TW201027245A - Resist composition, method of forming resist pattern, compound and acid generator - Google Patents

Abstract

A compound represented by general formula (b1-11) shown below: wherein R7'' to R9'' each independently represents an aryl group or an alkyl group, wherein two of R7'' to R9'' may be bonded to each other to form a ring with the sulfur atom in the formula, and at least one of R7'' to R9'' represents a substituted aryl group in which a part or all of the hydrogen atoms have been substituted with alkoxycarbonylalkyloxy groups; and X- represents an anion. An acid generator comprising the compound. A resist composition including: a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid; and an acid-generator component (B) which generates acid upon exposure, wherein said acid-generator component (B) includes an acid generator (B1) composed of the compound.

Description

[Technical Field] The present invention relates to a photoresist composition, a method for forming a photoresist pattern using the photoresist composition, and a compound suitable as an acid generator for a photoresist composition. And an acid generator formed from the compound. The present application claims priority based on Japanese Patent Application No. 2008462286, filed on Oct. 8, 2008, the content of which is incorporated herein by reference. [Prior Art] In the lithography technique, for example, a photoresist film obtained from a photoresist material is formed on a support such as a substrate, and a light-shielding film is formed on the photoresist film by forming a mask of a specific pattern. The radiation is selectively exposed, and the development process is performed to form the photoresist film into a photoresist pattern having a specific shape. The portion of the exposure which is changed to have a characteristic of being dissolved in the developer is referred to as a positive type, and the portion of the photoresist which is changed to have a property of not being dissolved in the developer is referred to as a negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography technique, the pattern has been rapidly refined. The method of miniaturization is generally carried out in such a manner as to shorten the wavelength of the exposure light source. Specifically, ultraviolet rays which are represented by g-line and i-line are conventionally used. But now it is starting to use KrF excimer lasers, or ArF excimer lasers for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUVs (polar 201027245 ultraviolet rays) or squall lines having shorter wavelengths for the aforementioned quasi-molecular lasers have also been studied. Among the photoresist materials, a lithographic etching property which reproducibly analyzes the sensitivity of the exposure light source, the pattern of the fine size, and the like, and the like is sought. The photoresist material which satisfies these requirements is generally a chemically amplified photoresist which contains a base resin which changes the solubility of an alkali developer by an action of an acid, and an acid generator which generates an acid by exposure. For example, a positive-type chemically amplified photoresist is a resin containing a resin which acts as an alkali resin to increase solubility in an alkali developing solution by an action of an acid, and an acid generator is formed by exposure during patterning of a resist pattern. When an acid generator generates an acid, the exposed portion is made alkali-soluble. The base resin of the chemically amplified photoresist is currently protected by a polyhydroxystyrene (PHS) having a high transparency to a KrF excimer laser (24 8 nm), or a hydroxyl group which is protected by an acid dissociation dissolution inhibiting group. Resin (PHS resin). However, since the PHS resin has an aromatic ring such as a benzene ring, it does not have sufficient transparency for short wavelengths shorter than 24 8 nm, for example, for 193 nm light. Therefore, a chemically amplified photoresist having a P H S-based resin as a base resin component, for example, in a process using light of 93 nm, has disadvantages such as low resolution. Therefore, the base resin used as a photoresist in ArF excimer laser lithography etching or the like is now excellent in transparency near 193 nm, which is generally derived from a (meth) acrylate having a main chain. The resin of the structural unit (acrylic resin). In the case of a positive type, the resin is usually a structural unit derived from a (meth) acrylate containing an acid dissociable dissolution inhibiting group containing a tricyclic alkyl ester type of an aliphatic polycyclic group, for example, main-6 - 201027245 A resin having a structural unit derived from 2-alkyl-2.adamantyl (meth) acrylate or the like is used (for example, Patent Document 1). Further, "(meth) acrylate" is one or both of a methacrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position. "(Meth)acrylate" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position. "(acrylic acid)" means an acrylic acid having a hydrogen atom bonded to the α-position, and one or both of methyl methacrylic acid bonded to the α-position. Further, there have been various proposals for acid generators used in chemically amplified photoresists, and key acid generators such as iodine salt or mirror salt, and sulfonate acid are known. A generator, a diazomethane acid generator, a nitrobenzyl sulfonate acid generator, an imiline sulfonate acid generator, a diterpenoid generator, and the like. Now, the acid generator is an acid generator containing a triphenylsulfonium skeleton, a dinaphthyl monophenyl stupid skeleton, or the like (Patent Document 2). [Patent Document 1] JP-A-2003-24 1 3 8 5 (Patent Document 2) Japanese Laid-Open Patent Publication No. 20-5-37 No. 88-88. SUMMARY OF THE INVENTION In recent years, with the increasing pattern of photoresist patterns The expectation of high resolution is improved, and the lithographic etching characteristics of the ball are improved. For example, when a photoresist pattern is formed, it is an important subject to suppress variations in pattern size (PEB Sensitivity: 201027245 or lower, also referred to as "PEBs") due to changes in temperature (ΡΕΒ temperature). When the PEBs deteriorates, when the photoresist pattern is formed, the size of the desired photoresist pattern cannot be stably formed, and the pattern having a fine size cannot be reproduced. The shape of the pattern or the reproducibility of the mask at the time of forming the photoresist pattern is more important as the pattern becomes finer. For example, mask defect factor (MEF), LWR, etc., are one of the indicators for displaying their characteristics, so these improvements will be extremely important. Moreover, the mask defect factor is a display of different sizes when the mask size (the line width in the line and space pattern or the diameter of the through hole in the contact hole pattern) is changed under the same exposure amount and at a fixed pitch state. How the mask pattern can faithfully reproduce (mask reproducibility) parameters. LWR is a phenomenon in which the line width of the formed line pattern is uneven, and the improvement is more important when the pattern is further miniaturized. In the improvement of the lithography etching characteristics, the improvement of the shape of the photoresist pattern or the improvement of the PEBs will be an important subject, and it is generally considered that the novel acid generator can be used for this purpose. The present invention has been proposed in view of the above circumstances, and proposes a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, a photoresist composition containing the acid generator, and A method of forming a photoresist pattern of the photoresist composition is used. A first aspect of the present invention for solving the above problems is a photoresist composition which is a substrate component (A) which contains a change in solubility of an alkali developer via an action of an acid, and is exposed via exposure. A photoresist composition for producing an acid generator component (B), characterized in that the acid generator component (B) is an acid generator formed by a compound represented by the following formula (bl-14) (B1), -8- 201027245 【化1】

· (b 1 - 1 4) [wherein, R7" to R9" each independently represent an aryl group or an alkyl group; among the R7" to R9", any two of them may be bonded to each other and to the sulfur in the formula The atoms may form a ring together; at least one of R7"~R9" is a substituted aryl group in which one part of the hydrogen atom is replaced by a group represented by the following formula (bl4-2); X· is an anion [Chemical 2] R51

Π • · (b 1 4 — 2) [wherein, R5e is a linear or branched alkyl group, R51 is an alkyl group having 1 to 6 carbon atoms, and R52 represents a hydrogen atom or a carbon number of 1 to 5. The alkyl group, η is an integer of 0 or 1 to 6, and -CH2- constituting the above monocyclic structure may be substituted by an oxygen atom (-〇-)]. Further, a second aspect of the present invention is a method for forming a photoresist pattern, comprising the step of forming a photoresist film on a support using a photoresist composition of a first aspect, and causing the photoresist a step of film exposure, and a step of causing the aforementioned photoresist film to be alkali developed to form a photoresist pattern. -9 - 201027245 For the 6k-like three-dimensional Mingfa, the object 'externalization' is shown in the following table. X +9" r'isir [in the formula 'R7"~R9" Any one of R7" to R9" may be bonded to each other and form a ring together with a sulfur atom in the formula; at least one of R7" to R9" is a part of a hydrogen atom. a substituted aryl group substituted with a group represented by the following formula (bl4-2); X- is an anion]

(b 1 4 - 2) [wherein RS0 is a linear or branched alkyl group, RS1 is an alkyl group having 1 to 6 carbon atoms, and R52 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. η is 〇 or an integer of 1 to 6, and _Ch2- constituting the above monocyclic structure may be substituted by an oxygen atom (-〇-). Further, the fourth aspect of the present invention is that the acid formed by the compound of the third aspect produces a uniformity. -10- 201027245 In addition, in the specification and the patent application, the "structural unit" is intended to mean a monomer unit (monomer; monomer unit) constituting a resin component (polymer, copolymer, resin). The "alkyl group" is a monovalent saturated hydrocarbon group containing a linear chain, a branched chain, and a cyclic group, unless otherwise specified. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. The "halogenated alkyl group" is a group in which a part or all of a hydrogen atom of an alkyl group is substituted by a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The "alkylene group" is a divalent saturated hydrocarbon group containing a linear chain, a branched-chain chain, and a cyclic group, unless otherwise specified. The alkyl group in the alkoxy group is also the same 〇 The "acid dissociable group" is an organic group which is dissociated by the action of an acid. "Exposure" is a mourning that includes the full illumination of the radiation. The present invention provides a photoresist composition, a method for forming an A photoresist pattern using the photoresist composition, a novel compound suitable as an acid generator for the photoresist composition, and an acid formed by the compound. Agent. Hereinafter, the present invention will be described in more detail. <Compound of Third Aspect> First, a compound of the third aspect of the present invention will be explained. The compound of the third aspect of the present invention is represented by the above formula (bl-Ι4). In the above formula (bl-ΙΟ 'R7'' to R9'', each independently represents an aryl group or an alkyl group, wherein at least one of R7" to R9" is a part of a hydrogen atom and is a part of the 201027245 alkoxycarbonyl alkane. a substituted aryl group substituted by a oxyalkyl group. The aryl group of R7" to R9" is not particularly limited, and for example, an aryl group having 6 to 20 carbon atoms, which may be an alkoxycarbonylalkyloxy group The substituent other than the substituent may be substituted or unsubstituted, for example, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, etc. The aryl group may be an inexpensive aryl group, and an aryl group having 10 carbon atoms is preferred. Specifically, for example, a phenyl group, a naphthyl group, etc. The alkyl group which may substitute the hydrogen atom of the above aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, and a η-butyl group. The base and tert-butyl are preferred. The alkoxy group which can replace the hydrogen atom of the above aryl group is, for example, an alkoxy group having a carbon number of 丨~5, preferably methoxy, ethoxy, η-propoxy The group, iso-propoxy, η-butoxy, tert-butoxy is most preferred. - The halogen atom which may substitute the hydrogen atom of the above aryl group is preferably a fluorine atom. R7"~R The alkyl group of 9" is not particularly limited, and is, for example, a linear one having a carbon number of 1 to 1 Å, a branched chain or a cyclic alkyl group, etc., and having excellent analytical properties, etc. More preferably, for example, methyl, oxime ethyl, η-propyl 'isopropyl 'n-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, decyl, fluorene The base or the like has excellent resolution and is preferably synthesized at a low cost, such as a methyl group, etc. At least one of R7 to R9 is partially substituted with an alkoxycarbonylalkyloxy group. Among the substituted aryl groups, R7 "~R9.. may be substituted with two or more of the above-mentioned substituted aryl groups, and any of R7" to R9" is preferably the substituted aryl group. The oxycarbonylalkyloxy group is, for example, represented by the following formula (bl4_2) -12 to 201027245.

[wherein RW is a linear or branched alkyl group, R5 is an alkyl group having 1 to 6 carbon atoms, and R52 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is 〇 or 1 An integer of ~6. -CH2- constituting the above monocyclic structure may be substituted by an oxygen atom (-Ο-)]. The linear or branched chain alkyl group in r5Q is preferably, for example, a carbon number of 1 to 5, for example, methyl, vinyl, trimethyl, tetramethyl, 1,1-dimethyl Vinyl and the like. The alkyl group having 1 to 6 carbon atoms in R51 is, for example, methyl, ethyl, n-propyl, i-propyl, η-butyl, tert-butyl, cyclopentyl 'cyclohexyl, as a carbon number ~ 4 is better, with a carbon number of 1 to 3 is the best. η is an integer of 0 or 1 to 6, preferably 0 or 1 to 4, and most preferably 1 to 2. R52 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which is the same as the alkyl group in which the hydrogen atom of the aryl group of the above R7" to R9" can be substituted. It preferably represents a hydrogen atom or a methyl group. Specific examples of the group represented by the above formula (bl4-2) are, for example, 1-methyl-b-cyclopentyloxycarbonylmethyloxy group, 1-ethyl-1-cyclopentyloxycarbonylmethyloxy group. , 1-isopropyl-1-cyclopentyloxycarbonylmethyloxy, 1-methyl-1-cyclohex-13-201027245 oxycarbonylmethyloxy, 1-ethyl-1-cyclo Hexyloxycarbonylmethyloxy, 1-isopropyl-1-cyclohexyloxycarbonylmethyloxy, 1-methyl-1-cyclooctyloxycarbonylmethyloxy, 1-ethyl- 1-cyclooctyloxycarbonylmethyloxy, 1-isopropyl-1-cyclooctyloxycarbonylmethyloxy, 4-methyltetrahydropyranyloxycarbonylmethyloxy, 4 -ethyltetrahydropyranyloxycarbonylmethyloxy, 3-methyltetrahydrofuranyloxycarbonylmethyloxy, 3-ethyltetrahydrofuranyloxycarbonylmethyloxy and the like. The number of the alkoxycarbonylalkyloxy group in the above substituted aryl group is preferably from 1 to 3, more preferably from 1 to 2, most preferably one. When it is within the above range, PEBs can be increased. Further, the shape of the photoresist pattern such as MEF or LWR can be improved. R7"~R9" other than the above substituted aryl group is preferably a phenyl group or a naphthyl group, respectively. In R7'' to R9", any two of these may be bonded to each other and form a ring together with the sulfur atom in the formula. In this case, it is preferable to form a ring containing a sulfur atom of 3 to 1 ,, and it is particularly preferable to form a ring of 5 to 7 members. In particular, benzoquinone, diphenyl thiophene, tetrahydrothiophene, thiopyran, and the like. In the above formula (bl-14), X· is an anion. The anion portion of X- is not particularly limited, and a component known as an anion portion of the key salt acid generator can be suitably used. In the formula (bl-14), the anion of X- is not particularly limited, and examples thereof include an anion such as a sulfonate anion, a quinone anion, or a methyl metal anion. An anion which is suitable as a sulfonate anion, for example, an anion represented by the following formula (-14 - 201027245 χ-i). 【化6】

(X-1) wherein R4 represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent. The alkyl group in R4" may be a linear chain or a branched chain. In the ring

-By. The linear or branched chain alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The cyclic alkyl group is preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 6 to 10. The ring may be monocyclic or polycyclic, specifically, for example, cyclopentyl, cyclohexyl, adamantyl, borneol, isobornyl, tricyclodecyl, tetracyclododecyl or the like.

In the case where R4" is an alkyl group, it is suitably used for, for example, a negative-type photoresist composition in order to form a weak acid strength. The halogenated alkyl group in R4" is, for example, the aforementioned linear chain, branched chain or cyclic group. A group in which a part or all of a hydrogen atom of an alkyl group is substituted by a halogen atom or the like. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. In the above halogenated alkyl group, the ratio of the number of halogen atoms (halogenation ratio (%)) to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group is preferably from 10 to 100%, and is from 50 to 100. % is better, and 100% is the best. When the halogenation rate is higher, the strength of the acid is higher, which is preferable. -15- 201027245 The aryl group in the above R4" is preferably an aryl group having 6 to 20 carbon atoms. The above-mentioned R4". It is preferable to use a carbon number of 2 to 10. In the above R4", "a substituent may be" a part or all of a hydrogen atom in the aforementioned alkyl group, alkyl group, aryl group or alkenyl group may be substituted (other than a hydrogen atom or Base) the meaning of the person replaced. The number of substituents in R4" may be one, or two or more. The above substituent is, for example, a halogen atom, a hetero atom, an alkyl group, and a formula: z_Q1-[wherein Q1 is a divalent bond group containing an oxygen atom, and Z is a hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. The base represented by]. The above halogen atom is the same as that exemplified for the halogen atom in the halogenated alkyl group exemplified in R4". The above-mentioned alkyl group is, for example, the same as the alkyl group exemplified in R4". The above hetero atom ', for example, an oxygen atom (=0, -0-), a nitrogen atom, a sulfur atom, etc., is represented by Z-Q1- Q1 is a divalent bond group containing an oxygen atom. Q1 may contain an atom other than an oxygen atom, and an atom other than an oxygen atom, such as a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or the like. The divalent bond group is, for example, an oxygen atom (ether bond; -0-), an ester bond (-C(= 〇)-〇_), a guanamine bond (_C(=0)_NH_), a carbonyl group a non-hydrocarbon-based bond group containing an oxygen atom such as (-C(=0)-), a carbonated bond (·〇<(=〇)_〇_); a combination of a base group and an alkylene group, etc. The combination 'for example, -R91-0-, -R92_0_C 卜0)...·〇_Κ92_〇- 201027245 c(=o)_, -c(=o)-o -r93-oc(=o)-, -c(=o)-o-r93- (wherein R91 to R93 each independently represent an alkylene group), etc. The alkylene group in R91 to r93 is, for example, a straight chain The alkyl group having a branched or branched chain shape is preferred, and the carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 5. 1 to 3 is particularly preferred. The above alkyl group, specifically, for example, methyl [-(:112-]; -CH(CH3)- '-CH(CH2CH3)- '-C(CH3)2-' -C(CH3)(CH2CH3)-, -c(ch3)(ch2ch2ch3)-, -(:((: η2(:η3)2-, etc. alkyl-extension methyl; exoethyl [-ch2ch2-]; Ch(ch3)ch2-, -ch(ch3)ch(ch3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-'-CH(CH2CH3)CH2-, etc. Base (n-propyl)[-CH2CH2CH2-]; -ch(ch3)ch2ch2-, -ch2ch(ch3)ch2-, etc. alkyl-extension trimethyl; tetramethyl [-ch2ch2ch2ch2-]; -ch( Ch3)ch2ch2ch2-, -CH2CH(CH3)CH2CH2-, etc. alkyl group extending tetramethyl; pentamethyl [-ch2ch2ch2ch2ch2-], etc. • Q1, a divalent bond group containing an ester bond or an ether bond Preferably, wherein -〇_, -R91_0_, -oc( = o)·, -o-r92-oc( = o)-, -r92-oc(=o)-, -c( = o)- O-r93-oc( = o)-, or -C( = 0)-0-R93- is preferred, especially -〇-C( = 0)-, -C( = 0)-0-R93- 0-C( = 0)-, or -C( = 0)-0-R93- is preferred. In the group represented by Z-Q1-, the hydrocarbon group of Z may be an aromatic hydrocarbon group, and an aliphatic hydrocarbon group may also be used. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, more preferably from 5 to 20, most preferably from -17 to 201027245 to from 15 to 15, and most preferably from 6 to 12. Among them, the carbon number is not including the carbon number in the substituent. The aromatic hydrocarbon group, specifically, an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a phenanthryl group, removes one hydrogen atom. An aralkyl group such as an aryl group, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group, or the like. The number of carbon atoms of the alkyl chain in the above aralkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. The above aromatic hydrocarbon group may have a substituent. For example, a part of the carbon atom constituting the aromatic ring which the aromatic hydrocarbon group has may be taken by a hetero atom, and the hydrogen atom to which the aromatic ring of the aromatic hydrocarbon group is bonded may be substituted by a substituent. . In the former, for example, a heteroaryl group in which a part of carbon atoms constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and a carbon constituting the aromatic hydrocarbon ring among the aralkyl groups A heteroarylalkyl group in which a part of an atom is substituted by the aforementioned hetero atom. In the latter case, the substituent of the aromatic hydrocarbon group is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= 0) or the like. The alkyl group of the substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an η-butyl group or a tert-butyl group. The alkoxy group of the substituent of the above aromatic hydrocarbon group is preferably, for example, an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an η-propoxy group, an iso-propoxy group, and an η-butyl group. The oxy group and the tert-butoxy group are preferred, and the methoxy group and the ethoxy group are most preferably 201027245. The halogen atom of the substituent of the aromatic hydrocarbon group, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. The halogenated alkyl group of the substituent of the above aromatic hydrocarbon group is, for example, a part or all of the hydrogen atom of the above-mentioned alkyl group, and the like. The aliphatic hydrocarbon group in Z may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain A shape, and a cyclic chain. The aliphatic hydrocarbon group in the Z is such that a part of the carbon atom constituting the aliphatic hydrocarbon group may be substituted by a substituent containing a hetero atom, and a part or all of the hydrogen atom constituting the aliphatic hydrocarbon group may be Substituted with a substituent containing a hetero atom. The "hetero atom" in Z is not particularly limited as long as it is an atom other than a carbon atom or a hydrogen atom, and may be, for example, a halogen atom, an oxygen atom, a sulfur atom or a nitrogen atom. A halogen atom such as a fluorine atom, a chlorine atom, an iodine Φ, a bromine atom or the like. The substituent containing a hetero atom may be formed by the above-mentioned hetero atom or may be a group derived from a group or an atom other than the above hetero atom. a substituent which may be substituted for a part of a carbon atom, specifically, for example, -0-, -C(=〇)-〇-, -c(=0)-, -〇-C(=〇)-〇- , -C(=0)-NH-, _NH- (H can be replaced by a substituent such as an alkyl group or a fluorenyl group), -S·, _ s( = 〇h-, -S( = 0) 2 -0-, etc. In the case where the aliphatic hydrocarbon group is cyclic, the substituents may be included in the ring structure. Substituting a part or all of the substituent of the hydrogen atom, specifically, Example -19 - 201027245 Alkoxy group, halogen atom, halogenated alkyl group, hydroxyl group 'oxygen atom (= 〇), cyano group, etc. The alkoxy group is, for example, preferably alkoxy group having 1 to 5 carbon atoms, and methoxy group and ethoxy group. The group, η-propoxy group, iso-propoxy group, η-butoxy group, tert-butoxy group are preferred, and methoxy group and ethoxy group are preferred. The above halogen atom 'such as fluorine atom or chlorine atom Further, a bromine atom, an iodine atom or the like is preferably a fluorine atom. The halogenated alkyl group is, for example, an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a η-butyl group, a tert-butyl group or the like. a part or all of the hydrogen atom of the alkyl group substituted by the aforementioned halogen atom, etc. The hydrocarbon group is preferably a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group). The saturated hydrocarbon group (alkyl group) preferably has a carbon number of from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10. Specifically, for example, methyl, ethyl, propyl, Butyl, pentyl, hexyl, heptyl, octyl, decyl φ, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecane Base, hexadecyl, isohexadecyl, hexadecanyl octadecyl, pentadecyl, eicosyl, twenty-one yard, twenty-two yards, etc. The saturated hydrocarbon group (alkyl group) preferably has a carbon number of 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, for example, 1-methylethyl, 1- Methylpropyl, 2-methylpropyl, butylmethyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methyl-20- 201027245 A pentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a cardiomethylpentyl group, and the like. The saturated hydrocarbon group is, for example, preferably having a carbon number of 2 to 10, preferably 2 to 5, more preferably 2 to 4, and particularly preferably 3, a linear monovalent unsaturated hydrocarbon group such as a vinyl group. And a propylene group (allyl), a butyl group, etc. a branched monovalent unsaturated hydrocarbon group, for example, a 1-methylpropyl group, a 2-methylpropenyl group, etc. An unsaturated hydrocarbon group, for example, the above The content is particularly preferably a propylene group. The aliphatic ring group may be a monocyclic group or a polycyclic group. The carbon number is preferably 3 to 30, preferably 5 to 30. 5 to 20 is better, 6 to 15 is especially good, and 6 to 12 is the best. Specifically, for example, a group obtained by removing one or more hydrogen atoms from a monocyclic alkane; and a polycyclic chain such as a bicycloalkane, a tricycloalkane or a tetracycloalkane is obtained by removing one or more hydrogen atoms. Base. More specifically, for example, a group obtained by removing one or more hydrogen atoms from a monocyclic chain such as cyclopentamidine or cyclohexyl fluorene; adamantane, norbornane, isobornane, tricyclodecane, and tetracyclic A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a hospital. In the aliphatic cyclic group, the ring structure does not contain a substituent containing a hetero atom, and the aliphatic ring group is preferably a polycyclic group, and a polycyclic chain is used to remove one or more hydrogen atoms. The basis is preferably that the base obtained by removing more than one hydrogen atom from the King Kong Institute is optimal. In the case of an aliphatic cyclic group, the ring structure contains a substituent containing a hetero atom, and the substituent containing the hetero atom is, for example, -〇-, -C(= 〇n , -S-, -S( = 0) 2-, -S(= 0) 2-0- is preferable. The aliphatic ring-based group - 21 - 201027245 is, for example, the following formula (L1 ) to (L5 ), (SI ) to (S4 ), etc. [Chem. 7]

[In the formula, Q" is an alkyl group having a carbon number of 1 to 5, -0-, -8-, -0-1194- or -S-R95-, and R94 and R95 each independently represent a carbon number of 1 to 5. The alkyl group, m is an integer of 0 or 1. In the formula, the alkylene group in Q", R94 and R95 is, for example, the same as the alkylene group in the above R91 to R93. The aliphatic cyclic group, a part of a hydrogen atom to which a carbon atom constituting the ring structure is bonded, may be substituted by a substituent. The substituent is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= oxime) or the like. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, an η-butyl group or a tert-butyl group. The alkoxy group and the halogen atom are respectively the same as the substituent in which one or all of the hydrogen atoms described above are substituted. In the present invention, Z is preferably a ring-based group which may have a substituent. The ring -22-201027245 is an aromatic hydrocarbon group which may have a substituent, and may have an aliphatic cyclic group which may have a substituent, and may be an aliphatic cyclic group which may have a substituent. The above aromatic hydrocarbon group is preferably a naphthyl group having a substituent or a phenyl group having a wm substituent. The aliphatic cyclic group which may have a substituent is preferably a polycyclic aliphatic cyclic group which may have a substituent. The polycyclic aliphatic cyclic group is, for example, preferably a group obtained by removing one or more hydrogen atoms by a polycyclic alkane, and the above (L2) to (L5), (S3) to (S4), etc. . In the present invention, 'R4'' is a case where the substituent is Z-Q1-, and R4" is ZQ^Y1-[wherein, Q1 and Z are the same as described above, and γΐ is a carbon number which may have a substituent The group represented by the alkylene group of 1 to 4 or the fluorinated alkyl group having 1 to 4 carbon atoms which may have a substituent is preferable. That is, when X· is a sulfonate anion, the following formula (X) -11) The anion represented is preferably _ [Chemical 8] 2~~Q1—V1—s〇3 ...(χ - ί,) [wherein Q1 is a divalent bond group containing an oxygen atom, Z a hydrocarbon group having 3 to 30 carbon atoms which may have a substituent, γ ΐ is a C 1 to 4 alkyl group which may have a substituent or a fluorinated alkyl group having 1 to 4 carbon atoms which may have a substituent In the case of χ-11), Z and Q1 are the same as those described above. For example, the extension of the 院 1 is the same as the case where the carbon number in the extension base listed in the above q 1 is - 201027245 1 to 4. The fluorinated alkyl group is, for example, a group substituted by a part or all of a fluorine atom of the hydrogen atom of the alkyl group, etc. Y1, specifically, for example, -〇?2-'4?2€?2-,- €?2€?2€?2·, -CF(CF3)CF2-, -CF(CF2CF3)-, -C(CF3)2- -CF2CF2CF2CF2-, -CF(CF3)CF2CF2-, -CF2CF(CF3)CF2-, -CF(CF3)CF(CF3)-, -C(CF3)2CF2-, -CF(CF2CF3)CF2-, -CF( CF2CF2CF3)-, -C(CF3)(CF2CF3)-; -CHF-, -CH2CF2-, -ch2ch2cf2-, -ch2cf2cf2-, -ch(cf3)ch2-, -CH(CF2CF3)-, -c(ch3) (cf3)-, -ch2ch2ch2cf2-, -CH2CH2CF2CF2- '-CH(CF3)CH2CH2- '-CH2CH(CF3)CH2-, -ch(cf3)ch(cf3)-, -c(cf3)2ch2-;-ch2 -, -ch2ch2-, -ch2ch2ch2-, -ch(ch3)ch2-, -ch(ch2ch3)-, • C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3) CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -CH(CH2CH2CH3)-, -C(CH3)(CH2CH3)-, etc. Y1, It is preferred to use a fluorinated alkyl group, especially a fluorinated fluorinated alkyl group in which a carbon atom bonded to an adjacent sulfur atom is bonded. For example, -cf2-, -cf2cf2- , -cf2cf2cf2-, -cf(cf3)cf2-, -CF2CF2CF2CF2- '-CF(CF3)CF2CF2- '-CF2CF(CF3)CF2- '-CF(CF3)CF(CF3)-, -C(CF3)2CF2 -, -CF(CF2CF3)CF2-; -CH2CF2- '-CH2CH2CF2- '-CH2CF2CF2-; -CH2CH2CH2CF2-, -CH2CH2CF2CF2-'-CH2CF2CF2CF2-, etc. 201027245 -CF2·, -CF2CF2-, -cf2cf2cf2-, or CH2CF2CF2- is preferred, and -CF2-, -CF2CF2- or -CF2CF2CF2- is more preferred, and -cf2- is particularly preferred. The aforementioned alkylene or fluorinated alkyl group may have a substituent. The "having a substituent" of an alkylene group or a fluorinated alkyl group is a part or all of a hydrogen atom or a fluorine atom in the alkylene group or the fluorinated alkyl group, which is partially or entirely replaced by a hydrogen atom and an atom other than a fluorine atom or The meaning of the replacement. The substituent which may have a stretching base or a gasification stretching base is, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group or the like. The anion represented by the formula (X-ll) is preferably an anion represented by the following formulas (b1) to (b8). 【化9】

H2g+1Cg—C—〇-(CH2)q2-〇-C—(CF2)rSO; (b 2)

25- 201027245 ο

(CH2)v2~〇· c4-(CF2)rS03 π2 (b 4) o II (CH2)v3~〇--C· (R7)w3-^|^ (R7)w4-

(CH2)v4—〇· -(CF2)p"S°3 n3 (b 5) (R7)w5 oII=—o+c- OII 〇-(CF2)pS〇3 04 (b 6) one (CF2) rS03 n5 ( b 7 ) (R7)r

C—0_(CH2)q1—p(F2C)·-S〇3 (b 8) [wherein p is an integer of 1 to 3' qi~q2 each independently represents an integer of 1 to 5, and rl is 〇~3 The integer 'g is an integer from 1 to 20' r7 is a substituent, nl~n5 respectively represent 0 or 1, v〇~V5 respectively represent integers of 〇~3, and wi~w5 respectively represent integers of 〇~3 'Q" is the same as the above.] The substituent of r7 is, for example, the same as the substituent which may have an aliphatic hydrocarbon group and a substituent which may have an aromatic hydrocarbon group in the above Z. The symbol (rl, W1 to w5) attached to R7 is an integer of 2 or more. The plural R7 of the compound may be the same or different, and the difference may be -26-201027245. Further, when X· is a quinone imine anion, for example, an anion represented by the following formula (b-3) or (b-4). [化1 〇]

· (b~4) [wherein, X" is an alkylene group having 2 to 6 carbon atoms which may be substituted by a fluorine atom; at least one of Y", Z" independently may have a substituent The alkyl group or the halogenated alkyl group] X" is a linear or branched chain alkyl group in which at least one hydrogen atom may be substituted by a fluorine atom, and the carbon number of the alkyl group is 2 to 6, Preferably, the carbon number is from 3 to 5, and most preferably the carbon number is 3. The carbon number of the alkyl group of X", within the range of the above carbon number, has excellent solubility for the photoresist solvent, and the like, the smaller the In the alkylene group of X", the more the number of hydrogen atoms which can be replaced by fluorine atoms, the stronger the acid strength and the transparency of high-energy light or electron lines with respect to 200 nm or less. Therefore, the ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably all of the hydrogen. A perfluoroproperylene group or a perfluorocarbon group in which an atom is replaced by a fluorine atom. Y", Z" are independently an alkyl group or a halogenated alkyl group which may have a substituent. The above Y", z" The base may be linear, branched, or ring-厶I · 201027245, and may be the same as the alkyl group in the above R4''. Halogen in the above Y", Z" The alkyl group is, for example, a group substituted by a part or all of a halogen atom of a hydrogen atom of the above-mentioned linear, branched or cyclic alkyl group, which is the same as the alkyl group in the above R4". In the alkyl group, the ratio of the number of halogen atoms (halogenation ratio (%)) to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group is preferably from 10 to 100%, and from 50 to 100. % is preferably 100%, and the higher the halogenation rate, the stronger the strength of the acid. Therefore, in the above Υ", Ζ", "may have a substituent" is the alkyl group. Any part or all of the hydrogen atom in the halogenated alkyl group may be replaced by a substituent (other than a hydrogen atom or a base). The number of bases in Υ",Ζ" can be one, or two or more. The above substituents are, for example, 'halogen atom, hetero atom, ortho group, formula: ζ_Q1-[wherein Q1 is a divalent bond group containing an oxygen atom' Ζ is a hydrocarbon group having 3 to 30 carbon atoms which may have a substituent ]Wait. The halogen atom is, for example, the same as those exemplified for the halogen atom in the halogenated alkyl group exemplified in R4". The above-mentioned alkyl group is, for example, the same as the alkyl group recited in r4", and the aforementioned hetero atom is the same as the one listed in 'and r4'. The z-Q1- represents the base 'Q1 It is a divalent bond group containing an oxygen atom. A divalent bond group containing an oxygen atom such as 'oxygen atom (awake bond; -〇·), vinegar bond (-C (= Ο) - 0 -) a non-hydrocarbon-based bond group containing an oxygen atom such as a thiol group (-C (= 0)-), a carbonic acid 201027245 ester bond (-oc(=o)-o-); The combination of a bonding group and an alkyl group, etc. The combination is, for example, -R91-〇-, -R92-0-C(=0)- (wherein, R91 to R92 each independently represent an alkylene group) and the like. The alkylene group in r9i to R92 is preferably a linear or branched alkyl group, and the carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 5, and is 1 Specifically, for example, the alkylene group of R91 to R92 in the above R4n is the same. Q1 is preferably a divalent bond group containing an ester bond or an ether bond. In the group represented by Q1, the hydrocarbon group of Z is the same as R91 in the above R4" The alkylene group of R92 is the same. More preferably, it is an aliphatic hydrocarbon group, and more preferably a linear or cyclic aliphatic hydrocarbon group. The anion of the formula (b-4) having a substituent of Z-Q1 is preferably an anion represented by the following formulas (b4-1) to (b4-ll). -29- -1 ) 201027245 [Chemical 1 1], S02-NS〇2—CgF2g+1 ... (b 4 (R21)w1 Shear S〇2—N—S〇2_CgF2g+ib 4 2) (R^ Jwr^T^· /J^7^CH2-S〇2-NS〇2-CgF2g+1 (b 4 —3) 4 - 4 ) (R )wi S02-NS〇2-CgF2g+i ... CH3 -(CH2)i〇-S〇2-NS〇2-CgF2g+i · · · ( b 4 - 5 )

O S〇2~N_S〇2~〇gF2g+1 -30 - 201027245 【化1 2】 (R21

ΟIIc- '(CF2)ti-S02-N-S02-CgF2g+i (b 4 - 7) (R22)w:

(CF2)t2-S02—N—S〇2—CgF2g +1 (b 4- 8 参(R23)w3" 0 II CH2_0一II - C- '(CF2)t3_S〇2 — N—S〇2-CgF2g +1 m3 • · · ( b 4 _ 9 )

(ch2)3—〇- 0II-c- '(CF2)t4-S02—N—S〇2—CgF2g+1 ΓΠ4 (b 4 - 1 0 )

oIIc- •(CF2)t5_S02—N—S02-CgF2g+1 m5 (b 4 - 1 1 ) [wherein g is an integer of 1 to 4] tl~t5 is an integer of 1 to 4' m ~xn5 is 0 Or 1, wl ”~w4" respectively represent an integer of 0~3, R2~R24 are substituents] -31 - 201027245 g' is a separate number of hits of 1~4, preferably 1 or 2, to 1 For the best. tl~t5, for each of the independent 丨~4 integers, 丨 or 2 is better, 2 is the best. For each independent 〇 or 丨, 0 is better.

Wl"~W4", which are independent integers of 0 to 3, preferably 〇 or 1 and 0 is the best. The substituents of R21 to R24, for example, and Z in the above Z-Qi- may have The content of the aliphatic hydrocarbon group is exemplified as the substituent. The symbols (W1,, w4") attached to R21 to R24 are integers of 2 or more, and the plural R2 1 to r24 in the compound may be They are the same or different. Further, in the above-mentioned Y", Z", one is an alkyl group, and the other one is a fluorinated alkyl group, and - s〇2· which is bonded to the hospital base can be substituted by -c(= 0)-. The disease group is, for example, the same as the above R4'', and particularly preferably, for example, a group having a fluorene-like alkyl group; for example, a methyladamantyl group, an adamantyl group or the like. Further, when X· is a methyl metal anion, for example, an anion represented by the following formula (b-cl). 【化1 3】

(b - c 1 ) • 32· 201027245 [wherein R1 is an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; R2 is a hydrocarbon group which may have a substituent ' or -Sh-R1] . In the formula (b-cl), R1 is an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group. In the present invention, R1 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the general formula (b-cl), when R2 is a hydrocarbon group which may have a substituent (also, a "hydrocarbon group which may have a substituent"), a part or all of the substituents of a hydrogen atom constituting the hydrocarbon group may be substituted The hydrocarbon group of R2 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Specifically, for example, it is the same as Z in the above formula: Z-Q1-. In R2, a halogenated aryl group, for example, an aryl group having 6 to 10 carbon atoms, and a part or all of hydrogen atoms of an aryl group such as a phenyl group or a naphthyl group are preferably a halogen atom (more preferably a fluorine atom). The base to be replaced. Further, when X· is a halogen anion, for example, a fluorine anion, a chlorine anion φ ion, a bromine anion, an iodine anion or the like. In the above, X. In the above, in the above formula (x-1), R4' is an anion of a fluorinated alkyl group which may have a substituent, that is, a fluorinated alkylsulfonic acid having a substituent Ions are preferred. The fluorinated alkyl group which may have a substituent, for example, R4", is a group substituted by a part or all of a fluorine atom of a hydrogen atom of an alkyl group of an alkyl group. In particular, an alkyl group having a carbon number of 6 or more or a fluorinated alkyl group is difficult to decompose, and is considered to have a carbon number of 4 or less, for example, a nonafluorobutanesulfonic acid ion, etc., from the viewpoint of handling safety of bioaccumulation. It is especially good. The ingredients of 201027245 (B1) may be used alone or in combination of two or more. In the component (B), the ratio of the component (B 1 ) is preferably from 1 to 100% by mass, more preferably from 2 to 100% by mass, most preferably from 5 to 100% by mass. Further, in the above formula (bl-14), X· may be a halogen anion. The halogen anion referred to herein is a fluoride ion, a chloride ion, a bromide ion, an iodide ion or the like. The details of X in the above (bl-14) are as follows, for example. 201027245 【化1 4】 C4F9S〇3 CF3SO3 c3f7sc| (b Ο - 1 ) (b Ο - 2) (b Ο - 3) 一Ί3 co^〇'cVo! (b 0-6) (b Ο - 7) (b Ο - 8) o2s*n*so2 f2c.c, cf2 f2 (b 0 — 4 ) 〇2 〇2 s, 1 _ .s, . F3CF2C N CF3 (b 0 — 5:

SO2CF3 F3C〇2S^S〇2CF3 (b 0 - 9)

(b 0 - 1 0 ) (b〇-ll) (b 0- 1 2) (b 0 - 1 3 ) (bO — 14)

i0Y〇-^〇A^Scf3 [j5^〇^c*S〇3 o f2 0 Bu 2 / f2 (b 0 - 2 2) (b 0 - 2 3) (b 0 - 2 4) 0 person fS〇 3 iQ^0 human production (b 0 - 2 5) (b 0 - 2 6) (b〇-2 7) 〇 & 〇V (b 0 - 2 8) -00 - 201027245 The third aspect of the invention Specific examples of the compound 'for example, the following compounds (b 14-1) to (bl-14-26)' and the compounds shown in the synthesis examples described later.

-36- 201027245

201027245 【化1 7】

-38- 201027245

[化1 8]

<Production Method of Compound of Third Aspect> The compound (b 1 · 1 4 ) of the third aspect of the present invention is produced, for example, in the following manner. That is, in the solution of the organic acid H + B- (B-, for example, an anion moiety of methanesulfonic acid from the acid), the following formula (bl-1 and (bl-14-02)) is added. After the compound is reacted, water and an organic solvent (for example, dichloromethane, tetrahydrofuran, etc.) are added to the organic layer to obtain a compound of the following formula (bl-l4_03) from the organic layer. a compound represented by bl-1 4-03 ), an organic solvent (for example, dichloromethane, tetrahydrofuran, etc.) and a water agent, to which a desired alkali metal salt L + of an anion X is added, for example, a lithium ion, Alkali metal cations such as potassium ions and sodium ions, 4-01) can be added purely, and the recovered solution is dissolved in the mixed solution X' (L + ion) 201027245 and then reacted by liquid separation and washing. A compound represented by the following formula (bl-14-04) is obtained from the organic layer. Next, 'the compound represented by the formula (bl-14-04) is dissolved in an organic solvent (for example, dichloromethane, tetrahydrofuran, etc.), and after ice-cooling, a base (for example, sodium hydride or the like) is added, and the desired addition is added. a halide of an alkoxycarbonylalkyl group (for example, a formula "Cl-R5°-C(=0)-0-R51", "Br-R5Q-C(=0)-0-R51", etc. R5° to R51 are the same as those of R5° to R51 in the above formula (bl 4-2), and the hydrogen atom of the -R1G"-〇H--OH group is substituted by the aforementioned alkoxycarbonylalkyl group. And the compound ( b 1 -1 4 ) ° [Chemical 19]

Ο

R8"—S~R9" + H—R10"-〇H (b 1 - 1 4-0 1) (b 1 -1 4-0 2) OH R10" L+X\ R8-S+ X-R9" b 1 -1 4-04) wherein R8" and R9" are the same as R8" and R9 in the above formula (bl-14); R1(>" is the above formula (bl-14) R7-40-201027245 of the aryl group in the aryl group obtained by removing one hydrogen atom; B_ is an anion moiety of the organic acid; L + is an alkali metal cation; X- is the above formula (bl-14) X· is the same content] and 'anion exchange of the compound (bl-14-03)' is -R1G-〇H of the compound (bl-14-03) before the reaction with L + X· Since the hydrogen atom of the OH group has been substituted with the above alkoxycarbonylalkyl group, the compound (b 1 -1 4 ) can be obtained only by anion exchange. ❿ <The fourth aspect of the acid generator> The acid generator of the fourth aspect of the invention (hereinafter also referred to as an acid generator (B1)) is composed of a compound represented by the above formula (bl-Ι4). In the formula, R7" to R9", X - is the same as those listed in the third aspect of the present invention. A photoresist composition of one aspect> φ Next, a photoresist composition of a first aspect of the present invention will be described. The photoresist composition of the first aspect of the present invention contains a substance via an acid The base component (A) (hereinafter, also referred to as (A) component) which changes the solubility of the alkali developer, and the acid generator component (B) which generates an acid by exposure (hereinafter, also referred to as (B) component And the component (B) is an acid generator (B1) containing a compound represented by the above formula (bl_14). The component (A) of the photoresist composition of the present invention can be used by an acid. Further, the polymer material which changes the solubility of the alkali developing solution or the low molecular material which changes the solubility of the alkali developing solution by the action of an acid may be used in 201027245. Further, the photoresist composition of the present invention, The negative-type photoresist composition may also be a positive-type photoresist composition. The photoresist composition of the present invention is a negative-type photoresist composition, for example, '(A) is an alkali-soluble resin, and then A crosslinking agent (C) is added to the negative photoresist composition. In the negative resist composition, when the photoresist pattern is formed, an acid is generated in the component (B) by exposure, and the exposed portion is subjected to the action of the acid to form a crosslink between the alkali-soluble resin and the crosslinking agent. The resin which is changed to an alkali-insoluble saponin-soluble resin in at least one unit selected from at least one selected from the group consisting of α-(hydroxyalkyl)acrylic acid or a lower alkyl ester of α-(hydroxyalkyl)acrylic acid can be formed into a relatively It is better to have a good photoresist pattern with less swelling. Further, α-(hydroxyalkyl)acrylic acid is an acrylic acid to which a hydrogen atom is bonded to a carbon atom at the α-position of a carboxyl group, and a hydroxyalkyl group is bonded to a carbon atom of the α-position (preferably, a carbon number of 1 to 1) One or both of the α-hydroxyalkylacrylic acid of 5 hydroxyalkyl). When the crosslinking agent (C) is usually an amine-based crosslinking agent such as acetylene urea having a methylol group or an alkoxymethyl group, it is possible to form a good photoresist pattern with less swelling. good. The amount of the crosslinking agent (C) to be added is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the photoresist composition of the present invention is a positive photoresist composition, the (Α) component is insoluble to the alkali developer before exposure, and is formed by exposure when the photoresist pattern is -42 - 201027245. B) When the action of the acid generated by the component acts, the acid dissociable dissolution inhibiting group is dissociated, and the solubility of the entire component (A) to the alkali developing solution is increased, and the alkali insoluble property changes to alkali solubility. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by applying the positive-type photoresist composition on the substrate is selectively exposed, the exposed portion can be converted into alkali solubility, and the unexposed portion still maintains the alkali. Alkali development was carried out in a state where the insolubleness was unchanged. In the resist composition of the present invention, the component (A) is preferably a component which increases the solubility in an alkali developer via an acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. Further, the component (A) is preferably a resin component (A1) (hereinafter also referred to as (A1) component) which increases alkali solubility by the action of an acid. < (A1) component> The component (A1) preferably used in the positive resist composition is preferably a structural unit (a 1 ) derived from an acrylate having an acid dissociable dissolution inhibiting group. . Further, the component (A1) is preferably a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone. Further, the component (A1) is preferably a structural unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. Here, in the specification and the patent application, the "structural unit derived from acrylate" means a structural unit composed of cleavage of an ethylenic double bond of acrylate. -43- 201027245 "Acrylate" means a carbon atom-bonding substituent (an atom or a group other than a hydrogen atom) bonded to the α-position in addition to the acrylate of a hydrogen atom bonded to a carbon atom. Mourning. The substituent is, for example, a lower alkyl group, a halogenated lower alkyl group or the like. Further, the α-position (the carbon atom at the α-position) of the structural unit derived from the acrylate means, unless otherwise specified, the meaning of the carbon atom to which the carbonyl group is bonded. In the acrylate, the lower alkyl group of the substituent at the α-position, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, A linear or branched lower alkyl group such as isopentyl or neopentyl. Further, the halogenated lower alkyl group is, for example, a group in which a part or all of a hydrogen atom of the above-mentioned "lower alkyl group of the substituent of the α-position" is substituted by a halogen atom. The halogen atom referred to herein, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. In the present invention, the α-position bonded to the acrylate is preferably a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and more preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group. The ease is preferably a hydrogen atom or a methyl group. • Structural unit (al) The structural unit (al) is a structural unit derived from an acrylate containing an acid dissociable dissolution inhibiting group. The acid dissociable dissolution inhibiting group in the structural unit (al) is a group in which the (A 1 ) component has a poorly soluble alkali dissolution inhibitory effect on the alkali developing solution before dissociation - 44- 201027245 (A1) The total amount of the components is increased in solubility in the alkali developing solution. As the acid dissociable dissolution inhibiting group, a base of an acid dissociable dissolution inhibiting group which has been proposed as a base resin for chemically amplified photoresist can be used. In general, for example, a carboxyl group in (meth)acrylic acid or the like can be used to form a cyclic or chain-like tertiary alkyl ester group; an alkoxyalkyl group-like acid dissociable dissolution inhibiting group or the like. Here, "(meth) acrylate" is an acrylate containing an α-bonded hydrogen atom, and one or both of a methyl methacrylate bonded to the α-position. Wherein the "trialkyl ester" is such that the hydrogen atom of the carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester, and the oxygen atom of the carbonyloxy group (-C (〇)-〇-) is bonded at the end. A structure having a tertiary carbon atom of the aforementioned chain or cyclic alkyl group. In the tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be cut off by the action of an acid. Further, the chain or cyclic alkyl group may have a substituent. Hereinafter, it is composed of a carboxyl group and a tertiary alkyl ester, and has an acid dissociable group. For convenience, it may be referred to as "a tertiary alkyl ester type acid dissociable dissolution inhibiting group j ° a tertiary alkyl ester type acid dissociable dissolution" The inhibitory group is, for example, an aliphatic branched chain acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, etc. Among them, in the scope of the specification and the patent application, "aliphatic" is relative to aroma. The relative commemoration of the family is defined as the meaning of the compound without the aromatic '-45- 201027245 compound. The "aliphatic branched chain" means "a structure having a branched chain shape which does not have an aromaticity." The structure of the "aliphatic branched chain acid dissociable dissolution inhibiting group" is not limited to the group formed by carbon and hydrogen (hydrocarbon group), but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is usually preferred to saturate. The aliphatic branched chain acid dissociable dissolution inhibiting group is preferably a tertiary alkyl group having 4 to 8 carbon atoms, and specifically, for example, tert-butyl group, tert-pentyl group, tert-heptyl group or the like. The "aliphatic cyclic group" is a monocyclic group or a polycyclic group which does not have an aromatic group. The "aliphatic cyclic group" in the structural unit (al) may have a substituent or may have no substituent. The substituent is, for example, a lower fluorenyl group having a carbon number of 丨5, a fluorine atom, a fluorinated lower alkyl group having a carbon number of 1 to 5 substituted by a fluorine atom, an oxygen atom (= 〇), or the like. The "cyclic ring group" is a basic ring structure for removing a substituent, and is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbyl group" may be either saturated or unsaturated, and it is usually saturated. The "aliphatic ring-based group" is preferably a polycyclic group. The aliphatic cyclic group 'for example' may be substituted by a lower alkyl group, a fluorine atom or a fluorinated alkyl group, or may be unsubstituted, a monocyclic alkane, a bicycloalkane, a bicycloalkane or a tetracyclic chain. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as an alkane. More specifically, the stomach 'such as cyclopentane, cyclohexane, etc. monocyclic -46 - 201027245 alkane, or adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and other polycyclic chains The base obtained by removing one or more hydrogen atoms from the alkane. An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom on a ring skeleton of a cyclic alkyl group, and the like, specifically, for example, 2-methyl-2-adamantyl, or , 2-ethyl-2-adamantyl and the like. Or, in the structural unit represented by the following formula (al"-l) to (al"-6), such as a group bonded to an oxygen atom of a carbonyloxy group (-C(0)-0-), An aliphatic cyclic group such as an adamantyl group, a cyclohexyl group, a cyclopentyl group, an borneol group, a tricyclodecanyl group or a tetracyclododecyl group, which is bonded thereto, and has a branched chain extension having a tertiary carbon atom. The base of an alkyl group, etc. [Chemical 2 0]

[wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and R15 and R16 represent an alkyl group (may be any of a linear chain or a branched chain, preferably a carbon number of 1 to 5). ]. The lower alkyl or halogenated lower alkyl group of the formula (a 1 " -1 ) to (a 1 " - 6 ) is a lower alkyl group which may be bonded to the above acrylate or -47- 201027245 The halogenated lower alkyl group is the same. The "acetal type acid dissociable dissolution inhibiting group" is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group. Subsequently, when an acid is generated by exposure, the bond between the acetal-type acid dissociable dissolution inhibiting group and the oxygen atom bonded to the acetal-type acid dissociable dissolution inhibiting group is cut off by the action of the acid. .

The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (ρ 1 ). [Chem. 2 1]

One C-〇

Cp 1) [wherein, R1' and R2' each independently represent a hydrogen atom or a lower alkyl group, η represents an integer of 0 to 3, and Υ represents a lower alkyl group or an aliphatic cyclic group]. @ In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and 〇 is the best. The lower alkyl group of R1', R2' is, for example, the same as the lower alkyl group of the above R, preferably a methyl group or an ethyl group, and most preferably a methyl group. In the present invention, it is preferred that at least one of R1' and R2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (ρ 1 ) is preferably a group represented by the following formula (ρ 1 -1 ). -48- 201027245 [Chem. 2 2] (p 1 — 1 )

—C-O^CH^Y

[In the formula, R1', η, and Y are the same as those of R1, n, and Y in the above formula (pi)]. The lower alkyl group of the hydrazine is an aliphatic cyclic group which is the same as the lower alkyl group of the above R, and can be a monocyclic or polycyclic aliphatic ring which is mostly proposed by conventional ArF photoresists and the like. The appropriate selection among the bases is, for example, the same as the above-mentioned "aliphatic cyclic group". Further, the acid-dissociable dissolution inhibiting group is, for example, a group represented by the following formula (P2). [化2 3]

Τ'' -C—O—R19 R18 .... (p 2) [wherein R17 and R18 each independently represent a linear or branched alkyl or hydrogen atom, and R19 is a linear branched chain. Alkyl or cyclic. Or 'R17 and R19' each independently represent a linear or branched chain alkyl group, and the end of R17 may be bonded to the end of R19 to form a ring]. In R17 and R18, the carbon number of the alkyl group is preferably 丨~:^, and it may be in the form of a linear chain of 49 to 201027245 or a branched chain, and it is preferably an ethyl group or a methyl group. The base is the best. In particular, it is preferred that one of R17 and R18 is a hydrogen atom and the other is a methyl group. R19 is a linear, branched or cyclic alkyl group, and the carbon number is preferably from 1 to 15, and may be any of a linear chain, a branched chain or a ring. In the case where R19 is a linear or branched chain, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and particularly preferably ethyl. In the case where R19 is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, for example, a polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane which may be substituted by a fluorine atom or a fluorinated alkyl group or may be unsubstituted may also be used. A group obtained by removing one or more hydrogen atoms. Specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane, or a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane is removed. The base obtained by more than one hydrogen atom, and the like. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R19 are each independently a linear or branched alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and a terminal of R19 and a terminal of R17 may form a bond. . In this case, the oxygen atom bonded to R17 and R19 and R19 forms a cyclic group with the oxygen atom and the carbon atom bonded to R17. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is more preferred. Specific examples of the cyclic group include, for example, 'tetrahydropyranyl group, tetrahydrofuranyl group and the like. The structural unit (al) is grouped by using the structural unit represented by the following general formula (al-0-l), the structural unit shown by the following formula (al-0-2) and the structural unit represented by the following general formula (al-0-2) One or more selected ones are preferred. [Chem. 2 4]

[wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and X1 represents an acid dissociable dissolution inhibiting group].

[wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X2 represents an acid dissociable dissolution inhibiting group; and γ2 represents an alkylene group or an aliphatic cyclic group]. a lower alkyl group or a halogenated lower alkyl group of the formula (al-0-1), which is the same as a lower alkyl group which may be bonded to the α-position of the above acrylate or a lower halogenated -51 - 201027245 alkyl group. content. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and is, for example, the above-mentioned tertiary alkyl ester type acid dissociable dissolution inhibiting group, acetal acid dissociating dissolution inhibiting group, and the like, and a tertiary alkyl ester type. The acid dissociable dissolution inhibiting group is preferred. In the formula (al-0-2), R is the same as described above. X2 is the same as X1 in the formula (al-0-l). Y2 is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aliphatic cyclic group, and the aliphatic cyclic group may be used, for example, in addition to a group obtained by removing two or more hydrogen atoms. The description of the aliphatic cyclic group is the same as the base of the same content. The structural unit (al), more specifically, for example, a structural unit represented by the following general formula (al-Ι) to (al-4). [Chem. 2 6]

(al-1) (a 1-2) (a 1-3) (a 1 -4) 52- 201027245 [In the above formula, χ' represents a tertiary alkyl ester type acid dissociable dissolution inhibiting group, and Y is a carbon number a lower alkyl group of 1 to 5 or an aliphatic cyclic group; η represents an integer of 〇~3; Υ2 represents an alkylene group or an aliphatic cyclic group; R is the same as the above, and R1' and R2' are respectively Independently represents a hydrogen atom or a lower alkyl group having a carbon number of 1 to 5. It is preferable that at least one of R1' and R2' is a hydrogen atom, and more preferably all of them are hydrogen atoms. η is preferably 0 or 1. X' is the same as the tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X1. The aliphatic cyclic group of hydrazine is the same as those exemplified in the above description of "aliphatic cyclic group". Υ2 is preferably an alkylene group having a carbon number of 1 to 1 Å or a divalent aliphatic cyclic group, and the aliphatic cyclic group may be used, for example, in addition to a group having two or more hydrogen atoms removed. The description of the aliphatic cyclic group is the same as the base of the same content. Υ2 is a case where the carbon number is 1 to 1 〇, and the carbon number is 1 to 6

The 巍 is better, and the carbon number is preferably 1 to 4, and the carbon number is preferably 1 to 3. When W Υ 2 is a divalent aliphatic cyclic group, two or more hydrogens are removed by cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane. The base obtained by the atom is particularly good. Hereinafter, specific examples of the structural unit represented by the above general formula (al-Ι) to (al-4) will be described. 201027245 【化2 7】

Ra Ra

(a1-1-2) Ra

Ra icH2—C

Ra r I, •ch2—c- CH2(CH2)2CH,°Ϊ0 (al-1-3)

Ra °Λ. CH3 ch3

(at-1-4) R° 〇H CH3 〇s(al-1-7) Re R«

(al-1-5) R° I

(CHahCHa

CH3 R° "/' CHg-C-\- 伽

—f-CHo—C-V (al-1-8) R° (al-1-9) R°

^2·?-)· -(·〇η2-ο-]- _^-ch2-c^- -(-ch2-c-)- -(-CH2-C-)- -f-CH2-C j -0=:\ 0=4 o=4 o=l 0=4 〇=\ n -· V - O CH \ 0 ?

Ch3 o^chj 〇 xh3 °wc2h5 ' 0 0)

R« R®

(a1-1-16) (a1-1-17) (al-1-18) (a1-1-19) (a1-1-20) (al 1 21) -54- 201027245 [Chem. 2 8]

Ra —i-CH2—C—. 4:

Ra -^-CH2—C-j- c2h5 fly) (a1-1-23) CH2—c-j—j°v ^

Re -ch2—c-J- CH〇—C*

PH3 hc-ch3 O

(a1-1-24) (alH-25) (at-1-26)

(a Bub 22)

(al 10 27) (a1-1-28) (al-1-31) (al-b 29) (a1~1~30) 201027245 [Chem. 2 9]

(a1-2-1) (a bu 2-2)

Ra R« R* Re Ϊθ 0 10 (a1-2-5) (a1-2-€)

(a1-2-8) (a1-2-7) (al-2-3) (al-2-4)

\ 〇 Ο (al-2-10). 〇 ό Ο (al-2-9) (al-2-11) (a1_2_12) (al-2-13) (a1-2-14) (al-2-15) (a1-2-16)

-56- 201027245 【化3 0】

Ra -(ch2-c^ -(ch2 Q={ Ο Ο

Ra

Ra -fcH2-C-)-

9

ο Ο Ο

❹ (*1-3-1)Ra :ch2-〇0=1 o (»t-3-2) («1-3-3)

0

0 O

H3c (at-3-7)Ra

(Call 1-3-8> (a Bu 3-9) (•1-3-10) (al-3-11) :0 1θ -(ch2-c-)- -(ch2-c-)- = 0

(at-3-15) (a I-3-1 β) (a Bu 3·ί3) (a Bu 3-14)

Ra

201027245 【化3 1

Ra, 〇

Ra Ra ^ch2-c-^ -{ch2-c 0=4^ o 0

Ra R« R« ~{ch2-c- P b 0 =0 =0 0 0= > (*1-3-19) (*1-3-20) (a Bu 3-21) (a1-» -22) (a Bu 3-23)

0= O

(a Bu 3-24) [Chemical 3 2 card η and points as 4 ten. Axe / ° / ° P .0

Ra R« 〇. 0

ο ο ο

0' 0==^ ο ο ο.

❹ /1⁄2 七 4 (al-3-25) (al-3-26) (a1-3-27) (a 1-3-28) -58- 201027245 [Chem. 3 3]

Trifluoromethyl. Or the combination of two or more groups a 1 - 3 ) al_l-l)~(al-1-

In the above formula, Ra represents a hydrogen atom, a methyl group or a structural unit (a 1 ), and may be used singly or in combination of one type. Wherein, the formula (al-Ι) or (the structural unit is preferred, specifically, for example, using (4) -1-20) (al-1-23) and 1-3.25) (al 28) At least one selected from the group is more preferred. L-1-1 ) In addition, the structural unit (al ), particularly the unit of the following general formula (a^1_()1) containing the structural unit of the formula 1 (al-1-3), contains the formula (al- 1-16) The following general formula (al_1-〇2) of the structural unit of ~(al-1-17) and formula (al-1_2〇)~(al-1-23)_$-59- 201027245 The unit is better. [化3 4]

[wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R11 represents a lower alkyl group]. [化3 5]

[wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R12 represents a lower alkyl group. h represents an integer of 1 to 3]» In the formula (al-1-Ol), R is the same as the above. The lower alkyl group of R11 is the same as the lower alkyl group of R, and a methyl group or an ethyl group is preferred. In the general formula (al-l-02), R is the same as described above. R12 of 201027245 The lower alkyl group is the same as the lower alkyl group in R, preferably methyl or ethyl. The ethyl group is most preferred. h is preferably 1 or 2, and 2 is optimal. The ratio of the structural unit (a 1 ) in the component (A 1 ) is preferably from 1 〇 to 80 mol%, and from 2 〇 to 7 〇 mol %, based on the total structural unit constituting the component (A1). Good, with 25~50 mol% as the best. When the lower limit is 値 or more, the pattern can be easily obtained as a positive resist composition, and when it is below the upper limit ,, a balance with other structural units can be obtained. • Structural unit (a2) The structural unit (a2) is a structural unit derived from an acrylate containing a cyclic group containing a lactone. Wherein the lactone-containing cyclic group is a cyclic group containing one ring (lactone ring) having a -O-C(O)-configuration. The lactone ring is counted as a ring, and only the inner vinegar ring is a monocyclic group, and the ruthenium has other ring structures, and the structure is called a polycyclic group. The lactone ring group of the structural unit (a2), in the case where the component (A1) is used to form a photoresist film, the adhesion between the photoresist film and the substrate is improved, and the affinity with the developer containing water is improved. Effective in effect. The structural unit (a2) is not particularly limited, and any substance can be used. Specifically, for example, a monocyclic group containing a lactone, for example, a group obtained by removing one hydrogen atom from γ-butyrolactone. Further, the polycyclic group having a lactone is, for example, a group obtained by removing one hydrogen atom from a dicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. -61 - 201027245 The structural unit (a2) is more specifically, for example, a structural unit represented by the following general formula (a2-l) to (a2-5). [Chem. 3 6]

Wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and represents a hydrogen atom, a lower alkyl group, or an alkoxy group having a carbon number of 1 to 5, m is an integer of 0 or 1, and A is a carbon number of 1 ~5 alkyl or oxygen atom]. R in the general formulae (a2-l) to (a2-5) is the same as R in the above structural unit (al). The lower alkyl group of R' is, for example, the same as the lower alkyl group of R in the above structural unit (al). The alkylene group having a carbon number of 1 to 5, and specifically, for example, a methyl group, a vinyl group, an η-propylene group, an isopropenyl group or the like. In the general formulae (a2-l) to (a2-5), R' is preferably a hydrogen atom from the viewpoint of easy industrial availability. The following are specific structural units for revealing the above general formulae (a2-l) to (a2-5). -62- 201027245 [Chem. 3 7 (a2-1-1) (Λ2-1-2) ❿ i〇H2-R -{chJ> (a2-1-6) [化3 8 CH3 , ?H3 CH3 -fcH2 —cfm. 4· (a2-2-1, O (a2-2-2) (a2.M) 〇 CH3 ch3 -fchk-cf -fcH2-cHf XcH, -kA ?H3 〇4 〇4 〇4 -f〇H24f ch3

o (a2-2-4) CHa (a2-2*5) 0 (five)〇«,

O' (32-2-7) 〇· CH,

O (a2-2-8)

-63 = 201027245 [Chem. 3 9]

-64- 201027245 [化4 0]

201027245 【化4 1】

(a2^-5) (a2«) e In the above, it is preferred to use at least one selected from the general formulae (a2-l) to (a2-5) to use the general formula (a2). -l) ~ (a2-3) It is preferable to select at least one or more types. Specifically, for example, using the chemical formulas (a2-ll), (a2-l-2), (a2-2-l), (a2- 2-2), (a2-3-1), (a2) It is preferred that at least one of -3-2), (a2-3 - 9) and (a2-3 -10) is selected. In the component (A1), the structural unit (a2) may be used alone or in combination of two or more types from -66 to 201027245. The ratio of the structural unit (a2) in the component (A1) is preferably 5 to mol%, more preferably 10 to 5 mol%, based on the total of the total structural units constituting the component (A1). 20 to 50% Mo is the best. When the thickness is less than or equal to the lower limit, the sufficient effect obtained by containing the structural unit (a2) can be obtained. When the upper limit is less than or equal to the upper limit, the balance with other structural units can be obtained. • Structural unit (a3) The structural unit (a3) is a structural unit derived from an acrylate having an aliphatic hydrocarbon group containing a polar group. When the component (A3) has a structural unit (a3), the hydrophilicity of the component (a) can be improved, and the affinity with the developer can be improved, the alkali solubility of the exposed portion can be improved, and the resolution can be improved. The polar group is, for example, a hydroxyl group, a cyano group, a hydroxy group in which a part of a hydrogen atom of an alkyl group is substituted by a fluorine atom, and the like, and particularly preferably a hydroxyl group. The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group (preferably an alkylene group) having a carbon number of 1 to 10, or a polycyclic aliphatic hydrocarbon group (polycyclic group). The polycyclic group may be, for example, a resin for use in an ArF excimer laser resist composition, and is appropriately selected from the contents of most proposals. The number of carbon atoms of the polycyclic group is preferably from 7 to 30. Further, the structural unit derived from an aliphatic polycyclic acrylate having a hydroxyalkyl group having a hydroxyl group, a cyano group, a carboxyl group, or a hydrogen atom in the alkyl group substituted by a fluorine atom is more preferable. . The polycyclic group, for example, a 'dicycloalkane, a tricycloalkane or a tetracycloalkane, is obtained by removing two or more hydrogen atoms -67-201027245. Specifically, for example, a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane is obtained by removing two or more hydrogen atoms. Among the plurality of cyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from the original borneol, and a tetracyclododecane removing two or more hydrogen atoms. The resulting base is more suitable for industrial use. In the structural unit (a3), in the aliphatic hydrocarbon group having a polar group, when the hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a structural unit derived from hydroxyethyl acrylate is preferred. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-l) to (a3-4) is preferred. [化4 2]

Wherein R represents a hydrogen atom, a lower-grade or a halogenated lower-grade courtyard, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, and 1 is an integer of 1 to 5 , s is an integer from 1 to 3, d is an integer from 1 to 3, and e is 0 or 1]. In the general formula (a3-l)~(a3·4), the lower grade base of the R or the low halogenation, the stomach can be the same as the lower-grade or halogenated lower alkyl group bonded to the α-position of the above-mentioned acrylic acid vinegar. The content. • 68- 201027245 In the formula (a3-l), j is preferably 1 or 2, and 1 is the best. When j is 2, the hydroxyl group is preferably bonded to the 3 and 5 positions of the adamantyl group. . In the case where j is 1, the hydroxyl group is preferably bonded to the 3-position of the adamantyl group. In the formula (a3 - 2 ), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the original borneol base. In the formula (a3-3), t' is preferably 1. 1 is better than 1. s is better than 1. The ends of the carboxyl groups of the acrylic acid are preferably bonded to 2-oriole or 3-oriole. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the original borneol base. In the formula (a3-4), d is preferably 1 or 2, and 1 is most preferred. The bonding position of the hydroxyl group is not particularly limited, and in the case where d is 1, it is easy to obtain a viewpoint of low price, and it is preferable to use 2 bits. In the case where d is 2 or 3, it may be a combination of any of the substitution positions. In the component (A1), the structural unit (a3) may be used alone or in combination of two or more. The ratio of the structural unit (a3) in the component (A1) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total structural unit constituting the component (A1). It is best to use 5 to 25 mol%. When the lower limit 値 or more, the sufficient effect is obtained when the structural unit (a3) is contained, and when it is less than the upper limit 値, the balance with other structural units can be obtained. • The structural unit (a4) (A1) component may contain other structural units (a4) other than the above structural units (al) to (a3) without departing from the effects of the present invention. -69 - 201027245 The structural unit (a4) is not particularly limited as long as it is not classified into other structural units of the above structural units (al) to (a3). It can be used for ArF excimer laser and KrF excimer. A conventionally known majority unit used for a resist resin such as a laser (preferably for ArF excimer laser). The structural unit (a4) is preferably, for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group. The polycyclic group may be, for example, the same as those exemplified in the case of the above structural unit (al), for ArF excimer laser, KrF excimer laser (preferably ArF excimer laser) A conventionally known majority unit used for the resin component of the photoresist composition such as the emitter. In particular, when at least one selected from the group consisting of a tricyclic fluorenyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and an original borneol group is industrially easy to obtain, it is preferred. The polycyclic group may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent. The structural unit (a4), specifically, for example, is a structure of the following general formula (a4-1) to (a4-5). [化4 3]

-70- 201027245 [wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group]. The lower alkyl group or the halogenated lower alkyl group of R in the above formula (a4-1) to (a4-5) is the same as the lower alkyl group or the halogenated lower alkyl group which may be bonded to the α-position of the above acrylate. The content.

The structural unit (a4) is included in the (Α1) component, and the ratio of the structural unit (a4) to the total structural unit constituting the (a1) component is preferably 1 to 30% by mole. 1 〇 ~ 20 mol % is better. In the invention, the component (A1) is a resin component (polymer) which increases the solubility to the alkali developer via the action of an acid, and is suitable as the resin component (polymer), for example, having a structural unit (ai). a copolymer of (u) and (a3), for example, a copolymer formed by structural units (al), (a2) and (a3), structural units (al), (a2), (a3) and (a4) The copolymer formed and the like are exemplified. The component (A1) may be used singly or in combination of two or more. In the present invention, the (A1) component 'in particular, the copolymer (A1-1) to (A1-4) having a combination of structural units represented by the following general formulae (A1-1) to (ai-4) is good. 201027245 【化4 4

(A 1 - 1

Seven b

OH

(A 1 -3) (A 1 -2)

❹ [wherein R represents a hydrogen atom 'lower alkyl group or a halogenated lower alkyl group, and the plural R's may be the same or different. R2G, R21" is a lower alkyl group, wherein the lower alkyl group of the R or the halogenated lower alkyl group is the same as the lower alkyl group or the halogenated lower alkyl group which may be bonded to the α-position of the above acrylate, wherein The hydrogen atom or the methyl group is preferred. wherein R2() is preferably a lower alkyl group, a methyl group or an ethyl group. In the formula, R21" is preferably a lower alkyl group, a methyl group or an ethyl group. - 201027245 (A) The copolymer (A1-1) to (Ab 4) may be used singly or in combination of two or more. Further, the copolymer (A1-1) to (A1) 4) In the case of using two or more combinations, a combination of preferred copolymers, for example, a combination of a copolymer (A 1 - 2 ) and a copolymer (A1-3), etc. (A) a copolymer ( The content of A1-1) to (A1-4) is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass. Among them, 100% by mass is most preferable. When the lower limit is 値 or more, as a positive photoresist composition, the lithographic etching property 〇(A 1 ) component can be improved, and a monomer derived from each structural unit can be used, for example, azobisisobutyronitrile (A). An azo radical polymerization initiator such as IBN) can be obtained by polymerization by a known radical polymerization method, etc. Further, in the component (A1), for example, HS-CH2-CH2- can be used for the polymerization. a chain transfer agent such as CH2-C(CF3)2-〇H, which introduces a -C(CF3)2-OH group at the terminal. As described above, for example, a part of a hydrogen atom introduced into an alkyl group is a fluorine atom. The copolymer obtained by substituting a hydroxyalkyl group is effective for reducing development defects or reducing LER (line edge unevenness: uneven unevenness of the line side wall). (A1) Mass average molecular weight (Mw) of the component (gel penetrating color layer) The polystyrene conversion standard of the analytical method is not particularly limited, and is generally preferably from 2000 to 50,000, more preferably from 3,000 to 30,000, more preferably from 4,000 to 20,000, and most preferably from 5,000 to 20,000. In the range, when used as a photoresist, it can have sufficient solubility to the photoresist solvent, and can obtain -73-201027245 to a good dry etching resistance or photoresist pattern cross-sectional shape. Also 'dispersion (Mw/Mn) It is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. Further, Μη represents a number average molecular weight. Further, as the component (Α1), an alkali-soluble resin component other than the copolymer (Α1-1) to (Α1-4), for example, another polymer compound used in the conventional positive-type photoresist composition, etc., can be used. In the positive resist composition, the content of the (Α1) component can be appropriately adjusted in accordance with the thickness of the photoresist film to be formed, etc. <(Β)Component> In the photoresist composition of the present invention, The Β) component is an acid generator (Β 1 ) (hereinafter, also referred to as a component (B1)) which is formed by the compound represented by the above formula (b 1 -1 4 ). In the above formula (bl-14), R7 "~R9", X· are the same as those recited in the third aspect of the present invention. (B) a composition which, when containing the above (B1) component, has a mask reproducibility at the time of forming a photoresist pattern, for example, a contact hole (C/H) pattern can be formed to improve the via hole The roundness, the uniformity of the diameter (CD) (CDU), the improvement of the mask defect factor (MEF), the excellent C/H pattern extraction, etc., can also improve the lithography etching characteristics. In addition, MEF and the like can be improved at the time of forming a line-and-space photoresist pattern (L/S pattern), and the lithography etching characteristics can be improved. Further, the photoresist composition of the present invention can be suitably used as a resist composition for immersion exposure in a method of forming a photoresist pattern of -74 to 201027245 containing an immersion exposure step, thereby obtaining good lithographic etching characteristics. Further, in the method of forming a photoresist pattern including a three-layer photoresist layer forming step, it is suitable as a positive photoresist composition for forming an upper photoresist film to obtain good lithographic saturation characteristics. (B1) component, using an anion represented by the above formula "r4"-S〇3-" or "Z-Qi-Y^SO〆", or the above formula (匕-3) • or (b) -4) When the anion is represented, it is preferable to enhance the lithography etching property. Further, an anion represented by the formula "R4"-S〇r" or "Z-Q^Y^scv" is more preferable. The component (B1) may be used alone or in combination of two or more kinds. In the photoresist composition of the present invention, the content of the component (B1) is preferably 40% by mass or more. It is more preferably 60% by mass or more, and may be 1% by mass. When the lower limit of the range is above ,, it can be shaped into a good photoresist pattern shape. In particular, the use of a resist composition for immersion exposure or a photoresist composition for forming an upper photoresist film to form a photoresist pattern can also improve the lithographic characteristics of the lithography. When the three-layer photoresist layer is formed, it is preferable to have good adhesion to the underlayer film of the photoresist, and it is possible to suppress curling of the photoresist pattern or the like. Further, in the resist composition of the present invention, the content of the component (B1) is preferably from 1 to 30 parts by mass, more preferably from 3 to 18 parts by mass, based on 100 parts by mass of the component (A). ~16 parts by mass is the best. When the lower limit of the range is above ,, in particular, the photoresist composition for immersion exposure-75-201027245 or the photoresist composition for forming an upper photoresist film is used to form a photoresist pattern, and the lithography etching can be improved. characteristic. Further, when the upper limit is less than or equal to 値, it is possible to form a product having good storage stability. In the component (B), an acid generator (B2) other than the above component (B1) (hereinafter referred to as a component (B2)) may be used in the above (B1) component. The component (B2) is not particularly limited as long as it is other than the above component (B1), and an acid generator which has been proposed as a chemically amplified photoresist has been used. These acid generators, for example, gun salt acid generators such as iodonium salts or phosphonium salts, 'sulfonate-based acid generators, dialkyl or bisarylsulfonyldiazomethanes are known. , a diazomethane acid generator such as poly(disulfonyl)diazomethane, a nitrobenzyl sulfonate acid generator, an imiline sulfonate acid generator, and a dicalcium generator A variety of substances. As the key salt acid generator, for example, a compound represented by the following formula (b-Ι) or (b-2) can be used. [化 4 5]

[wherein, R1" to R3", R5" to R6" each independently represent an aryl group or an alkyl group; and among R1" to R3" in the formula (b-Ι), any two of them may be bonded to each other and The sulfur atom in the formula may form a ring together; R4" represents a linear, -76-201027245 branched or cyclic alkyl or fluorinated alkyl group; at least one of R1"~R3" At least one of R5" to R6" represents an aryl group. In the formula (b-Ι), R1" to R3", except that the alkoxycarbonylalkyloxy group is not a substituent of a substituted hydrogen atom Others are the same as those of R7"~R9" in the above formula (bl-Ι4). Further, at least one of 'R1' to R3" represents an aryl group. Among R1 to R3, two or more aryl groups are preferred, and all of R1 "~R3" are preferably aryl groups. Further, R1 to R3" are preferably phenyl or naphthyl groups. The linear or branched alkyl group or the fluorinated alkyl group has a linear or branched alkyl group, for example, preferably having a carbon number of 1 to 10 and a carbon number of 1 to 8. It is best to have a carbon number of 1 to 4. The cyclic alkyl group has, for example, a ring group represented by the above R1", preferably a carbon number of 4 to 15, a carbon number of 4 to 10, more preferably a carbon number of 6 to 10. The alkyl group is preferably, for example, a carbon number of 1 to 1 Torr, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (in the alkyl group) The ratio of the fluorine atom is preferably from 10 to 1% by mole, most preferably from 50 to 100%, and particularly the group in which all of the hydrogen atoms are replaced by a fluorine atom, and it is more preferable to enhance the strength of the acid. R4" It is preferably a linear or cyclic alkyl group or a fluorinated alkyl group. In the formula (b-2), R5" and R6" each independently represent an aryl group or an alkyl group. Among the R5''~R6" At least one represents an aryl group. Also, R5" and R6" -77 - 201027245 are preferred for aryl. The aryl group of R5" and R6" is the same as the aryl group of R1" to R3". The alkyl group of R5" and R6" is the same as the alkyl group of R1" to R3". It is preferable that both R5" and R6" are a phenyl group. R4" in the formula (b-2) is the same as the above formula (b-Ι), R4". The formula (b-Ι), Or the specific salt-based acid generator represented by (b-2), for example, a triphenylmethanesulfonate or a nonafluorobutanesulfonate or a bis(4-tert-butylphenyl) Iodine trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate 'three (4- Methylphenyl) fluorene trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) fluorene trifluoromethane sulfonate, and heptafluoropropane a sulfonate or a nonafluorobutane sulfonate thereof, a triphenylmethanesulfonate of monophenyldimethylhydrazine, a heptafluoropropane sulfonate thereof or a nonafluorobutane sulfonate thereof; diphenylmonomethylhydrazine Trifluoromethanesulfonate, its heptafluoropropane sulfonate Ester or its nonafluorobutane sulfonate, (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-A) Phenoxyphenyl) diphenyl sulfonium trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-tert-butyl)phenyl fluorene trifluoromethane sulfonic acid Ester, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1-(4-methoxy)naphthyl) fluorene trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nine Fluorobutane sulfonate 'di(1-naphthyl)phenylhydrazine trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-phenyl 201027245 tetrahydrothiophene Trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(4-methylphenyl)tetrahydrothiophene-trifluoromethanesulfonate, its heptafluoropropane sulfonate or a nonafluorobutane sulfonate; a trifluoromethanesulfonate of a 1(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene gun, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof Acid ester; 1-(4-methoxynaphthalen-1-yl) a tetrahydrothienyl trifluoromethanesulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; a 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene-trifluoromethane Sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; trifluoromethanesulfonate of 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene gun, its heptafluoropropane sulfonate An acid ester thereof or a nonafluorobutane sulfonate thereof; a trifluoromethanesulfonate of 1-phenyltetrahydrothiophene gun, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; 1-(4-hydroxyl) Phenyl) tetrafluoromethanesulfonate trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrogen a trihalomethanesulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; a trifluoromethanesulfonate of 1-(4-methylphenyl)tetrahydrothiopyran, Heptafluoropropane sulfonate or its nonafluorobutane sulfonate. Further, the anion portion of the cerium salt may be a key salt which is replaced by a methanesulfonate, an n. propane sulfonate, a η-butane sulfonate or an η-octane sulfonate. In the formula (b-Ι) or (b-2), a key salt-based acid generator (cation which is substituted with an anion portion represented by the above formula (b-3) or (b-4) may also be used. The part is the same as (b-Ι) or (b-2) -79- 201027245 Further, a sulfonium salt having a cation moiety represented by the following formula (b-5) or (b-6) may be used as a key. Use of a salt acid generator. [Chem. 4 6]

Wherein R41 to R46 each independently represent an alkyl group, an ethylidene group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; each independently represents an integer of 0 to 3, and n6 is an integer of 0 to 2] to R46, The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group or a η-butyl group. Or tert-butyl is especially good. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group. The hydroxyalkyl group is preferably a group in which one of the above alkyl groups or a plurality of hydrogen atoms is substituted by a hydroxyl group, such as a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. In the case where the symbols ηι to n6 attached to R4] to R46 are integers of 2 or more, the plural numbers R41 to R46 may be the same or different, respectively. ~, preferably 0 to 2, more preferably 〇 or 1, most preferably 0. N2 and 113 preferably represent 〇 or 1, respectively, and more preferably 0. -80 - 201027245 n4, preferably 0 to 2, more preferably 〇 or 1. Η5, preferably 0 or 1, more preferably 0. 116, preferably 〇 or 1, more preferably 1. The anion portion represented by the formula (b-5) or (b-6) is not particularly limited, and the anion portion as the key salt acid generator may be the same portion, for example, the above formula (b- Ι ) or (b-2 ) an anion moiety (R4 "s〇r) of the agent of the raw material, such as an anion represented by the formula (b-3) or (b-4) The acid ion is preferred, and the carbon number 1 acid ion is more preferable, and the linear chain having a carbon number of 1 to 4 is particularly preferable. Specifically, for example, a trifluoromethanesulfonic acid ion acid ion, a nonafluoro-η-butylsulfonic acid ion or the like. In the present specification, the oxime sulfonate-based acid generator is a compound represented by the following formula (Β-1), and a compound which exhibits an acid property upon irradiation with a wire. These agents have been widely used in chemically amplified photoresists. [化4 7] -C==N—Ο——S02—R31 p32 · · · · (B — 1 )

In the formula (B-l), R31 and R32 are each independently represented. The organic group of R31 and R32 is an sulfonium salt of a cation portion containing a carbon atom, and has been proposed so far. The anion indicates that the key salt acid produces a sulfonic acid ion; the above. In the above, the fluorinated alkyl sulfonated perfluoroalkyl sulfonic acid group and the seven gas η-η-propyl ore have at least one and have a composition via a sulfonate sulfonate-based acid. Show organic base]. Further, it may have an atom other than the carbon -81 - 201027245 atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom 'chlorine atom, etc.), etc.). The organic group of R31 is preferably, for example, a linear, branched or cyclic alkyl group or aryl group. The alkyl group or the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear one having a carbon number of 1 to 6, a branched chain or a cyclic alkyl group. Wherein the "having a substituent" is an alkylene group substituted by a part or all of the substituent of the hydrogen atom in the alkyl group or the aryl group, for example, preferably having a carbon number of 1 to 20 and having a carbon number of 1 to 1 Preferably, it is preferably a carbon number of 1 to 8, and a carbon number of 1 to 6 is particularly preferred, and a carbon number of 1 to 4 is most preferred. The alkyl group is, for example, particularly a partially or completely halogenated alkyl group (hereinafter also referred to as a halogenated alkyl group). Further, a partially halogenated alkyl group means an alkyl group in which one part of a hydrogen atom is replaced by a halogen atom, and an alkyl group which is completely halogenated is an alkyl group in which all hydrogen atoms are replaced by a halogen atom. . The halogen atom 'e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like' is particularly preferably a fluorine atom. Namely, the halogenated alkyl group is preferably a fluorinated alkyl group, preferably having a carbon number of 4 to 20, more preferably a carbon number of 4 to 1 Å, and most preferably a carbon number of 6 to "0". The aryl group is, for example, particularly preferably an aryl group which is partially or completely halogenated. Further, a partially halogenated aryl group means an aryl group in which a part of a hydrogen atom is substituted by a halogen atom, and an aryl group which is completely halogenated is an aryl group in which all hydrogen atoms are replaced by a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. -82- 201027245 The organic group of R32 is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The alkyl group and the aryl group of R32 are, for example, the same as those of the alkyl group and the aryl group exemplified in the above R31. R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. Among the oxime sulfonate-based acid generators, a compound represented by the following formula (B-2) or (B-3) is more preferable. φ [化4 8] R34—C=N—〇—S02—R35 — · · (B — 2) [In the formula (B-2), R33 is a cyano group, an alkyl group having no substituent or an alkyl halide; base. R34 is an aryl group. R35 is an alkyl group having no substituent or a halogenated alkyl group]. [化4 9]

[In the formula (B-3), R3 6 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R37 is a 2 or 3 valent aromatic hydrocarbon group. R38 is an alkyl group or a halogenated alkyl group having no substituent. P" is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R3 3 is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and -83, 201027245. The carbon number of 1 to 6 is the best. R33 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group. The fluorinated alkyl group in R3 3 is preferably one in which the hydrogen atom of the alkyl group is fluorinated by 50% or more, more preferably 70% or more of the fluorinated group, and more preferably 90% or more of the fluorinated one. The aryl group of R34 is, for example, a group obtained by removing a hydrogen atom from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a phenanthryl group. And a heteroaryl group in which a part of carbon atoms constituting the ring of the group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. In this content, it is better to use the base. The aryl group of R34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an alkoxy group. The alkyl group or the halogenated alkyl group in the substituent preferably has a carbon number of 1 to 8, and preferably has a carbon number of 1 to 4. Further, the dentate alkyl group is preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group having no substituent of R35 is preferably a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 8, and most preferably a carbon number of from 1 to 6. R35' is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group. The fluorinated alkyl group in R35 is preferably one in which the hydrogen atom of the alkyl group is fluorinated by 50% or more, and the one which is fluorinated by 70% or more is more preferably fluorinated by 90% or more. It is particularly good for the strength of the acid. Most preferred is a perfluorinated alkyl group in which the hydrogen atom is replaced by 100% fluorine. In the above formula (B-3), the alkyl group or the halogenated alkyl group having no substituent of R3 6 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent of the above R33. -84- 201027245 A 2- or trivalent aromatic hydrocarbon group of R37, for example, a group obtained by removing one or two hydrogen atoms from the aryl group of the above r34. The alkyl group or the decyl group having no substituent of R3 8 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent of R35 described above. p " is preferably 2. Specific examples of the sulfonate-based acid generator include, for example, α-(ρ-toluenesulfonyloxyimine)-benzyl cyanide (cyanide), α-(ρ-chlorophenylsulfonyloxyimide)-benzyl Cyanide, α-(4-nitrophenylsulfonyloxyimide)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimide)-benzyl Cyanide, α-(phenylsulfonyloxyimide)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimide)-2,4-dichlorobenzyl cyanide, α-(benzene Sulfomethoxyimine)-2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimide)-4-methoxybenzyl cyanide, α-(2-chlorophenylsulfonate) Oxyimine)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimide)-thien-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxy) Imine)-benzyl cyanide, α-[(ρ-toluenesulfonyloxyimine)_4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxyimine)- [Methoxyphenyl]acetonitrile, α-(toluenesulfonyloxyimide)thiophenyl cyanide, α-(methylsulfonyloxyimine)-1-cyclopentenylacetonitrile, α-(A Alkylsulfonyloxyimine)-1-cyclohexenylacetonitrile --(methylsulfonyloxyimine)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimine)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonate醯oxyimine)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimine)-cyclohexylacetonitrile, heart (ethylsulfonyloxyimine)-ethyl acetonitrile, --(propylsulfonyloxyimide)-propylacetonitrile, α-(cyclohexylsulfonyloxyimide)-cyclo-85- 201027245 pentacetonitrile, α-(cyclohexylsulfonyloxyimide) -cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimide)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimine)-1-cyclopentenylacetonitrile, α-( Isopropylsulfonyloxyimine)-1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimide)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxy) Imine)-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimide)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimide)-1 -cyclohexenylacetonitrile, α-(methylsulfonyloxyimide)·phenylacetonitrile, α-(methylsulfonyloxyimine)-fluorene-methoxyphenylacetonitrile, α-(III Fluoromethylsulfonyloxyimine)- Acetonitrile, α-(trifluoromethylsulfonyloxyimide)-fluorene-methoxyphenylacetonitrile, α_(ethylsulfonyloxyimine)-fluorene-methoxyphenylacetonitrile, α- (propylsulfonyloxyimine)-fluorene-methylphenylacetonitrile, <x-(methylsulfonyloxyimine)-fluorene-bromophenylacetonitrile, and the like. Further, the oxime sulfonate-based acid generator disclosed in JP-A-H09-208554 (paragraph [0012] to [0014] [Chem. 18] to [Chem. 19], W02004/074242A2 (65 to 85 pages) The sulfonate-based acid generator disclosed by Exampl e 1 to 4 0) is also suitable for use. Further, a suitable compound is, for example, exemplified below. [化5 0]

〇4Η*—OjS H»C-C- H,C· C- -86- 201027245 【化5 1】

C3F7

O-O-p-0-80*-^ (CF2)e-Η

Among the above exemplified compounds, the following four compounds are preferred. 201027245 【化5 2】

Ο—S〇2—C«He

Among the diazomethane acid generators, specific examples of the dialkyl or bisarylsulfonyl nitromethanes are, for example, bis(isopropylsulfonyl)diazide, bis(P-toluenesulfonyl). Diazomethane, bis(I,1·dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl) ) Diazomethane and the like. Further, the diazomethane-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei 1 1 -03 5 5 5 No. 1 and JP-A No. 1 1 -03 55 . Further, poly(disulfonyl)diazomethane, for example, 1,3-bis(phenylsulfonyldiazomethylpropionic acid)propane disclosed in JP-A-H11-322707, 1,4 - bis(phenylsulfonyldiazomethylsulfonyl) butyl, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, ι, 1 〇 bis (phenyl Sulfhydrazinyldiazomethylsulfonyl)decane, 1,2-bis(cyclohexyldithiomethanediazepine), 1,3 -bis(cyclohexylaminediamine) Propylene, 1,6-bis(cyclohexylsulfonyldiazomethyl), hexane, 1,1 fluorene-bis(cyclohexylsulfonyldiazomethylsulfonyl)hydrazine Hospital and so on. (B2) Component 'The above-mentioned acid generator may be used singly or in combination of two or more. In the photoresist composition of the present invention, the content of the component (B) is from 0.5 to 30 parts by mass, preferably from 1 to 20 parts by mass, per 100 parts by mass of the component (A). When it is in the above range, the formation of the pattern can be sufficiently performed. Further, a homogeneous solution can be obtained, and it is preferable to have good storage stability and the like. < (D) Component> In the photoresist composition of the present invention, the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer And, etc., a nitrogen-containing organic compound (D) (hereinafter, also referred to as (D) component) of any component may be further added. As the component (D), various ingredients have been proposed so far, and any known component can be used, and among them, an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine is preferred. Here, the "aliphatic" in the scope of the patent application and the description of the present invention is defined as a group having no aromatic group, a compound, etc., relative to the relative enthusiasm of the aromatic. The "aliphatic cyclic group" is a monocyclic group or a polycyclic group which does not have an aromatic character. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group is preferably one having a carbon number of from 1 to 12. The aliphatic amine is, for example, an amine (alkylamine or alkanolamine) or a cyclic amine in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or a hydroxyalkyl group having 1 or more and 12 or less carbon atoms. Specific examples of the alkylamine and the alkanolamine are, for example, a monoalkylamine such as η-hexylamine, η-heptylamine, η-octylamine, η-decylamine, η-decylamine or the like; diethylamine -89 _ 201027245, di-n-amine of di-n-propylamine, di-n-heptylamine 'di-n-octylamine, dicyclohexylamine, etc.; trimethylamine, triethylamine' Tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n a trialkylamine such as mercaptoamine, tri-n-decylamine or tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n An alkanolamine such as octanolamine or tri-n-octanolamine. In this case, a trialkylamine having 5 to 10 carbon atoms is more preferred, and tri-η-pentylamine and tri-η-octylamine are preferred, and tri-n-pentylamine is preferred. . The cyclic amine is, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). The aliphatic monocyclic amine, specifically, for example, piperidine, piperazine or the like, an aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, for example, 1,5- Diazabicyclo[4.3.〇]-5-decene, I,8-diazabicyclo[5.4·0]-7-undecene, hexamethylenetetramine, 1,4-diaza Heterobicyclo[2·2.2] octane and the like. These may be used singly or in combination of two or more. The component (D) is usually in the range of 1 to 5.0 parts by mass based on 1 part by mass of the component (A). <Optional Component> [(E) Component] The photoresist composition of the present invention may contain any of the ingredients of 201027245 for the purpose of 'preventing sensitivity deterioration' or improving the shape of the photoresist pattern, and the stability of storage over time. At least one compound (E) (hereinafter also referred to as (E) component) selected from the group consisting of an organic carboxylic acid and a phosphoric acid and a derivative thereof, an organic carboxylic acid such as acetic acid, Malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferred. Phosphoric acid and its derivatives, such as phosphoric acid, Phosphonic acid, Phosphinic acid, etc., among which phosphonic acid is particularly preferred. The derivative of the phosphoric acid of the phosphorus, for example, an ester in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group is, for example, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms. A derivative of phosphoric acid, such as a phosphate such as di-n-butyl phosphate or diphenyl phosphate. a derivative of a phosphonic acid such as a phthalic acid dimethyl ester, a phosphonic acid-di-n-butyl ester, a phenylphosphonic acid, a diphenyl phthalate, a dibenzyl phthalate or the like. A derivative of a phosphonic acid, such as a phosphinate such as phenylphosphinic acid. The (Ε) component may be used singly or in combination of two or more. The (Ε) component is preferably an organic carboxylic acid, particularly salicylic acid. The (Ε) component is used in a ratio of 0.0 1 to 5 · 0 parts by mass relative to 100 parts by mass of the (Α) component. In the photoresist composition of the present invention, it is possible to appropriately add and contain a mixture of additives, such as an improved photoresist film performance, for example, to improve the properties of the photoresist, and to improve the coating property. Surfactant, dissolution inhibitor, plasticizer, stabilizer, colorant, antihalation agent, dye, etc. [(S) component] The photoresist composition of the present invention dissolves the material in an organic solvent (hereinafter, also referred to as It is manufactured in the form of (S) component. The (S) component may be a component which is a solution of a known solution which can be used as a solvent for a chemically amplified photoresist, as long as it can dissolve the components to be used, and one or more of them may be appropriately selected. use. For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-pentanone, methyl isoamyl ketone, and 2-heptanone; Polyols such as alcohol, diethylene glycol, propylene glycol, dipropylene glycol, etc.; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, etc. An ester-bonded compound, a polyalkyl ether or a monoalkyl ether of monomethyl ether, monopropyl ether or monobutyl ether, or a monophenyl ether or the like having the above-mentioned ester-bonded compound a derivative of a polyol such as an ether-bonded compound [in which propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) is preferred]; a ring such as dioxane Ethers, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy propyl Esters of ethyl acetate, etc.; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylbenzene-92- 201027245 ether, ethylbenzene, two Benzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. aromatic organic solvent. These organic solvents may be used singly or in combination of two or more. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), γ-butyrolactone are preferred, and PGMEA is mixed with a polar solvent. A mixed solvent is preferred. The addition ratio (mass ratio) may be appropriately determined in consideration of compatibility between PGMEA and a polar solvent, and is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. It is better. More specifically, for example, in the case of adding an EL of a polar solvent, the mass of PGMEA: EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Further, in the case of adding a polar solvent to PGME, the quality of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and most preferably 3: 7 to 7: 3. Further, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone may be used. In this case, the mixing ratio of the former and the latter is preferably 70: 30 to 95: 5 〇 In addition, the (S) component is a mixed solvent of the above PGMEA and PGME, and a mixed solvent of γ-butyrolactone. Also good. In this case, the mixing ratio is preferably 99.9: 0.1 to 80: 20, preferably 99.9: 0.1 to 90: 10, and 99.9: 0.1 to 95: 5 is optimal. -93- 201027245 When the range is within the above range, the rectangular shape of the photoresist pattern can be improved. The amount of the (S) component to be used is not particularly limited, and it can be appropriately set in accordance with the concentration which can be applied to a substrate or the like, and the thickness of the coating film is appropriately set. Generally, the solid content concentration of the photoresist composition is 2 to 20 mass. %, preferably in the range of 5 to 15% by mass, is used. In the present invention, an acid generator (B1) formed by using the compound represented by the above formula (bl-14) is used. In the (B1) component, the aryl group-bonded hydroxyl group has a structure protected by an acid-dissociable group having a tertiary alkyl ester type, and the structure is not changed in the non-exposed portion. Therefore, the compound represented by the above formula (bl-14) exhibits a dissolution inhibiting effect on the alkali developing solution for the component (A1) in the non-exposed portion of the resist film. Further, in the exposure portion, in the post-exposure heating (PEB) by the generated acid, the acid dissociable group is obtained by dissociating an oxygen atom constituting the hydroxyl group to form an aryl group-bonded hydroxyl group, for (A1) The composition can exert a dissolution promoting effect on the alkali developer. Therefore, the exposed portion/non-exposed portion can be formed with high contrast. Further, since the cation portion has a tertiary alkyl group having a monocyclic group, a good photoresist pattern shape can be formed, and the photoresist pattern can be formed. PEB Sensitivity is also a good compound.

The reason for this has not yet been determined, but it is presumed that the decomposition product produced by the tertiary alkyl group containing a monocyclic group disappears from the film in the PEB, and the result of suppressing the plastic effect can be suppressed. By suppressing the plasticizing effect, it is possible to suppress a decrease in Tg (glass transition temperature) in the photoresist film, and further suppress the diffusion of the acid generator. As a result, a good photoresist pattern shape can be formed, in particular, a pattern having a good LWR 201027245. For the above reasons, the photoresist composition of the present invention is a positive type, and the substrate component and the acid generator are used in combination. ( ) Ingredients) It is speculated that when forming a photoresist pattern, PEB Sensitivity can be changed, and the lithography etching characteristics can be improved. Further, the photoresist composition of the present invention is preferably used as an immersion exposure type φ in the formation method including the immersion exposure resistance pattern, and can obtain good lithography etching characteristics, and further comprises 3 layers. The formation of the photoresist pattern of the photoresist layer step cooperates to form a positive photoresist composition for forming the upper photoresist film, and has good lithographic etching characteristics. <Formation Method of Photoresist Pattern> Next, a photoresist pattern method of the second aspect of the present invention will be described. φ The method for forming the photoresist pattern of the present invention comprises the steps of: forming a photoresist on the support by using the photoresist composition of the first aspect of the invention to expose the photoresist film, and causing the photoresist film to be alkalized. The step of the photoresist pattern. As an example of a preferred method of forming the photoresist pattern of the present invention, the exposure of the photoresist film will be exemplified by the immersion exposure. However, the present invention is not limited thereto, and the exposure can also be carried out under normal exposure (dry exposure) in an inert gas. First, the photoresist composition of the present invention is formed by using a spin coating photoresist (B 1 善The LWR and the photo-resistance group for the photo-step are presumed to be in the coating method, and the step of forming the above-mentioned hair-producing film having the formation side is suitable for development, and the air or nitrogen argon coating such as the light is applied to the support - 95 - 201027245 After the body, a photoresist film is formed by pre-baking (Post Apply Bake (PAB) treatment). The support is not particularly limited, and a conventionally known material such as a substrate for an electronic component can be used, or An example of a support such as a sand wafer, a metal such as copper, chromium, iron, or aluminum, or a glass substrate is used. For example, a material of the circuit pattern can be used. Copper, aluminum, nickel, gold, etc. Further, the support may be used on the above-mentioned substrate, and an inorganic or/or organic film may be provided. An inorganic film such as an inorganic antireflection film (inorganic B ARC) )Wait An organic film, such as an organic anti-reflective film (organic B ARC ) or an organic film such as an underlying organic film in a multilayer photoresist method, etc. Among them, a multilayer photoresist method is provided with at least one organic film on a substrate. (lower organic film), and at least one layer of the photoresist film (upper photoresist film), using the photoresist pattern formed on the upper photoresist film as a mask to form a pattern of the lower organic film, and can be formed The pattern of high aspect ratio, that is, according to the multilayer photoresist method, since the lower organic film can ensure the required thickness, the photoresist film can be thinned, and a fine pattern with a high aspect ratio can be formed. In the photoresist method, basically, it can be roughly classified into a method having a two-layer structure such as an upper photoresist film and a lower organic film (two-layer photoresist method), and between the upper photoresist film and the lower organic film. A method of forming a multilayer structure of three or more layers of an intermediate layer (metal thin film or the like) (three-layer photoresist method). After the formation of the photoresist film, an organic anti-reflection film can be further disposed on the photoresist film. Formed by a support, with a photoresist film, and resistant A laminate of 3 - 96 - 201027245 formed of a film. The antireflection film provided on the photoresist film is preferably soluble in an alkali developer. The steps up to now can be carried out using well-known methods. Preferably, it is preferable to appropriately set the composition or characteristics of the photoresist composition to be used. Next, the photoresist film obtained above is subjected to selective immersion exposure through a desired mask pattern (Liquid Immersion). Lithography) At this time, a solvent (infiltration medium) having a refractive index larger than that of air is filled between the lens at the lowermost position of the photoresist film and the exposure device, and exposure is performed in this state (immersion type) Exposure) The wavelength used for the exposure is not particularly limited, and for example, radiation using an ArF excimer laser, a KrF excimer laser, or an F2 laser can be used. The photoresist composition of the present invention is effective for KrF or ArF excimer lasers, particularly ArF excimer lasers. The immersion medium is preferably a solvent having a refractive index larger than that of air and smaller than the refractive index of the photoresist film formed by using the above-described photoresist composition of the present invention. The refractive index of the solvent is not particularly limited as long as it is within the above range. A solvent having a refractive index higher than that of air and smaller than the refractive index of the resist film, for example, water, a fluorine-based inert liquid, an anthracene solvent, a hydrocarbon solvent, or the like. Specific examples of the fluorine-based inert liquid include, for example, liquids such as C3HC12F5, C4F9OCH3, C4F9, C2H5, and C5H3F7, which are mainly composed of a fluorine-based compound, and a boiling point of 70 to 180 ° C, and 80 to 160 ° C. Better. When the fluorine-97-201027245 is a liquid having a boiling point in the above range, it is preferable to remove the medium used for the immersion treatment after the end of the exposure. The fluorine-based inert liquid is preferably a perfluoroalkyl compound in which all of the hydrogen atoms of the hospital base are substituted by fluorine atoms. A perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further, specifically, for example, the above perfluoroalkyl ether compound, such as perfluoro(2-butyl-tetrahydrofuran) (boiling point: 1 〇 2 ° C), etc., the above perfluoroalkylamine compound, such as perfluorotributyl butyl Amine (boiling point 1 74 ° C) and the like. The photoresist composition of the present invention is particularly resistant to adverse effects caused by water, and has excellent lithographic etching characteristics such as sensitivity and photoresist pattern shape. Therefore, in the present invention, the medium is immersed in water. Preferably. Moreover, water is also preferable from the viewpoints of cost, safety, environmental problems, and extensive useability. Next, after the end of the immersion exposure step, post-exposure heating (post-exposure baking (PEB)) is performed. The PEB is usually carried out at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds. Subsequently, development treatment is carried out using an alkali developing solution formed of an alkaline aqueous solution, for example, 0.1 to 10% by mass of an aqueous solution of tetramethylammonium hydroxide (TMAH). After development, it is preferred to use pure water for water washing. The water washing is carried out, for example, by spraying water into the support body or by spraying the surface of the support to wash away the developer on the support and the photoresist composition dissolved by the developer. -98 - 201027245 Next, a photoresist film (coating film of the photoresist composition) is obtained by drying to form a resist pattern of a pattern shape according to the mask pattern. [Embodiment] [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. (Synthesis Example 1) <Synthesis of Compound A> Compound 1 (8.2 g) and dichloromethane (82 g) were added to a three-necked flask under a nitrogen atmosphere, and the mixture was cooled to 5 ° C or lower. After adding hydrazine, hydrazine-dimethylaminopyridine (〇.46g), and stirring at 5 ° C for 5 minutes, ethyl-N,N-dimethylaminopropyl carbodiimide was added ( 3.9g). After stirring for 10 minutes, the compound 2a (4.3 g) was added, and after the completion of the addition, the mixture was heated to room temperature, and stirred at room temperature for 15 hours, and then washed with diluted hydrochloric acid and washed with pure water φ. The organic phase was added dropwise to η-hexane (1 000 g), and after reprecipitation, Compound A (5.0 g) was obtained. The analysis results of the obtained compound by NMR are shown below: ^-NMRC DMSO-de, 400 MHz: δ (ppm) = 7.7 6 - 7.8 2 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.55 ( s, 2H, CH2), 2.29 (m, 6H, CH3), 1.90-1.93 (m, 4H, OCCH2 + cyclopentyl), 1.48- 1.75 (m, 6H, cyclopentyl), 0.77-0.81 (t, 3H, CH3) » From the above results, the compound A has the structure shown below. -99- 201027245 【化5 3】

(Synthesis Example 2) <Synthesis of Compound A-1> Compound A (2.2 g), dichloromethane (18.8 g) and pure water (7.3 g) were mixed, and perfluorobutanesulfonic acid was added thereto. Potassium (2.5 g) was stirred at room temperature overnight. Subsequently, the organic phase was separated, and the organic phase was washed 4 times with pure water (7.3 g). Subsequently, dichloromethane was distilled off under reduced pressure, and dried under reduced pressure to give Compound A-1 (2.8 g). The analysis results of the obtained compound by NMR are shown below. 'Η-ΝΜΚίΟΜΞΟ-άό, 400MHz) : δ(ρριη) = 7.76-7.82(m, 10H, ArH), 7.59(s, 2H, ArH), 4.55(s, 2H, CH2), 2.29(m, 6H, CH3), 1.90- 1.93 (m, 4H, OCCH2 + cyclopentyl), 1.48-1.75 (m, 6H, cyclopentyl), 0.77-0.81 (t, 3H, CH3). 19F-NMR (DMSO-d6, 3 76MHz): δ (ppm) = - 7 7.3, -1 1 1 · 5, -118.1, -122.4. From the above results, the compound A-1 had the structure shown below. -100- 201027245 【化5 4】

C4f9so3k ch2ci2-h2o

φ (Synthesis Examples 3 to 24) <Synthesis of Compounds A-2 to A-23> In the above Synthesis Example 2, the potassium perfluorobutanesulfonate was changed to the following Tables 1 to 6 Salt (equal molar amount), other than synthesis, the other methods are carried out in the same manner. λ λ ιυι - 201027245

Hydride NMR salt R for m X~M* Cationic anion 3 A-2 1 Η-NMR (DMSO-d6, 400MHz): d (ppm) = 7.76-7.B2(m, 1〇K ArH). 7.59 (s. 2K ArH), 4, 55ist 2H. CH2), 2.29Cm, 6H, CH3). 1.90-1.93 (m, 4H. OCCH2^cyclopentyl), 1.48-1.75 (m, 6H. cyclopentyl). 0.77- 0.81 (t 3H, CH3) «F-NMR (DMS0-d6, 37€MHz} : δ (ppm) = -75.0 Θ CF3SO3 ® K ΟΌ θ CF3SO3 4 A-3 'H-NMRCDMSO-dS, 400MHz): i (ppm) = 7.76-7.82 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.55 (s, 2H. CH2), 29 (m, 6H, CH3), 1.90-1.S3 (m , 4H, 0CCH2+cyclopentyl), Me-1.75 (m, 6H. cyclopentyO, 0.77-0.81 (t 3H, CH3) «F-NMR (DMS0-d6. 376MHz): δ (ppm) = -77.3. -112.5. -121.7 Θ C3F7SO3 Θ K :T°i) ΟΌ C3F7SO3 5 A-4 7H-NMR (OMSO-d6. 400MHz): 5 Cppm) = 7.76-7.B2(m* 1(H ArH)· 7.59(s. 2K ArH), 4.55U. 2H, CH2), 2.29(m, 6H, CH3). 1.90-1.93(m( 4H. OCCH2+cycl〇pentyl). 1.48-1.75(m, 6H, cyclopentyl). 0.77-0.81 (t. 3K CH3) tfF-NMR (DMSO-d6. 376 MHz); <5 (ppm) = -116.9. -123.0 G 02S'N'S〇2 f2c cf2 ^ c Φ Fa KV ΟΌ OjS^H'S〇2 FaC^ CFa Fa 6 A-5 1 H-NMR (D MSO-d6, 400MHz): 6 (ppm) = 7.76-7.82 (m. 10H. ArH), 7.59(8, 2H. ArH). 4.55(*t 2H, CH2). 2.29(m, 6H. CH3). 1.9〇-1.93(m. 4H. OCCH2+cycl〇pentyl), 1.48-1.75(m, 6H, cyclopentyl), 0.77-0.81 (t 3H, CH3) 19F-NMR (DMS〇-d6. 376MHz): < 5 (ppm) = -75.9, -76.0, -Π4.7 f2 i2 F3CF2CT, NT θκ® °Τββ ΟΌ 〇2 〇2 F3CF2C/S, yS, CF3 -102- 201027245 [Table 2]

Synthesis Example Compound m NMR Salt R xvr Cationic Anion 7 Α-β 'H-NMRC DMSO-dfi, 400 MHz): i (ppm) = 7.76-7.82 cm, 10 Η. ΑτΗλ 7.59 (s, 2H, ArH), 5.B3- 5.92(m, ΤΗ. anion CH), 5.41(dd, 1H, anion CH), 5.21(ddm. tH. anion CH). 4.55(s, 2H, CH2), 4.45(s, 2H. anion CH2), 2.29 (m. 6H, CH3), 1.90-1.93 (m, 4H. OCCH2+cycloperrty0, 1.4β-1.75(τη. 6H, cyclopentyl). 0.77-0.81 (t 3H, CH3) ieF-NMR (DMSO-d6. 376MHz ) : 6 (ppm) = -80.0, -113.0 ^^°^c^C'S〇t ® U ΟΌ 8 Α-7 W-NMFUDMSO-de, 400MHz): d(ppm) = 7.51-7.96(m, 19H, Arti+naph), 5.2〇Cs, 2H, anion CH2), 4.55<s, 2H, CH2), 2,29(m, 6H, CH3), 1.9〇-1.93(m. 4H, OCCH2+cydopenty(X 1.48-1.75(m, 6H, cyciopentyl). 0.77-0.81(1 3K CH3) 18F-NMR <DMSO-d6, 376MHz) : δ (ppm) = -60.5, 113.7 〇x〇iV0? ® Li ΟΌ οαΎ 9 Α-6 'H-NMRtDMSO-de. AOOMhizi: 6 (ppm) = 7.76-7.82 (m, 10H. ArH), 7.59 (5, 2H, ArH), 4.55 (s. 2H. CH2). 229 (m. 6H. CH3). 2.09(s. 3H. adamantan«), 1.90~1.9G(m. 10H, OCCH2+cyctopentyHadamantane), 1.48-1.75(m, 12H, cyciopentyH-adamantan e), 0.77-0.81 (t, 3H, CH3) 1SF-NMR (DMSO-d6. 376MHz): <5 (ppm) = -70.1. -113.4 ® U ΟΌ f2 10 Α-9 'H-NMR (DMS 〇-de. 400MHz): ί (ppm) = 7.76-7.82(m, 10H, ArH), 7.59(^ 2H, ArH), 4.55(3⁄4 2H, CH2)· 2^9(m. 6Ht CH3), 1.90 -H. s. F3co2s preparation so2cf3 H γ'β ΟΌ so2cf3 f3co2s each so2cf3 -103- 201027245 [Table 3] Synthetic gold NMR salt R cation anion η Α-10 1H-NMR (DMS0-d6, 400MHz): Λ (ppm) = 7.76 -7.82(^ 1〇K ArH), 7.59(5.2 Η, ArH), 4.55(s, 2H. CH2), 2.29(m. 0H, CH3). 1.90-1.93(m, 4H, 〇CCH2+cyclopentyi) , 1.48-t.75(m, 6Ht cyciopentyl), 0.77-0.81 (t 3H, CH3) , #F-NMR (DMSO-d6, 376MHz) : S (ppm) = -161.1, -149.7, -131.6, - 76.2 ;ψ: F3C02S"&'S02CF3 Θ Η :τ〇〇Ο^Ό ;γ; F3C〇2S Each SOjCF3 12 Α-” 'H-NMRiDMSO-de, 400MHz): 6 (ppm) = 7.76-7. B2(m. 10H. ArH). 7.59(a. 2H, ArH). 4.55(s, 2H. CH2). 2^9(m, 6H, CH3). 1.9(M.93(m. AH, OCC) H2+cyclopentyl), 1.48~1.88(m, 21H, cyciopentyt*^adam8ntane), 0.77-0,81 (t 3H. CH3) lfF-NMR (DMSO-d6. 376MHz): <5 (ppm) = -74.5 Ο °2 © Na Χ'β 03⁄4 S^yN's-CF3 〇〇2 13 Α-12 'H-NMRC DMSO-de, 400MHz): δ (ppm) = 7.76-7,82(m, 10H, ArH), 7.59 (e, 2H. ArH). 4.55(s, 2H, CH2). 4.19(s, 2H, anion CHZ), 2.29(m, 6H, CH3), 1.90-1.93 (111, 4H, OCCH2+cyclopenty〇, 1.48 -1.87(m, 21K cydopentyl+adamantane). 0.77-0.81 (t 3H, CH3) I#F-NMR (DMSO-d6. 376MHz) : δ <ppm) = -77.7 iS^AFs @ Na ΟΌ 14 Α- 13 'H-NMRi DMSO-dfi, 400 MHz): 5 (ppm) = 7.76-7.82 (m, 10H, ArH). 7.59 (s. 2H. ArtH), 4.55 (s. 2H. CH2), 2.77-2.81 (m , 1H, cyclohexyl), 2.29(m, 6H, CH3), 2.04-2.08(m. 2H. cyciohexyl), 1.90-1,93(m, 4H, OCCH2+cyclopentylX 1.48M.75 (m. 9K cyclopentyl+cyclohexyl 1.07-1.33(m, 5H, cyclohexyl). 0.77-〇.81(t 3H. CH3) ieF-NMR <DMSO-d6t 376MHz) : δ (ppm) = *74.7 0~H3 θ 9 θ Na ° Fh αο 0~^N^CF3 e -104- 201027245 [Table 4]

Synthetic gold NMR salt RX*M* Cationic anion 15 Α-14 'H-NMRC DMSO-dS, 400 MHz): 5 (ppm) = 7.76-7.82 (m, 10H, ArH). 7.59 (s, 2H. ArH} 4.55(3⁄4 2H. CH2)t 2.29(m, 6H, CH3), 2.13(m, 3H, adamantane), 1.90-1.99(m, 1〇K OCCH2+cydopenty(+adamantane). 1.48-t.75( m. 12H, cyclopentyl+adamantane), 0.77-〇.81(t 3H. CH3) '•F-NMR (DMS0-d6. 376MHz); 6 (ppm) = -69.2, -76.0. -112.9 F2 ° ® Na :T.乇Ο^Ό 16 Α-15 'H-NMRC DMSO-de. 400ΜΗϊ): $ (ppm) = 7.76-7.82 (mf 10H, ArH). 7.59(s. 2H. ArH), 4.55Cs. 2H, CH2)r 2.88Cd, 1H, anion CH), 2.66-2.74(m, 1H, anion CH). 2.37(d. 1H. anion GH). 2.17-2.29(m, 7K CH3+anion CH)t 1.4B- 1.93(m, 13H. OCCHS-^yclopentyl^anion CH+anion CH2). 1.22-U9(m. 2H. enion CH2), 1.03<s, 3H, anion CH3), 0.71-0.81^, 6H, CH3+ Anion CH3) \y ®〇aS^ 0 Na ΟΌ 〇17 Α-16 "H-NMRiDMSO-de. 400MHz): 5 (ppm) = 7.76-7.82(m, 10H, ArH), 7.59(s. 2K ArH 4.40-4.55(m. 6H. CH2+enion CH2), 2.29<m. 6H, CH3), l.90-1.93 (m. 4H, OCCH2+cyclopentyt), l-48-1.75 (m, 6H) Cyclope Ntyl), 0.77-0.8 Ut 3H. CH3) 19F-NMR (DMSO-d6, 376MHz): δ (ppm) - -106.7, -154.0, -1SO.O-161.5 F ® Na yiy "ότ 03⁄4 ΡΎ^ΓΡ Ft 丫Sc? 18 Α-17 'H-NMRiDMSO-dB, 400MHz): d (ppm) = 8.74-8.82(m, 2H. Py-H), 7.76-7.82(m, 1ZH, ArM+Py-Η) , 7.59(s, 2H. ArH), 4.55-4.61 (m, 6K CH2+ani〇n CH2CH2), 2.29(m, 6H, CH3)t 1.90-1.93 (mt4H, OCCH2+cyclopenty0, 1.48-1.75 (m. 6H. cyclopentyO, 0.77-0.81 (t 3H. CH3) l#F-NMR (DMS0-d6. 376MHz): 5 (ppm) = -106.5 1 〇? θ 丨广nV 〇Ο^Ό -ιυο - 201027245 [Table 5] Synthesis for «: NMR salt R) CM* Cationic anion 19 A-18 H-NMR (DMSO-d6. 400 MHz): 5 (ppm) = 7.76-7 82 (m. 1 〇K ArH), 7.59 (s, 2H, ArH), 5.46(t 1H, οκο-nori>omane), 4.97(s, 1H, oxo-norbomaneHTUcilH.oxo-norbomane), 4.55(m, 3H, CH2+ox〇-norbomane), 2.69 -2.73(m, 1H, oxo^ norbomane), 2.29(m, 6Ht CH3), 2.06-2.19Cnx ZH, oxo-norbomane), 1.90* t.93(m, AH, OCCH2+«yclopentyl), 1.48-1.75Cm 6K cyclopentyl), 0.77-0.81(t 3H CH3) '•F-NMR (DMS0-d6. 376MHz): $ (ppm) = -107.1 ® Na :Τ° > ΟΌ 20 Α-Ϊ9 1H-NMR (DMS〇-d6, 400MHz): 5 (ppm) = 7.76-7.82 (fa 1〇H. ArH>. 7.59Cs, 2H. ArH)f 4.55(*. 2H, CH2). 4.4Ut 2H anion CH2X 4.23Ct 2H. anion CH2). 0.77-2.89(fn. 40H, CHd+OCO^'^cyclopentyl+urKtecftnoyt) 1*F-NMR (DMSO~d6.376MHz): δ (ppm = -106.8 person CS〇3 O Fj H-fjP-/ °τ0ν6 ΟΌ 0 Fj 21 A-20 'H-NMRC DMSO-de, 400MHz): δ (ppm) = 7.76-7 82(m. 10H. ArH) , 7.59(s. 2K ArH). 4.55C*. 2H. CH2X 4.40(t 2H, anion CH2). 4^1 Ct 2H. anion CH2). 2.29(m. 6H. CH3), 1.48-1.98(m, 25H, OCCH2+cyclopentyl+adamantane>. 0.77-0.81(t, 3H, CH3), PF-NMR (DMSO-d6. 376MHz): 5 (ppm) = -106.B human g-scf O hV/ ΟΌ -106 - 201027245 [Table 6] B-formation NMR salt R for rM* cation anion 22 A-21 'H-NMRC DMSO-de, 400 MHz): 6 (ppm) = 7.76-7.82 (m, 1 〇H ArH), 7.59(s, 2H. ArfO. 4.55Cs, 2H, CH2), 4.4CKt 2H, anion CH2). 4.20(t 2K anion CH2). 2.29(m, 6H. CH3), Z05(s, 2H. anion CH2) , 1.48-1.93 (m, 25H, OCCH2^cyclopentyKa<tamantane}, 0.77-0.81 (t 3H, CH3), eF-NMR (DMSO-d6, 376MHz): d (ppm) = -111.2 0 hV/ °7°~6 ΟΌ 23 A-22 TH-NMR (DMSO-^6. 400MHz): d(ppm) = 7.7β-7.82(πι. 10K ArH). 7.59(s, 2H, ArH). 4.55 (m. 4H. CH2 + CF2CH2), 2.29 (m, 6H, CH3). 1.90-1.93 (m, 7H, OCCH2^cyclopentyH-adamantane). 1.82{m, 6H, adamantane), 1.48-1.75 (m. 12H, cydopentyKadamantane), 0.77* 0.81 (t3H. CH3) 1fF-NMR {DMSO-d6( 376MHz): <5 (ppm) = -111 *2 Na : 托V Ο^Ό 24 A-23 1H-NMR( DMSO-d6. 400ΜΗζ): δ (ppm) = 7.76-7.82 (m, 10Ht ArH). 7.5&(s, ZH. ArH). 4.78Cm. 1H, suitone), 4.6B(t 1H, sultone). 4.55(sf 2K CH2), 3.88(t, 1H, suitone), 3.34(m, 1H, suitone), 2.47-2.49(ιη, 1H, suttone), 2.29(m, 6H, CH3). 1.48-2.2 Urn. 14H, 0CCH2+cycl〇pentyi+sultone)f 0.77-0.8T(t 3H, CH3) '*F-NMR (DMS0-d6. 376MHz) : $ (ppm) = -107.7 O2S—O © Na 0〇Τ° ί> γ αο 0^-0

(Synthesis Example 25) <Synthesis of Compound B> Compound 1 (4.8 g) and dichloromethane (48 g) were added to a three-necked flask under a nitrogen atmosphere, and the mixture was cooled to the following. N,N-dimethylaminopyridine (〇.27g) was added thereto, and after stirring at 5 ° C or lower for 5 minutes, ethyl-ruthenium, dimethyl-dimethylaminopropyl carbodiimide was added ( 2.3g). After stirring for 10 minutes, compound 2b (2.2 g) was added. After the completion of the addition, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 15 hours, and then washed with diluted hydrochloric acid and washed with pure water -107-201027245. The organic phase was added dropwise to η-hexane (520 g), and after reprecipitation, Compound B (4.0 g) was obtained. The analysis results of the obtained compound by NMR are shown below. ^-NMRiDMSO-de, 400MHz) : δ (ppm) = 7.7 6 - 7.8 2 (m, 10H, ArH), 7.59(s, 2H, ArH), 4.55(s, 2H, CH2), 2.29(m, 6H , CH3), 1.90-2.08 (m, 2H, cyclopentyl), 1.4 8 -1 · 7 5 (m, 9 H, OCCH3 + cyclopentyl) From the above results, the compound B has the following structure. [5 5]

Compound B (2.5 g), dichloromethane (18.8 g) and pure water (7.1 g) were mixed, and potassium perfluorobutanesulfonate (2.5 g) was added thereto, and the mixture was stirred overnight at room temperature. Subsequently, the organic phase was separated, and the organic phase was washed 4 times with pure water (7.lg). Subsequently, dichloromethane was distilled off under reduced pressure, and dried under reduced pressure to give Compound B-1 (3·0 g). The analysis results of the obtained compound by NMR are shown below. i-NMRiDMSO-dG,400ΜΗζ) : δ(ρριη) = 7.76-7.82(m, 10H, ArH), 7.59(s, 2H, ArH), 4.55(s, 2H, CH2), 2.29(m, -108- 201027245 6H, CH3), 1,90-2.08 (m, 2H, cyclopentyl), 1. 4 8 - 1.7 5 (m, 9 H, OCCH3 + cyclopentyl). 19F-NMR (DMSO-d6, 3 76 MHz): δ (p pm) = - 7 7.3 , -111.5, -118.1, -122.4 ° From the above results, the compound B-1 had the structure shown below. 【化5 6】

C4F9SO3K ch2ci2-h2o

(Synthesis Examples 27 to 48) Synthesis of C Compounds b-2 to B-23> In the above Synthesis Example 24, except that the perfluorobutanesulfonic acid potassium salt was changed to be more as shown in the following Tables 7 to U. Salt (other molar amount), except for synthesis, is carried out in the same manner. λ r\ r\ 叫υ9 - 201027245

Synthesis Example Compound NMR Salt R cation anion 27 B-2 'H-NMRC DMSO-dB. 400 MHz): (5 (ppm) = 7.76-7.82 (m. 10H, ArH), 7.59 (s, 2H. ArH), 4.55 ( s. 2H, CH2), 2.29 (m, 6Ht CH3), 1.90-2-08 (m. 2H, cyclopentyl), 1.48-1.75 (01. 9Ht OCC H3+cyclopentyl) «F-NMR (DMSO-(i6. 376MHz) : δ (ppm) = -75.0 Θ CF3SO3 © K °T0i〇ΟΌ θ CF3S03 28 B-3 'H-NMRC DMSO-dfi, 400MHz): δ (ppm) = 7.76-7.82Cm, 10H, ArH), 7.59 (s, 2K ArH), 4.55 (s. 2H, CH2). 2.29 <mt 6H CH3), 1.90-2.08 (m, 2H, cyclopentyt), 1.48-1.75 (m, 9H, OCCH3+cyclopentyl) WF-NMR CDMSO-dfi. 376MHri : δ (ppm) = -77.3, -112.5.-121.7 G @ C3F7S03 k yb ΟΌ C3F7S03 29 B-4 'H-NMR (DMSO-d6. 400MHz): 6 (ppm) = 7.76-7.82 (m, 10H. ArH), 7.59 (s, 2H, ArH), 4.55 (8.22H. CH2). 2.29 (m. 6H, CH3), 1,90-2.08 (ϊα 2H. cyctopervtyD, 1.48-1.75 ( m, 9HT OCCH3+cyclopenty〇'•F-NMR (DMS0-d6, 376MHz): δ (ppm) = -116.9, -123.0 9 F2C, C/CF2 Kw °70i〇ΟΌ Θ S2S'N'S〇2 F20' c,0F2 Fa 30 B-5 'H-NMRiDMSO-dS, 400MHz): <5 (ppm) = 7.76-7.B2(m. 10H, ArH). 7.59(s, 2 H. ArH), 4.55 (3⁄4 2H, CH2), 2.29 (m, 6H. CH3), 1; 90-2.08 (m. 2H. cyckspentyl), l.48_1.75 (m, 9H, OCCH3+cycl〇pentyl ), #F-NMR (DM$0-d6. 376MHz): <5 (ppm) = -75.9, -76.0, -114.7 〇2 〇2 F3CF2C^S'N^SvCr3 θ K® °T°t> Xr 03⁄4 〇2 〇2 F3CF2<TS'f s, cf3 ©

110 201027245 [Table 8]

Synthesis Example Compound NMR Salt RX*M* Cationic Anion 31 B-6 (5 (ppm) = 7.76-7.82 (m, 10H. ArH), 7.59 (s, 2H, ArH), 5.83-5.92 (m, tH, anion CH), 5.41(dd, 1H, anion CH), 5^1(<W, 1H. anion CH), 4.45-4.55(m, 4H, CH2+anion CH2). 2.29(m, 6H. CH3), 1.50-2.08 (m, 2H. cyclopentyO, 1.48-l.75 (m, 9H, 〇CCH3+cydopenty〇t#F-NMR (DMS0-d6, 376MHz): δ (ppm) = -80.0. -113.0 ® Li °r°io ΟΌ I 32 B-7 'H-NMRiDMSO-dB, 400MHz); <5(ppm) = 7.51-7.96(m, 19H, ArH^Naph), 5.20(s, 2H, anion CH2), 4.55(s, 2H. CH2), 2^9(m. 6H.CH3), 1.90-2.08(m. 2H. cyclopentyl), 1.48-1.75 (m. 9H, OCCH3+cyclopentyl) lfF-NMR (DMS0-d6 , 376MHz): δ (ppm〉= -80.5, 113.7 〇〇r〇iV°? Li °T°t> ☆ 03⁄4 C〇r°V? 33 B-8 'H-NMRC DMSO-de. 400MHZ): 6 ( Ppm)-= 7.76-7.82(m, 10H, ArH), 7.59(s, 2H. ArHX 4.55(s, 2H, CH2). 2^9(m. 6H. CH3), 1.90-2.09(m. ItH, cyciopentyH-adamantane). 1.46H.75(m, 15H, OCCH3+cyclopentyl+adamantane>1#F*-NMR (DMS0-d6, 376MHz) : $ (ppm) = -70.1,-113.4 i^^crcVs〇3 ® ϋ °T0vb 0^0 i0^VSOjG F2 34 B-9 'H-NMRC DMSO-de, 400MHz): δ Cppm) = 7.76-7.82 (m. 10H, ArH), 7.59 (6.22H. ArH), 4.55 (s. 2H, CH2). 2.29 ( m, 6H, CH3). 1.90-2.08 (m. 2Ht cyclopentyl), 1.48-1.75{m, 9H, OCCH3+cycl〇penty() lfF-NMR (DMSO-d6, 376MHz): δ (ppm) = -73.7 SOjCF j f3co2s each so2cf3 ® H °T°t> ☆ 0^0 SO2CF3 f3co2s service so2cf3 111 - 201027245 [Table 9] Containing compound NMR salt R XM" Cationic anion 35 B-10 'H-NMRC DMSO-de, 400 MHz ): 5 (ppm) = 7.76-7.82Cm. 10H, Artt). 7.59(s, 2K ArH), 4.55(s, 2Η. CH2), BH, CH3), 1.90-2.08(m, 2H, cyclopentyl), 1.48-1.75{m, 9H, OCCH3+cyclopentyl> wF-NMR (DMSO-d6. 376MHz): δ Cppm) = -161.1.-149.7. -131.6. -76Λ ;Φ; F3C〇2S^S〇2CF3 Θ H :T°t> ΟΌ :ώ F3COjS Each S〇2CF3 36 B-11 'H-NMRiDMSO-de, 400MHz): <5 (ppm) = 7.76-7^2(m. 10H, ArH), 7.5»( s. 2K ArH). 4.55(5, 2H. CH2). 2J9(m, $H, CH3X 1.90-2.08(m, 2H, cyclopentyl), 1.48-t.88〇n, 24H, OCCH3+eyclopentyt*^adamantar&gt ;e) WF-NMR (DMSO-d6t 376MHz) : δ (ppm) = -74.5 @ Na 0^0 i〇v^^CF3 〇〇 2 37 B-12 1H-NMR (DMSO-d6. 400MHz): 6 (ppm) = 7.7β-7Λ2(ιη. 10H, ArH), 7.59(s, 2H, ArH), 4.55(8, 2H, CH2) , 4.19(s, 2H, anion CH2), 2.29(m, 6H, CH3), 1.9〇-2.08(γτι, 2H. cyclopentylX 1.4et.87(m. 24H. 〇CCH3+cyclopentyl+adamar>tane) ,# F-NMR (DMSO-d6. 376 MHi>: δ (ppm) = -77.7 ® Na ΟΌ 38 B-13 1H-NMR (DMSO-d6. 400 MHz): 5 (ppm) = 7.76-7.82 (m, 10H, ArH ), 7.5fi(s, 2H, ArH), 4.55(s. 2H, CH2), 2.77-2.81(m, 1H, cyclohexyl), 2^9(m, 6H, CH3), 1.90-2.08(^ 4H. Cyclopertyl+cyclohexyl), 1.48H.75 (m, 12H. OCCH3+cyclopentyl+cyclohexyl) (1.07-1.33 (m, 5H(cyclohexyt) WF-NMR (DMSO-d6, 376MHz): 6 (ppm) = -74.7 〇 2 〇2 ^~SyS, CF, ® Na °Τ°^0 0^0 Θ a -112- 201027245 Table 10] Synthesis of compound

NMR salt XM+ cation anion 39

BU 'H-NMRC DMSO-de. 400 MHz): 5 (ppm) = 7.76-7.82 (m, 10H, ArH), 7.59 <s, 2H. Arfl), 4.55 (s, 2H, CH2X 2.29 (m. 6H. CH3). 2.13(m, 3H. adamantane), 1.90-2.08 (m, 8H, cyclopentyi+adamarvtane), 1.48-1.75 (m, 15H, OCCH3+cyclopentyKadamantane), eF-NMR <DMSO-d6, 376MHz): δ (ppm) = -69.2, -76.0, -112.9 F2 〇2 〇acrc, crs, frs, cp3 ® Na :73⁄4 ΟΌ 7^1 f2 °2 〇a /^C^crc, fs, g, s, CF3 B-15 'H-NMRiDMSO-de, 400MHz): 5 (ppm) = 7.76-7.82 <m. 10H, ArH), 7.59 (s. 2K ArH), 4.55(s, 2H, CH2), 2*88 (ct 1H anion CH), 2.66-2·74(Γη, 1H, anion CH). 2.37(d. 1H, anion CH), 2.29(tn, 6H, CH3), 2A>Z2A{m, tHr anion CH) 1.9〇-2.〇a(m, 3H, cyclopantyl+anion CH), 1.48-1.89(m, ί 1H, OCCH3+c/clopentykanion CH2). 1.22-1.2$(m, 2H, anion CH2), 1.03 (s, 3H. anion CH3). 0.71 (s. 3H anion CH3) ®o9s

°T°t> αο

GOaS

41 B-16 1H-NMR (DMSO-d6, 400MHz): 5 (ppm) = 7.76-7.82Cm, 10H, ArH), 7.59(s, 2H, ArH), 4.4〇-4.55(mt 6K CH2+anion CH2 2_29(m, 6H. CH3), 1.90-2.08 (m. 2H, cyclopentyO, 1.48-1.75 (m, 9H, OCCH3+cyclopcnty〇T*F-NMR (DMSO-d6. 376MHz): δ (ppm) = -106.7. -154.0, -160.0-161.5

F ~.丫 C F 0

Na

丫'sc? 42 B-17 'H-NMRiDMSO-de. 4O0MHz): 5 (ppm) = 8.74-8.82 (m. 2H. Py-H)t 7.76-7.84 (m. 12H. Artt+Py-H) 7.59(s. 2H, ArH). 4.54-4.61<m, 6H, CH2+anion CH2CH2). 2.29(m. 6H, CH3). 1.90-2.08(m, 2H, cyclopentyl), 1.48-1.75(m , 9H, OCCH3+cyclopentyI) 19F-NMR <DMSO-d6, 376MHz) ; δ (ppm) = -106.5 so3 :T°t> αο

Μ M r\ -MO - 201027245

Table rL Synthesis Example Salt cation anion 43 B-18 ^-NMRC DMSO-de, 400 ΜΗϊ): 5 (ppm) = 7.76-7.82 (m. 10H, ArH), 7.59 (s, 2H, ArH). 5.46 (t 1H , ox〇-norbomane), 4.97($, 1H, oxo-norbomane), 4.71 (d. 1H. oxo-norbomane), 4.55(m, 3H, CH2+〇x〇-norbomane), 2.69-2.73(m. 1Η » oxo-norbomane), 2.29(m, 6H, CH3), 1.90-2.16(m, 4H, cyck>pentyl+oxo-norbomane), 1.48-1.75(m, 9K OCCH3+cycl〇pentyl),eF-NMR ( DMSO-dfi. 376MHz) : 6 (ppm) = -107.1 _

Na

;, s〇t 44 B-19 'H-NMRi DMSO-de, 400 MHz): δ (ppm) = 7.76-7.82 (mt 10H, ArH). 7.5S (s. 2H, ArH), 4.55 (s. 2H. CH2), 4.41 (t 2H, anion CH2), 4.23 (t 2H. anion CH2X 0.79-2.B9 (m, 38H, CH3+OCCH3+cyclopentyl+undecanoy〇'•F-NMR (DMS〇-d6. 376MHz) : S (ppm) = -106.8 _

45 B-20 'H-NMRC DMSO-de, 400 MHz): <5 Cppm) = 7.76-7.82 (m, 10H. ArH). 7.59 (s. 2K ArH). 4.55(3⁄4 2H, CH2). 4.40(t 2H, anion CH2), 4.21 (t. 2H. anion CH2). 2.29(mt 6H. CH3). 1.61-2.08(m, 26H. OCCH3 cut yclcpentyHadainantane> '•F-NMR (DMS〇-d6, 376MHz): δ (ppm) = -106.6 factory βhV/

i^Y. ❿ -114- 201027245 [Table 12] Synthesis Example Compound NMR Salt R cation anion 46 B-21 'H-NMR (DMS0-d6. 400MHr): 0<ppm) = 7.76-7.82 (m, 10H, ArH), 7.59(s, 2H. ArH)t 4.55(s, 2H, CH2), 4.40(t 2H, anion CH2). 4.20(t 2H, anion CH2). 2.29Cm, 6H, CH3X 1.53-2.08(m, Z8H, OCCH3+cyc 丨opentyl+anion CH2+a damantane) *»F-NMR (DMS0-d6, 376MHz): δ (ppm) = -111.2 On®/ n °T°t> O^O 47 B-22 'H -NMRiDMSO-de. 400MHz): 5 (ppm) = 7.76-7.82{m. 10H, ArH). 7.59(s. 2H, ArH). 4.55(m, 4H. CH2+CF2CH2), 2.29 (m. 6H, CH3). 1.90-^08(m, 5H, cyclopentyl+adamantane), 1.82(m, 6H, adamantane), 1.48~1.75(m, 15H, OCCH3^cyclopenty!+adamantane), 5F-NMR (DMS0-d6, 376MHz): δ (ppm) = -111.2. ® Na °Qy°-b αο 0 48 B-23 ^-NMRCDMSO-de, 400MHz): 6 (ppm) = 7.76-7.82 (m. 10H. ArH), 7.59 (s, 2H, suttone), 4.78 (t 1K suttone), 4.55 (s, 2H. CH2), 3.88 (t 1Hf sultone). 3.34 (m. 1H. suttone), 2.47~2.49Cm, 1H, sullone), 2.29(m. 6K CH3). 1.48-2.21 (m, 15H. OCCHS^ycfopentyl+sultone) ''F-NMR (DMS0-d6. 376M Hz): δ (ppm) = -107.7. ojs-o Φ Na °Τ〇Η0 ΟΌ /d^r°T°'sc§ 0^-0 ❹ (Synthesis Example 49) <Synthesis of Compound C> Compound 1 (8.81 g) and dichloromethane (88.lg) were added to a three-necked flask under a nitrogen atmosphere, and the mixture was cooled to 5 ° C or lower. N,N-dimethylaminopyridine (〇.49 g) was added thereto, and after stirring at 5 ° C or lower for 5 minutes, ethyl-N,N-dimethylaminopropyl carbodiimide was added ( 9.59g). After stirring for 10 minutes, a dichloromethane solution (30 g) of ethylcyclohexanol (5.13 g) was gradually added dropwise, and the mixture was heated to room temperature after completion of the dropwise addition. After stirring at room temperature for 3 hours, the diluted hydrochloric acid was repeated. Wash and wash with pure water. The organic phase was added dropwise to -115-201027245 η-hexane (100 g), and after reprecipitation, Compound C (2.0 g) was obtained. The analysis results of the obtained compound by NMR are shown below. ^-NMRCDMSO-de, 400ΜΗζ) : δ(ρριη) = 7.80-7.92 (m, 10H, ArH), 7.67 (s, 2H, ArH), 4.66 (s, 2H, CH2), 2.37 (s, 6H, Ar -CH3), 2.13-2.16 (m, 2H, cyclohexyl), 1.93 (q, 2H, CH2CH3), 1.14-1.57 (m, 8H, cyclohexyl), 0.84 (t, 3H, CH2CH3). From the above results, the compound c has the structure shown below. [化5 7]

(Synthesis Example 50) <Synthesis of Compound C-1> Compound C (4_lg), dichloromethane (57 g) and pure water (56.9 g) were mixed, and potassium perfluorobutanesulfonate (2.8) was added thereto. g), stirring at room temperature for one night. Then, the organic phase was separated, and the organic phase was washed 4 times with pure water (56.9 g). Subsequently, dichloromethane was distilled off under reduced pressure, and dried under reduced pressure to give Compound C-1 5.3 g. The analysis results of the obtained compound by NMR are shown below. H-NMR (DMSO-d6, 400MHz): δ(ρριη) = 7·80-7·92 (m, -116- 201027245 10H, ArH), 7.67 (s, 2H, ArH), 4.66 (s, 2H , CH2), 2.37 (s, 6H, Ar-CH3), 2.13-2.16 (m, 2H, cyclohexyl), 1.93 (q, 2H, CH2CH3), 1.14-1.57 (m, 8H, cyclohexyl), 0· 84 (t, 3H, CH2CH3). l9F-NMR (DMSO-d6, 3 76 MHz): δ (ppm) = - 7 7.3 , -111.5, -118.1, -122.4. From the above results, it was found that the compound c-1 has the structure shown below. φ [化5 8]

Compound C Br/Cl Compound C-1 C4F9S〇3 • (Synthesis Examples 51 to 72) <Synthesis of Compound C-2 to C-23> In addition to the perfluorobutanesulfonic acid potassium salt of the above Synthesis Example 50 The salt (the molar amount) shown in the following Tables 13 to 19 was changed and synthesized, and the others were carried out in the same manner. 201027245 [Table 13] Compound NMR Salt R 阳离子 Cationic anion 51 C~2 'H-NMRiOMSO-dfi, 400MHz): δ (ppm) = 7.SO-7.92 (m. 10H, ArH). 7.67 {s. 2H ArHX 4.66 (s, 2H, CH2), 2.37 (st 6H, Ar-CH3). 2.13-2.16 (m, 2H, cyclohexyl), 1.93 (α 2H. CH2CH3), 1.14-1.57 (m, 8H, cyclohexyl) , 0.84 (t 3H. CH2CH3). WF-NMR (DMSO-de, 376MHz): 6 (ppm) = -75.0. cf3so30 © K ^°t) ao θ CF 3SO3 52 C-3 1H-NMR (DMSO-d6 . . . 400 400 400 400 400 400 400 400 400 400 400 400 400 400 2.16 (m, 2H. cyciohexyl). 1.93 (a 2H, CH2CH3), 1.14-1.57 (m. 8H, cyclohexyO. 0.84 (t 3H. CH2CH3). **F-NMR (DMS〇-d6. 376MHz); δ (ppm) = -77.3. -112.5, -121.7. θ e c3f7s〇3 k rb 0^0 C3F7SO3 53 C-4 1H-NMR (DMSO-d6, 400MHi); <5 (ppm) = 7.80-7.92 ( m, 10H. ArH), 7.67 (s. 2H. ArH). 4.66 (β. 2K CH2). 2.37 ($. 6H. Ar-CH3), ^13-2.16 <m. 2H. cyclohexyl), 1.93 ( a 2K CH2CH3). 1.14-1.57 (m, 8H, cyclohexyl), 0.84 (t 3Ht CH2CH3). '*F-NMR (DMS0-d6, 376MHz): d (ppm) = -116.9, -123 .0. Θ KN o2s, , so2 F2〇^c^cf2 f2 yt ao θ M o2s,, so2 f2c^c.cf2 p2 54 C-5 'H-NMRC DMSO-de, 400MHz): 6 (ppm) = 7.80 -7.92 (m, 10H, ArH), 7.67 (s, 2H. ArH), 4.86 (s. 2H. CH2), 2.37 (s. 6H, Ar-CH3), 2.13-2.16 <m, 2H cyctehexyl). 1.93 Cq, 2H, CH2CH3). 1.14-1.57 (m, 8H, cyclohexyO, 0.84 (t, 3H. CH2CH3). 'F-NMR (DMS0-d6. 378MHz): 6 (ppm) = *75.9, -76.0, *1 Ϊ4.7. 〇2 〇2 F3CF2crs, rrs, cF3 θκ® :T°f) ao 〇2 〇2 F3CF2C, S, bat-S, CF3 -118- 201027245 Table 14] Synthesis of compound

NMR salt cation anion C-6 1 Η-NMR (DMSO-d6t 400MHz): 5 (ppm) = 7.80-7.92 (m, 10H. ArH), 7.67 (s, 2H. ArHX 5.83-5, 92 (m. 1H) Anion CH), 5.41(dd, 1H, anion CH), 5.21 (dd, 1H. anion CH). 4.66 (s, 2H. CH2), 4.45 (s. 2H. anion CH2). 2.37 (s. 6H Ar -CH3), 2.13-2.16 (m, 2H. cyciohexyl). 1.93 (q, 2H. CH2CH3). 1.14-1.57 (m, 8H, cyclohexyl), 0.84 (t 3H, CH2CH3). 1#F-NMR (DMSO -d6, 376MHz): 5 (ppm) = -80.0. -113.0. ^^0, c', sc^ Θ Li

C-7 'H-NMRiDMSO-de, 400MHz): 6 (ppm) = 7.51-7.96 (m. 19H, ArH+Naph), 5*20 (s· 2H, CH2). 4.66 (s. 2H, CH2) , 2.37 (s. 6K Ar<5H3). 2.13-2.16 (m. 2H, cyclohexyl), 1.93 (q, 2H, CH2CH3), 1.H-1.57 Cm. 8H. cyclohexyl). 0.84 (t 3H. CH2CH3) WF-NMR (DMSO-d6, 376MHz): 厶 (ppm) = -80.5, 113.7.

/SOT 08 ^-NMRC DMSO-de, 400MHz): δ (ppm) = 7Λ0-7.92 (m, 10H, ArH), 7.67 (s, 2H, ArH). 4.66 Cs, 2H, CH2), 2.37 (s, 6H Ar-CH3), 2.13-2.16 (m. 2H. cyclohexyl), 2.09 (s, 3H, adamantane), 1.96 (s, 6H, adamantane), 1.93 (q, 2H. CH2CH3). 1.14-1.57 (m. 14H. cyclohexyl+adamantane). 0.84 (t, 3H, CH2CH3). tsF-NMR (DMSO-d6, 376MHz): 5 (ppm) = -70.1, -113.4.

C-9 1H-NMR (DMSO-d6. 400MHz): δ (ppm) = 7.80-7.92 (m. 10H, ArH), 7.67 (s, 2H. ArH). 4.66 (s. 2K CH2). 2.37 (s , 6H. AP-CH3X 2.13-2.16 (m. 2H. cyclohexyl), 1.93 (α 2H. CH2CH3), 1.14-1.57 (mf 8K cyclohexyl), 0.84 (t, 3H, CH2CH3). , BF-NMR (DMS〇 -d6. 376MHz): (ppm) = -73.7.

SO2CF3F3C〇2S^S〇2CF3 H

SO2CF3 f3co2s preparation so2cf3 -119- 201027245 [Table 15]

Synthesis Example NMR Salt R Compound KVi* Cationic Anion 59 C-ΊΟ 1 H-NMR (DMS0-d6 (400MHz): δ (ppm) = 7.80-7.92 (m. 10H, ArH), 7.67 (s. 2Ht ArH) , 4.66 (s. 2H, CH2), 2.37 (s, 6H, Ar-CH3), 2.13-2.16 (m. 2H, cyclohexyl), 1.93 (q, 2H, CH2CH3). 1.14-1.57 Cm, 8H. cyclohexyO. NMR: DMSO-d6. 376MHz; ΟΌ A: F3C〇2S Each S〇2〇F3 60 C-11 1 H-NMRCDM$0-d6. 400MHz): δ (ppm) = 7.ΘΟ-7.92 (m, 10H. ArH), 7.67 (s. 2.H (2.H.H.H.H. 23H, cyclohexyKAdamantAne), 0.84 (t, 3K CH2CH3). 19F-NMR (DMSO-de. 376MHz): 6 (ppm) = -74.5. Θ Na °0ft) Xr 0^0 i©Y~CF3 61 C- 12 ΊΗ-NMR (DMSO-.400MHzh <5(ppm) = 7.80-7.92 (m. 10H. ArH). 7.67 {*. 2H. ArH), 4.66 (s, 2Ht CH2)t 4.19 (s, 2H , CH2), 2.37 (s. 6H, Ar-CH3). 2.13-2.16 (m, 2H, cyclohexyl), 1.93 (ς, 2H, CH2CH3), 1.14-1.87 (m, 23H. cydohexyH-Adamant Ane), 0.84 (t. 3H, CH2CH3). 19F-NMR (DMSO-d6. 376MHz): ^ (ppm) = -77.7. iQ^AFs Na 0^0

120- 201027245 Table 16] Synthesis Examples Compounds

NMR salt x*vr cation anion C-13 'H-NMRiDMSO-de. 400MHz): 6 (ppm) = 7.80-7.92 (m, 10H. ArHX 7.67 (s. 2H, ArH), 4.66 (s, 2H. CH2 ), Z.77-2.81 (m, 1H, anion- Cyclohexyl), 2.37 (s. 6H. Ar-CH3). 2.13-2.16 (m. 2H, cation^cyclohexyl), 2.04-2.08 (m, 2H, anion -Cydohexyl), 1.93 (q, 2H, CH2CH3), 1.73-1.75 (m« 2H, anion-CyclohexyD.I.'MI.SSOivHH.anion-cyclohexy^cation-cyciohexylD, 0.S4 (t, 3H, CH2CH3) lfF-NMR (DMSO-d6, 376MHz): i (ppm) = -74.7. ν', cf3 ®Na :T°t)ΟΌ Oi C-14 1H-NMR (DMSO-d6. 400MHz): d (ppm ) = 7.80-7.92 (m, 10H, ArH). 7.67 (s, 2H, ArH), 4.66 (3⁄4 2H, CH2), 2.37 (s. 6H, Ar-CH3). Μ3-2.Ί6 (m. 5H cyciohexyH*adamantaneX 1.99 (m ,6H, adamantane), 1.93 (qr 2H. CH2CH3). 1.59 (s, 6H, adamantane), 1.14-1.57 Cm, 8H, cyciohexyl), OM (t 3H, CH2CH3). ,eF -NMR (DMSO-d6r 376 MHz): δ (ppm) = -69.2. -76.0, -112.9.

ΟΌ 〇2 〇2 S, N'S, CF: C-15 1H-NMR (DMS0-d6, 400MHz): δ (ppm) = 7.80-7.92 (m, 10H, Ar+〇, 7.67 (s. 2H. ArH) 4.66 (s, 2H, CH2)( 2 B8 (d, 1H. CH). 2.66-2.74 Cm, ΊΚ CH). 2.37 (m. 7H, Ar-CH3+CH), 2.17-2.24 Cm, 1H, CH 2.13-2.16 (m, 2H, cyclohexyl). 1.93 (q, ZH, CH2CH3). 1.90 Ct, 1H. CH), 1.74-1.89 Cm. 2H, CH2). U4-1.57 (m, 10H, cyclohexyl+ Camphor)., 1.03 <s. 3H, camphor-CH3). 0.84 (t ZH, CHZCH3)^ 0.71 (s. 3H.camphor- CH3). eo3s^ ° ΘNa

201027245

Table rL synthesis example

NMR salt X*M+ cation anion 1H-NMR (DMSO-d6, 400MHz): d (ppm) = 7.80-7.92 (m, 10H, ArH). 7.67 (s. 2H. ArH), 4.66 (s. 2H, CH2 ), 4.40-4.50 (m, 4H. CH2), 2.37 (s. 6H, Ar-CH3), 2.13-116 (m, 2H, cyclohexyt), 1.93 (q, 2H, CH2CH3), 1.HI.57 ( m. 8H, cyclohexyl), 0.84 (t 3H, CH2CH3). '•F-NMR (DMSO~d6. 376MHz): d〇>pm) s -)06.7, -154.0, -160.0-161.5.

F

F O ΘNa

FX°^T 'SO% 'H-NMRC DMSO-de, 400MHz): 5 (ppm) = B.74-B.8Z (m. 2H, Py-H), 7.80-7.92 (m. Ί2Η, ΑιΉ+Py -H), 7.67 (s. 2H, ArH). 4.66 (s. 2H. CH2). 4.54-4.61 (m. 4H, CH2CH2). 2.37 (s, 6H Ar-CH3)t 2.13-2.16 (m, 2H , cyclohexy!), 1.93 (q, 2H, CH2CH3). 1.14-1.57 <m, 6K cyciohexyi), 0.84 (t 3H. CH2CH3). '*F-NMR (DMSO-d6, 376MHz): 5 (ppm) = -106.5.___ 'H-NMRC DMSO-de. 400MHz): 5 (ppm) = 7.80-7.92 (m, 10H, ArH), 7.67 (s. 2H. ArH), 5.46 (t. 1H. oxo-norbomane) , 4.97 (s, 1H, oxo-norbomane), 4.71(d, 1H, oxo-norbomane), 4.66 (s, 2H, CH2)f 4.57 (d, 1K oxo-norbomane), 2.69-2.73 Cm, 1H, oxo -norbomane), 2.37 (s, 6H. Ar-CH3). 2.13-2.16 (m, 2H, cyclohexyi), 2.06-2.12 (m, 2H ox〇-r>orbornane)f 1.93 (q. 2H CH2CH3). 1.14 -1.57 (m. 8H cyclohexyl), 0.84 (t, 3H. CH2CH3). 1#F-NMR (DMSO-de. 376MHz): 5 (ppm) = -107.1. -°YCSC^

~OyC.sc?®Na

-122- 201027245 [Table 18]

Synthesis Example Compound NMR Salt R Χ·Μ* Cationic Anion 68 C-19 'H-NMRiOMSO-de, 400MHz) : i(ppm) = 7.80-7.92 (m. 10H. ΑγΗ), 7.67 (s, 2H. ArH) , 4.66 (s, ZK CH2). 4.41 (t 2H. CH2). 4.23 (t, CH2), 0.7S-2.®9 (m. 42H Ai^CH3+ cyclohexyl+ CH2CH3+ CH2CH3+ Undecanoyl). , fF-NMR (DMSO -d6. 376MHz): d(ppm)= -106.8. 0 f2 hV :τ°ί) ΟΌ person es〇3 0 FZ 69 C-20 1H-NMR (DMS0-d6, 400MHz): 6 (ppm) = 7.80 -7.92 (m, 10H. ArH), 7.67 (s. 2H, ArH), 4.66 (s. 2H, CH2). 4.40 (t 2Hf CH2), 4.21 (t 2H. CH2), 2.37 (s. 6H. Ar -CH3), 2.13-2.16 (m, 2H. cyclohexyO. 193 (q. 2H, CH2CH3). 1.61-1.92 (mt 15HT Adamantane), 1.14-1.57 (m, 8H, cyclohexyl), 0.84 (t, 3H, CH2CH3 ). '*F-NMR (DMSO-d6. 376MHz): 5(ppm)= -106.6 person "so? k 0rt) 'tV Ο^Ό Ren Guang?

-123 - 201027245 [Table 19] Synthesis Example Compound NMR Salt R X'M+ Cationic Anion 70 C-21 'H-NMRiDMSO shout 400 MHz): 5 (ppm) = 7.80-7.92 (m. 10H, ArH), 7.67 (s , 2H, ArH), 4.66 (s, 2H, CH2), 4.40 Ct 2Ht CH2X 4.20 (t 2H. CH2), 2.37 (s, 6H, Ar-CH3), 2.13-2.16 (m. 2H. cyclohexyl). 2.05 (s. 2H. CH2). 1.93 (q. 2H. CH2CH3). U4-1.92 (m. 23H. cyclohexykadamantane), 0.84 (t, 3H, CH2CH3)., eF-NMR (DMS0-d6. 376MHz): 6 (ppm) = -111.2. ~.丫Xb V 0^0 71 C-22 'H-NMRC DMSO-de, 400MHz): δ (ppm) = 7.80-7.92 (m. 10H, ArH), 7.67 (s. ArH). 4.66 (s. 2R CH2) , 4.55 (t, 2H, CF2CH2), 2.37 (s. 6H. Ar-CH3), 2.13-2.16 (m, 2H, cyclohexyl), 1.94 (m. 3H. Ad), 1.93 (q. 2H. CH2CH3). 1.62 (m, 6H. Ad). 1.64 (m. 6H, Ad), 1.14-1.57 (m, 8H, cyclohexyl), 0.84 (t 3H, CH2CH3). 1#F-NMR (DMS0-d6, 376MHz): d(ppm) = -t 1 Ϊ.2. o Θ Na ao 72 C-23 'H-NMRC DMSO-de, 400MHz): 6 (ppm) = 7.80-7.92 (m, 10H, ArH), 7.67 (s. 2H, ArH), 4.78 (m, 1Ht CH), 4.66 (m, 3H. CH2+anion). 3.88 (t 1H, anion-CH), 3.34 (m, 1H, anion-CH), 2.47-2.49 (m , 1H. anion-CH), 2.37 (s, 6H, Ai-CH3). 1.73-2.21 (m. 8H. cyclohexyl+ CH2CH3+anion-CH2). 1.14-1.57 (m. 8H, cyclohexyl), 0.84 Ct 3H. CH2CH3). 1SF-NMR (DMS0-d6. 376MHz): δ (pfwn) - -107.7. ^r°rc's〇3 Ο》-. / Na ΟΌ 〇W °

<Preparation of Photoresist Composition> (Examples 1 to 1 2, Comparative Example 1) As shown in Table 20, each component was mixed and dissolved to prepare a positive resist composition. -124- 201027245 [Table 20]

(A) Component (Β) Component (D) Component (E) Component (5) Component Comparison Example (A)-1 (Β)-1 (D)-1 (E)-1 (S) — 1 (S)-2 1 [too] [6.19] [0-75] [0.75] [10] [2400] Example Α -1)-1 (Β)-2 (D)-1 (E)-1 (s)-1 (S) -2 1 [100] [6.53] [0-75] [0.75] [10] [2400] Example (Α)-Ί (Β)—3 (D)-1 (E)-1 (S)-1 (5) A 2 2 EtOO] [6,41] [0.75] [0.75] [103 [2400] Example (Α)-1 (8) - 4 (D)-1 (E)-1 (s)-1 (S) —2 3 [100] [6.59] [0-75] [0.75] [to] [2400] Example (Α)_Ί (Β) -5 (D)-1 (E)-1 (S)-1 ( S)-2 4 [100] [7.01] [0-75] [0.75] [10] [2400] Example (Α)-1 (Β)-6 (D)-1 (E)-1 (s) -1 (S)-2 5 [100] [6.89] [0.75] [0.75] [10] [2400] Example (Α)-1 (Β)-7 (D)-1 (E)-1 < S)-1 (S)-2 6 [1003 [7.07] [0.75] [0-75] [TO] 12400] Example (Α)-1 (Β)-8 (D)-1 (E)-1 (S)-1 (S)-2 7 [1003 [6.45] [0.75] [0.75] [10] [2400] Example (Α)-1 (Β)-9 (D)-1 (E) — 1 (S)-1 (S)-2 8 [1〇〇] [6.33] [0.75] [0.75] [to] [2400] Example (Α)-1 (B)-t0 (D)-1 (E )-1 (S)-1 (S)-2 9 [100] [6.51] [0.75] (10) [2400] Example (Α)- 1 ίΒ)-11 (D)-1 (E) — 1 (S)-1 (S)-2 10 [100] [6,73] [0-753 [0.75] 1103 [2400] Example (Α) — 1 (8) - 12 (D)-1 (E)-1 (S)-1 (S)-2 11 [too] [6.61] [0-753 C0.75] [t〇3 [2400] Example ( Α)-1 (Β)-13 (D)-1 (E)-1 (S)-1 (S)-2 12 [tool [6.79] [0.75] [0.75] [10] [2400] Table 20 Each abbreviation indicates the following content, and the number in [] is λ r\ -1^0 - 201027245 Addition amount (parts by mass). (A) -1: The copolymer represented by the following chemical formula (A 11-1), Mw7000, Mw/Mn = 1.5. In the formula, a 1/a2/a3/a4 = 40/25/25/1 0 > represents the ratio of each structural unit (% by mole). The copolymer is composed of α-methacryloxy-γ-butyrolactone, 1-ethyl-1-cyclohexyl methacrylate, 1-methyl-1-cyclopentyl methacrylate, 3-hydroxyl The 1-adamantyl methacrylate is polymerized by a known radical polymerization method. [化5 9]

(Β) -1: A compound represented by the following chemical formula (Β)-1. (Β) -2: A compound represented by the following chemical formula (Β) -2 (compound Α-22). (Β) -3: A compound represented by the following chemical formula (Β) -3 (compound Β-22). (Β) -4 : A compound represented by the following chemical formula (Β) -4 (compound C-22). (Β) -5: A compound represented by the following chemical formula (Β) -5 (compound Α-20). (Β) -6 : a compound represented by the following chemical formula (Β)-6 (compound Β-20). -126-201027245 (B) -7 : a compound represented by the following chemical formula (B)-7 (compound C-20). (B) -8 : a compound represented by the following chemical formula (B)-8 (Compound A -1 8 ). (B) -9 : a compound represented by the following chemical formula (B)-9 (compound B -1 8 ). (B) - 1 0 : a compound represented by the following chemical formula (B) -10 (compound C -1 8 ). (B) -11: a compound represented by the following chemical formula (B)-11 (compound A - 2 3 ). (B) -12: a compound represented by the following chemical formula (B)-12 (compound B - 2 3 ). (B) -13: a compound represented by the following chemical formula (B)-13 (compound C - 2 3 ). [化60]

-127 201027245

(B)-8 -128- 201027245

(D ) -1 : Tri-n-pentylamine. (Ε ) - 1 : Salicylic acid. (S ) -1 : γ-butyrolactone. (S ) -2 : PGMEA/PGME = 6/4 (mass ratio) of mixed solvent <Evaluation of lithographic etching characteristics> ^ Using the obtained photoresist composition, a photoresist pattern was formed in the following order, and evaluated Photolithography etching characteristics. [Formation of resist pattern] The organic anti-reflective film composition "ARC29" (trade name, manufactured by Puliwa Co., Ltd.) was applied onto a 8 inch silicon wafer using a spin coater on a hot plate. The organic antireflection film having a thickness of 77 nm was formed by baking and drying at 205 ° C for 60 seconds. The positive-type photoresist composition prepared above was applied onto the anti-reflection film by a spin coater, and calcined at 90 ° C for 60 seconds on a hot plate -129-201027245. The baking (PAB) treatment was dried to form a photoresist film having a film thickness of 150 nm. Next, using an ArF immersion exposure apparatus NSR-S302B (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60 'σ2/3 Annu ) ' with a 6% halftone mask pattern, the ArF excimer for the aforementioned photoresist film' Laser (193 nm) for selective illumination. Subsequently, the PEB treatment at 90 ° C for 60 seconds was carried out, and at 23 ° C, the TMAH aqueous solution NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) of 2.38 mass% was subjected to development for 30 seconds, and thereafter After 30 seconds, it was washed with pure water, vibrated and dried, and further baked at 1 ° C for 60 seconds. As a result, in any of the examples, a line and space pattern (hereinafter also referred to as "L/S pattern") having a line width of 130 nm and a pitch of 260 nm is formed on the photoresist film. The sensitivity at the time of forming the L/S pattern of 1 30 nm described above was taken as the optimum exposure amount Eop (mJ/cm2). The Εορ of each positive-type photoresist composition is shown in Table 21. <ΡΕΒ Sensitivity evaluation> Using the obtained positive-type photoresist composition solution, the evaluation of PEB Sensitivity (hereinafter, also referred to as "PEBs") was performed as follows. The PEB temperature conditions at this time were set to 88 ° C, 90 ° C, and 92 ° C. The following is the order. Based on the above three PEB temperatures (88 ° C, 90 ° C, and 92 ° C), a calibration curve was prepared for each of the relationship between the pattern size (measured 値) of the exposure amount of 201027245. Next, at 90 °C of the PEB temperature, EOP at a line width of 130 nm and a pitch of 260 nm is formed at a PEB temperature of 90 ° C (calculation 値). The calculation of the EOP is carried out by a calibration line at a PEB temperature of 88 ° C and a calibration line at a PEB temperature of 90 ° C at a PEB temperature of 92 ° C to calculate the pattern size. Next, the calculation is performed by taking the calculation of the three pattern sizes as the vertical axis, and the _ temperature (88 ° C, 90 t, 92 ° C) is plotted as the horizontal axis, and the slope of the calibration curve is accompanied by the PEB. The change in temperature is the amount of change in the size of the pattern per unit temperature (nm/°C). The results are shown in Table 21. [LWR (Line Edge Bump) Evaluation] In the L/S pattern with a line width of 130 nm and a pitch of 260 nm formed by the above Εορ, a length measuring SEM (scanning electron microscope, acceleration voltage of 800 V, trade name: S-) was used. 9220, manufactured by Hitachi, Ltd.), measuring 5 line widths according to the length direction of the line φ path, and calculating 3 times 値 (3s) of the standard deviation (s) calculated by the result as the index scale of the LWR. The results are shown in Table 21. The smaller the number of 3s is, the smaller the line width and unevenness is, and the L/S pattern with a more uniform width can be obtained. [MEF (Mask Defect Factor) Evaluation] In the above Εορ, the S/L pattern with a spatial width of 1 2 〇 nm and a pitch of 240 nm is used as the mask pattern of the target, and the S/L with a space width of 130 nm and a pitch of 260 nm. The pattern as the target mask pattern forms the S/L pattern, and the number of MEFs is obtained by the following formula -131 - 201027245. The results are summarized in Table 21. MEF = |CD)3〇-CD,2〇|/|MDi3〇-MD12〇| In the above formula, CD13Q and CD12Q are S/L formed by a mask pattern with a space width of 130 nm and 120 nm as targets. The actual space width (urn) of the pattern. MD13Q and MD12〇 are the space width (nm) with the mask pattern as the target, MD13〇=130, MD12〇=120. The closer the enthalpy of the MEF is to 1, the more the resistive pattern of the faithful response mask pattern can be formed. [Evaluation of Exposure Tolerance (EL Tolerance)] In the above EOP, the space of the S/L pattern is formed within ±5% (123_5 nm to 136.5 nm) of the target size (space width 1 30 nm). The amount of exposure, and the EL latitude (unit: %) is obtained according to the following formula. The results are summarized in Table 21. EL latitude (%) = (|Ε1-Ε2|/ΕΟΡ)χ100

El: Exposure amount (mJ/cm2) at the time of forming an S/L pattern having a space width of 123.5 nm E2: Exposure amount (mJ/cm2) at the time of forming an S/L pattern having a space width of 136.5 nm Further, EL tolerance When the number is larger, it means that the amount of change in the pattern size is smaller as the amount of exposure changes. -132- 201027245 [Table 21] Εορ (mJ/cm2) PEB sensitivity (nm/°C) LWR (nm) EL 04) MEF Comparative Example 1 36.6 2.45 7.82 7.76 2.83 Example 1 37.1 1.35 7.42 7.50 2.84 Example 2 38.2 2.10 6.22 7.19 2.79 Example 3 37.5 1.80 7.25 7.23 2.81 Example 4 36.3 1.45 7.49 7.55 2.87 Example 5 35.9 2.07 6.28 7.24 2.82 Example 6 37.4 1.92 7.32 7.28 2.84 Example 7 43.7 1.39 7.28 7.58 2.56 Example 8 45.9 2.24 6.05 7.26 2.51 Example 9 44.2 1.91 7.18 7.30 2.53 Example 10 46.8 1.34 7.22 7.68 2.40 Example 11 43.4 2.09 5.99 7.36 2.26 Example 12 41.2 1.95 7.12 7.40 2.42

From the above results, in the present invention, the photoresist compositions of Examples 1 to 12 were confirmed to have better PEB Sensitivity and LWR than either of the photoresist compositions of Comparative Example 1. Further, in the present invention, the photoresist compositions of Examples 1 to 12 can be obtained with the same EL latitude as compared with the photoresist composition of Comparative Example 1. Further, -133 - 201027245 The photoresist compositions of the first to twelfth embodiments of the present invention were confirmed to have an MEF or a superior MEF equivalent to that of Comparative Example 1 as compared with the comparative example. The above is a description of preferred embodiments of the invention, but the invention is not limited by the embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the scope of the invention. The present invention is not limited by the description, but is only limited by the scope of the appended claims. -134-

Claims (1)

201027245 VII. Patent application: 1 · A photoresist composition which is a substrate component (A) containing a change in solubility of an alkali developer via an acid and an acid generated by exposure to an acid The photoresist composition of the component (B), wherein the acid generator component (B) is an acid generator (B1) formed by a compound represented by the following formula (bl-14). 1] • # R8:4+ χ- L· ... (b 1-1 4) [wherein, R7"~R9", respectively, independently represent an aryl group or an alkyl group; and among R7"~R9'', any two of them may be bonded to each other and form a ring together with a sulfur atom in the formula; R7' At least one of _~R9'' is a substituted aryl group in which one part of a hydrogen atom is substituted by a group represented by the following formula (bl4-2); X. is an anion] [Chemical 2] R51 [wherein, R5C) is a linear or branched alkyl group, and R51 is a group having a carbon number of 1 to 6 'R52 represents a hydrogen atom or a carbon number of 1 to 5, and η -135-201027245 is An integer of 0 or 1 to 6; -CH2- constituting the above monocyclic structure may be substituted by an oxygen atom (-〇-)]. 2. The photoresist composition according to claim 1, wherein the substrate component (A) is a substrate component which increases solubility in an alkali developer via an action of an acid. 3. The photoresist composition according to claim 2, wherein the substrate component (A) is a resin component (A1) which is a structural unit derived from an acrylate having an acid dissociable dissolution inhibiting group ( Al). 4. The photoresist composition according to claim 2, wherein the substrate component (A) is a resin component (A1) which is a structural unit derived from an acrylate having a lactone-containing cyclic group. (a2). 5. The photoresist composition according to claim 3, wherein the substrate component (A) is a resin component (A1), and the oxime has a structural unit derived from an acrylate containing a lactone-containing cyclic group. (a2). 6. The photoresist composition according to claim 2, wherein the substrate component (A) is a resin component (A1) which is a structural unit derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. (a3). 7. The photoresist composition according to claim 3, wherein the substrate component (A) is a resin component (A1), and the oxime has a structural unit derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. (a3). 8. The photoresist composition according to claim 5, wherein the substrate component (A) is a resin component (A1), and the oxime has a structural unit derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. (a3). 9. The photoresist composition according to item 1 of the patent application, which contains -136-201027245 nitrogen-containing organic compound (D). 10. A method for forming a photoresist pattern, comprising the steps of forming a photoresist film on a support using the photoresist composition of claim 1 and exposing the photoresist film, and The step of alkali developing the aforementioned photoresist film to form a photoresist pattern. 11. A compound represented by the following formula (bl-14), [Chemical Formula 3] f R8-S+ λ' Meaning 9" 1 1 (b1-i4) [wherein R7"~R9"' are independently represented Any one of aryl or alkyl; R7" to R9" may be bonded to each other and form a ring together with a sulfur atom in the formula; at least one of R7"~R9'' is a part of a hydrogen atom a substituted aryl group substituted by a group represented by the following formula (bl4-2); X· is an anion] [Chemical 4] R51 η -137- 1 · ( b 1 4 - 2 ) [wherein, R5Q is a linear or branched alkyl group, R51 is a hospital group having a carbon number of 1 to 6, and R represents a gas atom or a carbon number. The base of 1 to 5, η 201027245 is an integer of 0 or 1 to 6; -CH2- constituting the above monocyclic structure, may be substituted by an oxygen atom (-〇-)]. 12. An acid generator characterized by being formed by a compound of claim 11 of the scope of the patent application. -138- 201027245 IV. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is a simple description ·· 201027245 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: [1] [Chemical 1] -4-