JP2011001319A - Alicyclic compound, method for producing the same, composition containing the same, and method for forming resist pattern using the composition - Google Patents

Abstract

Useful as a positive photoresist monomer or dissolution inhibitor used in the manufacture of semiconductor devices. Excellent dissolution characteristics, exposure sensitivity, resolution, roughness, heat resistance, etc. An alicyclic compound, a production method thereof, a composition containing the same, and a resist pattern formation method using the same are provided.
An alicyclic compound in which one or two cholic acid ester structure-containing groups are bonded to an adamantane skeleton, a production method thereof, a composition containing the same, and a resist pattern formation method using the same.
[Selection figure] None

Description

  The present invention, cycloaliphatic compounds, to a process for their preparation, relates a method of forming a resist pattern using the composition comprising and it it, more particularly, alicyclic compounds that function as positive photoresist, i.e., usually an alkali has a dissolution inhibiting effect of the solution, by receiving acidolysis due photoacid generator, alicyclic compounds that may be alkali soluble, a method for producing a resist pattern forming method using the composition and it comprises the same About.

In recent years, with the progress of miniaturization of semiconductor elements, further miniaturization is required in the photolithography process in the manufacture thereof, and a photoresist corresponding to irradiation light with a short wavelength such as KrF, ArF or F ₂ excimer laser light. Various methods for forming fine patterns using materials have been studied. The appearance of a new photoresist material capable of dealing with short-wavelength irradiation light such as the excimer laser light is desired.
Conventionally, many polymers based on phenolic resins have been developed as photoresist materials, but these materials contain an aromatic ring, so they absorb a lot of light, and can obtain pattern accuracy sufficient for miniaturization. I can't.
Moreover, although the phenolic compound represented by diazonaphthoquinone (DNQ) is also used as a compound which has a dissolution inhibitory effect, in the same way as the said polymer, a short wavelength irradiation light absorbs light, so that a fine pattern is formed. There are limits to formation.

For this reason, a polymer obtained by copolymerizing a polymerizable compound having an alicyclic skeleton such as 2-methyl-2-adamantyl methacrylate has been proposed as a photosensitive resist in semiconductor production using an ArF excimer laser (for example, Patent Document 1).
However, with further advancement of microfabrication technology, a line width of 32 nm or less is currently being achieved, but the conventional technology alone requires various requirements such as exposure sensitivity, resolution, pattern shape, exposure depth, and surface roughness. The performance has not been cleared. Specifically, problems of smoothness such as roughness and swell of the pattern surface called LER and LWR have become apparent. Further, in recent methods using immersion exposure, development defects such as resist pattern defects = defects caused by the immersion medium are sometimes found. Furthermore, in a semiconductor manufacturing process using extreme ultraviolet rays (EUV) of 13.5 nm, it is desired to develop a resist with higher sensitivity in order to improve throughput.
Although it is possible to improve each required performance by making full use of conventional technology, it is said that it is difficult to simultaneously achieve “exposure sensitivity, resolution, surface roughness” which are in a trade-off relationship with each other. It has been broken. Among them, unlike a conventional polymer compound, a monomolecular compound called a low molecular resist is expected as a material that can greatly reduce not only exposure sensitivity and resolution but also surface roughness due to its molecular size.

As low molecular weight resists, for example, Patent Documents 2 to 7 have developed polyphenolic low molecular weight compounds such as calixarene and calixresorcinalene as materials for semiconductor production by lithography. Although these are easy to synthesize, since they have an aromatic ring, they cannot be used for light sources with short wavelengths such as KrF and ArF due to light absorption. Usually, the wavelength that can be used for exposure is limited to g-line or i-line of a high-pressure mercury lamp, or soft X-ray.
Thus, several various alicyclic low-molecular compounds have been proposed for application to ArF excimer laser, which is the current state-of-the-art mass production exposure technology (see Patent Documents 8 to 11). Furthermore, the present inventors have also developed a fully alicyclic low-molecular compound (see Patent Document 12). Since the compound group described in these is an all alicyclic compound, it has high transparency and lithography with an arbitrary light source is possible. Furthermore, it is possible to build a process having a thermal margin with a material having an adamantane skeleton and excellent thermal stability. However, a specific compound (see Compound No. GR-5 of Patent Document 12) has a high solubility in a developing solution, and there is a problem that it is necessary to use a diluted developing solution.
On the other hand, various low molecular weight compounds have been proposed as dissolution inhibitors in the lithography technology using existing polymer resists (see Patent Documents 13 to 14). However, these compounds have a low heat resistance because their molecular weight is too small. It can be said that the material is unsuitable for the recent high-temperature semiconductor manufacturing process.

Japanese Patent Laid-Open No. 4-39665 US Pat. No. 6,093,517 JP 2004-191913 A Japanese Patent Laying-Open No. 2005-075757 JP 2007-197389 A Japanese Patent No. 4076789 JP 2008-089709 A JP 2007-191468 A JP 2007-193328 A JP 2007-210996 A JP 2007-316508 A International Publication WO2007 / 0949484 JP 2001-183839 A JP 2005-055864 A

  The present invention is, under the above circumstances, useful as such a flat panel display (FPD) for dissolution inhibitor or an interlayer insulating film, a semiconductor device positive photoresist monomer or other dissolution inhibitor used in the manufacture, dissolution characteristics, exposure sensitivity, resolution, roughness, alicyclic compounds having excellent heat resistance and the like, a method of manufacturing the same, it is an object to provide a composition and a resist pattern forming method using the same comprising the same .

（式中、Ｒ^a〜Ｒ^cのうち、１つ又は２つは、下記一般式（ａ）で表わされるコール酸類エステル構造含有基を示し、それ以外のＲ^a〜Ｒ^cは、それぞれ独立に、水素原子、水酸基又はハロゲン原子を示す。）

（式中、Ｒ^d、Ｒ^e及びＲ^fは、水素原子、水酸基又は下記一般式（ｂ１）〜（ｂ５）のいずれかで示される炭素数２〜３０の酸素含有有機基を示し、Ｒ^g及びＲ^hは、それぞれ独立に、水素原子又はヘテロ原子を有してもよい炭素数１〜１０の直鎖状、分岐状または環状の炭化水素基を示し、ｎは、１又は２を示す。Ａは、単結合又は炭素数１〜５の二価の炭化水素基を示す。）

（式中、Ｚ¹は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示す。）

（式中、Ｚ²は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示す。）

（式中、Ｚ³は、ヘテロ原子を有してもよい炭素数１〜９の直鎖状、分岐状または環状の炭化水素基であり、Ｒⁱ及びＲ^jは、それぞれ独立に、水素原子あるいはヘテロ原子を有してもよい炭素数１〜１０の直鎖状、分岐状または環状の炭化水素基を示す。）

（式中、Ｚ⁴は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示す。）

（式中、Ｚ⁵〜Ｚ⁷は、それぞれ独立に、ヘテロ原子を有してもよい炭素数１〜１０の直鎖状、分岐状または環状の炭化水素基を示す。）
２．前記一般式（ａ）におけるＲ^g及びＲ^hが水素原子であり、かつ、Ａが単結合である上記１記載の脂環式化合物、
３．前記一般式（ａ）におけるｎが１である上記１又は２記載の脂環式化合物、
４．前記一般式（ａ）におけるＲ^d、Ｒ^e及びＲ^fが、それぞれ独立に、水素原子又は水酸基である上記３記載の脂環式化合物、
５．前記一般式（１）中、Ｒ^a〜Ｒ^cのうち１つ又は２つが前記一般式（ａ）で示され、それ以外のＲ^a〜Ｒ^cが水素原子である上記４記載の脂環式化合物、
６．前記一般式（ａ）において、Ｒ^d、Ｒ^e及びＲ^fが、いずれも水酸基である上記５記載の脂環式化合物、
７．下記一般式（ｃ１）〜（ｃ５）のいずれかで示されるコール酸類と、１−ビニルオキシアダマンタン、１−ハロゲノメトキシアダマンタン、１−ビニルオキシメチルアダマンタン及び１−メチルチオメトキシアダマンタンから選択される１種以上とを反応させることを特徴とする上記１〜６のいずれかに記載の脂環式化合物の製造方法、

８．アダマンタン構造含有アルコールを、酸無水物の存在下、アルキルスルホキシドと反応させてアルキルチオアルキルエーテル体を得る工程と、該アルキルチオアルキルエーテル体をハロゲン化剤によりハロゲン化アルキルエーテル体とする工程と、該ハロゲン化アルキルエーテル体とコール酸類とのエステル化反応工程を有する上記１〜６のいずれかに記載の脂環式化合物の製造方法、
９．少なくとも上記１〜６のいずれかに記載の脂環式化合物を含有することを特徴とする組成物、
１０．さらに溶媒及び酸発生剤を含有する上記９記載の組成物、
１１．さらにクエンチャーを含有する上記９又は１０記載の組成物、
１２．ポジ型レジスト組成物である上記９〜１１のいずれかに記載の組成物、及び
１３．上記９〜１２のいずれかに記載の組成物をポジ型レジストとして用いて支持体上にレジスト膜を形成する工程と、該レジスト膜を露光する工程と、該レジスト膜をアルカリ現像してレジストパターンを形成する工程とを含むレジストパターン形成方法、
を提供する。 As a result of intensive studies to achieve the above object, the present inventors have solved the above problems by using an alicyclic compound in which one or two cholic acid ester structure-containing groups are bonded to the adamantane skeleton. The present invention has been completed.
That is, the present invention
1. An alicyclic compound represented by the following general formula (1):

(In the formula, one or two of R ^{a to} R ^c represents a cholic acid ester structure-containing group represented by the following general formula (a), and other R ^{a to} R ^c are each independently , Represents a hydrogen atom, a hydroxyl group or a halogen atom.)

(Wherein, R ^d, R ^e and R ^f represents a hydrogen atom, a hydroxyl group or the following general formula (b1) ~ (b5) an oxygen-containing organic group having 2 to 30 carbon atoms represented by any one of, R ^g And R ^h each independently represents a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hydrogen atom or a hetero atom, and n represents 1 or 2. A represents a single bond or a divalent hydrocarbon group having 1 to 5 carbon atoms.)

(Wherein, Z ¹ represents straight-chain carbon atoms of 1 to 15 it may contain a hetero atom, a branched or cyclic hydrocarbon group.)

(In the formula, Z ² represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom.)

(In the formula, Z ³ is a linear, branched or cyclic hydrocarbon group having 1 to 9 carbon atoms which may have a hetero atom, and R ⁱ and R ^j are each independently a hydrogen atom. Or a C1-C10 linear, branched or cyclic hydrocarbon group which may have a hetero atom is shown.)

(Wherein, Z ⁴ is a straight-chain carbon atoms of 1 to 15 may contain a hetero atom, branched or cyclic hydrocarbon group.)

(Wherein, Z ⁵ to Z ⁷ are each independently a straight-chain carbon atoms 1 to 10 may contain a hetero atom, branched or cyclic hydrocarbon group.)
2. 2. The alicyclic compound according to 1 above, wherein R ^g and R ^h in the general formula (a) are hydrogen atoms, and A is a single bond,
3. 3. The alicyclic compound according to 1 or 2 above, wherein n in the general formula (a) is 1.
4). 4. The alicyclic compound according to 3 above, wherein R ^d , R ^e and R ^f in the general formula (a) are each independently a hydrogen atom or a hydroxyl group,
5). In the general formula (1), R ^a is to R 1 or two of ^c indicated by the general formula (a), cycloaliphatic the 4 described other R ^a to R ^c is hydrogen atom Compound,
6). 6. The alicyclic compound as described in 5 above, wherein in the general formula (a), R ^d , R ^e and R ^f are all hydroxyl groups.
7). One selected from cholic acids represented by any one of the following general formulas (c1) to (c5) and 1-vinyloxyadamantane, 1-halogenomethoxyadamantane, 1-vinyloxymethyladamantane and 1-methylthiomethoxyadamantane The method for producing an alicyclic compound according to any one of the above 1 to 6, characterized by reacting the above,

8). A step of reacting an adamantane structure-containing alcohol with an alkyl sulfoxide in the presence of an acid anhydride to obtain an alkylthioalkyl ether, a step of converting the alkylthioalkyl ether into a halogenated alkyl ether with a halogenating agent, The manufacturing method of the alicyclic compound in any one of said 1-6 which has an esterification reaction process of chlorinated alkyl ether body and cholic acid,
9. A composition comprising at least the alicyclic compound according to any one of 1 to 6 above,
10. Furthermore, the composition of said 9 containing a solvent and an acid generator,
11. Furthermore, the composition of said 9 or 10 containing a quencher,
12 12. The composition according to any one of 9 to 11 above, which is a positive resist composition, and 13. A step of forming a resist film on a support using the composition according to any one of 9 to 12 as a positive resist, a step of exposing the resist film, and developing the resist film by alkali development to form a resist pattern A resist pattern forming method including a step of forming
I will provide a.

  The alicyclic compound of the present invention is excellent in dissolution characteristics, exposure sensitivity, resolution, roughness, heat resistance and the like, and particularly excellent in dissolution inhibiting effect on a developer.

It is a figure which compares the change of the film thickness with respect to the TMAH density | concentration in the resist film formed on the untreated silicon wafer using the composition obtained in Example 3 and 4 and the comparative example 1. FIG. Using the composition obtained in Example 3 and 4 and Comparative Example 1 is a diagram comparing the changes in thickness against TMAH concentration in the resist film formed on a silicon wafer that has been HMDS treated.

（式中、Ｒ^a〜Ｒ^cのうち、１つ又は２つは、下記一般式（ａ）で表わされるコール酸類エステル構造含有基を示し、それ以外のＲ^a〜Ｒ^cは、それぞれ独立に、水素原子、水酸基又はハロゲン原子を示す。）
上記一般式（１）中、Ｒ^a〜Ｒ^cのうち１つ又は２つが前記一般式（ａ）で示され、それ以外のＲ^a〜Ｒ^cが水素原子であることが好ましい。 The present invention provides an alicyclic compound represented by the following general formula (1).

(In the formula, one or two of R ^{a to} R ^c represents a cholic acid ester structure-containing group represented by the following general formula (a), and other R ^{a to} R ^c are each independently , Represents a hydrogen atom, a hydroxyl group or a halogen atom.)
In the general formula (1), one or two of R ^{a to} R ^c are preferably represented by the general formula (a), and other R ^{a to} R ^c are preferably hydrogen atoms.

R ^d in the general formula (a) represents a hydrogen atom, a hydroxyl group or an oxygen-containing organic group having 2 to 30 carbon atoms represented by any of the following general formulas (b1) to (b5), preferably a hydroxyl group or The oxygen-containing organic group having 2 to 30 carbon atoms represented by any one of the general formulas (b1) to (b5), more preferably a hydroxyl group or an oxygen-containing oxygen group having 2 to 15 carbon atoms represented by the following general formula (b1) Organic group.
R ^e and R ^f in the general formula (a) are each independently a hydrogen atom, a hydroxyl group, or an oxygen-containing organic group having 2 to 30 carbon atoms represented by any of the following general formulas (b1) to (b5). Preferably a hydrogen atom, a hydroxyl group or an oxygen-containing organic group having 2 to 15 carbon atoms represented by any of the following general formulas (b1) to (b5), more preferably a hydrogen atom or a hydroxyl group.
R ^g and R ^h in the general formula (a) are each independently a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom. It is preferably a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms which may have a hetero atom, and more preferably a hydrogen atom.
In the general formula (a), n represents 1 or 2, and preferably 1.
A in the general formula (a) represents a single bond or a divalent hydrocarbon group having 1 to 5 carbon atoms, preferably a single bond.

Specific examples of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a heteroatom represented by R ^g and R ^h in the general formula (a) include a methyl group, Linear hydrocarbon group such as ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, isopropyl group, sec-butyl group, tert-butyl group, isopentyl Group, a branched hydrocarbon group such as neopentyl group, and a cyclic hydrocarbon group such as cyclopentyl group, cyclohexyl group and adamantyl group. Specific examples of the hetero atom that R ^g and R ^h have include a nitrogen atom, an oxygen atom, and a sulfur atom.
Specific examples of the divalent hydrocarbon group having 1 to 5 carbon atoms represented by A in the general formula (a) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

Z ¹ in the general formula (b1) represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, preferably a straight chain having 1 to 5 carbon atoms. A chain, branched or cyclic hydrocarbon group is shown.

Z ² in the general formula (b2) represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, preferably a straight chain having 1 to 8 carbon atoms. A chain, branched or cyclic hydrocarbon group is shown.

Z ³ in the general formula (b3) represents a linear, branched or cyclic hydrocarbon group having 1 to 9 carbon atoms which may have a hetero atom, preferably a straight chain having 1 to 4 carbon atoms. A chain, branched or cyclic hydrocarbon group is shown.
R ⁱ and R ^j in the general formula (b3) each independently represent a straight-chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hydrogen atom or a hetero atom, Preferably, it represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 5 carbon atoms.

Z ⁴ in the general formula (b4) represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, preferably a straight chain having 1 to 8 carbon atoms. A chain, branched or cyclic hydrocarbon group is shown.

Z ^{5 to} Z ⁷ in the general formula (b5) each independently represent a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, A linear, branched or cyclic hydrocarbon group having 1 to 5 carbon atoms is shown.

A linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a heteroatom represented by Z ¹ in the general formula (b1), represented by Z ² in the general formula (b2). A linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, and a carbon number which may have a hetero atom represented by Z ³ in the general formula (b3) 1 to 9 linear, branched or cyclic hydrocarbon group, linear or branched or 1 to 15 carbon atoms which may have a hetero atom represented by Z ⁴ in the general formula (b4). Specific examples of the cyclic hydrocarbon group and the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom represented by Z ^{5 to} Z ⁷ in the general formula (b5). Examples include methyl, ethyl, n-propyl, n-butyl, n-pep N-hexyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and other linear hydrocarbon groups, isopropyl group, isobutyl group, sec-butyl group, tert-butyl Group, isopentyl group, branched hydrocarbon group such as neopentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, decalyl group (perhydronaphthyl group), norbornyl group, bornyl group, Cyclic hydrocarbon groups such as isobornyl group and adamantyl group, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] monovalent residue of polycyclic alkyl such as dodecane ring, γ-butyrolactyl ring, 4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane-5-one 4,8-dioxa-tricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 4-oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one, etc. Monovalent residues of monocyclic or polycyclic lactones, monovalent residues of monocyclic or polycyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and perfluoro compounds thereof. .

The alicyclic structure-containing compound of the present invention can be produced by various methods, and typical examples thereof include, but are not limited to, the following production methods A to D.
Manufacturing method A:
A method in which an adamantane structure-containing alcohol is reacted with a hydrogen halide gas in the presence of an aldehyde to obtain a halogenated alkyl ether, and an esterification reaction between the halogenated alkyl ether and cholic acids is performed.
Production method B:
By reacting an adamantane structure-containing alcohol with an alkyl sulfoxide in the presence of an acid anhydride, an alkylthioalkyl ether is obtained, and a halogenated alkyl ether is obtained with a halogenating agent. Further, the halogenated alkyl ether and a cholic acid are obtained. A method of performing an esterification reaction with
Production method C:
A method of carrying out an esterification reaction between an adamantane structure-containing vinyl ether and cholic acids in the presence of an acid catalyst.
Manufacturing method D:
A method in which an oxygen-containing organic compound is used to perform a hydroxyl-protecting reaction of the alicyclic compound obtained by the production methods A to C.

(Production method A)
Examples of the adamantane structure-containing alcohol in Production Method A include 1,3,5-adamantanetriol, 1,3,5-tris (hydroxymethyl) adamantane, 1,3-adamantanediol, and 1,3-bis (hydroxymethyl). Examples thereof include adamantane, 1-adamantanol, 1- (hydroxymethyl) adamantane, and the like. 1,3-adamantanediol, 1,3-bis (hydroxymethyl) adamantane, 1-adamantanol, 1- (hydroxymethyl) adamantane Is preferred.
Examples of the aldehydes in production method A include linear or branched aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.
Examples of the hydrogen halide gas in the production method A include a single gas such as hydrogen fluoride gas, hydrogen chloride gas, and hydrogen bromide gas, or a mixed gas thereof.
Examples of cholic acids in Production Method A include lithocholic acid represented by the following formula (c1), deoxycholic acid represented by the following formula (c2), ursodeoxycholic acid represented by the following formula (c3), Examples thereof include saturated cholic acid analogs such as chenodeoxycholic acid represented by c4) and cholic acid represented by the following formula (c5).

The halogenated alkyl ether compound in Production Method A can be obtained by reacting an adamantane structure-containing alcohol with hydrogen halide gas in the presence of aldehydes. At this time, it can be carried out in the presence or absence of an organic solvent, but when an organic solvent is used, there is no particular limitation as long as it is below the saturated solubility of the adamantane structure-containing alcohol, but the substrate concentration is 0. It is preferable to adjust so that it may become 1 mol / liter-10 mol / liter. When the substrate concentration is 0.1 mol / liter or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / liter or less, the temperature control of the reaction solution is controlled. It is easy and preferable.
Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane (DME), etc. Examples of the solvent include halogen solvents such as dichloromethane and carbon tetrachloride. Halogen solvents having a high dissolved amount of hydrogen halide gas are preferable, and these may be used alone or in combination.
Moreover, although reaction temperature can take arbitrary temperature, when too high, the solubility of hydrogen halide gas will fall, and since progress of reaction itself will become slow when too low, 0 to 40 degreeC is preferable.
Although the pressure can be any pressure, normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.
Specific examples of the halogenated alkyl ether thus obtained include 1,3-bis (halogenomethoxy) adamantane.

  The esterification reaction in Production Method A can be performed by reacting a halogenated alkyl ether with cholic acids in the presence of a base. From the viewpoint of reactivity, it is preferable to react with an α-haloalkyl ether. Moreover, it can be carried out in the presence or absence of an organic solvent, when an organic solvent is used, it is preferred that the substrate concentration is adjusted to be 0.1 mol / l to 10 mol / liter . When the substrate concentration is at least 0.1 mol / l, since the amount required in conventional reactor obtained economically Preferably, the substrate concentration is not more than 10 mol / l, the temperature control of the reaction solution It is easy and preferable. Usable organic solvents include hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene and other hydrocarbon solvents, diethyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane (DME), and other ethers. Solvents, halogen solvents such as dichloromethane and carbon tetrachloride, DMF (N, N-dimethylformamide), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), hexamethylphosphoric triamide (HMPA), Examples include aprotic polar solvents such as hexamethylphosphorous triamide (HMPT) and carbon disulfide, and these may be used alone or in combination. Examples of the base include sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, silver oxide, sodium phosphate, potassium phosphate, disodium monohydrogen phosphate, dipotassium hydrogen phosphate. , Monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, sodium methoxide, potassium t-butoxide, triethylamine, tributylamine, trioctylamine, pyridine, N, N-dimethylaminopyridine, 1,5-diazabicyclo [4,3 , 0] non-5-ene (DBN), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and organic amines are used.

  After the esterification reaction, the reaction product liquid is separated into water and an organic layer, and the product is extracted from the aqueous layer as necessary. The solvent is distilled off from the reaction solution under reduced pressure to obtain the alicyclic compound of the present invention. You may refine | purify as needed and may use a reaction liquid for next reaction, without refine | purifying. As the purification method, distillation, extraction washing, crystallization, reprecipitation, activated carbon adsorption, from the general purification methods such as silica gel column chromatography, production scale, taking into account the required purity may be selected The method by extraction washing, crystallization or reprecipitation is preferable because it can be handled at a relatively low temperature and can process a large amount of sample at one time. Particularly raw materials used, various methods as a method of removing from the alicyclic compound is present invention may be employed, the operability and economical viewpoints, the raw material with a poor solvent for the alicyclic compound A method of washing is preferred. Among the poor solvent for the alicyclic compound is preferably a low boiling point, typically diethyl ether, methanol, ethanol, n- hexane, n- heptane and the like.

(Production method B)
As the adamantane structure-containing alcohol and cholic acids in the production method B, those similar to the production method A are used.
Examples of the alkyl sulfoxide in Production Method B include dimethyl sulfoxide, diethyl sulfoxide, di-n-propyl sulfoxide, diisopropyl sulfoxide, di-n-butyl sulfoxide, diisobutyl sulfoxide, di-sec-butyl sulfoxide, and di-tert-butyl sulfoxide. Symmetric or asymmetrical aliphatic sulfoxides such as diisopentyl sulfoxide, methylethyl sulfoxide, methyl-tert-butyl sulfoxide, etc., but considering the unity of the reaction product, symmetric aliphatic sulfoxide is preferable. Further, dimethyl sulfoxide having a short chain length alkyl group is more preferable.
Examples of the acid anhydride in Production Method B include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, benzoic anhydride, chloroacetic anhydride, tri Aliphatic or aromatic carboxylic acid anhydrides such as fluoroacetic anhydride can be mentioned, and one or more can be used.
Examples of the halogenating agent in the production method B include sulfur halide compounds such as thionyl chloride, sulfuryl chloride, thionyl bromide, sulfuryl bromide, thionyl chlorobromide, sulfuryl bromide bromide, phosphorus trichloride, and three odors. And phosphorus halide compounds such as phosphorus iodide, phosphorus triiodide, phosphorous trichloride, phosphorous tribromide, phosphorus pentachloride, phosphorus pentabromide.

The alkylthioalkyl ether compound in Production Method B can be obtained by reacting an adamantane structure-containing alcohol in the presence of an alkyl sulfoxide and an acid anhydride. At this time, the reaction can be carried out in the presence or absence of an organic solvent, but usually the reaction proceeds by using alkylsulfoxide and acid anhydride as a reaction reagent and solvent in a large excess. Separately, when an organic solvent is used, the substrate concentration is preferably adjusted to 1 mol / liter to 10 mol / liter. If the substrate concentration is 1 mol / liter or more, the necessary amount can be obtained in a normal reactor, which is economically preferable. If the substrate concentration is 10 mol / liter or less, the temperature of the reaction solution can be easily controlled. preferable. Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethers such as diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane, DME (dimethoxyethane), etc. Examples of the solvent include halogen solvents such as dichloromethane and carbon tetrachloride, and these may be used alone or in combination. The reaction temperature can be any temperature, but if it is too high, the selectivity decreases due to side reactions, and if it is too low, the reaction itself proceeds slowly. Although the pressure can be any pressure, normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.
Specific examples of the alkylthioalkyl ether thus obtained include 1-methylthiomethoxyadamantane and 1,3-bis (methylthiomethoxy) adamantane.

The halogenated alkyl ether compound in Production Method B can be obtained by reacting the alkylthioalkyl ether compound with a halogenating agent. At this time, the reaction can be carried out in the presence or absence of an organic solvent, but a halogenating agent may be used in a large excess as a reaction reagent and a solvent. Separately, when an organic solvent is used, it is preferable to adjust the substrate concentration to be 0.1 mol / liter to 10 mol / liter. When the substrate concentration is 0.1 mol / liter or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / liter or less, the temperature control of the reaction solution is controlled. It is easy and preferable. Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane (DME), etc. Examples of the solvent include halogen solvents such as dichloromethane and carbon tetrachloride, and these may be used alone or in combination. The reaction temperature can be any temperature, but if it is too high, the selectivity decreases due to side reactions, and if it is too low, the reaction itself proceeds slowly. Although the pressure can be any pressure, normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.
Specific examples of the halogenated alkyl ether thus obtained include 1,3-bis (halogenomethoxy) adamantane.
The esterification reaction in production method B can be carried out in the same manner as the esterification reaction in production method A.

(Manufacturing method C)
Examples of the adamantane structure-containing vinyl ether in the production method C include 1-vinyloxyadamantane, 1-vinyloxymethyladamantane, 1,3-bis (vinyloxy) adamantane, 1,3-bis (vinyloxymethyl) adamantane, and the like. Can be mentioned.
As the cholic acids in the production method C, the same ones as in the production method A are used.
Examples of the acid catalyst in production method C include any organic and inorganic acids defined by Lewis acid, Bronsted acid, Arrhenius acid, etc., preferably formic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, methanesulfone. Examples thereof include Bronsted acids such as acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.
In the production method C, an adamantane structure-containing vinyl ether is reacted with cholic acids in the presence of an acid catalyst. At this time, it can be carried out in the presence or absence of an organic solvent, but when an organic solvent is used, there is no particular limitation as long as it is below the saturated solubility of the adamantane structure-containing vinyl ether. It is preferable to adjust so that it may become 1 mol / liter-10 mol / liter. When the substrate concentration is 0.1 mol / liter or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / liter or less, the temperature control of the reaction solution is controlled. It is easy and preferable.
Organic solvents that can be used include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, and dimethoxyethane (DME). Examples of the solvent include halogen solvents such as dichloromethane and carbon tetrachloride. Halogen solvents having a high dissolved amount of hydrogen halide gas are preferable, and these may be used alone or in combination.
Moreover, although reaction temperature can take arbitrary temperature, when it is too high, the side reaction which superposition | polymerization of adamantane structure containing vinyl ether will occur, and since progress of reaction itself will become slow when too low, 0 to 40 degreeC is preferable.
Although the pressure can be any pressure, normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.

（式中、Ｒ^a〜Ｒ^cのうち、１つ又は２つは、それぞれ独立に、下記一般式（ａ−１）で表わされるコール酸類エステル構造含有基を示し、好ましくは下記一般式（ａ−２）で表わされるコール酸類エステル構造含有基を示し、それ以外のＲ^a〜Ｒ^cは、それぞれ独立に、水素原子、水酸基又はハロゲン原子を示す。） (Production method D)
You may perform the hydroxyl-protection reaction shown below with respect to the alicyclic compound obtained by the said manufacturing method AC.
As an alicyclic compound used for the manufacturing method D, what is shown by the following general formula (1-1) is preferable.

(In the formula, one or two of R ^{a to} R ^c each independently represents a cholic acid ester structure-containing group represented by the following general formula (a-1), preferably the following general formula (a -2) represents a cholic acid ester structure-containing group, and other R ^{a to} R ^c each independently represent a hydrogen atom, a hydroxyl group or a halogen atom.)

（式中、Ｒ^k及びＲ^lは、それぞれ独立に、水素原子又は水酸基である。）

(In the formula, R ^k and R ^l are each independently a hydrogen atom or a hydroxyl group.)

  Oxygen-containing organic compound in the production method D is a carboxylic acid halide represented by the following general formula (d1), carbonate anhydrides represented by the following general formula (d2), a halogenated alkyl represented by the following general formula (d3) One or more selected from ethers, halogenated acetates represented by the following general formula (d4) and silyl halides represented by the following general formula (d5) are used.

（式中、Ｚ¹は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示し、Ｘはハロゲン原子を示す。）

(In the formula, Z ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, and X represents a halogen atom.)

（式中、Ｚ²は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示す。）

(In the formula, Z ² represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom.)

（式中、Ｚ³は、ヘテロ原子を有してもよい炭素数１〜９の直鎖状、分岐状または環状の炭化水素基であり、Ｒ^m及びＲⁿは、それぞれ独立に、水素原子あるいはヘテロ原子を有してもよい炭素数１〜１０の直鎖状、分岐状または環状の炭化水素基を示し、Ｘはハロゲン原子を示す。）

(In the formula, Z ³ is a linear, branched or cyclic hydrocarbon group having 1 to 9 carbon atoms which may have a hetero atom, and R ^m and R ⁿ are each independently a hydrogen atom. Alternatively, it represents a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, and X represents a halogen atom.)

（式中、Ｚ⁴は、ヘテロ原子を有してもよい炭素数１〜１５の直鎖状、分岐状または環状の炭化水素基を示し、Ｘはハロゲン原子を示す。）

(In the formula, Z ⁴ represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom, and X represents a halogen atom.)

（式中、Ｚ⁵〜Ｚ⁷は、それぞれ独立に、ヘテロ原子を有してもよい炭素数１〜１０の直鎖状、分岐状または環状の炭化水素基を示し、Ｘはハロゲン原子を示す。）
上記一般式（ｄ１）〜（ｄ５）におけるＺ¹〜Ｚ⁷及びＸは、前記（ｂ１）〜（ｂ５）におけるものとそれぞれ同様である。

(In the formula, Z ^{5 to} Z ⁷ each independently represents a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom, and X represents a halogen atom. .)
Z ^{1 to} Z ⁷ and X in the general formulas (d1) to (d5) are the same as those in the above (b1) to (b5).

In the hydroxyl group protection reaction in the production method D, an oxygen-containing organic compound is reacted with the hydroxyl group of the alicyclic compound obtained in the production methods A to C. At this time, it can be carried out in the presence or absence of an organic solvent, but when an organic solvent is used, there is no particular limitation as long as it is below the saturated solubility of the alicyclic compound, but the substrate concentration is 0. It is preferable to adjust so that it may become 1 mol / liter-10 mol / liter. When the substrate concentration is 0.1 mol / liter or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / liter or less, the temperature control of the reaction solution is controlled. It is easy and preferable.
Organic solvents that can be used include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, and dimethoxyethane (DME). Examples of the solvent include halogen solvents such as dichloromethane and carbon tetrachloride. Halogen solvents having a high dissolved amount of hydrogen halide gas are preferable, and these may be used alone or in combination.
Moreover, although reaction temperature can take arbitrary temperature, when too high, decomposition | disassembly of the existing ester bond and acetal bond will occur, and when too low, progress of reaction itself will become slow, Therefore 0 to 40 degreeC is preferable.
Although the pressure can be any pressure, normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.

The present invention also provides a composition containing the alicyclic compound of the present invention.
The composition of the present invention preferably further contains a solvent, an acid generator, a quencher, various additives and the like.
The composition of the present invention can be used for various applications such as circuit forming materials (resist for semiconductor production, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.), and in particular flat panel displays. It is preferably used as a dissolution inhibitor for (FPD), an interlayer insulating film, or a photoresist composition, and more preferably used as a positive photoresist composition.
The present invention further provides a positive resist composition comprising the composition of the present invention.
The positive resist composition of the present invention is not particularly limited as long as it contains the alicyclic structure-containing compound of the present invention, but contains the alicyclic structure of the present invention based on the total amount of the positive resist composition of the present invention. What contains 2-50 mass% of compounds is preferable, and what contains 5-15 mass% is more preferable.

In addition to the alicyclic structure-containing compound, the positive resist composition of the present invention includes a photoacid generator (PAG), a quencher such as an organic amine, an alkali-soluble resin (for example, novolak resin, phenol resin, imide resin, carboxyl Group-containing resins) and other alkali-soluble components, colorants (for example, dyes), organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, cellosolves) , Carbitols, glycol ether esters, a mixed solvent thereof, and the like) can be added.
Examples of the photoacid generator include conventional compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimonate, Triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonate esters [for example, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-trisulfonyloxy Methylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzoylmeta Etc.], oxathiazole derivatives, s- triazine derivatives, (such as diphenyl disulfone) disulfone derivatives, imide compound, an oxime sulfonate, a diazonaphthoquinone, and a benzoin preparative rate.
These photoacid generators can be used alone or in combination of two or more. Furthermore, these photoacid generators can also be used as thermal acid generators.
The amount of the photoacid generator used in the positive resist composition of the present invention can be appropriately selected according to the strength of the acid generated by light irradiation, the content of the alicyclic structure-containing compound, etc. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of whole quantity of a ring structure containing compound, More preferably, it is 1-25 mass parts, More preferably, 2-20 mass parts is contained.

The quencher may be arbitrarily selected from known ones such as aliphatic amines, cyclic amines, aromatic amines, etc. Among them, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferable. Here, the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 20 carbon atoms.
Examples of the aliphatic amine include amines (alkyl amines or alkyl alcohol amines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 20 or less carbon atoms. .
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Li isopropanolamine, di -n- octanol amine, tri -n- octanol amine, stearyl diethanolamine, alkyl alcohol amines such as lauryl diethanolamine. Among these, a C5-C10 trialkylamine and alkyl alcohol amine are preferable, and tri-n-pentylamine, diethanolamine, and stearyl diethanolamine are particularly preferable.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.
Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, and tribenzylamine.
Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxy Ethoxy) ethoxy} ethylamine and the like.
These may be used alone or in combination of two or more.

The amount of quencher used in the resist composition of the present invention can be selected as appropriate in order to improve the resist pattern shape, stability over time, etc., for example, preferably with respect to 100 parts by mass of the alicyclic compound. It contains 0 to 10 parts by mass, more preferably 0.01 to 5.0 parts by mass of a quencher.
The positive resist composition of the present invention is a mixture of the alicyclic structure-containing compound, a photoacid generator, a quencher, and, if necessary, the organic solvent and the like, and a contaminant such as a conventional solid such as a filter. It can be prepared by removing by separation means. The positive resist composition is applied onto a substrate or substrate, dried, and exposed to light (or further post-exposure baked) to expose the coating film (resist film) through a predetermined mask. By forming an image pattern and then developing it, a fine pattern can be formed with high accuracy.

The present invention includes a step of hydrophobizing the support as necessary, a step of forming a resist film on the support using the positive resist composition, and a step of selectively exposing the resist film. And a step of forming a resist pattern by subjecting the selectively exposed resist film to an alkali development treatment.
The hydrophobizing agent used for the hydrophobizing treatment may be arbitrarily selected from known ones, and is preferably bis (alkylsilyl) amine, more preferably hexamethyldisilazane (HMDS), for example.
Examples of the support include a silicon wafer, metal, plastic, glass, and ceramic. The photoresist composition can be applied using a conventional application means such as a spin coater, a dip coater, or a roller coater. The thickness of the coating film is, for example, preferably 0.01 to 20 μm, more preferably 0.05 to 1 μm.
In the process of selectively exposing the resist film, light beams of various wavelengths, such as ultraviolet rays and X-rays, can be used. For semiconductor resists, usually g-line, i-line, and excimer lasers (for example, XeCl, KrF, KrCl). , ArF, ArCl, etc.), soft X-rays, etc. are used. Exposure energy, for example 0.1~1000mJ / cm ^2, preferably about 1 to 100 mJ / cm ^2.
Since the alicyclic compound contained in the positive resist composition has an acetal structure, it has an acid decomposition function. Therefore, an acid is generated from the photoacid generator by the selective exposure, and the acetal structure portion of the structure based on the alicyclic compound is rapidly eliminated by this acid, thereby generating a carboxyl group and a hydroxyl group contributing to solubilization. To do. Therefore, a predetermined pattern can be formed with high accuracy by performing development using water or an alkali developer.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited at all to these.
Various analysis methods were performed as follows.
[Differential scanning calorimetry (DSC)]
The measurement was performed using EXSTAR DSC7020 manufactured by SII Nano Technology.
[Thermogravimetric / differential thermal analysis (TG / DTA)]
Measurement was performed using EXSTAR TG / DTA7200 manufactured by SII Nano Technology.
[Film thickness and normalized film thickness]
The film thickness was measured using an optical film thickness meter (F20-UV manufactured by Filmetrics Co., Ltd.), and the normalized film thickness was calculated with the film thickness before development set to 1.00.

Example 1 (Synthesis of cholic acid adamantane-1-oxymethyl)
To a 300 ml flask, 1-adamantanol [formula weight: 152.23, 15 g, 98.5 mmol], dimethyl sulfoxide (DMSO) 150 ml and acetic anhydride 75 ml were added and stirred for 20 hours. 50 ml of water and 100 ml of diethyl ether were added to the reaction mixture, and after shaking and standing, the aqueous layer and the organic layer were separated. 50 ml of diethyl ether was added to the aqueous layer again, and after shaking and standing, the aqueous layer and the organic layer were separated. This was repeated two more times. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off to remove a colorless liquid of target 1-methylthiomethoxyadamantane [20.1 g, 94.6 mmol, isolated yield 96%] Got.
1-methylthiomethoxyadamantane synthesized above (formula: 212.35, 1486 mg, 7 mmol) was placed in a 50 ml two-necked flask and thionyl chloride [formula: 118.97, 0.6 ml, 8.4 mmol]. Was slowly added dropwise and stirred for 15 minutes. The remaining thionyl chloride was removed with a vacuum pump. The residue from which the solvent was removed was dissolved in 5 ml of THF, and cholic acid [formula: 408.57, 3146 mg, 7.7 mmol, 1.1 eq] and triethylamine [formula: 101.19] dissolved in 20 ml of tetrahydrofuran (THF). , D = 0.726, 1.18 ml, 8.47 mmol, 1.1 equivalents] was slowly added dropwise to a 100 ml two-necked flask, and the reaction solution immediately became cloudy and slightly exothermic. Subsequently, after stirring for 20 hours, 50 ml of water was added to stop the reaction. 100 ml of diethyl ether was added to the reaction mixture, and after shaking and standing, the aqueous layer and the organic layer were separated. 50 ml of diethyl ether was added to the aqueous layer again, and after shaking and standing, the aqueous layer and the organic layer were separated. This was repeated two more times. The obtained organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The residue from which the solvent has been removed is dissolved in 20 ml of diethyl ether and added dropwise to 500 ml of hexane. The white solid [3079 mg, 5.38 mmol, isolated yield 76.8] of the target product, adamantane-1-oxymethyl cholic acid shown below. %].

<Physical property data>
Thermogravimetric / differential thermal analysis (TG / DTA): Td ₅ = 131.4 ° C.
Differential scanning calorimetry (DSC): Tg = 86.1 ° C.

Example 2 (Synthesis of dicholate adamantane-1,3-dioxymethyl)
1,3-adamantanol [formula: 168.23, 10 g, 59.4 mmol], dimethyl sulfoxide (DMSO) 150 ml and acetic anhydride 75 ml were added to a 300 ml flask and stirred for 50 hours. 50 ml of water and 100 ml of diethyl ether were added to the reaction mixture, and after shaking and standing, the aqueous layer and the organic layer were separated. 50 ml of diethyl ether was added to the aqueous layer again, and after shaking and standing, the aqueous layer and the organic layer were separated. This was repeated two more times. The obtained organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off to obtain a colorless liquid [16.28 g, 56.4 mmol, isolated yield of the desired product, 1,3-dimethylthiomethoxyadamantane. 95%].
The 1,3-dimethylthiomethoxyadamantane synthesized above (formula: 288.47, 1442 mg, 5 mmol) was placed in a 50 ml two-necked flask and thionyl chloride [formula: 118.97, 0.44 ml, 6 mmol]. ] Was slowly added dropwise and stirred for 15 minutes. The remaining thionyl chloride was removed with a vacuum pump. The residue from which the solvent was removed was dissolved in 5 ml of THF, and cholic acid [formula: 408.57, 4903 mg, 12 mmol, 1.2 eq] and triethylamine [formula: 101.19, d dissolved in 25 ml of tetrahydrofuran (THF). = 0.726, 2 ml, 14.4 mmol, 1.2 equivalents] was slowly added dropwise to a 100 ml two-necked flask, and the reaction solution immediately became cloudy and slightly exothermic. Subsequently, after stirring for 20 hours, 50 ml of water was added to stop the reaction. 100 ml of diethyl ether was added to the reaction mixture, and after shaking and standing, the aqueous layer and the organic layer were separated. 50 ml of diethyl ether was added to the aqueous layer again, and after shaking and standing, the aqueous layer and the organic layer were separated. This was repeated two more times. The obtained organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. When the residue from which the solvent has been removed is dissolved in 10 ml of THF and added dropwise to 500 ml of diethyl ether, a white solid of the following product, adamantane-1,3-dioxymethyl dicholate [3650 mg, 3.62 mmol, isolated yield 72.3% ]

<Physical property data>
Thermogravimetric / differential thermal analysis (TG / DTA): Td ₅ = 120.3 ° C.
Differential scanning calorimetry (DSC): Tg = 80.4 ° C.

Example 3 (Preparation of composition)
To the adamantane-1-oxymethyl cholic acid obtained in Example 1, 5% by mass of triphenylsulfonium nonafluorobutanesulfonate was added as a photoacid generator, and dissolved in cyclohexanone so that these were 5% by mass. Composition R3 was prepared. The prepared resist composition was applied on an untreated silicon wafer and a silicon wafer treated with HMDS (hexamethyldisilazane), and baked at 110 ° C. for 60 seconds to form a resist film. The silicon wafer thus obtained was developed with a TMAH (tetramethylammonium hydroxide) aqueous solution (2.38% by mass) diluted with water for 30 seconds. The change in film thickness with respect to the TMAH concentration at this time is shown in Table 1 and FIG.

Example 4 (Preparation of composition)
Example 3 except that resist composition R4 was prepared using adamantane-1,3-dioxymethyl dicholate obtained in Example 2 instead of adamantane-1-oxymethyl cholic acid obtained in Example 1. The same was done. The change of the film thickness with respect to the TMAH concentration is shown in Table 1 and FIG.

Comparative Example 1 (Preparation of composition)
A resist composition R5 was prepared using a compound GR-5 represented by the following formula in place of the adamantane-1-oxymethyl cholic acid obtained in Example 1, except that ethyl lactate was used instead of cyclohexanone. The same operation as in Example 3 was performed. The change of the film thickness with respect to the TMAH concentration is shown in Table 1 and FIG.
Even if the resist composition R5 was applied on a silicon wafer that had been subjected to HMDS treatment, the resist composition R5 was repelled and could not be formed.

  Thus, in Examples 3 and 4 of the present invention, it was possible to confirm the maintenance of the film thickness with the TMAH standard concentration (2.38% by mass) or the TMAH solution having a higher concentration than Comparative Example 1. Further, when a silicon wafer was HMDS treatment whereas could not deposited in Comparative Example 1, it is possible to film formation in Examples 3 and 4 was confirmed to improve the film-forming properties. When GR-5 of Comparative Example 1 is used, the reason why a film cannot be formed on a silicon wafer treated with HMDS is that the compounds of Examples 3 and 4 using a compound having a small proportion of cholic acid and a small number of hydroxyl groups have low polarity. However, since GR-5 of Comparative Example 1 having a high ratio of cholic acid and a large number of hydroxyl groups has high polarity, the composition R5 of Comparative Example 1 is repelled on a wafer that has become hydrophobic by HMDS treatment. It is thought that the film could not be formed.

  As explained in detail above, the alicyclic compound of the present invention is useful for positive resist composition applications.

Claims (13)

An alicyclic compound represented by the following general formula (1).

(In the formula, one or two of R ^{a to} R ^c represents a cholic acid ester structure-containing group represented by the following general formula (a), and other R ^{a to} R ^c are each independently , Represents a hydrogen atom, a hydroxyl group or a halogen atom.)

(Wherein, R ^d, R ^e and R ^f represents a hydrogen atom, a hydroxyl group or the following general formula (b1) ~ (b5) an oxygen-containing organic group having 2 to 30 carbon atoms represented by any one of, R ^g And R ^h each independently represents a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a hydrogen atom or a hetero atom, and n represents 1 or 2. A represents a single bond or a divalent hydrocarbon group having 1 to 5 carbon atoms.)

(Wherein, Z ¹ represents straight-chain carbon atoms of 1 to 15 it may contain a hetero atom, a branched or cyclic hydrocarbon group.)

(In the formula, Z ² represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms which may have a hetero atom.)

(In the formula, Z ³ is a linear, branched or cyclic hydrocarbon group having 1 to 9 carbon atoms which may have a hetero atom, and R ⁱ and R ^j are each independently a hydrogen atom. Or a C1-C10 linear, branched or cyclic hydrocarbon group which may have a hetero atom is shown.)

(Wherein, Z ⁴ is a straight-chain carbon atoms of 1 to 15 may contain a hetero atom, branched or cyclic hydrocarbon group.)

(Wherein, Z ⁵ to Z ⁷ are each independently a straight-chain carbon atoms 1 to 10 may contain a hetero atom, branched or cyclic hydrocarbon group.) The alicyclic compound according to claim 1, wherein R ^g and R ^h in the general formula (a) are a hydrogen atom, and A is a single bond.   The alicyclic compound according to claim 1 or 2, wherein n in the general formula (a) is 1. The alicyclic compound according to claim 3, wherein R ^d , R ^e and R ^f in the general formula (a) are each independently a hydrogen atom or a hydroxyl group. In the general formula (1), one or two of R ^a to R ^c is represented by the general formula (a), alicyclic according to claim 4, wherein the other R ^a to R ^c is hydrogen atom Formula compound. The alicyclic compound according to claim 5, wherein in the general formula (a), R ^d , R ^e and R ^f are all hydroxyl groups. One selected from cholic acids represented by any one of the following general formulas (c1) to (c5) and 1-vinyloxyadamantane, 1-halogenomethoxyadamantane, 1-vinyloxymethyladamantane and 1-methylthiomethoxyadamantane The method for producing an alicyclic compound according to any one of claims 1 to 6, wherein the above is reacted.

  A step of reacting an adamantane structure-containing alcohol with an alkyl sulfoxide in the presence of an acid anhydride to obtain an alkylthioalkyl ether, a step of converting the alkylthioalkyl ether into a halogenated alkyl ether with a halogenating agent, The manufacturing method of the alicyclic compound in any one of Claims 1-6 which has the esterification reaction process of chlorinated alkyl ether body and cholic acids.   A composition comprising at least the alicyclic compound according to any one of claims 1 to 6.   The composition according to claim 9, further comprising a solvent and an acid generator.   Furthermore, the composition of Claim 9 or 10 containing a quencher.   The composition according to claim 9, which is a positive resist composition.   A step of forming a resist film on a support using the composition according to any one of claims 9 to 12 as a positive resist, a step of exposing the resist film, an alkali development of the resist film, and a resist Forming a pattern. A resist pattern forming method.

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