0 1 E-2 0.002 F-1 Example 12 B-6 2.0 D-2 / D-3 0.1 E-2 0.002 F-1 Example 13 B-1 2.0 D-4 0.1 E-2 0.002 F-2 Implementation Example 14 B-2 2.0 D-5 0.1 E-2 0.002 F-2 Example 15 B-3 2.0 D-4 0.1 E-3 0.002 F-1 Example 16 B-4 2.0 D-5 0.1 E-2 0.002 F-1 Example 17 B-5 2.0 D-4 0.1 E-2 0.002 F-2 / F-1 Example 18 B-6 2.0 D-2 / D-4 0.1 E-2 0.002 F-2 / F- 1 Example 19 B-6 2.0 D-2 / D-6 0.1 E-2 / E-3 0.002 F- 2 Example 20 B-6 2.0 D-2 / D-5 0.1 E-2 / E-3 0.002 F-2 Example 21 B-6 2.0 D-4 / D-5 0.1 E-3 0.002 F-1 Implementation Example 22 B-6 2.0 D-2 / D-3 0.1 E-1 / E-2 0.002 F-1 Comparative Example 1 C-1 2.0 D-2 0.1 E-2 0.002 — Comparative Example 2 C-2 2.0 D- 7 0.1 E-2 0.002 — Comparative Example 3 C-1 2.0 D-7 0.1 E-2 0.002 — -168- 594383 V. Description of the invention (167) Table 2 shows D-2 / D-3, D-2 / D-4, D-2 / D-6, D-2 / D-5, D-4 / D-5 are all used at a ratio of 50:50. The ratio of F-2 / F-1 in Example 17 and 18 was 50:50. The use ratio of E-2 / E-3 in Examples 19 and 20 was 60:40. The use ratio of E-1 / E-2 of Example 22 is 50:50. These usage ratios are the same as in Table 5. The photoresist film was irradiated with an electron beam irradiation device (acceleration voltage: 50 KeV). After the irradiation, it was heated on a 100 ° C hot plate for 60 seconds, then immersed in a 0. 26N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and washed with water for 30 seconds to dry. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope and the performance of the photoresist was evaluated. The results are shown in Table 4. The resolution indicates the critical resolution of the exposure amount that reproduces the mask pattern of the 0.15 μm line and the gap. The obtained photoresist pattern was observed with an optical microscope or SEM, and the reverse cone shape of the photoresist pattern was observed. The inverse taper of the pattern is very rare (almost rectangular outline) is ◎, the less is 0, and the inverse taper of the pattern is obvious to the observer X. The photoresist film obtained above was allowed to stand in an electron beam irradiation device under high vacuum for 240 minutes, and then exposed and developed in the same manner as described above to form a photoresist pattern. The critical resolution line width (A) of the pattern obtained by placing it under high vacuum for 240 minutes as described above and the critical resolution line width (B) of the pattern obtained without placing it under high vacuum were measured, and the rate of change was calculated as follows. The smaller the salamander, the better. Change rate = {1-丨 (B)-(A) I / (B)} X 100

-169- 594383 V. Description of the invention (168) Table 4 Example No. Resolution (&quot; m) Photoresist pattern shape line width change rate (%) 1 0.13 ◎ &lt; 2 2 0.12 ◎ &lt; 2 3 0.12 ◎ &lt; 2 4 0.12 〇 &lt; 2 5 0.13 〇 &lt; 2 6 0.12 ◎ &lt; 2 7 0.12 〇 &lt; 2 8 0.12 ◎ &lt; 2 9 0.13 〇 &lt; 2 10 0.13 〇 &lt; 2 11 0.13 ◎ &lt; 2 12 0.12 ◎ &lt; 2 13 0.13 〇 &lt; 2 14 0.12 ◎ &lt; 2 15 0.13 〇 &lt; 2 16 0.13 〇 &lt; 2 17 0.12 ◎ &lt; 2 18 0.12 〇 &lt; 2 19 0.13 〇 &lt; 2 20 0.12 ◎ &lt; 2 21 0.13 〇 &lt; 2 22 0.12 ◎ &lt; 2 Comparative Example 1 0.12 X 8 Comparative Example 2 0.13 X 10 Comparative Example 3 0.13 X 8 -170- 594383 V. Description of the invention (169) As a result, it can be seen that the positive electron photoresist composition of each example in the present invention can obtain satisfactory results. 'The electron photoresist composition of each comparative example, especially the photoresist pattern shape and Line width fluctuations are unsatisfactory. (Example 2 3 to 5 6 and Comparative Examples 4 to 6) Except for the resins that prepared the structural units shown by the general formulae (I), (II), and (III) shown in Table 5 below, they were the same as those in Examples 1 to 2 2 Photoresist solution was made in the same way, and a photoresist film of 0.3 μm was obtained in the same way. In the same manner as in Examples 1 to 22, the evaluation results regarding the resolution, the photoresist pattern profile, and the line width variation in the vacuum chamber due to the standing time are shown in Table 6. -171-594383 V. Description of the invention (17〇) Table 5 Resin Resin 0 Composition ratio Resin amount (g) Acid generator acid generator dosage (g) Organic base Organic base amount (g) Surfactant Example 23 B-13 20/10/70 2.0 D-1 0.1 E-2 0.002 F-2 Example 24 B-14 18/10/72 2.0 D-1 0.1 E-2 0.002 F-1 Example 25 B-15 20/10 / 70 2.0 D-1 0.1 E-3 0.002 F-1 Example 26 B-16 20/10/70 2.0 D-1 0.1 E-2 0.002 F-1 Example 27 B-17 18/10/72 2.0 D- 2 0.1 E-1 0.002 F-2 Example 28 B-18 20/10/70 2.0 D-3 0.1 E-2 0.002 F-1 Example 29 B-7 15/7/78 2.0 D-1 0.1 E- 3 0.002 F-1 Example 30 B-8 15/7/78 2.0 D-2 0.1 E-2 / E-3 0.002 F-2 Example 31 B-9 15/7/78 2.0 D-2 0.1 E- 3 0.002 F-1 Example 32 B-10 17/7/25 2.0 D-3 0.1 E-2 / E-3 0.002 F-1 Example 33 B-11 17/7/78 2.0 D-1 0.1 E- 2 0.002 F-1 Example 34 B-12 15/7/78 2.0 D-2 0.1 E-2 / E-3 0.002 F-1 Example 35 B-19 18/10/72 2.0 D-3 0.1 E- 2 0.002 F-2 Example 36 B-20 18/10/72 2.0 D-1 0.1 E-2 0.002 F-1 Example 37 B-21 20/10/70 2.0 D-2 0.1 E-3 0.002 F- 1 Example 38 B-22 20/10/70 2 .0 D-3 0.1 E-2 0.002 F-2 Example 39 B-23 18/10/72 2.0 D-1 0.1 E-3 0.002 F-1 Example 40 B-24 18/10/72 2.0 D- 1 0.1 E-2 0.002 F-1 Example 41 B-14 18/10/72 2.0 D-2 0.1 E-2 0.002 F-1 Example 42 B-14 18/10/72 2.0 D-3 0.1 E- 2 0.002 F-2 Example 43 B-14 18/10/72 2.0 D-4 0.1 E-2 0.002 F-1 Example 44 B-14 18/10/72 2.0 D-5 0.1 E-2 0,002 F- 1 Example 45 B-14 18/10/72 2.0 D-6 0.1 E-3 0.002 F-1 Example 46 B-12 15/7/78 2.0 D-1 0.1 E-2 0.002 F-1 Example 47 B-12 15/7/78 2.0 D-3 0.1 E-2 0.002 F-2 Example 48 B-12 15/7/78 2.0 D-4 0.1 E-2 0.002 F-2 Example 49 B-12 15 / 7/78 2.0 D-5 0.1 E-3 0.002 F-1 Example 50 B-12 15/7/78 2.0 D-6 0.1 E-2 0.002 F-1 Example 51 B-14 18/10/72 2.0 D-2 / D-3 0.1 E-2 0.002 F-2 / F-1 Example 52 B-12 15/7/78 2.0 D-2 / D-3 0.1 E-2 0.002 F-2 / F- 1 Example 53 B-14 18/10/72 2.0 D-2 / D-3 0.1 E-2 / E-3 0.002 F-2 Example 54 B-12 15/7/78 2.0 D-2 / D- 3 0.1 E-2 / E-3 0.002 F-2 Example 55 B-14 18/10/72 2.0 D-2 / D-3 0.1 E-3 0.002 F-1 Example 56 B-12 15/7 / 78 2.0 D-2 / D-3 0.1 E-2 / E-3 0.002 F-1 Comparative Example 4 C-1 40/0/60 2.0 D-2 0.1 E-2 0.002-Comparative Example 5 C-2 30/10/60 2.0 D-7 0.1 E-2 0.002- Comparative Example 6 C-1 40/0/60 2.0 D-7 0.1 E-2 0.002--172- 594383 V. Description of the invention (17〇 Table 6 Example No. Resolution (μιη) Photoresist pattern shape line width variation Rate (%) 23 0.12 ◎ &lt; 2 24 0.12 ◎ &lt; 2 25 0.13 〇 &lt; 2 26 0.12 ◎ &lt; 2 27 0.12 〇 &lt; 2 28 0.12 〇 &lt; 2 29 0.13 ◎ &lt; 2 30 0. 12 〇 &lt; 2 31 0.12 〇 &lt; 2 32 0.12 〇 &lt; 2 33 0.13 〇 &lt; 2 34 0.12 ◎ &lt; 2 35 0.12 〇 &lt; 2 36 0.13 〇 &lt; 2 37 0.12 〇 &lt; 2 38 0.13 ◎ &lt; 2 39 0.12 〇 &lt; 2 40 0.12 〇 &lt; 2 41 0.13 ◎ &lt; 2 42 0.13 〇 &lt; 2 43 0.12 ◎ &lt; 2 44 0.13 〇 &lt; 2 45 0.12 〇 &lt; 2 46 0.12 ◎ &lt; 2 47 0.13 〇 &lt; 2 48 0.12 〇 &lt; 2 49 0.12 ◎ &lt; 2 50 0.13 〇 &lt; 2 51 0.13 〇 &lt; 2 52 0.12 ◎ <2 53 0.12 〇 &lt; 2 54 0.12 〇 &lt; 2 55 0.13 ◎ &lt; 2 56 0.12 〇 &lt; 2 Comparative Example 4 0.12 X 10 Comparative Example 5 0.13 X 8 Comparative Example 6 0.12 X 10 -17 3- 594383 V. Description of the invention (172) From the results in Table 6, it can be seen that the positive electron beam photoresist composition of each embodiment of the present invention, in particular, can improve the photoresist pattern profile, Satisfactory results were obtained for the line width variation of the placement time, but the electronic line photoresist composition of each comparative example, especially the photoresist pattern profile, could not be caused by the line width variation of the placement time in a vacuum chamber. The person satisfies the effect of the present invention. The present invention provides a chemically amplified positive electron beam photoresist composition having a contour of a photoresist pattern and an improved line width variation due to a standing time in a vacuum chamber. -174-

Claims (1)

594383 λ The scope of the patent application is supplemented with the patent case No. 90 1 3 1 484 "Positive Electron Wire Photoresist Composition" (as amended on October 31, 1992) Λ The scope of patent application: 1. A positive electronic wire A photoresist composition includes: (a) a resin having a structural unit containing a group represented by the following general formula (X) and decomposed by an acid to increase solubility in an alkali developing solution, and (b) At least one of the following general formulae (eight-l), (A-2), (A-3), (A-4), (A-5), (A-6) ) &amp; (A-7) m * compound,, -〇——C (X) I urge you to make it clear that #iitunt In formula (X), R1 and R2 represent the same or different hydrogen atoms and alkyl groups having 1 to 4 carbon atoms, and R3 and R4 represent the same or different hydrogen atoms and may have substituents. Straight-chain, branched-chain, and cyclic alkyl, R5 represents a linear, branched, cyclic alkyl, aryl that may have a substituent, aralkyl that may have a substituent, and m represents 1 to An integer of 20, n represents an integer of 0 to 5, Scope of patent application (A-2) In the formulae (Al) and (A-2), the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, _ prime atom, or _S-R6, R6 袠 not Academic group, or aryl group, x_ means at least one alkyl group and alkoxy group with at least one branched or cyclic carbon number of 8 or more, or at least 2 linear, branched or cyclic carbons 4 to 7 alkyl and alkoxy groups, or at least 3 groups selected from linear or branched carbon with 1 to 3 alkyl and alkoxy groups, or 1 to 5 halogen atoms Benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid anion having a linear or branched ester group with 1 to 10 carbon atoms, -2- 594383 t, patent application scope (A-3) In the formula (A-3), R7 to h. Each represents the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, or halogen atom, XIS has the same meaning as above, m, η, p, and q each represent an integer of 1 to 3, In the formula (A-4), .RM to R13 represent the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, halogen atom or -S-R6 group, and R6 and X · are synonymous with the above. , 1, m, and η may be the same or different integers of 1 to 3. When l, m, and η are each 2 or 3, 2 of each of 2 to 3 Rh to R13 are bonded to each other to form a carbon-containing ring, A ring formed by 5 to 8 elements of a heterocyclic ring or an aromatic ring, -3- 594383 This year, the month and the month of the amendment / f fp / supplementary patent application scope X (Rl5) n3 (A-5) In the formula (A-5), R14 to R16 represent the same or different hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, halogen atom or _S_R6 group, and R6 and X- are synonymous with the above, 1, De and n can be the same or different integers of 1 to 3. When 1, m and η are each 2 or 3, 2 to 3 Rm to R] each of 2 is bonded to each other to form a carbon-containing ring, hetero A ring formed by 5 to 8 elements of a ring or an aromatic ring, 0 X // XsN—0S02Y Ο (A-6) @ y ψ, γ represents a linear, branched, cyclic alkyl group, a substituted aralkyl group, which may have a substituent, Application scope of patent R49 The groups shown (r31 to r51 represent the same or different hydrogen atoms, linear, branched, cyclic alkyl, alkoxy, alkoxy, fluorenyl, fluorenylamino, sulfonamido, and aryl groups which may have substituents) , Fluorenyl, aralkyl or alkoxycarbonyl, or methylol, nitro, chlorine, bromine, iodine, warp, or cyano, Rn ~ R35, R36 ~ R42, and R43 ~ R51 In each group, two bonds are formed to form a 5 to 8 carbocyclic ring formed by a hydrogen atom and / or a heteroatom), and γ may be bonded to the residues of other sulfonium imine sulfonate compounds. X means that Substituent straight chain, branched chain alkylene, heteroatom-containing monocyclic or polycyclic cyclic alkylene group which may have substituent, straight chain which may be substituted, branched chain alkenyl group, which may be substituted Heteroatomic monocyclic or polycyclic cyclic alkenyl, arylene which may be substituted, arylene which may be substituted, and X may be bonded to other sulfonyl imide sulfonate residues, -5 -594383 彳, one year and one month) I said correction / heavier 7m: Six, the scope of patent application A r] S 0 2 — S Ο μ — A r 2 (A-7) In the formula (A-?), ΑΓι, Ah means the same or different Substituted or non-substituted aryl group. —A kind of positive electron beam photoresist composition, including: (a) having the following general formula (1), general formula (11), and general formula (ΠΙ); Resin that is soluble in alkaline imaging solution, (b) Compound K21 I that produces acid by electron beam irradiation R21 I (CH2 — c &gt; In the formulae (1) to (III), R2 1 represents a hydrogen atom or a methyl group; R2 2 represents a group that does not decompose by the action of an acid; R23 represents a hydrogen atom, a functional element atom, a radical, an aryl group, an alkoxy group, A fluorenyl group or a fluorenyl group, η represents an integer of 1 to 3, and W represents a group other than the general formula (X). 1-6-594383 6. Scope of patent application 3. For example, the positive electron beam photoresist composition in the scope of patent application item 2, wherein the structure shown by the general formula (I), general formula (II) and general formula (III) The ratio of the unit can satisfy the following conditions (1) to (4), ① 0. 10 &lt; (I) / (I) + (II) + (III) &lt; 〇.25 ② 0.〇1 &lt; (II ) / (I) + (II) + (III) &lt; 0 · 15 ③ ⑴ &gt; (II) ④ 0 · 5 &lt; (I) / (I) + (II) &lt; 0.85 where (I), (II) and (III) are Mohr fractions each representing a structural unit represented by the general formula (I), the general formula (Π), and the general formula (III). 4. The positive electron beam photoresist composition according to item 2 or 3 of the scope of patent application, wherein (b) the compound that generates an acid by irradiation with an electron beam is at least one of the following that generates a sulfonic acid by irradiation with an electron beam Compounds represented by the general formulae (A-1), (A-2), (A-3), (VI-4), (VI-5), (VI-6) and (VI-7), r3 (A-1) 594383, in the patent application formulae (A-1), (A-2), R! ~ R5 represents the same or different hydrogen atom, a radical 'cycloalkyl, an alkoxy group, a hydroxyl group, a halogen atom, or -S_R6, Heart represents an alkyl group or an aryl group, and X. represents at least one selected from a branched or cyclic alkyl group having 8 or more carbon atoms and an alkoxy group, or at least 2 linear, branched, or cyclic groups. 4 to 7 alkyl and alkoxy carbons, or at least 3 selected from linear or branched 1 to 3 alkyl and alkoxy carbons, or 1 to 5 A halogen atom or an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having a linear or branched ester group having 1 to 10 carbon atoms, In the formula (A-3), R7 to R !. Each represents the same or different hydrogen atom. In the formula (A-3), κ7〜Ι ^ Synonymous, m, n, p, and q each represent an integer from 1 to 3 Rev. 594383 dated March 26/26. In the patent application formula (A-4), RH ~ R13 represents the same or different hydrogen atom, alkyl group, alkyl group, oxygen group, oxygen group, halogen Atom or -S-R6 group, R6, X — are synonymous with the above, 1, 1, and η may be the same or different integers of 1 to 3; when l, m and η are each 2 or 3, 2 to 3 Each of Rn to R13 is bonded to each other to form a ring formed by 5 to 8 elements containing a carbocyclic, heterocyclic, or aromatic ring. In the formula (A-5), R14 to R16 represent the same or different hydrogen atoms. , Courtyard, cycloalkyl, alkoxy, hydroxyl, halogen atom or -S-R6 group, R6 and X_ are synonymous with the above, l, m and η may be the same or different integers from 1 to 3, 1, When πι and η are 2 or 3 each, 2 to 3 R] 4 to R) 6 each 2 are bonded to each other to form a ring formed by 5 to 8 elements containing a carbon ring, heterocyclic ring or aromatic ring, 〇Person XN——0S02Y 〇 (A-6) -9- In the straight-chain, branched-chain, and cyclic alkyl groups of the substituted group (A-6), Y represents an optionally substituted, substituted aralkyl group, The radicals shown (R31 ~ R51 radicals, straight-chain, branched-chain, sulfonamido, aryl,% $ different or different hydrogen atoms, may have a substituted or unsubstituted k group, alkoxy group, fluorenyl group, Fluorenylamino, enzymeoxy, aralkyl or alkoxycarbonyl, or methyl iodide, hydroxyl, or cyanofluorenyl, nitro, chlorine, bromine atoms hi ~ R35, R3 6 ~ β42, and β43 ~ R5i In each group, two bonds are formed to form a 5-8 carbon ring formed by a hydrogen atom and / or a hetero atom. In addition, Y may be bonded to the residues of other sulfonium imine sulfonate compounds. X represents Substituent straight chain, branched alkylene, heteroatom-containing monocyclic or polycyclic cyclic alkylene with substituent, straight-line bond that can be substituted-10- 594383 This year (October Introduce amendments / submissions 6. Scope of patent application, branched alkenyl, heterocyclic monocyclic or polycyclic cyclic alkynyl, substitutable arylene, substitutable arylene Alkyl, and X may be bonded to other sulfonium imine sulfonate residues. Ar, -S02-S0, ~ Ar2 (A — 7) where A r I and A r 2 represent the same Or different, substituted or not Substituted aryl groups. 5. The positive electron beam photoresist composition according to any one of claims 1 to 3 in the scope of patent application, which further contains a cyclic amine compound. 6 · As in the scope of claims 1 to 3 in the scope of patent application The positive-electron-ray photoresist composition of any one, which further contains a fluorine-based surfactant, a silicon-based surfactant, or both. 7. As described in any one of the claims 1 to 3 The positive electron beam photoresist composition further contains a compound which is decomposed by an acid to increase the solubility in an alkali image liquid. -11-