TW201040136A - Alicyclic compound, method for manufacturing same, composition containing same and resist pattern formation method using same - Google Patents

Abstract

Disclosed are an alicyclic compound in which a cholic acid ester structure-containing group is bound to an adamantane skeleton, method for manufacturing the same, composition containing the same, and resist pattern formation method using the same, that provide an alicyclic compound which has superior solvent properties, light exposure sensitivity, resolution, roughness, and heat resistance, etc., and especially excellent dissolution inhibiting effect against development fluids, and is useful as a positive photoresist monomer or dissolution inhibitor used in semiconductor device fabrication, and that provide a method for manufacturing the same, composition containing the same, and resist pattern formation method using the same.

Description

201040136 VI. Description of the Invention: [Technical Field] The present invention relates to an alicyclic compound, a method for producing the compound, a composition containing the compound, and a method for forming a photoresist pattern using the same, and more specifically This is an alicyclic compound having a positive photoresist function, which means that it is usually a solution which has a dissolution inhibitory effect on an alkali solution, but which is decomposed by an acid generated by a photoacid generator to become an alkali-soluble fat. A cyclic compound, a method for producing the compound, a composition containing the compound, and a method for forming a photoresist pattern using the same. [Prior Art] In recent years, as the miniaturization of semiconductor elements progresses, in the photolithography step in the manufacture thereof, it is required to be more refined, and various uses correspond to KrF, ArF or F2 excimers. A method of forming a fine pattern by a short-wavelength light-shielding material such as laser light is reviewed. Further, the appearance of a new photoresist material which can correspond to short-wavelength illumination light such as excimer laser light is more desirable. In terms of photoresist materials, although a large number of polymers based on phenol resins have been developed in the past, these materials have a large absorption of light due to the inclusion of aromatic rings, and they have not been obtained. The accuracy of the pattern is determined in accordance with the miniaturization. Further, in the case of the compound having a dissolution-inhibiting effect, a phenol-based compound typified by diazonaphthoquinone (DNQ) may be used. However, similarly to the above-mentioned polymer, light is generated by irradiation light of a short wavelength. Absorption, so -5 - 201040136 has a limit on the formation of fine patterns. Therefore, in terms of photosensitive photoresist in semiconductor fabrication by ArF excimer laser, it is proposed to have an alicyclic skeleton such as 2-methyl-2-adamantyl methacrylate. A polymer obtained by copolymerizing a polymerizable compound (for example, refer to Patent Document 1). However, with the further development of microfabrication technology, at this stage, if only the line width of 32 nm or less is desired with the prior art, the exposure sensitivity, resolution, pattern shape, exposure depth, surface roughness, etc. cannot be solved. All kinds of requirements require performance. Specifically, the problem of smoothness such as the roughness (roughness) or the ridge of the surface of the pattern called LER and LWR has become more prominent. Further, in recent years, in the method of liquid immersion exposure, it is also common to cause image defects due to 光 = defects such as a photoresist pattern caused by a liquid immersion medium. Further, in the semiconductor manufacturing process using the extreme ultraviolet (EUV) of 13.5 nm, in order to increase the throughput, it is more desirable to develop a high-sensitivity photoresist. Due to the driving force of the prior art, although the required performance can be improved, it is difficult to achieve the "exposure sensitivity, resolution, and surface roughness" under the trade-off relationship at the same time. Among them, a monomolecular compound called a low molecular resist is different from a conventional polymer compound in that it is expected to be a material which is greatly reduced in surface roughness from its molecular size, not only in terms of exposure sensitivity and resolution. In the case of the low molecular resistance, for example, in the patent documents 2 to 7, a polyphenol-based low molecular compound such as caHxarene or calixresorcinarene has been developed as a semiconductor manufacturing material for lithography-6- 201040136 material. Although these are easy to synthesize, they absorb light due to an aromatic ring and a short-wavelength light source of KrF or ArF, and cannot be used. Generally, the wavelength that can be used for exposure is limited to the g-line or i-line of a high-pressure mercury lamp, or a soft X-ray. Therefore, there are several alicyclic low molecular compounds which are applicable to the most advanced mass production exposure technique ArF excimer lasers (refer to Patent Documents 8 to 1 1). Furthermore, the present inventors have also developed a low-molecular compound of a full-aliphatic ring type (refer to Patent Document 12). The ruthenium compound group described in these is highly transparent due to a full-alicyclic compound, and can be lithographically formed by any light source. Further, a material excellent in thermal stability with an adamantane skeleton can be combined with a heat resistance process. However, in the case of a specific compound (refer to the compound number G R - 5 of Patent Document 12), it is necessary to use a dilute developing solution which has high solubility in a developing liquid and which causes a film to be reduced. On the other hand, various oligo-molecular compounds have been proposed as dissolution inhibitors in the lithography technique of the existing polymer-based photoresist (refer to Patent Documents 〇 13 to 15). However, such compounds have low heat resistance due to their low molecular weight, and are not considered to be used in semiconductor manufacturing processes that have been subjected to high temperature in ancient and modern times. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei-4-39665 (Patent Document 2) U.S. Patent No. 6, pp. 93,517 (Patent Document 3) JP-A-2004-191913 (Patent Literature) (4) Patent No. 2007-197389 (Patent Document 5) JP-A-2007-197389 (Patent Document 6) Patent No. 4 0 7 6 7 8 9 [Patent Document 7] JP-A-2008-089709 Japanese Laid-Open Patent Publication No. 2007-193328 (Patent Document 10) JP-A-2007-210996 (Patent Document 1) Opens 2 0 0 7 - 3 1 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei 2 0 0 5 - 1 8 3 8 3 9 (Patent Document I 4) Special Opening 2 0 0 5 [Patent Document 15] [Patent Document 15] JP-A-2008- 1 1 6720 SUMMARY OF INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a situation as described above. A positive photoresist or a dissolution inhibitor used in the manufacture of a semiconductor device It is excellent in solubility characteristics, exposure sensitivity, resolution, roughness, heat resistance, and the like, and particularly an alicyclic compound excellent in dissolution inhibitory effect on a developing solution, a method for producing the compound, and a composition containing the compound. And a method of forming a photoresist pattern using the same. [Means for Solving the Problem] The present inventors have found that in order to achieve the above-mentioned object, it has been found that an alicyclic ring having a structure of a bile acid ester-containing group - 8 - 201040136 bonded to an adamantane skeleton is used. The compound of the formula solves the above problems, and thus the present invention has been completed. That is, the present invention provides the following inventions: 1. An alicyclic compound represented by the following formula (丨), [Chemical Formula 1] R*2

(wherein Ral~ are each independently a group containing a cholic acid ester structure represented by the following general formula (&)) [Chemical 2]

(In the formula, Rb represents a hydroxyl group or an oxygen-containing organic group having a carbon number of 2 to 30 as defined in the general formula (Μ)~(b5); 11° and Rd each independently represent a hydrogen atom; And a hydroxyl group or an oxygen-containing organic group having a carbon number of 2 to 30 as defined in any one of the following formulas (b5); and Rf each independently represents a hydrogen atom or a carbon number which may have a hetero atom a linear, branched or cyclic hydrocarbon group of 1 to 1 ;; η represents 1 or 2; a represents a single bond or a hydrocarbon group having a carbon number of 1 to 5; however, there are no 3 Rb, RC and Rd systems. In the case of a hydroxyl group at the same time) [Chemical 3] ζι 〇 A (b1) -9 - 201040136 In the formula C, Z1 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to ι 5 of a hetero atom) [Chemical 4 z^°Y°v (b2) Ο (wherein Ζ2 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 of a hetero atom) [Chemical 5] Ζ3

(b 3) (wherein Z3 represents a linear, branched or cyclic hydrocarbon group which may have a carbon number of 1 to 9 of a hetero atom; and Rg and Rh each independently represent a hydrogen atom or may have a hetero atom a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms)

(b 4) (wherein Z4 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 which may have a hetero atom) [Chemical 7] Z5-

(b 5) (wherein, Z5 to Z7 each independently represent a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 10 which is a hetero atom); 2- an alicyclic compound as described above 'Where' in the above general formula (a) -10- 201040136 Re and. It is a hydrogen atom, and VIII is a single bond; 3. The alicyclic compound as in the above 1 or 2 wherein η in the above general formula (a) is 1, and Re is. The alicyclic compound of any one of the above 1 to 3, wherein Rb of the above general formula (a) is as defined by the general formula (bl) The alicyclic compound according to any one of the above 1 to 3, wherein Rb in the above general formula (a) is a hydroxyl group; A method for producing an alicyclic compound of 3 or 5, which is characterized in that 'the following bile acids are represented by any one of the general formulae (cl) to (C4) and from 1,3,5-paran (ethyleneoxy) Adamantane, anthracene, 3,5-g (halomethoxy) adamantane, 1,3,5-gin (vinyloxymethyl)adamantane and 1,3,5-paran (methylthio One or more reactions selected from methoxy) adamantane;

-11 - 201040136

(c4) 7. The method for producing an alicyclic compound according to any one of the above 1 to 6 which is characterized by the following alicyclic compound represented by the general formula (1 - 1) and the following One or more kinds of reactions of the oxygen-containing organic compound represented by any one of the formulas (d1) to (d5), [Chem. 9]

(1-1) (In the formula, Ra4 to Ra6 are each independently a general formula (the group containing a cholic acid ester structure) [Chemical 1 〇]

(wherein Rh and each independently are a hydrogen atom or a hydroxyl group) [Chemical "] (d1)

Z1 乂X (wherein Z1 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 of a hetero atom; X represents a halogen atom) [Chemical 1 2] 汝〇丫〇Y〇'z2 (d2) ο ο -12- 201040136 状,分分(wherein, Z2 represents a straight-bonded or cyclic hydrocarbon group which may have a carbon number of a hetero atom of ～15) [Chemical Formula 1]

(d3) a hydrocarbon having a shape, a molecule or a shape (wherein Z3 represents a straight-bonded or cyclic hydrocarbon group which may have a carbon number of 1 to 9 of a hetero atom; and Rg and Rh each independently represent a hydrogenogen 0 may have a linear, branched or cyclic group having a carbon number of 1 to 10 in a hetero atom; X is a halogen atom; (1) a broad 0 丫, (d4) 0 shape, and a fraction (wherein Z4 represents a miscellaneous a linear branched or cyclic hydrocarbon group having 1 to 15 carbon atoms; X represents a halogen atom) [Chemical 1 5] Z*

Zs-Si—X (d5) z7 number 1 to sub); as shown in the above (wherein, Z5 to Z7 each independently represent a linear, branched or cyclic group of carbon which may have a hetero atom; a hydrocarbon group; x represents a halogen precursor. 8. A method for producing an alicyclic compound according to the above 7, wherein Ra4 to Ra6 in the general formula (1 -1) is a structure containing a cholic acid ester of the following general formula (a.2). Base; -13- 201040136 〔化1 6〕

9. A composition comprising the alicyclic compound of any one of the above 1 to 5; 1 〇. The composition of the above 9, further comprising a solvent and an acid generator t 11. as described above 9 or a composition of 10, further comprising a digestor; 1 2 _ a composition according to any one of the above 9 to 1 1 which is a positive photoresist composition; and, 13. A method for forming a pattern, comprising: a step of forming a photoresist film on a support by using the composition of any one of the above 9 to 12 as a positive photoresist; and exposing the photoresist film, The photoresist film is subjected to alkali development to form a photoresist pattern. [Effects of the Invention] The alicyclic compound of the present invention is excellent in solubility characteristics, exposure sensitivity, resolution, roughness, heat resistance, and the like, and is particularly excellent in the effect of suppressing dissolution of a developing solution. [Embodiment] [Formation for carrying out the invention] -14- 201040136 The present invention provides an alicyclic compound represented by the following formula (1). 〔化1 7〕

(In the formula, Ral to Ra3 are each independently a group having a cholic acid ester structure represented by the following general formula (a).) Ral to Ra3 in the above general formula (1) may be the same or each other. It is preferable that the base containing the cholic acid ester is all the same as Ra 1 to Ra 3 . 〔化1 8〕

Rb in the above general formula (a) represents a hydroxyl group or an oxygen-containing organic group having 2 to 30 carbon atoms represented by any one of the general formulas (Q bl) to (b5), more preferably a hydroxyl group or the following An oxygen-containing organic group having a carbon number of 2 to 15 represented by the general formula (bl). In the above general formula (a), 1 and R each independently represent a hydrogen atom, a hydroxyl group or an oxygen-containing organic group having a carbon number of 2 to 30 represented by any one of the general formulae (b1) to (b5). Preferably, it is a hydrogen atom, a hydroxyl group or an oxygen-containing organic group having a carbon number of 2 to 15 represented by the general formula (b1) to (b5), and more preferably a hydrogen atom or a hydroxyl group. Re and Rf in the above general formula (a) each independently represent a hydrogen atom or a linear, branched or -15-201040136 cyclic hydrocarbon group having a carbon number of 1 to 1 杂 having a hetero atom. It is preferably a hydrogen atom or a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 6 which is a hetero atom, and more preferably a hydrogen atom. η in the above general formula (a) represents 1 or 2, preferably 1. The above formula (a) represents a single bond or a divalent hydrocarbon group having a carbon number of 丨5, preferably a single bond. However, in the above general formula (a), 'Rb, R. And there are no three cases in which the Rd system is a hydroxyl group at the same time. In the above general formula (a), specific examples of the linear, branched or cyclic hydrocarbon group which may have a carbon number of 1 to 1 杂 of a hetero atom represented by Re and 1 are a methyl group and a a linear hydrocarbon group such as a η-propyl group, an η-butyl group, an n-pentyl group, an n-hexyl group or an η-heptyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, A cyclic hydrocarbon group such as a branched hydrocarbon group such as a neopentyl group, a cyclopentyl group, a cyclohexyl group or an adamantyl group. Specific examples of the hetero atom of Re and Rf include a nitrogen atom, an oxygen atom, and a sulfur atom. In the above general formula (a), specific examples of the divalent hydrocarbon group having 1 to 5 carbon atoms represented by A include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. [Chemical Formula 1] ζΛΛ (b1) Z1 in the above general formula (b1) represents a linear, branched or cyclic ketone group having a carbon number of 1 to 15 which may have a hetero atom, preferably a carbon number of 1~ a linear, branched or cyclic hydrocarbon group of 5. -16- 201040136 〔化20〕

(b2) The z2 in the above general formula (μ) represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 which is a hetero atom, preferably a linear or branched carbon number of 1 to 8. Hydrocarbon group or cyclic. 〔化 2 1〕

〇早, 〆 (b3) Z3 in the above general formula (b3) represents a linear, branched or cyclic hydrocarbon group which may have a carbon number i to 9 of a hetero atom, preferably a carbon number of 1 to 4. a linear, branched or cyclic hydrocarbon group. Rg and Rh in the above general formula (b3) each independently represent a hydrogen atom or a linear, branched or cyclic ketone group having a carbon number of 1 to 10 which may have a hetero atom, preferably a hydrogen atom or It is a linear, branched or cyclic hydrocarbon group having 1 to 5 carbon atoms. 4 [Chemical Formula 22] z4/Oyv〇A (b4) Z4 in the above general formula (b4) represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 which may have a hetero atom, preferably A linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. ZE Z*—SiO Ί ( b 5 ) -17- 201040136 Z5 to Z7 in the above general formula (b5) each independently represent a linear or branched shape having a carbon number of 1 to 10 which may have a hetero atom. The cyclic hydrocarbon group ' is preferably a linear, branched or cyclic hydrocarbon group having 1 to 5 carbon atoms. a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 1 represented by Z1 in the above general formula (bl), which may have a hetero atom as shown by Z2 in the above general formula (b2) a linear, branched or cyclic hydrocarbon group having a number of 丨-15, which is a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 9 which may have a hetero atom as represented by Z3 in the above general formula (b3). The linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 1 杂 of a hetero atom represented by RS and Rh in the above general formula (b3), and Z4 shown in the above general formula (b4) a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 of a hetero atom and a linear chain having a carbon number of 1 to 10 which may have a hetero atom as shown by Z5 to Z7 in the above general formula (b5) Specific examples of the hydrocarbon group in the form of a branched, branched or cyclic ring include a linear chain of a methyl group, an ethyl group, an η-propyl group, an η-butyl group, an η-pentyl group, an η-hexyl group, and an η-heptyl group. a cyclic hydrocarbon group such as a branched hydrocarbon group such as a hydrocarbon group, an isopropyl group, an sec-butyl group, a tert-butyl group, an isopentyl group or a neopentyl group; a cyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group or an adamantyl group; Specific examples of the hetero atom of Z1 to Z7 include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The alicyclic structure-containing compound of the present invention can be produced by various methods. Representative examples are the following production methods A to D', but are not limited thereto. Production Method A: After the halogenated alkyl ether body is obtained by reacting an alcohol containing an adamantane structure in the presence of an aldehyde with a hydrogen halide gas, the halogenated alkyl ether body-18·201040136 and the cholic acid are carried out. The method of esterification reaction. Production method B: an alkylthioalkyl ether body obtained by using an adamantane-structured alcohol in the presence of an alkylarylene and an acid anhydride, and a halogenated alkyl ether body by a halogenating agent, further performing the halogenated alkyl ether A method of esterification of a body with a bile acid. Production Method C: A method of performing an esterification reaction of a vinyl ether having an adamantane structure with a cholesteric acid in the presence of an acid catalyst. Production Method D: A method of performing a hydroxy protecting reaction of the alicyclic compound obtained by the above Production Methods A to C using an oxygen-containing organic compound. (Production Method A) The alcohol containing the adamantane structure in the above Production Method A may, for example, be 1,3,5-adamantane triol or 1,3,5-parax (hydroxymethyl)adamantane.方面 The aldehyde in the production method A may, for example, be a linear or branched aliphatic aldehyde such as formaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, and one type or 2 or more types. The hydrogen halide gas in the production method A may, for example, be a hydrogen fluoride gas, a hydrogen chloride gas or a monomer gas such as hydrogen bromide gas or a mixed gas thereof. The bile acid in the production method A may, for example, be a cholic acid represented by the following formula (c): lithocholic acid represented by the following formula (Cl), and the following formula (c2) Deoxycholic acid (-19-201040136 deoxycholic acid), ursodeoxycholic acid represented by formula (C3), and gooseoxycholic acid represented by formula (C4) below A saturated bile acid derivative such as an acid (Chenodeoxycholic acid) may be used alone or in combination of two or more. However, in the case of the bile acid, when the following bile acid represented by the formula (c 0 ) is used, the alicyclic compound of the present invention which satisfies the above general formula (a) cannot be obtained, and the production method described later must be further carried out. D. 〔化 24〕

The halogenated alkyl ether system in the production method A can be obtained by reacting an alcohol containing an adamantane in the presence of a wake-up with a hydrogen halide gas. In this case, the organic solvent may be used in the presence or absence of the organic solvent. However, when the organic solvent is used in the case of -20-201040136, the amount of the alcohol having the adamantane structure is not particularly limited, and is not particularly limited. It is preferred to adjust the substrate concentration to 01 mol/l to 10 m/l. If the substrate concentration is 〇. Moer / liter or more, since the necessary amount can be obtained in a general reactor, it is economically preferable, and the right substrate concentration is 1 〇 mol / liter or less 'the reaction liquid Temperature control is easy and preferred. Examples of the organic solvent that can be used include hydrocarbon-based solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, and tetrahydrofuran ( An ether-based solvent such as THF), dioxane or dimethoxyethane (DME); a halogen-based solvent such as dichloromethane or carbon tetrachloride; wherein the halogen-based solvent having a high dissolved amount of hydrogen halide gas is It is preferable to use one type or a mixture of two or more types. Further, although the reaction temperature may be any temperature, if the temperature is too high, the solubility of the hydrogen halide gas may be lowered. If the temperature is too low, the progress of the reaction itself may be slow, so that 〇°C~4〇°C It is better. Although the pressure can be any pressure, it is necessary to control the side reaction under pressure, and it is preferable to use normal pressure. Also, when the pressure is too high, it is necessary to have a special pressure-resistant device, which is not economically good. Specific examples of the halogenated alkyl ether body thus obtained include, for example, a 1,3-, 5-thio(halomethoxy) fused house. The esterification reaction in Production Method A can be carried out by reacting a sulfonate group with a cholic acid. Further, it may be carried out in the presence or absence of an organic solvent, but in the case of using an organic solvent, it is preferred to adjust the substrate concentration to ι·m mole/liter to 10 m/liter. If the substrate concentration is -21 - 201040136 0.1 mol/liter or more, it is economical because it is in a general reactor, and if the substrate concentration is 10, the temperature control of the reaction liquid is easy and preferable. The surface to be used may be a hydrocarbon-based solvent such as hexane, heptane, cyclohexane, ethylcyclohexyl or xylene; diethyl ether, dibutyl (THF), dioxane or dimethoxy group. Ethane (DME) medium; halogen-based solvent such as dichloromethane or carbon tetrachloride; methyl formamidine, dimethyl hydrazine (DMSO), N-ketone (NMP), trimethyl hexamethyl phosphate Apron (HMPA) Aminoproline (HMPT), a disulfide, or the like may be used alone or in combination of two or more. Sodium hydride, sodium hydroxide, lithium hydroxide, lithium 'sodium hydrogencarbonate, lithium argon carbonate, silver oxide, sodium citrate monohydrogenate, lithium dihydrogen citrate, lithium monohydrogen citrate, sodium Methoxide, lithium t-butoxide, triethylamine trioctylamine, pyridine, N,N-dimethylaminopyridine, 1 [4,3,0]non-5-ene (DBN), An inorganic base such as l,8-diazabicyclocarbon-7-ene (DBU) or an organic amine. After the above esterification reaction, the reaction product liquid is separated to extract the product from the water layer as needed. The alicyclic compound of the present invention can be obtained by distilling off the solvent from the reaction liquid. Alternatively, the reaction solution may be supplied to the next reverse side without purification, and may be obtained by distillation, extraction, washing, crystallization, re-precipitation, cerium oxide colloidal column chromatography, and the like. An alcohol-soluble DMF (n,N-dimethyl-2-pyrrolidine or hexamethylphosphorous polar solvent) of the organic solvent pentane, benzene, toluene, tetrahydrofuran or the like Base, sodium carbonate, carbonic acid, lithium niobate, ruthenium, dihydrogen monobutyrate, tributylamine, 5-diazabicyclo[5,4,0] eleven water and organic layer, by decompression It can be purely as needed. Purification method, activated carbon adsorption, considering the production scale of -22-201040136, the necessary purity to choose, but because it can be operated at a lower temperature, and can process a large number of samples at a time' It is preferred to use a method of washing, crystallization or reprecipitation, especially in the method of removing the raw material used from the alicyclic compound of the present invention, although various methods can be employed, but it is operative or economical. From the point of view, it is based on the use of alicyclic compounds. The method of washing the raw material with a poor solvent is preferred. Among the poor solvents for the alicyclic compound, the lower boiling point is preferred, and representative examples include diethyl ether 0, methanol, ethanol, η- Hexane, η-heptane, etc. (Production Method Β) The alcohol and the bile acid having the adamantane structure in the above production method can be used in the same manner as the above-mentioned production method. The hydrazine side may, for example, be dimethyl hydrazine, diethyl hydrazine, di-η-propyl fluorene, diisopropyl hydrazine, di-η-butyl fluorene, diisobutyl fluorene, Symmetrical or asymmetrical symmetry or asymmetry of di-sec-butyl hydrazine, di-ter t-butyl fluorene, triisoamyl sulfoxide, methyl ethyl hydrazine, methyl-tert-butyl fluorene The aliphatic hydrazine may be used singly or in combination of two or more kinds. However, considering the unity of the reaction product, a symmetrical aliphatic fluorene is preferable, and a dimethyl fluorene having a short chain length alkyl group is more preferable. Examples of the acid anhydride in the production method B include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, geishic anhydride, trimethyl acetic anhydride, benzoic anhydride, and chlorine B. An aliphatic or aromatic carboxylic acid anhydride such as an anhydride or a trifluoroacetic acid anhydride may be used alone or in combination of two or more. Examples of the halogenating agent in the production method B include sulfonium chloride, -23-201040136 chlorination. a halogenated sulfur compound such as a sulfonyl group, a sulfonium bromide group, a brominated sulfonium sulfonate group, a sulfonium bromide sulfonate group, a brominated sulfonium sulfonate group, or a phosphorus trichloride, phosphorus tribromide or triiodide A phosphorus halide compound such as phosphorus, trichlorophosphoric acid, phosphorous tribromide, phosphorus pentachloride or phosphorus pentabromide may be used alone or in combination of two or more. The system can be obtained by reacting an alcohol having an adamantane structure in the presence of an alkyl sub-milling and an acid anhydride. In this case, although it can be carried out in the presence or absence of an organic solvent, it is usually used in a large excess. The alkyl hydrazine and the acid anhydride are reacted as a reaction reagent and a solvent. Particularly in the case of using an organic solvent, it is preferred to adjust the substrate concentration to 1 mol/l to 10 m/l. If the substrate concentration is 1 mol/L or more, the necessary amount can be obtained in a general reactor, so it is economically preferable, and if the substrate concentration is 10 mol/liter or less, the temperature of the reaction liquid Control is easy and better. Examples of the organic solvent that can be used include hydrocarbon-based solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, and THF ( An ether-based solvent such as tetrahydrofuran), dioxane or DM E (dimethoxyethane); or a halogen-based solvent such as dichloromethane or carbon tetrachloride; and one type or a mixture of two or more types may be used. Use it. Although the reaction temperature can be any temperature, if the temperature is too high, the selectivity caused by the side reaction will decrease. If the temperature is too low, the reaction itself will be slowed down, and the room temperature will be ~60. °C is better. Although the pressure can be any pressure, it is necessary to control the side reaction under pressurized conditions, and it is preferable to use normal pressure. When the pressure is too high, it is necessary to have a special pressure-resistant device, which is not economically good. Specific examples of the alkylthioalkyl ether body thus obtained include -24-201040136, 1,3,5-glycol(methylthiomethoxy)adamantane and the like. The halogenated alkyl ether system in Production Process B can be obtained by reacting the above alkylthioalkyl ether body with a halogenating agent. In this case, the halogenating agent may be used in a large amount as a reaction reagent and a solvent, although it may be carried out in the presence or absence of an organic solvent. Particularly in the case of using an organic solvent, it is preferred to adjust the substrate concentration to 0.1 mol/l to 10 m/l. If the substrate concentration is 0.1 mol/L or more, since it is necessary to obtain a necessary amount in a general reactor, it is economically preferable, and if the substrate concentration is 10 mol/liter or less, the temperature of the reaction liquid is higher. Control is easy and better. Examples of the organic solvent that can be used include hydrocarbon-based solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, and tetrahydrofuran ( An ether-based solvent such as THF), dioxane or dimethoxyethane (DME); a halogen-based solvent such as dichloromethane or carbon tetrachloride; and one or a mixture of two or more of them may be used. It. Although the reaction temperature can be any temperature, if the temperature is too high, the selectivity caused by the side reaction will decrease. If the temperature is too low, the reaction itself will slow down, and the room temperature will be ~1. 0 0 °c is preferred. Although the pressure can be any pressure, it is preferable to control the side reaction because of the pressure under the pressurized condition. When the pressure is too high, it is necessary to have a special pressure-resistant device, which is not economically good. Specific examples of the halogenated alkyl ether body thus obtained include 1,3,5-gin(halomethoxy)adamantane and the like. The esterification reaction in the production method B can be carried out in the same manner as in the esterification reaction in the above production method a. -25-201040136 (Manufacturing Method c) The vinyl ether structure of the adamantane structure in the above production method c is exemplified by 1,3,5-glycol (ethyleneoxy)adamantane, 1,3,5-parameter (Vinyloxymethyl) King Kong Institute and the like. In the case of the cholic acid in the production method C, the same method as the above production method A can be used. Examples of the acid catalyst in the production method C include any organic and inorganic acid defined by Lewis acid, Brucenic acid, and arrhenic acid, but preferably, formic acid, acetic acid, and hydrochloric acid are mentioned. , sulphuric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and the like. In the above production method C, a vinyl ether having an adamantane structure is reacted with a cholic acid in the presence of an acid catalyst. In this case, the organic solvent may be used in the presence or absence of an organic solvent. However, when the organic solvent is used, it is not particularly limited as long as it is equal to or less than the saturated solubility of the vinyl ether having an adamantane structure. The substrate concentration is 〇. 1 mol / liter ~ 1 0 m / liter is preferred. If the substrate concentration is 0.1 mol/L or more, since the necessary amount can be obtained in a general reactor, it is economically preferable, and if the substrate concentration is 1 〇 mol/liter or less, the temperature of the reaction liquid Control is easy and better. Examples of the organic solvent that can be used include hydrocarbon-based solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, and tetrahydrofuran ( An ether-based solvent such as THF), dioxane or dimethoxyethane (DM E ); halogen-26-201040136-based solvent of methylene chloride or carbon tetrachloride, wherein the dissolved amount of hydrogen halide gas is high. The halogen-based solvent is preferable, and one type of these may be used or two or more types may be used in combination. Further, although the reaction temperature may be any temperature, if the temperature is too high, the vinyl ethers containing the adamantane structure will polymerize each other to cause the occurrence of side reactions. If the temperature is too low, the progress of the reaction itself becomes slow. It is better to use 〇乞 ~ 4 0 °C. Although the pressure can be any pressure, it is necessary to control the side reaction under pressure conditions, and it is preferable to use normal pressure. Also, when the pressure is too high, it is necessary to have a special pressure-resistant device, which is not economically good. (Production Method D) For the alicyclic compound obtained by the above Production Methods A to C, the hydroxy protection reaction shown below can be carried out. In particular, in the above production methods A to C, 'in the case where cholic acid represented by the above formula (c〇) is used as the cholic acid, etc., 'Rb 〇, Re in the above general formula (a) of the alicyclic compound. When the three Rd groups are simultaneously hydroxyl groups, it is necessary to carry out the following hydroxy protection reaction. The alicyclic compound used in the production method D is preferably the one represented by the general formula (1-1). [Chem. 2 5]

(In the formula, '4 to Ra6 are each independently a group containing a cholic acid ester structure which is not represented by the general formula (a-Ι), and is preferably represented by the following formula (a-2)-27 - 201040136 The base of the cholic acid ester structure.) [Chem. 2 6]

(wherein 'R and Ri are each independently a hydrogen atom or a hydroxyl group.) [Chem. 2 7]

The oxygen-containing organic compound in the production method D can be a carboxylic acid halide represented by the following formula (d1), a carbonate anhydrate represented by the following formula (d2), and the following The halogenated alkyl acids represented by the formula (d3), the halogenated acetates represented by the general formula (d4), and the halogenated decanes represented by the following formula (d5) are selected from the above. [Chem. 2 8] A W1) (wherein Z1 represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom; X represents a halogen atom.) [Chem. 2 9] Z2〆

(d2) (wherein Z2 represents a linear, branched or cyclic hydrocarbon group which may have a carbon number of 1 to 15 of a hetero atom.) -28- 201040136 [Chemical 3 0]

(wherein Ζ3 represents a linear, branched or cyclic hydrocarbon group which may have a carbon number of 1 to 9 of a hetero atom; and Rh each independently represents a hydrogen atom or a carbon number which may have a hetero atom of 1 to 1 〇 a linear, branched or cyclic hydrocarbon group; X represents a halogen atom.)

(wherein Z4 represents a linear, branched or cyclic hydrocarbon group which may have a carbon number of 杂 15 of a hetero atom; χ represents a halogen atom.) [Chemical 3 2]

(In the formula, 'Z5 to Z7 each independently represent a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 10 which is a hetero atom; X represents a dentate atom.) Hydroxyl protection in the above production method D The reaction is carried out by reacting the oxygen-containing organic compound with the radical of the alicyclic compound obtained in the above Production Methods A to C. In this case, 'it may be carried out in the presence or absence of an organic solvent', but in the case of using an organic solvent, 'if the saturated solubility of the alicyclic compound is below', there is no particular limitation, and the substrate concentration is adjusted to 0.1. Moer / liter ~ 10 m / liter is better. If the substrate concentration is more than mol/L, the necessary amount can be obtained in a general reactor, so it is economically preferable. And if the substrate concentration is 10 mol/L or less, the temperature control of the reaction 201040136 liquid Easy and better. Examples of the organic solvent that can be used include hydrocarbon-based solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, and tetrahydrofuran ( An ether-based solvent such as THF), dioxane or dimethoxyethane (DME); a halogen-based solvent such as dichloromethane or carbon tetrachloride; wherein a halogen-based solvent having a high dissolved amount of hydrogen halide gas is It is preferable to use one type or a mixture of two or more types. Further, although the reaction temperature may be any temperature, if the temperature is too high, decomposition of the existing ester bond or acetal bond may occur, and if the temperature is too low, the progress of the reaction itself may be slow, so 0 ° C ~ 4 0 °C is preferred. Although the pressure can be any pressure, it is necessary to control the side reaction under pressure, and it is preferable to use normal pressure. Also, when the pressure is too high, it is necessary to have a special pressure-resistant device, which is not economically good. The present invention further provides a composition comprising the above alicyclic compound of the present invention. The composition of the present invention preferably further contains a solvent, an acid generator, a quener, various additives and the like. The composition of the present invention can be used for various applications such as circuit forming materials (photoresist for semiconductor manufacturing, printed wiring boards, etc.), image forming materials (printing plates, relief images, etc.), etc., particularly It is preferably used as a photoresist composition, and is preferably used as a positive photoresist composition. The present invention provides a positive resist composition comprising the above composition of the present invention. The positive resist composition of the present invention is not particularly limited as long as it contains the compound of the present invention containing the alicyclic structure-30-201040136, and the present invention is based on the full amount of the positive resist composition of the present invention. The compound having an alicyclic structure is preferably 2 to 50% by mass, more preferably 5 to 15% by mass. In addition to the above-mentioned compound containing an alicyclic structure, the positive-type photoresist composition of the present invention may be a photo-acid generator (PAG) or a quencher of an organic amine or the like, and a soluble resin (for example, a phthalic acid varnish resin). An alkali soluble component such as a phenol resin, a quinone imine resin or a carboxyl group-containing resin, a coloring agent (for example, a dye), and an organic solvent (for example, a hydrocarbon, a halogenated hydrocarbon, an alcohol, an ester, a ketone, or the like). Ethers, cellosolves, carbitols, glycol ether esters, mixed solvents, etc.). The photoacid generator is a conventional compound which can efficiently form an acid by exposure, and examples thereof include a diazide iron salt, a phosphonium salt (for example, diphenylphosphonium hexafluorophosphate), and a phosphonium salt (for example, six). Triphenylsulfonium fluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonate [eg 1-phenyl-1-(4-methylphenyl)sulfonate Mercaptooxy-1-benzylidene methane oxime, 1,2,3-trisulphonyloxymethylbenzene, 1,3-dinitro-2-(4-phenylsulfonyloxy) Methyl)benzene, 1-phenyl-1-(4-methylphenylsulfonyloxymethyl)-1-hydroxy-1-benzomethylmethane, etc., oxathiazole derivatives, s- A triazine derivative, a second mill derivative (diphenyldifluorene, etc.), a quinone imine compound, an anthracene sulfonate, a diazonaphthoquinone, a benzoin tosylate or the like. These photoacid generators may be used singly or in combination of two or more. Further, these photoacid generators can also be used as a thermal acid generator. The amount of the photoacid generator to be used in the positive resist composition of the present invention can be appropriately selected depending on the strength of the acid generated by the irradiation of light or the content of the above-mentioned compound containing the alicyclic structure -31 - 201040136, and the like. For example, the total amount of the alicyclic structure-containing compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass of the photoacid generator. The quencher may optionally use an aliphatic amine, a cyclic amine, an aromatic amine or the like, among which an aliphatic amine, particularly a secondary aliphatic amine or a third aliphatic amine, is further used. It is better. Here, the aliphatic amine means an amine having at least one or more aliphatic groups, and the aliphatic group is preferably a carbon number of from 1 to 20. The aliphatic amine may, for example, be an amine (alkylamine or alkylolamine) or a cyclic amine in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl group having 20 or less carbon atoms or a hydroxyalkyl group. Specific examples of the alkylamine and the alkylolamine include monoalkylamines such as η-hexylamine, η-heptylamine, η-octylamine, η-decylamine, and η-decylamine. Diethylamine, di-n-propylamine, di-η-heptylamine, di-η-octylamine, monocyclohexylfee#-household amine; 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 decylamine, tri-n-decylamine 'tri-n- + dialkylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n_ An alkyl alcohol amine such as octanolamine, tri-n-octanolamine, stearin diethanolamine or lauryl diethanolamine. Among these, a trialkylamine or an alkylolamine having 5 to 10 carbon atoms is preferred, and tris-n-pentylamine and diethanolamine 'stearyl bismuth diethanolamine are particularly preferred. The cyclic amine aspect may, for example, be a heterocyclic ring-32-201040136 compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic one (aliphatic monocyclic amine) or a polycyclic one (aliphatic polycyclic amine). Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, and specifically, 'I,5-diazabicyclo[4.3.0]-5 perylene, 1,8-diaza Heterobicyclo[5.4.0]_7_undecene, hexamethylenetetramine, 1,4-diazabiguanide ring [2.2.2] octane, and the like. Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyrrolidine, pyrrole, 吲哚'pyridinium, imidazole or derivatives thereof, diphenylamine 'triphenylamine, triphenylene Methylamine, etc. Other aliphatic amines include gin(2-methoxymethoxyethyl)amine, gin {2-(2-methoxyethoxy)ethyl}amine, and {2-( 2 _methoxyethoxymethoxy)ethyl}amine, gin {2-(1-methoxyethoxy)ethyl}amine, gin {2-(1-ethoxyethoxy)B Amine, hydrazine M2-(l-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethylamine, and the like. These may be used alone or in combination of two or more. The amount of the quencher used in the photoresist composition of the present invention can be appropriately selected in order to increase the shape of the resist pattern, the stability over time of stretching, and the like, for example, the aforementioned alicyclic compound. The amount of the 00 parts by mass is preferably 0 to 10 parts by mass, more preferably 0.01 to 5.0 parts by mass, based on the quencher. The positive-type photoresist composition of the present invention is obtained by mixing the above-mentioned alicyclic structure-containing compound-33-201040136 compound with a photoacid generator, a digestive body (qUencher), and the above-mentioned organic solvent, and the like, and filtering as needed. The inertial separation means such as a device removes inclusions and is modulated. Applying the positive photoresist to the substrate or the substrate, and drying, and then exposing (or further exposing) the light through a predetermined light coating film (photoresist film) to form a latent image pattern, and then By visualization, fine patterns are made with high precision. The present invention also provides a method for forming a photoresist pattern, comprising the steps of performing a hydrophobic treatment on a support, and forming a photoresist film on the support by using the resist composition, and making the photoselectivity The step of exposing and the step of treating the selectively exposed photoresist film to form a photoresist pattern. The hydrophobization treatment agent used in the above hydrophobization treatment is preferably used arbitrarily. For example, the bis(alkyl decyl)amine is preferably hexamethyldioxane (HMDS). Examples of the support include silicon wafers, metals, plastics, and ceramics. The coating of the photoresist composition can be carried out by a conventional coating means such as spin coating, cloth, or roll coating. The coating film is, for example, preferably 0.01 to 2 0 μm, more preferably 0.0 5 to 1 μm. In the step of selectively exposing the photoresist film, light of a species such as ultraviolet rays, X-rays, or the like can be utilized, and g-line, i-line, excimer laser (for example, XeCl, KrCl) can be generally used for semiconductor photoresist. , ArF, ArCl, etc.), soft X-ray, etc. The exposure energy is preferably -1000 mJ/cm2, preferably 1 to i〇〇mJ/cm2. The solid composition cover to be mixed and used for post-baking to form a micro-image of the positive-type resist film can be selected from the public, better, glass dip coating thickness, wavelength, KrF, such as 0.1-34 - 201040136 The alicyclic compound contained in the above positive resist composition has an acetal structure and has an acid decomposition function. Therefore, an acid is generated from the photoacid generator by the selective exposure described above, and by the acid, according to the configuration of the alicyclic compound, the acetal structure portion is rapidly detached, and the formation contributes to solubilization. Carboxyl or hydroxy. Therefore, by performing development processing using water or an alkali developing solution, a predetermined pattern can be formed with high precision. [Examples] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples, but the present invention is not limited thereto. In addition, various analytical methods are implemented as follows. [Gas Chromatography (GC)] Analysis was carried out using a 6 8 50 series manufactured by Agilent. [Nuclear Magnetic Resonance Spectrometry (N M R )] The solvent was measured using chloroform-d or dimethyl arylene-d6, and JNM-ECA500 manufactured by Sigma-Aldrich Co., Ltd. [Gas chromatography-mass spectrometry (GC-MS)] The GCMS-QP2010 manufactured by Shimadzu Corporation was used for the measurement by the EI method. [Attenuated total reflection infrared spectroscopy (ATR-FTIR)] Measurement was carried out by Fourier transform-total reflection (FT-ATR) using a Spectrum One' manufactured by PerkinElmer. [Colloidal Permeation Chromatography (GPC)] Measured by HLC-8220GPC manufactured by TOSOH Co., Ltd. -35- 201040136 [Differential Scanning Thermal Analysis (DSC)] Measurement was carried out using EXSTAR DSC7020 manufactured by SII NanoTechnology Co., Ltd. [Thermal weight/differential thermal analysis (TG/DTA)] The measurement was carried out using EXSTAR TG / DTA7200 manufactured by SII NanoTechnology Co., Ltd. [Thickness and normalized film thickness] An optical film thickness meter (F20-UV manufactured by FILMETRICS Co., Ltd., or FE-3 000 manufactured by Otsuka Electronics Co., Ltd.) or a contact film thickness meter (ET produced by the company) -4000A) The film thickness was measured, and the film thickness before development was 1.00, and the normalized film thickness was calculated. Example 1 (Synthesis of adamantane-1,3,5-trisyloxymethyl ester) was placed in a 50 mL two-necked flask, and placed in International Gazette W〇2〇〇7〇947 8 4A i,3,5-parade (methylthiomethoxy)adamantane synthesized by the method described in the above [molecular weight: 364.59, 1823 mg, 5 mmo1] 'slowly dropping thiosulfanyl group [molecular weight: 1. 18.97 , l-32mL· '18mm〇l〕, and stirred for 2 hours. The residual sulfonium chloride is removed by vacuum pumping. Lithocholic acid (molecular weight: 3 76.5 7,5 649 mg, 15 mmol, 1.0 equivalent) dissolved in 20 mL of tetrahydrofuran (THF) was dropped using a cannula, and washed with THF 5 mL twice. Next, when triethylamine (molecular weight: 101.19, -36 - 201040136 d = 0.726, 2.51 mL, 18.0 mmol, 1.2 equivalent) was dropped, the reaction liquid quickly became cloudy, and a little heat was observed. After stirring continuously for 20 hours, 50 mL of water was added to stop the reaction. After adding 20 mL of THF and 100 mL of diethyl ether to the reaction mixture, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. Repeat this operation twice more times. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The residue after removal of the solvent was dissolved in 20 mL of THF and added dropwise to 500 mL of diethyl ether to obtain a white solid of the target product of adamantane-1,3,5-trisyloxymethyl vinegar [ 3.051 mg, 2.26 mmol, isolated yield 4 5 · 2 %]. <Physical data> Thermal weight/differential thermal analysis (TG/DTA): Td5 = 164.8 °C Attenuated total reflection infrared spectroscopy (ATR-FTIR): 3313.6, 2926.6 ❹ , 2863.3 > 1706.1 , 1100.3 > 1034.5 Nuclear magnetic resonance spectroscopy (NMR): 'H-NMR: 0.62 (s, 9 Η) 0.87 to 0.89 (m, 18 Η), 1.06 to 2.21 (m, 97H), 3.42 to 3.5 2 (br - s, 3 Η), 3.60 to 3.63 (m > 3 Η ) , 4.58 to 4.80 ( m, 6H) , 3C-NMR : 1 1.8 1 ( a2 ) , 18.07 ( al ) , 20.40 , 23.16 ( a3 ), 23.79 , 25.13 , 26.86 , 27.70 , 29.50 - 30.64 , 30.68 , 34.27 , 34.79 , 3 5.33 , 39.65 - 39.94 , 4 1.48 , 42.26 , 43.00 , 52.3 0,55.53 , 56.04 , 65.70 , 67.0 1 , 7 5.5 6, -37- 201040136

Example 2 (Synthesis of ginseng (3-ethylmercaptocholic acid) adamantane-1,3,5-trisyloxymethyl ester) In a 200 mL two-necked flask, it was placed in the international publication WO2007094784A. The obtained method was carried out to obtain adamantane tris, 1,3,5-trisyloxymethyl group (molecular weight: 1 44 5.98, 434 0 m g, 3 mmol), and dissolved in 45 mL of THF. The ethyl sulfonate group (molecular weight: 78.50, d = 1.104, 〇.64 mL, 9 mmol) was slowly added dropwise to the above solution. Next, when triethylamine (molecular weight: 101.19, d = 0.726, 1.5 mL, 10-8 mmol, 1.2 equivalent) was dropped, the reaction liquid quickly became cloudy, and a little heat was observed. After stirring for 20 hours, water was added at 50 ml to stop the reaction. After adding THF 5 〇 mL and diethyl ether 100 mL to the reaction mixture, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. This operation was repeated twice more. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The solvent-removed residue was dissolved in 60 mL of THF and dropped into diethyl ether 500 ml, to obtain the target (3-ethoxycholic acid) adamantane-1,3,5-tribasic ginseng. A white solid of oxymethyl ester [4233 mg, 2.693 mmol, isolated yield 89-8%]. -38- 201040136 <Physical data> Thermal weight/differential thermal analysis (TG/DTA): Td5 = 24 9.8 °C Attenuated total reflection infrared spectroscopy (ATR-FTIR): 3 45 0.1,293 5 _0 ,2859.6 > 1725.5 , 1090.7 , 1034.1 Nuclear Magnetic Resonance Spectroscopy (NMR): h-NMRiO.SS^OWCsm), 0.82(s,9H) - 0.93 (

s,9H),1.10~2.40(m,87H) - 2.50 ( s - 1Η ) , 3.19 (br-s,3H) ,3.3 3 ( br-s,3H ) ,3.6 2 ( b rs,3 H ), 3.78 ( br-s,3 H ) ,4.09 ( m,6H ) ,4 · 6 5 ( m,3 H ), 5.22 ( s,6H )

13c-NMR: 10.58, 12.24,1 6.86, 22.52, 22 • 72, 26 • 13 26. 69 '27. 20 , 2 8.43, 3 0. 35, 30. .50, 30. 80, 3 4. 30 34. 42 , 34_ 80 , 3 4.8 9, 3 5. 25, 36. .02, 4 1. 28, 4 1 . 47 45 . 50 > 45. 7 1 , 46.0 1 , 6 6. 19, 70 .39, 70. 9 5, 76. 57 86. 47, 1 72 • 64 , 174.89 [Chem. 3 4] Example 3 (Ref. (3 - (Adamantylcarbonyl) cholic acid) adamantane - 1 Synthesis of 3,5-trisyloxymethyl ester) The tricholic acid-39-201040136-cyclohexane-1 was synthesized by a method described in International Publication WO0094094784A in a 200 mL two-necked flask. 3,5-Trisyloxymethyl group [molecular weight: 1454.98, 2895 mg, 2 mmol), and dissolved in 45 mL of THF. 1 -adamantylcarbonyl chloride was slowly dropped in the above solution [molecular weight: 198.69, 1788 mg, 9 mmol]. Then, when triethylamine (molecular weight: 101.19, d = 0.726 '1.5 mL, 10.8 mmol' 1.2 eq) was added dropwise, the reaction liquid became cloudy quickly, and a little heat was observed. After stirring continuously for 20 hours, 50 mL of water was added to stop the reaction. After adding 50 mL of THF and 100 mL of diethyl ether to the reaction mixture, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. This operation was repeated twice more. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The solvent-removed residue was dissolved in 60 mL of THF, and the mixture was added dropwise to 500 mL of diethyl ether to obtain the target (3-(1-adamantylcarbonyl)cholate)adamantan-1,3,5- Trisyloxymethyl ester as a white solid [2 3 89 mg, 1.24 mmol, mp. <Physical data> Thermal weight/differential thermal analysis (TG/DTA): Td5 = 270.5 °C Attenuated total reflection infrared spectroscopy (ATR - FT IR ) : 3 4 6 0.1, 2 9 3 5.6 , 2870.6 , 1727.2 , 1090.7, 1033.9 -40 - 201040136 〔化3 5〕

Example 4 (Synthesis of ginseng (3-cyclohexylcarbonylcholic acid) adamantane-1,3,5-triyloxymethyl ester) 〇In a 200 mL two-necked flask, placed in International Publication W〇2三07〇9478 4A synthesized by the method described in the synthesis of adamantane-1,3,5-trisyloxymethyl group (molecular weight: 1445.98, 29〇4 mg, 2 mmol), and dissolved in THF4 5 mL. The cyclohexylcarbonyl chloride [molecular weight: 146.01' d = 1.096, 1.2 mL, 9 m mol) was slowly dropped in the above solution. Next, when triethylamine (molecular weight: 101.19, d = 0.726, 1.5 mL, 10.8 mmol' 1.2 equivalent) was dropped, the reaction liquid quickly became cloudy, and less heat was observed. After stirring for 20 hours, water was added at 50 m to stop the reaction. After adding 50 mL of THF and 1 mL of diethyl ether to the reaction mixture, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 m of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. This operation was repeated twice more. The resulting organic layer was dried over magnesium sulfate and filtered to remove solvent. The solvent-removed residue was dissolved in 60 mL of THF, and the mixture was added dropwise to 500 mL of diethyl ether to obtain the target (3-cyclohexylcarbonylcholic acid) adamantane-1,3,5-trienyloxy The white solid of the methyl ester [2200 mg, i_24 mmol, isolated yield 61.7%]. -41 - 201040136 <Physical data> Thermal weight/differential thermal analysis (TG / DTA) : Td5 = 165.3 °C Attenuated total reflection infrared spectroscopy (ATR-FTIR) : 3425.4, 293 5.8 , 2868.3 , 1713.0 > 1091.7 > 1034.1 [Chem. 3 6]

Example 5 (Synthesis of adamantane-1,3,5-trisyloxymethyl ester) The 5 mL mL two-necked flask was placed in International Publication No. WO 〇 〇 07094784A. The method was synthesized by the method - ginseng (methylthiomethoxy) Jingangyuan (molecular weight: 364.59, 1823 mg, 5 mmol), and slowly dropping thiosulfanyl chloride [molecular weight: ι 8.8.97, 1 _2 mL, 1 6.5 After stirring for 2 hours. The residual sulfonium chloride is removed by vacuum pumping. Deoxycholic acid (molecular weight: 392.57 '58 8 9 mg, 15 mmol, 1.0 equivalent) dissolved in THF 10 mL was dripped with a cannula and washed again with THF 5 mL twice. Next, when triethylamine was dropped (molecular weight: 101.19, d = 0.726, 2.3 mL, 16.5 mmol, 1.1 equivalent), the reaction liquid quickly became cloudy, and a little heat was observed. After stirring for 20 hours, water ι 〇 m l was added to stop the reaction. After adding THF 100 mL and diethyl ether 200 mL to the reaction mixture - 42 - 201040136, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. This operation was repeated twice more. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The solvent-removed residue was dissolved in TH F 3 0 m L and dropped into 750 mL of diethyl ether to obtain the desired product, adamantane-1,3,5-trisyloxymethyl ester. White solid [3 93 9 mg, 2.82 mmol, 56.4% yield. <Physical data> Thermal weight/differential thermal analysis (TG/DTA): Td5 = 122.7 °C Attenuated total reflection infrared spectroscopy (ATR-FTIR): 3423.8 '293 3.3, 2863.0, 1709.6 > 1090.1, 1033.0 &gt 1017.3 〔化3 7〕

Example 6 (Synthesis of Ursodeoxycholic acid - 1 ,3,5-trisyloxymethyl ester) was placed in a 5 〇 mL two-necked flask in International Publication WO 02007094784A I,3,5-parade (methylthiomethoxy)adamantane synthesized by the method described (molecular weight: 3 64.5 9,1 823 mg, 5 mmol), slowly dropping thiosulfanyl chloride [molecular weight: 1 1 8 _ 97, -43- 201040136 1 · 2 m L, 1 6.5 mm ο 1〕 After 2 hours of search. The residual sulfurized sulfur base was removed by vacuum pumping. Ursodeoxycholic acid (molecular weight · 392.57, 5889 mg, 15 mmol, 1.0 equivalent) dissolved in THF 10 mL was dropped using a cannula, and washed with THF 5 mL twice. Next, when triethylamine [molecular weight: 101.19, d = 0.726, 2.3 mL, 16.5 mmol, 1.1 equivalent) was dropped, the reaction solution quickly became cloudy, and a little heat was observed. After stirring for 20 hours, 100 mL of water was added to stop the reaction. To the reaction mixture, THF 100 mL and diethyl ether (200 mL) were added, shaken, and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 50 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. Repeat this operation twice more. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The solvent-removed residue was dissolved in 5 mL of THF 2 and added dropwise to 800 mL of diethyl ether to obtain white of the target product: dimethylglycolate -1,3,5-trisyloxymethyl ester. Solid [523〇1^, 3.74111111〇1, isolated yield 7 4 _ 8 %]. <Physical data> Thermal weight/differential thermal analysis (TG/DTA): Td5 = 118.6 °C Attenuated total reflection infrared spectroscopy (ATR - F TIR ) : 3 4 2 3.8, 2 9 3 2.0 ' 2864.7' 1709.1 , 1092.6, 1013.6 -44- 201040136 〔化3 8〕

Example 7 (Synthesis of (3-(oxymethoxy-2,6-norbornanecarboxylactone)cholic acid) adamantane-1,3,5-triyloxymethyl ester) 0 In a 2-liter 3-neck flask equipped with a stirrer, a thermometer, and a hydrogen chloride gas introduction nozzle, 3-hydroxy-2,6-norbornanecarboxylactone (molecular weight: 154.16, 1.297 mol, 200 g) was placed. Trimerization (molecular weight: 30.03, 1.687 mol, 50.64 g), magnesium sulfate (molecular weight: 120.37, 1.297 mmol, 1 5 6 · 1 g) and dichloromethane 1,300 mL, while maintaining at 〇 ° C Stir. Hydrogen chloride gas generated by mixing 1,070 g of sodium chloride and 9 〇〇mL of concentrated sulfuric acid was blown into the dichloromethane solution through the introduction nozzle for 5 hours. After stirring for 3 hours, the result of GC_MS analysis of the reaction liquid was confirmed by Q to obtain that 3-hydroxy-2,6·norbornanecarboxyl lactone was completely converted, and 3-chloromethoxy was obtained at a selectivity of 96%. Base-2,6-norbornanecarboxylactone. <Physical data> Gas chromatography-mass analysis (GC-MS): 204 (M+ (37C1), 1.83%), 202 (M + (35C1), 5.39%) > 174 (9.29%), 16 7 ( 4.01%) , 144 ( 1 5. Π % ) , 138 ( 25.31% ) , 119 ( 13.04% ) - 1 05 ( 1 00% ) 5 80 ( 60.96% ) , 6 6 ( 44.62% ) , 5 5 ( 1 6.02%) -45- 201040136 〔化3 9〕

Into a 5 OmL two-necked flask, the amantadine-1,3,5-trisyloxymethyl ester (molecular weight: 1445.98, 1000 mg) synthesized by the method described in International Publication No. WO2007094784A was placed. > 0.69 mmol] and 3 -chloromethoxy-2,6-norbornol vinegar (molecular weight: 202.63, 558111 §, 2.48 mmol, 1_2 equivalent) synthesized as described above and dissolved in THF lOmL . Next, when triethylamine (molecular weight: 101.19, d = 0.726, 0.4 mL, 3.lmmol, 1.25 equivalent) was dropped, the reaction liquid quickly became cloudy, and a little heat was observed. After continuously stirring for 20 hours, 50 mL of water was added to stop the reaction. After adding 30 mL of THF and 100 mL of diethyl ether to the reaction mixture, the mixture was shaken and allowed to stand, and then separated into an aqueous layer and an organic layer. Further, 5 mL of diethyl ether was added to the aqueous layer, and after shaking and standing, it was separated into an aqueous layer and an organic layer. This operation was repeated twice more. After the obtained organic layer was dried over magnesium sulfate and filtered, solvent was evaporated. The residue after removal of the solvent was dissolved in THF 2 mL, and 400 mL of diethyl ether was added dropwise to obtain a target (3-(oxymethoxy-2,6-norbornanecarboxylactone)cholate). The white solid of the genus-1,3,5-di-glycoloxymethyl vinegar [1〇48 mg, 0-54 mmol, 78.2% yield). <Physical data>

Thermal Weight / Differential Thermal Analysis (TG/DTA) : Td5 = 243.3 °C -46- 201040136 Attenuated Total Reflection Infrared Spectrometry (ATR_FTIR): 3455·1, 2937.0 2869.3, 1780.9, 1709.1, 1089.5, 1037.4

Example 8 (Preparation of a composition) With respect to 100 parts by mass of the alicyclic compound obtained in Example 1, 5 parts by mass of a triphenylsulfonium nonafluorobutanesulfonate was added as a photoacid generator. The composition was prepared by dissolving with cyclohexanone to make these 5% by mass. The composition was coated on a ruthenium hexamethyldioxane (HMD S )-treated wafer and baked at 110 ° for 60 seconds to form a photoresist film. The wafer thus obtained was subjected to development with a water-diluted aqueous solution of tetramethylammonium hydroxide (TMAH) (2.38 mass%) for 30 seconds. Film thickness at this time

The change in G concentration for TMAH is shown in Table 1 and Figure 1. Example 9 to 14 (Preparation of composition) The alicyclic compound obtained in Example 1 was used in place of the alicyclic compound obtained in Example 1, except that the prepared composition was applied to The same procedure as in Example 8 was carried out except that the untreated ruthenium wafer or the HMD S-treated ruthenium wafer was used to form a photoresist film and develop the image. The change in film thickness to the T M A Η concentration at this time is shown in Table 1 and Figure 1. -47-201040136 Comparative Example 1 (Preparation of Comparative Composition) In Example 8, the compound alicyclic compound represented by the following formula was used instead of the alicyclic compound obtained in Example 1, and replaced with ethyl lactate. The cyclohexanone was prepared in the same manner as in Example 8 except that the comparative composition was applied to an untreated tantalum wafer to form a photoresist film and developed. The change in film thickness to TMAH concentration at this time is shown in Table 1 and Figure 1. 〔化 4 1〕

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S ο ο ο ο ο ο ο [ift s (I) i 丨 (Embodiment 2) i (Embodiment 3) i (Embodiment 4) 1 (Embodiment 5): (Embodiment 6) (Embodiment 7) Embodiment 9 1 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13: Embodiment 14: i-so Yao Your father "Μ ν (ί 震) is : (Example 2) (Example 3) (Example 4 : (Embodiment 5) (Embodiment 6) (Embodiment 7) Embodiment 9 Embodiment 10: Embodiment 11 ! Embodiment 12 ! Embodiment 13 Example 14 so I ι fi - qq -49 - 201040136 It was confirmed that the photoresist film formed by using the composition prepared in Examples 8 to 14 of the present invention was compared with the photoresist film formed by using the comparative composition prepared in Comparative Example 1, even at a higher concentration of TMAH. The film thickness can still be maintained in the solution. In particular, the photoresist film formed using the compositions prepared in Examples 1 to 3 and 7 can maintain the film thickness even in the standard concentration of TMAH (2.38 mass%). [Industrial Applicability] As described in detail above, the alicyclic compound of the present invention is used for a positive resist composition. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A comparison of the dissolution suppressing effects in the resist films formed in Examples 7 to 12 and Comparative Example 1. -50-

Claims (1)

201040136 VII. Patent application scope: 1 · An alicyclic compound represented by the general formula (丨1) (in the formula, Ral~Ra3 are each independently the following general formula (a) The basis of the structure containing the bile acid ester) Ο [Chemical 2] (wherein Rb represents a hydroxyl group or an oxygen-containing organic group having 2 to 30 carbon atoms represented by the following formula (b1) to (b5); and the Rd and the independently represent each independently represent a hydrogen atom or a hydroxyl group. Or an oxygen-containing organic group having 2 to 30 carbon atoms which are not in any of the general formulas (b1) to (b5); and the Rf groups each independently represent a hydrogen atom or may have a hetero atom. a linear, branched or cyclic group of cigarettes having a carbon number of 1 to 10; η represents 1 or 2; A represents a single bond or a hydrocarbon group having a carbon number of 1 to 5; but 'Rb, Re and Rd are not When three are simultaneously hydroxyl groups) [Chemical 3] 21 Further 〇A (b1) (wherein Z1 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 of a hetero atom) 201040136 , 〇Y0v (b2) Ο (wherein ζ2 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 15 of a hetero atom) [Chemical 5] (b3) (wherein z3 represents a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 9 of a hetero atom; Rg and Rh each independently represent a hydrogen atom or a linear or branched carbon number of 1 to 10 which may have a hetero atom Hydrocarbon group (b 4) (wherein Z4 represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom) (b 5) (wherein, Z5 to Z7 each independently represent a linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 10 which is a hetero atom). 2. The alicyclic compound of claim 1, wherein Re and the above general formula (a). It is a hydrogen atom and A is a single bond. 3. The alicyclic compound of claim 1 or 2, wherein η in the above formula (a) is 1 and Re and Rd are each independently a hydrogen atom or a hydroxyl group. 4. The alicyclic compound according to any one of claims 1 to 3, wherein the above-mentioned general formula (a) is an oxygen-containing organic group represented by the general formula (bl), and Re and Rd It is a hydroxyl group. 5. The alicyclic compound according to any one of claims 1 to 3, wherein the general formula (a) is a hydroxyl group. A method for producing an alicyclic compound of claim 1, 2, 3 or 5, characterized in that the following bile acids are represented by any one of the general formulas (c1) to (c4) 1,3,5-glycol (ethyleneoxy) adamantane, 1,3,5-glycol(halomethoxy)adamantane, 1,3,5-gin(vinyloxymethyl)adamantane and 1 One or more reactions selected from 3,5-parade (methylthiomethoxy)adamantane, The method for producing an alicyclic compound according to any one of claims 1 to 6, which is characterized in that the following alicyclic compound which is not represented by the general formula (1-1) and the following One or more kinds of reactions of the oxygen-containing organic compound represented by any one of the general formulas (d1) to (d5)' (in the formula, Ra 4 to Ra6 are each independently the following general formula (a-). 1) The base of the bile-containing ester structure shown) (Chemical 1 〇) (wherein, Rh and R' are each independently a hydrogen atom or a hydroxyl group) [Chemical Formula 1 &quot; (wherein Z1 represents a linear, branched or cyclical smoke having a carbon number of 1 to 15 which may have a hetero atom) Base; X represents a halogen atom) [Chemical 1 2] (wherein Z2 represents a linear, branched or cyclic hydrocarbon group which may have a carbon number of 1 to 15 of a hetero atom) -54 - 201040136 [Chemical Formula 1] (d3) (wherein z3 represents a miscellaneous a hydrocarbon group having a carbon number of a ring or a ring; Rg and Rh each independently may have a linear or basic group having a carbon number of 1 to 1 Å of a hetero atom; X represents a halogen atom) [Chemical 1 4] ^°Y^ X (d4) Ο (wherein ζ4 represents a hydrocarbon group having a carbon number of 1 or a ring of a hetero atom; X represents a halogen atom) [Chemical 1 5] Z"i-X (d5) (wherein Ζ5 ～7 each independently represents a linear, branched or cyclic hydrocarbon group which may have 10; χ 8. The alicyclic compound of claim 7 is Ra4 to Ra6 in the above general formula (1-1) The base of the bile acid ester-containing structure represented by the butyl group is a linear or sub-group of a hydrogen atom or a branched or cyclic hydrocarbon of ～1 5 . : the carbon number of the hetero atom is 1 to represent a halogen atom). The manufacturing method, wherein, the general formula (a-2) 9. A composition </ RTI> characterized by an alicyclic compound of any one of § 靑 -55- Item 1 to 5, 201040136. 10. The composition of claim 9 further comprising a solvent and an acid generator. 11. The composition of claim 9 or 10, further comprising a quencher. The composition of any one of claims 9 to 1 which is a positive resistive composition. And a method for forming a photoresist pattern, comprising: forming a photoresist film on a support by using the composition of any one of claims 9 to 12 as a positive photoresist; The step of exposing the photoresist film, and performing the alkali development on the photoresist film to form a photoresist pattern. -56 -