JP2009280538A - Alicyclic structure-containing compound, (meth)acrylic acid esters, (meth)acrylic polymer and positive-type resist composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alicyclic structure-containing compound useful as a monomer raw material for photoresist usable for the production of a semiconductor device or a monomer therefor, and excellent in exposure sensitivity, solubility, compatibility, defect reduction, roughness improvement or the like, to provide (meth)acrylic acid esters and a method for producing the same, and to provide a (meth)acrylic polymer and a positive-type resist composition. <P>SOLUTION: The alicyclic structure-containing compound contains a linking group having an ester bond, and a linking group containing an ether bond. The (meth)acrylic acid esters are derived from the alicyclic structure-containing compound. The method for producing the esters is also provided. The (meth)acrylic polymer contains a monomer unit based on the (meth)acrylic acid esters. The positive-type resist composition contains the (meth)acrylic polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel alicyclic structure-containing compound, (meth) acrylic acid esters and methods for producing the same, (meth) acrylic polymers, positive resist compositions, and resist pattern forming methods. More specifically, the alicyclic structure-containing compound having a useful alicyclic structure for a photoresist and excellent in high sensitivity, solubility, compatibility, defect reduction, roughness improvement, etc., (meth) acrylic acid esters and Method for producing the same, (meth) acrylic polymer containing monomer units based on the (meth) acrylic acid esters, positive resist composition containing the (meth) acrylic polymer, and the positive resist composition The present invention relates to a resist pattern forming method including a step of forming a resist film using an object.

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.
Many photoresist materials based on phenolic resins have been developed in the past. However, these materials contain aromatic rings, so they absorb a lot of light, and can obtain pattern accuracy sufficient for miniaturization. I can't.

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 progress in microfabrication technology, we are currently trying to achieve a line width of 32 nm or less, but with the conventional technology alone, various required performances such as exposure sensitivity, resolution, pattern shape, exposure depth, surface roughness, etc. Can not clear. 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.

Under such circumstances, LER can be improved with a resist material using a glycolic acid ester having many carbonyl groups (see Patent Document 2), or a long alkylene chain is extended from a rigid (meth) acrylic acid main chain. As a result, solubility in a resist solvent is improved (see Patent Document 3). The required performance is not only high for ArF but also for EUV photosensitive resists (see Patent Documents 9 and 10). However, in Patent Documents 4 to 8, the sensitivity of photosensitive resists is increased. It is illustrated.
However, it is difficult to satisfy the above-mentioned required performance only with these techniques, and further resist improvement is required.

Japanese Patent Laid-Open No. 4-39665 JP 2005-331918 A Japanese Patent No. 3952946 JP 2006-96965 A JP 2006-113140 A JP 2006-349864 A JP 2007-177016 A JP 2007-240718 A JP 2006-227398 A JP 2006-285075 A

  The present invention is excellent in exposure sensitivity, solubility, compatibility, defect reduction, roughness improvement, etc., useful as a monomer raw material for photoresist used in the manufacture of semiconductor devices and the monomer under the circumstances as described above. In general, exposure sensitivity and roughness are in a contradictory (trade-off) relationship, but in any of these, excellent alicyclic structure-containing compounds, (meth) acrylic acid esters and production methods thereof, (meth) acrylic An object of the present invention is to provide a polymer and a positive resist composition.

（式中、Ｚは、ヘテロ原子を有してもよい炭素数５〜２０の脂環構造であり、Ｒ²は、ヘテロ原子を有してもよい炭素数１〜５の２価の置換もしくは無置換の炭化水素基であり、Ｒ³は、ヘテロ原子を有してもよい置換もしくは無置換のアルキル基、ハロゲン原子、水酸基、シアノ基、カルボキシル基、オキソ基又はアミノ基を示す。ｐ及びｑは、それぞれ独立に、０以上の整数を示す。複数のＲ²は同一であっても、異なっていてもよく、複数のＲ³は同一であっても、異なっていてもよい。）
−｛（Ｌ^a）_k−（Ｌ^b）_m−（Ｌ^c）_n｝− （ｉｉ）
（式中、Ｌ^aは下記式（ａ）で示される連結基であり、Ｌ^bは下記式（ｂ）で示される連結基であり、Ｌ^cは下記式（ｃ）で示される連結基であり、また、Ｌ^a、Ｌ^b及びＬ^cは任意の結合順をとる。ｋ及びｍは、それぞれ独立に、１以上の整数であり、ｎは０以上の整数である。）

（式中、Ｒ⁴は、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基である。）
２．下記一般式（１）〜（４）のいずれかで表される上記１に記載の脂環構造含有化合物、

（式中、Ｒ¹は、上記一般式（ｉ）で示される炭素数５〜２０の脂環構造含有基であり、Ｒ⁴は、それぞれ独立に、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基であり、Ｘは、ハロゲン原子又は水酸基である。）
３．一般式（ＩＩ）で表される（メタ）アクリル酸エステル類、

（式中、Ｒ¹は、下記一般式（ｉ）で示される炭素数５〜２０の脂環構造含有基であり、Ｒ⁸は、水素原子、メチル基、フッ素原子又はトリフルオロメチル基であり、Ｌは、下記一般式（ｉｉ）で示される連結基である。）

（式中、Ｚは、ヘテロ原子を有してもよい炭素数５〜２０の脂環構造であり、Ｒ²は、ヘテロ原子を有してもよい炭素数１〜５の置換もしくは無置換の２価の炭化水素基であり、Ｒ³は、ヘテロ原子を有してもよい置換もしくは無置換のアルキル基、ハロゲン原子、水酸基、シアノ基、カルボキシル基、オキソ基又はアミノ基を示す。ｐ及びｑは、それぞれ独立に、０以上の整数を示す。複数のＲ²は同一であっても、異なっていてもよく、複数のＲ³は同一であっても、異なっていてもよい。）
−｛（Ｌ^a）_k−（Ｌ^b）_m−（Ｌ^c）_n｝− （ｉｉ）
（式中、Ｌ^aは下記式（ａ）で示される連結基であり、Ｌ^bは下記式（ｂ）で示される連結基であり、Ｌ^cは下記式（ｃ）で示される連結基であり、また、Ｌ^a、Ｌ^b及びＬ^cは任意の結合順をとる。ｋ及びｍは、それぞれ独立に、１以上の整数であり、ｎは０以上の整数である。）

（式中、Ｒ⁴は、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基である。）
４．下記一般式（５）〜（８）のいずれかで表される、上記３に記載の（メタ）アクリル酸エステル類、

（式中、Ｒ¹は、上記一般式（ｉ）で示される炭素数５〜２０の脂環構造含有基であり、Ｒ⁴は、それぞれ独立に、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基であり、Ｒ⁸は、水素原子、メチル基、フッ素原子又はトリフルオロメチル基である。）
５．前記Ｚが、アダマンチル環である上記３又は４に記載の（メタ）アクリル酸エステル類、
６．上記１又は２に記載の脂環構造含有化合物と、（メタ）アクリル酸類、（メタ）アクリル酸ハライド類、（メタ）アクリル酸無水物類及び（メタ）アクリル酸２−ヒドロキシアルキル誘導体から選択される１種以上とをエステル化して、上記３又は４に記載の（メタ）アクリル酸エステル類を得る、（メタ）アクリル酸エステル類の製造方法、
７．上記３又は４に記載の（メタ）アクリル酸エステル類に基づく単量体単位を含む（メタ）アクリル系重合体、
８．上記７に記載の（メタ）アクリル系重合体を含有するポジ型レジスト組成物、及び
９．上記８に記載のポジ型レジスト組成物を用いて支持体上にレジスト膜を形成する工程と、該レジスト膜を選択露光する工程と、選択露光されたレジスト膜をアルカリ現像処理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、
を提供するものである。 As a result of intensive studies, the present inventors have found that (meth) acrylic acid esters derived from alicyclic structure-containing compounds having many carbonyl groups and ester bonds and actively introducing oxygen-containing groups. The polymer can improve compatibility and solubility in a resist solution, and also increase the solubility in an alkali developer after exposure, leading to a reduction in defects. Sensitivity and roughness are in a trade-off relationship, but by extending the (meth) acrylic acid main chain and terminal group, it becomes possible to control the polymerization without depending on the terminal group, and to narrow the molecular weight distribution. It was found that the roughness can be improved and the exposure sensitivity can be improved at the same time. The present invention has been completed based on such findings.
That is, the present invention
1. An alicyclic structure-containing compound represented by the following general formula (I):
R ¹ -L-X (I)
(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), L is a linking group represented by the following general formula (ii), and X is , A halogen atom or a hydroxyl group.)

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ² is a divalent substitution having 1 to 5 carbon atoms which may have a hetero atom, or An unsubstituted hydrocarbon group, R ³ represents a substituted or unsubstituted alkyl group, halogen atom, hydroxyl group, cyano group, carboxyl group, oxo group or amino group which may have a hetero atom, p and q independently represents an integer greater than or equal to 0. The plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different.
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b, and L ^c are in any combination order, k and m are each independently an integer of 1 or more, and n is an integer of 0 or more.)

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. And may be bonded to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.)
2. The alicyclic structure-containing compound according to 1 above, represented by any one of the following general formulas (1) to (4):

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and X represents a halogen atom or a hydroxyl group.)
3. (Meth) acrylic acid esters represented by the general formula (II),

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), and R ⁸ is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. , L is a linking group represented by the following general formula (ii).)

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ² is a substituted or unsubstituted group having 1 to 5 carbon atoms which may have a hetero atom. R ³ represents a divalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkyl group, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, an oxo group or an amino group, which may have a hetero atom. q independently represents an integer greater than or equal to 0. The plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different.
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b, and L ^c are in any combination order, k and m are each independently an integer of 1 or more, and n is an integer of 0 or more.)

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. And may be bonded to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.)
4). (Meth) acrylic acid esters according to 3 above, represented by any one of the following general formulas (5) to (8):

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.)
5. (Meth) acrylic acid esters according to 3 or 4 above, wherein Z is an adamantyl ring,
6). The alicyclic structure-containing compound according to 1 or 2 above and a (meth) acrylic acid, a (meth) acrylic acid halide, a (meth) acrylic anhydride, and a (meth) acrylic acid 2-hydroxyalkyl derivative Esterifying one or more kinds to obtain the (meth) acrylic acid esters according to 3 or 4 above, a method for producing (meth) acrylic acid esters,
7). (Meth) acrylic polymer containing a monomer unit based on the (meth) acrylic acid ester according to 3 or 4 above,
8). 8. a positive resist composition containing the (meth) acrylic polymer according to 7 above; A step of forming a resist film on a support using the positive resist composition described in 8 above, a step of selectively exposing the resist film, and an alkali development treatment of the resist film that has been selectively exposed to form a resist pattern A resist pattern forming method including a forming step,
Is to provide.

  The (meth) acrylic acid ester derived from the alicyclic structure-containing compound of the present invention is useful as a photoresist monomer and the like, and is excellent in solubility, compatibility, defect reduction, roughness improvement, exposure sensitivity, and the like.

The alicyclic structure-containing compound of the present invention is represented by the following general formula (I).
R ¹ -L-X (I)
(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), L is a linking group represented by the following general formula (ii), and X is , A halogen atom or a hydroxyl group.)

（式中、Ｚは、ヘテロ原子を有してもよい炭素数５〜２０、好ましくは炭素数７〜１２の脂環構造であり、アダマンチル環であるとより好ましい。Ｒ²は、ヘテロ原子を有してもよい炭素数１〜５の２価の置換もしくは無置換の炭化水素基であり、炭素数１又は２の２価の炭化水素基であると好ましい。Ｒ³は、ヘテロ原子を有してもよい置換もしくは無置換のアルキル基、ハロゲン原子、水酸基、シアノ基、カルボキシル基、オキソ基又はアミノ基を示し、ハロゲン原子、水酸基又はオキソ基であると好ましい。ｐ及びｑは、それぞれ独立に、０以上の整数を示し、好ましくは０〜５であり、より好ましくは０〜２である。複数のＲ²は同一であっても、異なっていてもよく、複数のＲ³は同一であっても、異なっていてもよい。）
−｛（Ｌ^a）_k−（Ｌ^b）_m−（Ｌ^c）_n｝− （ｉｉ）
（式中、Ｌ^aは下記式（ａ）で示される連結基であり、Ｌ^bは下記式（ｂ）で示される連結基であり、Ｌ^cは下記式（ｃ）で示される連結基であり、また、Ｌ^a、Ｌ^b及びＬ^cは任意の結合順をとる。ｋ及びｍは、それぞれ独立に、１以上の整数であり、好ましくは１又は２である。ｎは０以上の整数であり、好ましくは０又は１である。）

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms, preferably 7 to 12 carbon atoms which may have a hetero atom, and more preferably an adamantyl ring. R ² represents a hetero atom. It is a divalent substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms that may have, and is preferably a divalent hydrocarbon group having 1 or 2 carbon atoms, and R ³ has a hetero atom. A substituted or unsubstituted alkyl group, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, an oxo group or an amino group, which is preferably a halogen atom, a hydroxyl group or an oxo group, and p and q are independent of each other; Represents an integer of 0 or more, preferably 0 to 5, more preferably 0 to ^{2. The} plurality of R ² may be the same or different, and the plurality of R ³ are the same. Or it may be different.)
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b and L ^c are in any bond order, k and m are each independently an integer of 1 or more, preferably 1 or 2. n is an integer of 0 or more And preferably 0 or 1.)

（式中、Ｒ⁴は、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷はそれぞれ独立に、水素原子又はメチル基である。）

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. It may combine to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.)

Examples of the halogen atom in the above formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic structure having 5 to 20 carbon atoms that may have a hetero atom in the above formula (i) include, for example, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctyl ring, a cyclononyl ring, a cyclodecanyl ring, and a decalyl ring. (Perhydronaphthalene ring), norbornyl ring, bornyl ring, isobornyl ring, adamantyl ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . Monocyclic or polycyclic structures such as 1 ^7,10 ] dodecane ring, γ-butyrolactyl ring, 4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 4,8-dioxa- Monocyclic or polycyclic lactones such as tricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 4-oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one Monocyclic or polycyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and perfluoro compounds thereof.
Specific examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms which may have a heteroatom in the above formula (i) include straight chain such as methylene group, ethylene group and trimethylene group Or a branched alkylene group, those perfluoro forms, etc. are mentioned.
Specific examples of the substituted or unsubstituted alkyl group that may have a hetero atom in the above formula (i) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , Tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group and the like, and perfluoro compounds thereof.
The alicyclic structure having 5 to 20 carbon atoms that may have a heteroatom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms that may have a heteroatom, and a heteroatom Specific examples of the hetero atom that the optionally substituted alkyl group may have include a nitrogen atom, a sulfur atom, and an oxygen atom.
Examples of the alkyl group in the above formula (a) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and hexyl group. Straight chain or branched alkyl groups such as heptyl group, octyl group, nonyl group and decanyl group.
Further, the above R ^4, by bonding the alicyclic structure-containing group represented by the general formula (i), or as an annular structure in which a plurality of R ⁴ is formed by mutual bonding, tetrahydrofuran, tetrahydropyran , [1,4] dioxane and the like.

L in the above general formula (I) is a divalent linking group represented by the general formula (ii), the linking group L ^a, composed of L ^b and L ^c. These linking groups take an arbitrary bonding order and constitute the linking group L. Linking group L is a linking group L ^a, when having a plurality of at least one of L ^b and L ^c, the linking group L ^a between the linking group L ^b each other, the linking group L ^c each other, different from one another respectively identical In addition, the same kind of linking groups may not be adjacently bonded. Specifically, the bond order may be L ^a -L ^b -L ^a .
The linking group L is most preferably a linking group represented by the following general formula (iii) or (iv).
-L ^a -L ^b- (iii)
-L ^a -L ^b -L ^c- (iv)
(In the formula, L ^a is a linking group represented by the above formula (a), L ^b is a linking group represented by the above formula (b), and L ^c is a linking group represented by the above formula (c). is there.)

Moreover, the alicyclic structure-containing compound of the present invention is preferably one represented by any one of the following general formulas (1) to (4).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and X represents a halogen atom or a hydroxyl group.)
The R ⁴ to R ⁷ in the general formula (1) to (4), respectively, can be the same as R ⁴ to R ⁷ in the general formula (a) - (c).
In addition, the R ⁴ in the general formulas (1) to (4) and the alicyclic structure-containing group represented by the general formula (i) are bonded to each other, or a plurality of R ⁴ are bonded to each other. Examples of the cyclic structure include residues such as tetrahydrofuran, tetrahydropyran, and [1,4] dioxane.
Examples of the halogen atom in the general formulas (1) to (4) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As a specific example of the alicyclic structure-containing compound of the present invention represented by the general formulas (1) to (4),
2- (cyclopentyloxymethoxy) -2-oxoethanol, 2- (cyclohexyloxymethoxy) -2-oxoethanol, 2- (cycloheptyloxymethoxy) -2-oxoethanol, 2- (cyclooctyloxymethoxy) -2 -Oxoethanol, 2- (cyclononyloxymethoxy) -2-oxoethanol, 2- (cyclodecanyloxymethoxy) -2-oxoethanol, 2- (cyclodecanyloxymethoxy) -2-oxoethanol, 2- (Cyclonorbornyloxymethoxy) -2-oxoethanol, 2- (bornyloxymethoxy) -2-oxoethanol, 2- (isobornyloxymethoxy) -2-oxoethanol, 2- (3-tricyclo [ 5.2.1.0 ^{2, 6]} deca oxy) -2- Kiso ethanol, 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-oxy) -2- oxo ethanol, 2- (1-adamantyloxy) -2- oxo Ethanol, 2- (2-adamantyloxymethoxy) -2-oxoethanol, 2- (1-adamantylmethoxymethoxy) -2-oxoethanol, 2- (2- (1-adamantyl) ethoxymethoxy) -2-oxoethanol , 2- (5-hydroxy-2-adamantyloxymethoxy) -2-oxoethanol, 2- (3,5-dihydroxy-1-adamantylmethoxymethoxy) -2-oxoethanol, 2- (4-oxo-1- Adamantyloxymethoxy) -2-oxoethanol, 2- (4-oxo-2-adamantyloxymethoxy) 2-oxoethanol, 2- (2-cyanomethyl-2-adamantyloxymethoxy) -2-oxoethanol, 2- (1-γ-butyrolactyloxymethoxy) -2-oxoethanol, 2- (5- (2 , 6-Norbornanecarbolactyl) oxymethoxy) -2-oxoethanol,

2- (5- (7-oxa-2,6-norbornanecarbactyl) oxymethoxy) -2-oxoethanol, 2- (8- (4-oxa-tricyclo [4.3.1.1 ^3,8 ] Undecan-5-one) oxymethoxy) -2-oxoethanol, 2- (perfluorocyclopentyloxymethoxy) -2-oxoethanol, 2- (perfluorocyclohexyloxymethoxy) -2-oxoethanol, 2- (per Fluoro-1-adamantyloxymethoxy) -2-oxoethanol, 2- (perfluoro-1-adamantylmethoxymethoxy) -2-oxoethanol, 2- (3-hydroxymethyl-perfluoro-1-adamantylmethoxymethoxy)- 2-oxoethanol, 2- (1- (1-adamantyloxy) ethoxy) -2 Oxoethanol, 2- (1- (2-adamantyloxy) ethoxy) -2-oxoethanol, 2- (2-tetrahydrofuranyloxymethoxy) -2-oxoethanol, 2- (2-tetrahydropyranyloxymethoxy)- 2-oxoethanol, 2- (2- (1,4-dioxanyl) oxymethoxy) -2-oxoethanol, 2- (2- (1-adamantyloxymethoxy) -2-oxoethoxy) ethanol, 2- (2 -(2-adamantyloxymethoxy) -2-oxoethoxy) ethanol, 2- (1-adamantyloxymethoxymethoxy) -2-oxoethanol, 2- (2-adamantyloxymethoxymethoxy) -2-oxoethanol, 2- (2- (1-adamantyloxymethoxymethoxy) -2-oxoeth Xyl) ethanol, 2- (2- (2-adamantyloxymethoxymethoxy) -2-oxoethoxy) ethanol,

2- (cyclopentyloxymethoxy) -2-oxoethyl chloride, 2- (cyclohexyloxymethoxy) -2-oxoethyl chloride, 2- (cycloheptyloxymethoxy) -2-oxoethyl chloride, 2- (cyclooctyloxymethoxy) ) -2-Oxoethyl chloride, 2- (cyclononyloxymethoxy) -2-oxoethyl chloride, 2- (cyclodecanyloxymethoxy) -2-oxoethyl chloride, 2- (cyclodecanyloxymethoxy) -2 -Oxoethyl chloride, 2- (cyclonorbornyloxymethoxy) -2-oxoethyl chloride, 2- (bornyloxymethoxy) -2-oxoethyl chloride, 2- (isobornyloxymethoxy) -2-oxo Ethyl chloride, 2- (3-to Cyclo [5.2.1.0 ^{2, 6]} deca oxy) -2- oxoethyl chloride, 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecanyl Oxymethoxy) -2-oxoethyl chloride, 2- (1-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (2-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (1-adamantylmethoxymethoxy) ) -2-oxoethyl chloride, 2- (2- (1-adamantyl) ethoxymethoxy) -2-oxoethyl chloride, 2- (5-hydroxy-2-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (3,5-dihydroxy-1-adamantylmethoxymethoxy) -2-oxoethyl chloride, 2- (4-oxo 1-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (4-oxo-2-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (2-cyanomethyl-2-adamantyloxymethoxy) -2-oxo Ethyl chloride, 2- (1-γ-butyrolactyloxymethoxy) -2-oxoethyl chloride, 2- (5- (2,6-norbornanecarbactyl) oxymethoxy) -2-oxoethyl chloride, 2- (5- (7-oxa-2,6-norbornanecarbactyl) oxymethoxy) -2-oxoethyl chloride,

2- (8- (4-Oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one) oxymethoxy) -2-oxoethyl chloride, 2- (perfluorocyclopentyloxymethoxy) -2 -Oxoethyl chloride, 2- (perfluorocyclohexyloxymethoxy) -2-oxoethyl chloride, 2- (perfluoro-1-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (perfluoro-1-adamantylmethoxy) Methoxy) -2-oxoethyl chloride, 2- (3-hydroxymethyl-perfluoro-1-adamantylmethoxymethoxy) -2-oxoethyl chloride, 2- (1- (1-adamantyloxy) ethoxy) -2-oxo Ethyl chloride, 2- (1- (2-adamantyloxy) ester Xy) -2-oxoethyl chloride, 2- (2-tetrahydrofuranyloxymethoxy) -2-oxoethyl chloride, 2- (2-tetrahydropyranyloxymethoxy) -2-oxoethyl chloride, 2- (2- ( 1,4-dioxanyl) oxymethoxy) -2-oxoethyl chloride, 2- (2- (1-adamantyloxymethoxy) -2-oxoethoxy) chloride, 2- (2- (2-adamantyloxymethoxy) -2 -Oxoethoxy) chloride, 2- (1-adamantyloxymethoxymethoxy) -2-oxochloride, 2- (2-adamantyloxymethoxymethoxy) -2-oxochloride, 2- (2- (1-adamantyloxymethoxymethoxy) ) -2-Oxoethoxy) chloride, 2- (2- (2- Adamantyloxymethoxymethoxy) -2-oxoethoxy) chloride,

2- (cyclopentyloxymethoxy) -2-oxoethyl bromide, 2- (cyclohexyloxymethoxy) -2-oxoethyl bromide, 2- (cycloheptyloxymethoxy) -2-oxoethyl bromide, 2- (cyclooctyloxymethoxy) ) -2-Oxoethyl bromide, 2- (cyclononyloxymethoxy) -2-oxoethyl bromide, 2- (cyclodecanyloxymethoxy) -2-oxoethyl bromide, 2- (cyclodecanyloxymethoxy) -2 -Oxoethyl bromide, 2- (cyclonorbornyloxymethoxy) -2-oxoethyl bromide, 2- (bornyloxymethoxy) -2-oxoethyl bromide, 2- (isobornyloxymethoxy) -2-oxo Ethyl bromide, 2- (3-to Cyclo [5.2.1.0 ^{2, 6]} deca oxy) -2- oxoethyl bromide, 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecanyl Oxymethoxy) -2-oxoethyl bromide, 2- (1-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (2-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (1-adamantylmethoxymethoxy) ) -2-oxoethyl bromide, 2- (2- (1-adamantyl) ethoxymethoxy) -2-oxoethyl bromide, 2- (5-hydroxy-2-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (3,5-dihydroxy-1-adamantylmethoxymethoxy) -2-oxoethyl bromide, 2- (4-oxo 1-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (4-oxo-2-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (2-cyanomethyl-2-adamantyloxymethoxy) -2-oxo Ethyl bromide, 2- (1-γ-butyrolactyloxymethoxy) -2-oxoethyl bromide,

2- (5- (2,6-norbornanecarbolactyl) oxymethoxy) -2-oxoethyl bromide, 2- (5- (7-oxa-2,6-norbornanecarbolactyl) oxymethoxy) -2- Oxoethyl bromide, 2- (8- (4-oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one) oxymethoxy) -2-oxoethyl bromide, 2- (perfluorocyclopentyloxy Methoxy) -2-oxoethyl bromide, 2- (perfluorocyclohexyloxymethoxy) -2-oxoethyl bromide, 2- (perfluoro-1-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (perfluoro- 1-adamantylmethoxymethoxy) -2-oxoethyl bromide, 2- (3-hydroxy Tyl-perfluoro-1-adamantylmethoxymethoxy) -2-oxoethyl bromide, 2- (1- (1-adamantyloxy) ethoxy) -2-oxoethyl bromide, 2- (1- (2-adamantyloxy) ethoxy ) -2-oxoethyl bromide, 2- (2-tetrahydrofuranyloxymethoxy) -2-oxoethyl bromide, 2- (2-tetrahydropyranyloxymethoxy) -2-oxoethyl bromide, 2- (2- (1 , 4-dioxanyl) oxymethoxy) -2-oxoethyl bromide, 2- (2- (1-adamantyloxymethoxy) -2-oxoethoxy) bromide, 2- (2- (2-adamantyloxymethoxy) -2- Oxoethoxy) bromide, 2- (1-adamantyloxymethoxymethoxy) Ii) -2-oxobromide, 2- (2-adamantyloxymethoxymethoxy) -2-oxobromide, 2- (2- (1-adamantyloxymethoxymethoxy) -2-oxoethoxy) bromide, 2- (2- (2-adamantyloxymethoxymethoxy) -2-oxoethoxy) bromide and the like.

  Among these alicyclic structure-containing compounds, 2- (1-adamantyloxymethoxy) -2-oxoethanol, 2- (2-adamantyloxymethoxy) -2-oxo are used from the viewpoints of performance and ease of production. Ethanol, 2- (1-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (2-adamantyloxymethoxy) -2-oxoethyl chloride, 2- (1-adamantyloxymethoxy) -2-oxoethyl bromide, 2- (2-adamantyloxymethoxy) -2-oxoethyl bromide and the like are preferable.

  Specific examples of chemical formulas in the alicyclic structure-containing compound of the present invention are shown below, but the present invention is not limited thereto.

The alicyclic structure-containing compound of the present invention can be produced by various methods, and representative examples thereof include the following methods, but are not limited thereto.
a. Esterification of a halogenated methyl ether obtained by reacting an alicyclic structure-containing alcohol with a hydrogen halide gas in the presence of an aldehyde, and a 2-hydroxycarboxylic acid.
b. In the presence of an alkyl sulfoxide and an acid anhydride, an alicyclic structure-containing alcohol is converted into a halogenated alkyl ether with a halogenating agent, and further esterified with 2-hydroxycarboxylic acids.
c. Esterification of a halogenated methyl ether obtained by reacting an alicyclic structure-containing alcohol with a hydrogen halide gas in the presence of an aldehyde, and a 2-halogenated carboxylic acid.
d. In the presence of an alkyl sulfoxide and an acid anhydride, an alicyclic structure-containing alcohol is converted into a halogenated alkyl ether with a halogenating agent, and further esterified with a 2-halogenated carboxylic acid.
e. Etherification of the alicyclic structure-containing compound obtained in the above a or b with 1,2-dihaloethanes or 2-haloethanols (halohydrins) f. Etherification of the alicyclic structure-containing compound obtained in c or d above with 2-haloethanol (halohydrin) or ethylene glycol

Examples of the aldehydes include linear or branched aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.
Examples of the hydrogen halide gas include a single gas such as hydrogen fluoride gas, hydrogen chloride gas, and hydrogen bromide gas, or a mixed gas thereof.
Examples of the alkyl sulfoxide include dimethyl sulfoxide, diethyl sulfoxide, di-n-propyl sulfoxide, diisopropyl sulfoxide, di-n-butyl sulfoxide, diisobutyl sulfoxide, di-sec-butyl sulfoxide, di-tert-butyl sulfoxide, diisosulfide. Examples include symmetric or asymmetric aliphatic sulfoxides such as pentyl sulfoxide, methyl ethyl sulfoxide, methyl-tert-butyl sulfoxide.

Examples of the acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, benzoic anhydride, chloroacetic anhydride, trifluoroacetic anhydride. And aliphatic or aromatic carboxylic acid anhydrides.
Examples of the halogenating agent include thionyl chloride, sulfuryl chloride, thionyl bromide, sulfuryl bromide, thionyl chlorobromide, sulfuryl bromide, and the like, phosphorus trichloride, phosphorus tribromide, Examples thereof include phosphorus halide compounds such as phosphorus triiodide, phosphorous trichloride, phosphoric tribromide, phosphorus pentachloride, and phosphorus pentabromide.
Examples of the 2-hydroxycarboxylic acids include aliphatic-2-hydroxycarboxylic acids such as glycolic acid, lactic acid (2-hydroxypropionic acid), 2-hydroxybutanoic acid, and acid anhydrides thereof. Examples of the carboxylic acids include 2-halogenated aliphatic carboxylic acids such as 2-chloroacetic acid, 2-bromoacetic acid, 2-chloropionic acid, 2-bromopropionic acid, and acid anhydrides thereof.

Examples of the 1,2-dihaloethanes include 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1-bromo-2-chloroethane, 1-bromo-2-iodoethane, 1-chloro. Symmetrical or asymmetrical 1,2-halogenated aliphatic hydrocarbons such as 2-iodoethane, 1-bromo-2-chloropropane, 1-bromo-2-iodopropane and the like.
Examples of the 2-haloethanol (halohydrin) include 2-chloroethanol (chlorohydrin), 2-bromoethanol (bromohydrin), 2-iodoethanol (iodohydrin), 2-chloro-n-propanol, 2-bromo- n-propanol, 2-iodo-n-propanol, 2-chloro-n-butanol, 2-bromo-n-butanol, 2-iodo-n-butanol, 2-chloroisopropanol, 2-bromoisopropanol, 2-iodoisopropanol , 2-chloro-sec-butanol, 2-bromo-sec-butanol, 2-iodo-sec-butanol, 2-chloro-tert-butanol, 2-bromo-tert-butanol, 2-iodo-tert-butanol, etc. Linear or branched 2-halo Emissions fatty alcohols.
Examples of the ethylene glycol include symmetric or asymmetric 1,2-dihydroxy aliphatic hydrocarbons such as 1,2-ethanediol (ethylene glycol), 1,2-propanedicol (propylene glycol), diethylene glycol, and the like. Can be mentioned.

  The halogenated methyl ether is obtained by reacting an alicyclic structure-containing alcohol with hydrogen halide gas in the presence of an aldehyde. At this time, the reaction can be performed in the presence or absence of an organic solvent. The substrate concentration in the case of using an organic solvent is not particularly limited as long as it is equal to or lower than the saturated solubility of the alicyclic structure-containing alcohol, but the substrate concentration can be adjusted to be about 0.1 mol / L to 10 mol / L. preferable. When the substrate concentration is 0.1 mol / L or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / L or less, temperature control of the reaction solution becomes easy. 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. Preferably, a halogen-based solvent with a high dissolved amount of hydrogen halide gas is desirable. 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.

  The alkylthioalkyl ether can be obtained by reacting an alicyclic 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, it is preferable to adjust the substrate concentration to be about 1 mol / L to 10 mol / L. When the substrate concentration is 1 mol / L or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / L or less, the temperature control of the reaction solution is facilitated. 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.

  The halogenated alkyl ether can be obtained by reacting an alkylthioalkyl ether with a halogenating agent. At this time, the reaction can be performed 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 about 0.1 mol / L to 10 mol / L. When the substrate concentration is 0.1 mol / L or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / L 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 progress of the reaction itself slows, so room temperature to 100 ° C. is preferred. 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.

In the esterification and etherification, a salt can be generated in the system by allowing a base to act on the alicyclic structure-containing alcohol and the reaction reagent, but the water generated by the azeotropic dehydration reaction is forced out of the system. By removing, the reaction can be promoted.
The esterification and etherification can be performed in the presence or absence of an organic solvent. When an organic solvent is used, the substrate concentration is about 0.1 mol / L to 10 mol / L. It is preferable to adjust. When the substrate concentration is 0.1 mol / L or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / L or less, temperature control of the reaction solution becomes easy. preferable. Usable organic solvents include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene, and ethers such as diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane, DME (dimethoxyethane). Solvents, halogen solvents such as dichloromethane and carbon tetrachloride, DMF (N, N-dimethylformamide), DMSO (dimethylsulfoxide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethylphosphoric triamide), Examples include aprotic polar solvents such as HMPT (hexamethyl phosphite triamide) 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, DBN (1,5-diazabicyclo [4 , 3,0] non-5-ene), DBU (1,8-diazabicyclo [5,4,0] undec-7-ene) and organic amines are used.

In the case of the azeotropic dehydration reaction, a hydrocarbon solvent such as cyclohexane, ethylcyclohexane, toluene, xylene or the like is preferably selected as the solvent. The charging ratio of the reaction reagent to the alicyclic structure-containing alcohol is about 0.01 to 100 times mol, preferably 1 to 1.5 times mol. The addition amount of the base is about 0.1 to 10 times mol, preferably 1 to 1.5 times mol for the alicyclic structure-containing alcohol. The reaction temperature should just be about -200-200 degreeC, Preferably it is -50-100 degreeC. The reaction pressure is about 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. When the reaction time is long, the residence time is long, and when the pressure is too high, a special pressure device is required, which is not economical.
In any of the above reactions, after the 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 alicyclic structure-containing compound of the present invention is obtained by distilling off the solvent from the reaction solution under reduced pressure. You may refine | purify as needed and may use a reaction liquid for next reaction, without refine | purifying. The purification method can be selected from general purification methods such as distillation, extraction washing, crystallization, activated carbon adsorption, and silica gel column chromatography in consideration of production scale and required purity. The method by extraction washing or crystallization is preferable because it can be handled at a low temperature and can process a large amount of sample at a time.

（式中、Ｒ¹は、下記一般式（ｉ）で示される炭素数５〜２０の脂環構造含有基であり、Ｒ⁸は、水素原子、メチル基、フッ素原子又はトリフルオロメチル基であり、Ｌは、下記一般式（ｉｉ）で示される連結基である。） The (meth) acrylic acid esters of the present invention are represented by the following general formula (II).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), and R ⁸ is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. , L is a linking group represented by the following general formula (ii).)

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms, preferably 7 to 12 carbon atoms which may have a hetero atom, and more preferably an adamantyl ring. R ² represents a hetero atom. It is a divalent substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms that may have, and is preferably a divalent hydrocarbon group having 1 or 2 carbon atoms, and R ³ has a hetero atom. A substituted or unsubstituted alkyl group, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, an oxo group or an amino group, which is preferably a halogen atom, a hydroxyl group or an oxo group, and p and q are independent of each other; Represents an integer of 0 or more, preferably 0 to 5, more preferably 0 to ^{2. The} plurality of R ² may be the same or different, and the plurality of R ³ are the same. Or it may be different.)
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b and L ^c are in any bond order, k and m are each independently an integer of 1 or more, preferably 1 or 2. n is an integer of 0 or more And preferably 0 or 1.)

（式中、Ｒ⁴は、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基である。）

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. And may be bonded to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.)

Examples of the alicyclic structure having 5 to 20 carbon atoms that may have a hetero atom in the above formula (i) include, for example, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctyl ring, a cyclononyl ring, a cyclodecanyl ring, and a decalyl ring. (Perhydronaphthalene ring), norbornyl ring, bornyl ring, isobornyl ring, adamantyl ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . Monocyclic or polycyclic structures such as 1 ^7,10 ] dodecane ring, γ-butyrolactyl ring, 4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 4,8-dioxa- Monocyclic or polycyclic lactones such as tricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 4-oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one Monocyclic or polycyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and perfluoro compounds thereof.
Specific examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms which may have a heteroatom in the above formula (i) include straight chain such as methylene group, ethylene group and trimethylene group Or a branched alkylene group, those perfluoro forms, etc. are mentioned.
Specific examples of the substituted or unsubstituted alkyl group that may have a hetero atom in the above formula (i) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , Tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group and the like, and perfluoro compounds thereof.
The alicyclic structure having 5 to 20 carbon atoms that may have a heteroatom, a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms that may have a heteroatom, and a heteroatom Specific examples of the hetero atom that the optionally substituted alkyl group may have include a nitrogen atom, a sulfur atom, and an oxygen atom.
Examples of the alkyl group in the above formula (a) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and hexyl group. Straight chain or branched alkyl groups such as heptyl group, octyl group, nonyl group and decanyl group.
Further, the above R ^4, by bonding the alicyclic structure-containing group represented by the general formula (i), or as an annular structure in which a plurality of R ⁴ is formed by mutual bonding, tetrahydrofuran, tetrahydropyran , [1,4] dioxane and the like.

L in the above general formula (II) is a divalent linking group represented by the general formula (ii), the linking group L ^a, composed of L ^b and L ^c. These linking groups take an arbitrary bonding order and constitute the linking group L. Linking group L is a linking group L ^a, when having a plurality of at least one of L ^b and L ^c, the linking group L ^a between the linking group L ^b each other, the linking group L ^c each other, different from one another respectively identical In addition, the same kind of linking groups may not be adjacently bonded. Specifically, the bond order may be L ^a -L ^b -L ^a .
The linking group L is most preferably a linking group represented by the following general formula (iii) or (iv).
-L ^a -L ^b- (iii)
-L ^a -L ^b -L ^c- (iv)
(In the formula, L ^a is a linking group represented by the above formula (a), L ^b is a linking group represented by the above formula (b), and L ^c is a linking group represented by the above formula (c). is there.)

（式中、Ｒ¹は、上記一般式（ｉ）で示される炭素数５〜２０の脂環構造含有基であり、Ｒ⁴は、それぞれ独立に、水素原子又はアルキル基であり、上記一般式（ｉ）で示される脂環構造含有基と結合して環状構造を形成していてもよく、複数のＲ⁴が互いに結合して環状構造を形成していてもよく、Ｒ⁵〜Ｒ⁷は、それぞれ独立に、水素原子又はメチル基であり、Ｒ⁸は、水素原子、メチル基、フッ素原子又はトリフルオロメチル基である。）
上記一般式（５）〜（８）におけるＲ⁴〜Ｒ⁷としては、それぞれ、上記一般式（ａ）〜（ｃ）におけるＲ⁴〜Ｒ⁷と同様のものを用いることができる。
また、上記一般式（５）〜（８）における上記Ｒ⁴と、上記一般式（ｉ）で示される脂環構造含有基とが結合して、あるいは、複数のＲ⁴が互いに結合して形成される環状構造としては、テトラヒドロフラン、テトラヒドロピラン、［１，４］ジオキサン等の残基が挙げられる。 The (meth) acrylic acid esters of the present invention are preferably those represented by any one of the following general formulas (5) to (8).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.)
As R < ⁴ > -R < ⁷ > in the said general formula (5)-(8), the thing similar to R < ⁴ > -R < ⁷ > in the said general formula (a)-(c) can be used, respectively.
In addition, the R ⁴ in the general formulas (5) to (8) and the alicyclic structure-containing group represented by the general formula (i) are bonded to each other, or a plurality of R ⁴ are bonded to each other. Examples of the cyclic structure include residues such as tetrahydrofuran, tetrahydropyran, and [1,4] dioxane.

Specific examples of the alicyclic structure-containing compound of the present invention represented by the general formulas (5) to (8) include 2- (cyclopentyloxymethoxy) -2-oxoethyl methacrylate and 2- (cyclohexyloxymethoxy) -2. -Oxoethyl methacrylate, 2- (cycloheptyloxymethoxy) -2-oxoethyl methacrylate, 2- (cyclooctyloxymethoxy) -2-oxoethyl methacrylate, 2- (cyclononyloxymethoxy) -2-oxoethyl methacrylate, 2- (cyclo Decanyloxymethoxy) -2-oxoethyl methacrylate, 2- (cyclodecanyloxymethoxy) -2-oxoethyl methacrylate, 2- (cyclonorbornyloxymethoxy) -2-oxoethyl methacrylate, 2- (bornyloxy) Butoxy) -2-oxoethyl methacrylate, 2- (isobornyloxycarbonyl methoxy) -2-oxoethyl methacrylate, 2- (3-tricyclo [5.2.1.0 ^{2, 6]} deca oxy) -2- oxoethyl methacrylate, 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-oxy) -2- oxoethyl methacrylate, 2- (1-adamantyloxy methoxy) -2-oxoethyl methacrylate , 2- (2-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (1-adamantylmethoxymethoxy) -2-oxoethyl methacrylate, 2- (2- (1-adamantyl) ethoxymethoxy) -2-oxoethyl methacrylate, 2- (5-hydroxy-2-adamantillo) Xymethoxy) -2-oxoethyl methacrylate, 2- (3,5-dihydroxy-1-adamantylmethoxymethoxy) -2-oxoethyl methacrylate, 2- (4-oxo-1-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (4-oxo-2-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (2-cyanomethyl-2-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (1-γ-butyrolactyloxymethoxy)- 2-oxoethyl methacrylate, 2- (5- (2,6-norbornanecarbolactyl) oxymethoxy) -2-oxoethyl methacrylate, 2- (5- (7-oxa-2,6-norbornanecarbolactyl) oxymethoxy ) -2-O Soechiru methacrylate,

2- (8- (4-Oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one) oxymethoxy) -2-oxoethyl methacrylate, 2- (perfluorocyclopentyloxymethoxy) -2- Oxoethyl methacrylate, 2- (perfluorocyclohexyloxymethoxy) -2-oxoethyl methacrylate, 2- (perfluoro-1-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (perfluoro-1-adamantylmethoxymethoxy) -2 -Oxoethyl methacrylate, 2- (3-hydroxymethyl-perfluoro-1-adamantylmethoxymethoxy) -2-oxoethyl methacrylate, 2- (1- (1-adamantyloxy) ethoxy) -2-oxoethyl methacrylate, 2- ( -(2-adamantyloxy) ethoxy) -2-oxoethyl methacrylate, 2- (2-tetrahydrofuranyloxymethoxy) -2-oxoethyl methacrylate, 2- (2-tetrahydropyranyloxymethoxy) -2-oxoethyl methacrylate, 2- (2- (1,4-dioxanyl) oxymethoxy) -2-oxoethyl methacrylate, 2- (2- (1-adamantyloxymethoxy) -2-oxoethoxy) ethyl methacrylate, 2- (2- (2-adamantyloxy) Methoxy) -2-oxoethoxy) ethyl methacrylate, 2- (1-adamantyloxymethoxymethoxy) -2-oxoethyl methacrylate, 2- (2-adamantyloxymethoxymethoxy) -2-oxoethyl methacrylate, 2- (2 -(1-adamantyloxymethoxymethoxy) -2-oxoethoxy) ethyl methacrylate, 2- (2- (2-adamantyloxymethoxymethoxy) -2-oxoethoxy) ethyl methacrylate, 2- (1-adamantyloxymethoxy)- 2-oxoethyl acrylate, 2- (2-adamantyloxymethoxy) -2-oxoethyl acrylate, 2- (1-adamantyloxymethoxy) -2-oxoethyl 2-trifluoromethyl acrylate, 2- (2-adamantyloxymethoxy)- Examples include 2-oxoethyl 2-trifluoromethyl acrylate.

  Among these alicyclic structure-containing compounds, 2- (1-adamantyloxymethoxy) -2-oxoethyl methacrylate, 2- (2-adamantyloxymethoxy) -2-oxoethyl, from the viewpoints of performance and ease of production, etc. Methacrylate is preferred.

  Specific examples of chemical formulas in the alicyclic structure-containing compound of the present invention are shown below, but the present invention is not limited thereto.

The (meth) acrylic acid esters of the present invention can be produced by various methods and are not particularly limited, but specific examples include (meth) acrylic acid esters provided by the present invention shown below. The manufacturing method of these is mentioned.
The method for producing (meth) acrylic acid esters provided by the present invention comprises an alicyclic structure-containing compound of the present invention, (meth) acrylic acids, (meth) acrylic halides, (meth) acrylic anhydrides and This is a production method by esterification with one or more selected from (meth) acrylic acid 2-hydroxyalkyl derivatives.
Examples of the (meth) acrylic acids include acrylic acid, methacrylic acid, 2-fluoroacrylic acid, and 2-trifluoromethylacrylic acid.
Examples of the (meth) acrylic acid halides include acrylic acid fluoride, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid fluoride, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, and 2-fluoroacrylic acid. Fluoride, 2-fluoroacrylic acid chloride, 2-fluoroacrylic acid bromide, 2-fluoroacrylic acid iodide, 2-trifluoromethyl acrylic acid fluoride, 2-trifluoromethyl acrylic acid chloride, 2-trifluoromethyl acrylic acid bromide, Examples thereof include 2-trifluoromethylacrylic acid iodide.
Examples of the (meth) acrylic anhydrides include acrylic anhydride, methacrylic anhydride, 2-fluoroacrylic anhydride, 2-trifluoromethylacrylic anhydride, and the like.
As said (meth) acrylic-acid 2-hydroxyalkyl derivative, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. are mentioned, for example.

The esterification is selected from the alicyclic structure-containing compound of the present invention and (meth) acrylic acids, (meth) acrylic acid halides, (meth) acrylic anhydrides and (meth) acrylic acid 2-hydroxyalkyl derivatives. It is possible to generate a salt in the system by allowing a base to act on one or more types, but the reaction can be promoted by forcibly removing water generated by the azeotropic dehydration reaction out of the system. .
The esterification can be performed in the presence or absence of an organic solvent, but when an organic solvent is used, the substrate concentration should be adjusted to about 0.1 mol / L to 10 mol / L. Is preferred. When the substrate concentration is 0.1 mol / L or more, a necessary amount can be obtained in a normal reactor, which is economically preferable. When the substrate concentration is 10 mol / L or less, temperature control of the reaction solution becomes easy. 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. Solvents, halogen solvents such as dichloromethane and carbon tetrachloride, DMF (N, N-dimethylformamide), DMSO (dimethylsulfoxide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethylphosphoric triamide), Examples include aprotic polar solvents such as HMPT (hexamethyl phosphite triamide) 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, DBN (1,5-diazabicyclo [4 , 3,0] non-5-ene), DBU (1,8-diazabicyclo [5,4,0] undec-7-ene) and organic amines are used.

In the case of the azeotropic dehydration reaction, a hydrocarbon solvent such as cyclohexane, ethylcyclohexane, toluene, xylene is preferably selected as the solvent. The charging ratio of the reaction reagent to the alicyclic structure-containing alcohol is about 0.01 to 100 times mol, preferably 1 to 1.5 times mol. The addition amount of the base is about 0.1 to 10 times mol, preferably 1 to 1.5 times mol for the alicyclic structure-containing alcohol. The reaction temperature should just be about -200-200 degreeC, Preferably it is -50-100 degreeC. The reaction pressure is about 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. When the reaction time is long, the residence time is long, and when the pressure is too high, a special pressure device is required, which is not economical.
After the 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 alicyclic structure-containing compound of the present invention is obtained by distilling off the solvent from the reaction solution under reduced pressure. You may refine | purify as needed and may use a reaction liquid for next reaction, without refine | purifying. The purification method can be selected from general purification methods such as distillation, extraction washing, crystallization, activated carbon adsorption, and silica gel column chromatography in consideration of production scale and required purity. The method by extraction washing or crystallization is preferable because it can be handled at a low temperature and can process a large amount of sample at a time.

The present invention also provides a (meth) acrylic polymer containing monomer units based on the (meth) acrylic acid esters of the present invention.
The (meth) acrylic polymer may be a polymer containing a monomer unit based on one or more of the (meth) acrylic esters of the present invention described above, and the (meth) acrylic esters of the present invention. A homopolymer using one type may be used, or a copolymer using two or more types of (meth) acrylic acid esters of the present invention may be used, and (meth) acrylic acid esters 1 of the present invention may be used. It may be a copolymer using more than one kind and other polymerizable monomers.
The (meth) acrylic polymer of the present invention preferably contains 10 to 90 mol% of monomer units based on the (meth) acrylic acid esters of the present invention, and more preferably contains 25 to 75 mol%. .
The polymerization method is not particularly limited and can be carried out by a conventional polymerization method. For example, known polymerization methods such as solution polymerization (boiling point polymerization, polymerization below boiling point), emulsion polymerization, suspension polymerization, bulk polymerization, etc. Can be used. The smaller the amount of the high-boiling unreacted monomer remaining in the reaction solution after polymerization, the better. It is preferable to perform an operation for removing the unreacted monomer as necessary during the polymerization or after the completion of the polymerization. Among the above polymerization methods, a polymerization reaction using a radical polymerization initiator in a solvent is preferable. Although there is no limitation in particular as a polymerization initiator, A peroxide type polymerization initiator, an azo type polymerization initiator, etc. are used.

Peroxide-based polymerization initiators include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester (lauroyl peroxide, benzoyl peroxide). Is mentioned. Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvalero). Nitrile) and azo compounds such as dimethyl 2,2′-azobisisobutyrate.
The said polymerization initiator can use suitably 1 type (s) or 2 or more types of polymerization initiators according to reaction conditions, such as superposition | polymerization temperature.
After the polymerization is completed, various methods can be adopted as a method for removing the (meth) acrylic acid esters and other copolymerization monomers of the present invention used from the produced polymer. Therefore, a method of washing the acrylic polymer using a poor solvent for the acrylic polymer is preferable. Among poor solvents for acrylic polymers, those having a low boiling point are preferred, and representative examples include methanol, ethanol, n-hexane, and n-heptane.
The resin composition containing the (meth) acrylic polymer of the present invention has various uses such as circuit forming materials (resist for semiconductor production, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.). In particular, it is preferably used as a photoresist resin composition, and more preferably as a positive photoresist resin composition.

The present invention further provides a positive resist composition containing the (meth) acrylic polymer of the present invention.
The positive resist composition of the present invention is not particularly limited as long as it contains the (meth) acrylic polymer of the present invention, but with respect to 100 parts by mass of the positive resist composition of the present invention, What contains 2-50 mass parts of (meth) acrylic-type polymers is preferable, and what contains 5-15 mass parts is more preferable.
In addition to the (meth) acrylic polymer, the positive resist composition of the present invention includes quenchers such as PAG (photo acid generator) and organic amines, and alkali-soluble resins (for example, novolak resins, phenol resins, imide resins). Alkali-soluble components such as carboxyl group-containing resins), colorants (for example, dyes), organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, Cellosolves, carbitols, glycol ether esters, mixed solvents 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.

The content of the photoacid generator in the positive resist composition of the present invention is determined based on the strength of the acid generated by light irradiation and the monomer based on the (meth) acrylic acid esters in the (meth) acrylic polymer. Although it can select suitably according to content of a unit etc., Preferably it is 0.1-30 mass parts with respect to 100 mass parts of said (meth) acrylic-type polymers, More preferably, 1-25 mass parts, Furthermore, Preferably it contains 2 to 20 parts by mass of a photoacid generator.
In the positive resist composition of the present invention, the (meth) acrylic polymer, a photoacid generator, and, if necessary, the organic solvent or the like are mixed, and if necessary, impurities are used 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 forming a resist film on a support using the positive resist composition, a step of selectively exposing the resist film, and a resist pattern formed by subjecting the selectively exposed resist film to an alkali development treatment. And a resist pattern forming method including a forming step.
Examples of the support include a silicon wafer, metal, plastic, glass, and ceramic. The step of forming a resist film using a positive resist composition can be performed using a conventional coating means such as a spin coater, a dip coater, or a roller coater. The thickness of the resist film is, for example, preferably 50 nm to 20 μm, more preferably 100 nm to 2 μm. In the step of selectively exposing the resist film, light of various wavelengths, such as ultraviolet rays and X-rays, can be used. For resist, g-line, i-line, excimer laser (for example, XeCl, KrF, KrCl, ArF, ArCl, etc.), soft X-ray, etc. are usually used. Exposure energy, for example 0.1~1000mJ / cm ^2, preferably about 1 to 100 mJ / cm ^2.
Since the (meth) acrylic polymer contained in the positive resist composition has an acetal structure, it has an acid-decomposable function. Therefore, an acid is generated from the photoacid generator by the selective exposure, and the cyclic portion of the structural unit based on the (meth) acrylic acid ester of the (meth) acrylic polymer is rapidly detached by this acid. A carboxyl group and a hydroxyl group that contribute to solubilization are generated. Therefore, a predetermined pattern can be formed with high accuracy by performing development using 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.
In addition, the measuring method of a physical property is as follows.
(Measuring method)
Nuclear magnetic resonance spectroscopy (NMR): Measured with JNM-ECA500 (manufactured by JEOL Ltd.) using chloroform-d as a solvent.
Gas chromatograph-mass spectrometry (GC-MS): Measured using EI (Shimadzu Corporation GCMS-QP2010).
Film thickness and standardized film thickness: Film thickness was measured using an optical film thickness meter (FE-3000 manufactured by Otsuka Electronics Co., Ltd.) and a contact film thickness meter (ET-4000A manufactured by Kosaka Laboratories). The normalized film thickness was calculated with a thickness of 1.0.

Example 1 (Synthesis of alicyclic structure-containing compound: chloroacetic acid 2-adamantyloxymethyl)
A 100 mL two-necked flask was charged with 5134 mg of 2-chloromethoxyadamantane (molecular weight: 200.71, 25.6 mmol) and 2661 mg of chloroacetic acid (molecular weight: 95.50, 28.2 mmol, 1.1 eq.), Tetrahydrofuran (THF). 50 mL was added and stirred to dissolve. Subsequently, when 4.6 mL of triethylamine (molecular weight: 101.19, specific gravity: 0.726, 33.0 mmol, 1.3 eq) was added dropwise, the reaction solution immediately became cloudy and slightly exothermic was observed. Subsequently, after stirring for 2 hours, 50 mL of water was added to stop the reaction. To the reaction mixture was added 100 mL of diethyl ether, and after shaking and standing, the aqueous layer was removed. 50 mL of water was added again, and after shaking and standing, the aqueous layer was removed. 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 solvent was completely removed, 6288 mg of a white solid of 2-adamantyloxymethyl chloroacetate as the target product was obtained (24.3 mmol, isolated yield 95.0%, GC purity 94.4%).

The measurement results of the obtained resin were as follows.
GC-MS: 257 (M ⁺ −1, 0.01%), 231 (0.2%), 230 (1.3%), 229 (0.6%), 228 (4.0%), 164 (22.3%), 135 (47.4%), 134 (100%), 92 (57.8%), 79 (36.7%), 67 (17.4%)
¹ H-NMR: 1.50 (d, J = 12.2 Hz, 2H), 1.68 (d, J = 12.2, 2H), 1.71 (s, 2H), 1.80-1. 87 (m, 4H), 2.01 (s, 3H), 2.04 (s, 1H), 3.77 (s, 1H, d), 4.07 (s, 2H, a), 5.47 (S, 2H, c)
¹³ C-NMR: 27.02 (g or g ′), 27.24 (g ′ or g), 31.30 (for or f ′), 32.40 (e), 36.40 (f ′ or f ), 37.36 (h), 40.90 (a), 83.14 (d), 89.55 (c), 166.90 (b)

Example 2 (Synthesis of (meth) acrylic acid esters: methacrylic acid 2- (2-adamantyloxymethoxy) -2-oxoethyl)
A 50 mL two-necked flask was charged with 66 mg of potassium iodide (molecular weight: 166.00, 0.4 mmol) and 207 mg of potassium carbonate (molecular weight: 138.21, 1.5 mmol), and 2 mL of N, N-dimethylformamide (DMF) was added. And stirring was started. 0.1 mL of methacrylic acid (molecular weight: 86.09, specific gravity: 1.015, 1.2 mmol) was added to the resulting slurry, and the reaction solution was brought to 45 ° C. with an oil bath. Subsequently, 258 mg (molecular weight: 258.74, 1.0 mmol) of chloroacetic acid 2-adamantyloxymethyl dissolved in 1 mL of DMF was added dropwise using a cannula, and further washed twice with 1 mL of DMF. After 3 hours, 5 mL of water was added to stop the reaction. 20 mL of diethyl ether was added to the reaction mixture, and after shaking and standing, the aqueous layer was removed. 5 mL of water was added again, and after shaking and standing, the aqueous layer was removed. 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 solvent was completely removed, 304 mg of 2- (2-adamantyloxymethoxy) -2-oxoethyl methacrylate was obtained as the target product (0.99 mmol, isolated yield 98.6%, GC purity 88 .3%).

The measurement results of the obtained resin were as follows.
GC-MS: 278 (M ⁺ -30, 32.9%), 202 (5.2%), 164 (%), 135 (100%), 134 (79.3%), 92 (63.3%) ), 69 (51.8%), 41 (38.1%)
¹ H-NMR: 1.49 (d, J = 11.6 Hz, 2H), 1.67 (d, J = 12.3 Hz, 2H), 1.71 (s, 2H), 1.79-1. 86 (m, 4H), 1.95 to 2.04 (m, 4H), 1.98 (s, 3H, c), 3.74 (s, 1H, h), 4.69 (s, 2H, e), 5.46 (s, 2H , g), 5.66 (t, J = 1.5Hz, 1H, a 2), 6.22 (s, 1H, a 1)
¹³ C-NMR: 18.03 (c), 26.96 (k or k ′), 27.17 (K7 or k), 31.23 (j o j ′), 32.28 (i), 36, 31 (j ′ or j), 37.30 (l), 60.73 (e), 82.79 (h), 88.78 (g), 126.65 (a), 135.25 (b), 166.39 (d or f), 167.36 (f or d)

Example 3 (Synthesis of (meth) acrylic polymer)
Methyl isobutyl ketone was charged with 2,2′-azobis (isobutyric acid) dimethyl / monomer A / monomer C at a mass ratio of 0.1 / 1.0 / 1.0, and stirred for 2 hours while heating under reflux. After that, the reaction solution was purified by pouring it into a large amount of methanol / water mixed solvent and precipitating three times. As a result, a copolymer P1 having a monomer A: monomer C copolymer composition (mol) = 52: 48, a weight average molecular weight (Mw) of 7382, and a dispersity (Mw / Mn) of 1.30 was obtained.

Synthesis Example 1 (Synthesis of polymer)
Polymerization was conducted in the same manner as in Example 3 using separately synthesized monomer B. As a result, copolymerization composition (mol) of monomer B: monomer C = 55: 45, weight average molecular weight (Mw) was 7535, dispersity (Mw / A copolymer P2 of (Mn) 1.32 was obtained.

Example 4 (Preparation of positive resist composition)
5 parts by weight of triphenylsulfonium nonafluorobutanesulfonate as a photoacid generator is added to 100 parts by weight of the copolymer P1 obtained in Example 3, and propylene glycol monomethyl is added to 10 parts by weight of the obtained resin composition. It melt | dissolved using 90 mass parts of ether acetate, and prepared resist composition R1. The prepared resist composition R1 was applied onto a silicon wafer, and baked at 110 ° C. for 60 seconds to form a resist film. The wafer thus obtained was subjected to several points of open exposure with light having a wavelength of 248 nm at different exposure amounts. Immediately after the exposure, the film was heated at 110 ° C. for 60 seconds, and then developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds. The change in film thickness with respect to the exposure amount at this time is shown in Table 1 and FIG.

Comparative Example 1 (Synthesis of 2- (2-adamantyloxymethoxy) -2-oxoethyl methacrylate)
A 50 mL two-necked flask was charged with 66 mg of potassium iodide (molecular weight: 166.00, 0.4 mmol) and 258 mg of 2-adamantyloxymethyl chloroacetate (molecular weight: 258.74, 1.0 mmol). did. To the obtained slurry, 0.20 mL (molecular weight: 86.09, specific gravity: 1.015, 2.4 mmol), triethylamine 0.42 mL (molecular weight: 101.19, specific gravity: 0.726, 3.0 mmol) were added. In addition, the reaction solution was brought to 60 ° C. with an oil bath. After 5 hours, 5 mL of water was added to stop the reaction. 20 mL of diethyl ether was added to the reaction mixture, and after shaking and standing, the aqueous layer was removed. 5 mL of water was added again, and after shaking and standing, the aqueous layer was removed. 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 solvent was completely removed, the desired product could not be obtained, and 193 mg of 2-adamantyloxymethyl methacrylate was obtained (0.77 mmol), in which 2-adamantyloxymethyl chloroacetate and methacrylic acid were transesterified.

^{GC-MS: 220 (M +} -CH 2 O, 29.9%), 164 (57.5%), 134 (93.5%), 135 (100%), 122 (21.4%), 92 (68.9%), 79 (43.2%), 69 (51.5%), 41 (47.6%)
¹ H-NMR: 1.50 (d, J = 12.3 Hz, 2H), 1.68 (d, J = 12.3 Hz, 2H), 1.71 (s, 2H), 1.79-1. 87 (m, 4H), 1.95 (s, 3H, a), 2.03 to 2.05 (m, 3H), 2.07 (s, 1H), 3.76 (t, J = 3. 4 Hz, 1 H, f), 5.46 (s, 2 H, e), 5.59 (t, J = 1.9 Hz, ¹ H, b ¹ ), 6.13 (s, 1 H, b ² )
¹³ C-NMR: 18.19 (a), 27.11 (i or i ′), 27.33 (i ′ or i), 31.40 (g), 32.52 (h or h ′), 36 .50 (h 'or h), 37.47 (j), 82.95 (f), 88.61 (e), 125.89 (b), 136.32 (c), 166.88 (d)

Comparative Example 2 (adjustment of resin composition)
Resist composition R2 was prepared in the same manner as in Example 4 except that copolymer P2 obtained in Synthesis Example 1 was used instead of copolymer P1, and the change in film thickness with respect to the exposure amount was measured. The results are shown in Table 1 and FIG.

  In Example 4 of this invention, the film thickness change by the exposure amount was confirmed, and it has confirmed that resist composition R1 had a function as photosensitive resin.

  The alicyclic structure-containing compound and (meth) acrylic acid esters of the present invention are particularly excellent as a photoresist material corresponding to irradiation light with a short wavelength.

It is a figure which shows the change of the film thickness with respect to the exposure amount of resist composition R1 obtained in Example 4, and resist composition R2 obtained by the comparative example 2. FIG.

Claims (9)

An alicyclic structure-containing compound represented by the following general formula (I).
R ¹ -L-X (I)
(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), L is a linking group represented by the following general formula (ii), and X is , A halogen atom or a hydroxyl group.)

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ² is a divalent substitution having 1 to 5 carbon atoms which may have a hetero atom, or An unsubstituted hydrocarbon group, R ³ represents a substituted or unsubstituted alkyl group, halogen atom, hydroxyl group, cyano group, carboxyl group, oxo group or amino group which may have a hetero atom, p and q independently represents an integer greater than or equal to 0. The plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different.
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b, and L ^c are in any combination order, k and m are each independently an integer of 1 or more, and n is an integer of 0 or more.)

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. And may be bonded to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.) The alicyclic structure-containing compound according to claim 1 represented by any one of the following general formulas (1) to (4).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and X represents a halogen atom or a hydroxyl group.) (Meth) acrylic acid esters represented by the general formula (II).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the following general formula (i), and R ⁸ is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. , L is a linking group represented by the following general formula (ii).)

(In the formula, Z is an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ² is a substituted or unsubstituted group having 1 to 5 carbon atoms which may have a hetero atom. R ³ represents a divalent hydrocarbon group, and R ³ represents a substituted or unsubstituted alkyl group, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, an oxo group or an amino group, which may have a hetero atom. q independently represents an integer greater than or equal to 0. The plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different.
-{(L ^a ) _k- (L ^b ) _m- (L ^c ) _n }-(ii)
(In the formula, L ^a is a linking group represented by the following formula (a), L ^b is a linking group represented by the following formula (b), and L ^c is a linking group represented by the following formula (c). And L ^a , L ^b, and L ^c are in any combination order, k and m are each independently an integer of 1 or more, and n is an integer of 0 or more.)

(In the formula, R ⁴ is a hydrogen atom or an alkyl group, and may be bonded to the alicyclic structure-containing group represented by the general formula (i) to form a cyclic structure, and a plurality of R ⁴ may be bonded to each other. And may be bonded to form a cyclic structure, and R ^{5 to} R ⁷ are each independently a hydrogen atom or a methyl group.) The (meth) acrylic acid esters according to claim 3, which are represented by any one of the following general formulas (5) to (8).

(In the formula, R ¹ is an alicyclic structure-containing group having 5 to 20 carbon atoms represented by the above general formula (i), each R ⁴ is independently a hydrogen atom or an alkyl group, and the above general formula It may be bonded to the alicyclic structure-containing group represented by (i) to form a cyclic structure, or a plurality of R ⁴ may be bonded to each other to form a cyclic structure, and R ^{5 to} R ⁷ are And each independently represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.)   The (meth) acrylic acid esters according to claim 3 or 4, wherein Z is an adamantyl ring.   The alicyclic structure-containing compound according to claim 1 or 2, and selected from (meth) acrylic acids, (meth) acrylic acid halides, (meth) acrylic anhydrides, and (meth) acrylic acid 2-hydroxyalkyl derivatives. A method for producing (meth) acrylic acid esters, wherein the (meth) acrylic acid esters according to claim 3 or 4 are obtained by esterifying one or more of them.   The (meth) acrylic-type polymer containing the monomer unit based on the (meth) acrylic acid ester of Claim 3 or 4.   A positive resist composition containing the (meth) acrylic polymer according to claim 7.   A step of forming a resist film on a support using the positive resist composition according to claim 8; a step of selectively exposing the resist film; and a step of subjecting the selectively exposed resist film to an alkali development treatment to form a resist. Forming a pattern. A resist pattern forming method.

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