JP2015038072A - Polymerizable compound having alkali-dissociable group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide (meth) acrylic acid ester useful as immersion exposure resist.SOLUTION: This invention relates to (meth) acrylic acid ester represented by the formula (m-1-1a) and having alkali-dissociable group, where Ris C1-10 fluorine substituted hydrocarbon group; Rf is F or C1-10 perfluoroalkyl group; n1 is an integer of 0-4; Ris single bond, methylene group or the like; Ris methylene group or the like; and R is H, methyl group or the like.

Description

  The present invention relates to a polymerizable compound having an alkali dissociable group that can be suitably used as a chemically amplified resist, particularly a resist for immersion exposure.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, a resist film is formed on a substrate with a resin composition containing a polymer having an acid-dissociable group, and the resist film has a short wavelength via a mask pattern. A fine resist pattern is formed by irradiating with radiation (excimer laser or the like) and exposing, and removing the exposed portion by alkali development. At this time, a “chemically amplified resist” is used in which a radiation-sensitive acid generator that generates an acid upon irradiation with radiation is contained in the resin composition, and the sensitivity is improved by the action of the acid.

  In addition, as a method for forming a finer resist pattern (for example, a line width of about 45 nm), the use of “immersion exposure (liquid immersion lithography)” is expanding. In this method, the exposure optical path space (between the lens and the resist film) is immersed in an immersion exposure liquid (for example, pure water or a fluorine-based inert liquid) having a refractive index (n) larger than that of air or an inert gas. Exposure is performed in the satisfied state. Therefore, even when the numerical aperture (NA) of the lens is increased, there is an advantage that the depth of focus is hardly lowered and high resolution can be obtained.

  The resin composition used in the immersion exposure method has hydrophobicity for the purpose of preventing elution of an acid generator and the like from the resist film to the immersion exposure liquid and improving drainage of the resist film. A resin composition containing a high fluorine-containing polymer has been proposed (see Patent Document 1).

  Furthermore, for the purpose of suppressing development defects and the like in the unexposed areas associated with the hydrophobization of the resist film, a fluorine-containing polymer that is hydrophobic during immersion exposure and hydrophilic during alkali development, specifically, phenol. A fluorine-containing polymer in which a highly hydrophobic fluoroacyl group is introduced into a functional hydroxyl group has also been proposed (see Patent Documents 2 and 3).

International Publication No. 2007 / 116664A JP 2009-132843 A JP 2009-139909 A

  The fluorine-containing polymers shown in Patent Documents 2 and 3 exhibit hydrophobicity due to the fluoroacyl group during immersion exposure, while the fluoroacyl group is removed during alkali development to exhibit hydrophilicity due to the phenolic hydroxyl group. . Therefore, the effect of suppressing development defects in the unexposed areas can be expected.

  However, the fluorine-containing polymers as shown in Patent Documents 2 and 3 exhibit a certain degree of effect of suppressing development defects in the unexposed portions, but the occurrence of scum during development and the pattern shape after development are round-top shapes. There were problems such as becoming.

  The present invention has been made in order to solve the problems of the prior art as described above, and can improve the hydrophilicity during alkali development while ensuring the hydrophobicity during immersion exposure. In addition to being able to suppress development defects, a compound capable of synthesizing a resist polymer that gives a resist coating film with excellent pattern shape after development, specifically, a polymerizable compound having an alkali-dissociable group is provided. To do.

  As a result of intensive studies to solve the problems of the prior art as described above, the present inventors have found that a hydrophilic group (alcoholic hydroxyl group, amino group, carboxyl group) other than the phenolic hydroxyl group of the (meth) acrylic monomer. It has been found that the above problems can be solved by synthesizing a resist polymer using a compound in which a group or the like is modified with an alkali dissociable group, and the present invention has been completed. Specifically, the present invention provides a polymerizable compound having the following alkali dissociable group.

［一般式（ｍ−１−２）中、Ｒ^９は下記一般式（１）〜（３）で表される基のうちいずれかを示す。Ｘ^１は単結合、ジフルオロメチレン基又は炭素数２〜２０の直鎖状若しくは分岐状の全フッ素置換２価炭化水素基、Ｒ^２は単結合、メチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示す。Ｒ^３１はメチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示し、Ｒ^２側の末端に酸素原子、硫黄原子、イミノ基、カルボニル基、−ＣＯ−Ｏ−又は−ＣＯ−ＮＨ−が結合された構造のものも含む。Ｒは水素原子、メチル基又はトリフルオロメチル基を示す。］

［一般式（１）及び（２）中、Ｒ^１０は相互に独立にハロゲン原子又は炭素数１〜１０のアルキル基、アルコキシル基、アシル基若しくはアシロキシ基を示す。ｍ_１は０〜５の整数を示し、ｍ_２は０〜４の整数を示す。一般式（３）中、Ｒ^１１及びＲ^１２は相互に独立に水素原子又は炭素数１〜１０のアルキル基を示す。また、Ｒ^１１及びＲ^１２が相互に結合してそれぞれが結合する炭素原子とともに炭素数４〜２０の脂環式構造を形成していてもよい。］

[1] A compound represented by the following general formula (m-1-2), which is a compound other than the compounds represented by the following formulas (4) and (5).

[In General Formula (m-1-2), R ⁹ represents any one of groups represented by the following General Formulas (1) to (3). X ¹ is a single bond, a difluoromethylene group or a linear or branched perfluorinated divalent hydrocarbon group having 2 to 20 carbon atoms, R ² is a single bond, a methylene group, or a straight chain having 2 to 10 carbon atoms. Or a branched divalent hydrocarbon group or a C4-C20 divalent cyclic hydrocarbon group is shown. R ³¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an oxygen atom or sulfur at the terminal on the R ² side. A structure in which an atom, an imino group, a carbonyl group, —CO—O— or —CO—NH— is bonded is also included. R represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

[In General Formulas (1) and (2), R ¹⁰ independently represents a halogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an acyl group, or an acyloxy group. m ₁ represents an integer of 0 to 5, and m ₂ represents an integer of 0 to 4. In General Formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ¹¹ and R ¹² may be bonded to each other to form an alicyclic structure having 4 to 20 carbon atoms together with the carbon atom to which each is bonded. ]

［一般式（６）及び（ｍ−１−２ａ）中、Ｒｆは相互に独立にフッ素原子又は炭素数１〜１０のパーフルオロアルキル基、ｎ２は１〜４の整数を示す。一般式（ｍ−１−２ａ）中、Ｒ^９及びＲは一般式（ｍ−１−２）の説明と同義である。Ｒ^２１はメチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示す。］ [2] In the general formula (m-1-2), the R ³¹ is a group represented by R ²¹ , the R ² is a single bond, and the X ¹ is represented by the following general formula (6). The compound according to [1], which is a group represented by the following general formula (m-1-2a):

[In General Formulas (6) and (m-1-2a), Rf is independently a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms, and n2 is an integer of 1 to 4. In the general formula (m-1-2a), R ⁹ and R have the same meaning as in the description of the general formula (m-1-2). R ²¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. ]

[3] The compound according to [2], wherein in the general formula (m-1-2a), n2 is an integer of 1 to 2, and Rf is a fluorine atom or a trifluoromethyl group.

[4] The compound according to [2], wherein in the general formula (m-1-2a), n2 is an integer of 1 to 2, and Rf is a fluorine atom.

[5] The compound according to [2], wherein in the general formula (m-1-2a), n2 is 1 and Rf is a trifluoromethyl group.

［一般式（６）及び一般式（ｍ−１−２ｂ）中、Ｒｆは相互に独立にフッ素原子又は炭素数１〜１０のパーフルオロアルキル基、ｎ２は０〜４の整数を示す。一般式（ｍ−１−２ｂ）中、Ｒ^９、Ｒ^２及びＲは一般式（ｍ−１−２）の説明と同義である。Ｒ^２１はメチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価の環状炭化水素基を示す。］ [6] In the general formula (m-1-2), the R ³¹ is a group represented by —R ²¹ —O—CO—, and the X ¹ is a group represented by the following general formula (6). The compound according to [1], which is represented by the following general formula (m-1-2b).

[In general formula (6) and general formula (m-1-2b), Rf is a fluorine atom or a C1-C10 perfluoroalkyl group mutually independently, n2 shows the integer of 0-4. In general formula (m-1-2b), R ⁹ , R ^2, and R have the same meaning as in the description of general formula (m-1-2). R ²¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. ]

[7] The compound according to [6], wherein in the general formula (m-1-2b), n2 is 0.

［一般式（ｍ−１−１ａ）中、Ｒ^８は少なくとも一の水素原子がフッ素原子に置換された、炭素数１〜１０のフッ素置換炭化水素基を示す。Ｒｆは相互に独立にフッ素原子又は炭素数１〜１０のパーフルオロアルキル基、ｎ１は０〜４の整数を示す。Ｒ^２は単結合、メチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示す。Ｒ^３１はメチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示し、Ｒ^２側の末端に酸素原子、硫黄原子、イミノ基、カルボニル基、−ＣＯ−Ｏ−又は−ＣＯ−ＮＨ−が結合された構造のものも含む。Ｒは水素原子、メチル基又はトリフルオロメチル基を示す。］ [8] A compound represented by the following general formula (m-1-1a).

[In General Formula (m-1-1a), R ⁸ represents a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Rf is a fluorine atom or a C1-C10 perfluoroalkyl group mutually independently, n1 shows the integer of 0-4. R ² represents a single bond, a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. R ³¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an oxygen atom or sulfur at the terminal on the R ² side. A structure in which an atom, an imino group, a carbonyl group, —CO—O— or —CO—NH— is bonded is also included. R represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

［一般式（ｍ−１−１ｂ）中、Ｒ^８は少なくとも一の水素原子がフッ素原子に置換された、炭素数１〜１０のフッ素置換炭化水素基を示す。Ｒｆは相互に独立にフッ素原子又は炭素数１〜１０のパーフルオロアルキル基、ｎ１は相互に独立に０〜４の整数を示す。Ｒ^２は単結合、メチレン基、炭素数２〜１０の直鎖状若しくは分岐状の２価炭化水素基又は炭素数４〜２０の２価環状炭化水素基を示す。Ｒ^３２は炭素数１〜１０で直鎖状若しくは分岐状の３価炭化水素基又は炭素数４〜２０の３価環状炭化水素基を示し、Ｒ^２側の末端に酸素原子、硫黄原子、イミノ基、カルボニル基、−ＣＯ−Ｏ−又は−ＣＯ−ＮＨ−が結合された構造のものも含む。Ｒは水素原子、メチル基又はトリフルオロメチル基を示す。］ [9] A compound represented by the following general formula (m-1-1b).

[In General Formula (m-1-1b), R ⁸ represents a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Rf is independently a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms, and n1 is independently an integer of 0 to 4. R ² represents a single bond, a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. R ³² represents a linear or branched trivalent hydrocarbon group having 1 to 10 carbon atoms or a trivalent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an oxygen atom, a sulfur atom, and an imino group at the terminal on the R ² side. A structure in which a group, a carbonyl group, —CO—O— or —CO—NH— is bonded is also included. R represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

[10] The compound according to [8] or [9] above, wherein in the general formula (m-1-1a) or the general formula (m-1-1b), all R ⁸ are trifluoromethyl groups.

  The compound of the present invention can improve hydrophilicity during alkali development while ensuring hydrophobicity during immersion exposure, and can suppress development defects in unexposed areas, and after development. It is possible to synthesize a resist polymer capable of providing a resist coating film having an excellent pattern shape.

  Hereinafter, the form for implementing the compound of this invention is demonstrated concretely. However, the present invention includes all embodiments provided with the invention-specific matters, and is not limited to only the embodiments described below.

  In the following description, the same type of substituent is given the same reference numeral, and the description is omitted. In addition, the “hydrocarbon group” referred to in this specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. This “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

  The term “chain hydrocarbon group” means a hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain, and includes both a linear hydrocarbon group and a branched hydrocarbon group. Shall be. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be constituted only by the structure of the alicyclic hydrocarbon, and a part thereof may include a chain structure. The “aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

[1] First embodiment of the compound of the present invention:
1st Embodiment of the compound of this invention is a compound represented by the following general formula (m-1-2) (henceforth "compound (m-1-2)" may be described).

In General Formula (m-1-2), R ⁹ is any one of groups represented by the following General Formulas (1) to (3).

In the general formula (1) and (2), R ¹⁰ are mutually independently a halogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an acyl group or an acyloxy group.

In the general formulas (1) and (2), examples of the halogen atom represented by R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, fluorine atoms are preferred.

In the general formula (1) and ^(2), the alkyl group having 1 to 10 carbon atoms represented as ^{R 10,} for example, a methyl group, an ethyl group, 1-propyl, 2-propyl, 1-butyl group 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2 -(2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3- Methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2- Methylpentyl) group, 3- (3-methylpentyl) group, etc. Can be mentioned.

In the general formulas (1) and (2), examples of the alkoxyl group having 1 to 10 carbon atoms represented by R ¹⁰ include a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a propoxy group, A propoxy group etc. can be mentioned.

In the general formulas (1) and (2), examples of the acyl group having 1 to 10 carbon atoms represented by R ¹⁰ include an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group.

In the general formulas (1) and (2), examples of the acyloxy group having 1 to 10 carbon atoms represented by R ¹⁰ include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, n -A hexane carbonyloxy group, n-octane carbonyloxy group, etc. can be mentioned.

In the general formula (1) and (2), _{m 1} represents an integer of 0 to 5, _{m 2} represents an integer of 0 to 4. That is, the group represented by the general formula (1) is an unsubstituted or 1 to 5 substituted benzyl group, and the group represented by the general formula (2) is an unsubstituted or 1 to 4 substituted phthalimidylmethyl group. It is.

In General Formula (3), R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the general formula (3), examples of the alkyl group having 1 to 10 carbon atoms represented as R ¹¹ or R ¹² include the groups exemplified as the R ¹⁰ .

R ¹¹ and R ¹² may be bonded to each other to form an alicyclic structure having 4 to 20 carbon atoms together with the carbon atom to which each is bonded.

  Examples of the alicyclic structure include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, a 1- (2-cyclopentylethyl) group, a cyclohexyl group, a cyclohexylmethyl group, and 1- (1-cyclohexylethyl). Groups, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group and the like. be able to.

  Specific examples of the compound represented by the general formula (3) include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, and a 2-pentyl group. 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group , 3- (2-methylpentyl) group and the like. Among these, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, and a 2-butyl group are preferable.

In General Formula (m-1-2), X ¹ represents a single bond, a difluoromethylene group, or a linear or branched perfluorinated divalent hydrocarbon group having 2 to 20 carbon atoms.

Examples of the X ^1, may include those represented by the following general formula (X-1).

  In general formula (X-1), p is an integer of 1-4. Rf is a fluorine atom or a C1-C10 perfluoroalkyl group mutually independently.

Specific examples of the structure represented by the formula (X-1) include those represented by the following formulas (X-2) and (X-3).

R ² is a single bond, a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms.

Among the groups represented by R ² in the general formula (m-1-2), examples of the linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms include ethane, propane, butane, 2 hydrogen atoms from a straight or branched hydrocarbon having 2 to 10 carbon atoms such as 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc. Examples thereof include a divalent hydrocarbon group having a structure removed.

Among the groups represented by R ² , the divalent cyclic hydrocarbon group having 4 to 20 carbon atoms includes, for example, 2 hydrogen atoms from an alicyclic hydrocarbon or aromatic hydrocarbon having 4 to 20 carbon atoms. Examples include groups with structures removed.

Specific examples of the alicyclic hydrocarbon include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1.0. ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . And cycloalkanes such as 0 ^2,7 ] dodecane. Specific examples of the aromatic hydrocarbon include benzene and naphthalene.

In the general formula (m-1-2), the methylene group represented by R ² , the divalent hydrocarbon group or the divalent cyclic hydrocarbon group has at least one hydrogen atom of these groups, C1-C12 linear, branched such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group It also includes those substituted by one or more of a linear or cyclic alkyl group, hydroxyl group, cyano group, hydroxyalkyl group having 1 to 10 carbon atoms, carboxyl group, oxygen atom and the like.

In the general formula (m-1-2), R ³¹ is a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. . R ³¹ is synonymous with R ² except that the concept does not include a single bond. Examples of the linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms or the divalent cyclic hydrocarbon group having 4 to 20 carbon atoms include those exemplified in the description of R ² .

R ³¹ includes those having a structure in which an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O— or —CO—NH— is bonded to the terminal on the R ² side.

As the structure of R ³¹ in which an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O— or —CO—NH— is bonded to the terminal on the R ² side, for example, those represented by the following general formula Can be mentioned. In the following general formula, R ²¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. That has ^the same meaning as ^{R 31.} “*” Represents a bond that binds to R ² .

  In general formula (m-1-2), R represents a hydrogen atom, a methyl group or a trifluoromethyl group. That is, the compound (m-1-2) is a compound derived from either acrylic acid, methacrylic acid or trifluoromethacrylic acid (hereinafter, these monomers are referred to as “(meth) acrylic compounds”). May be.)

In addition, the compounds represented by the following formulas (4) and (5) are excluded from the compound (m-1-2). The compound represented by the following formula (4) is a compound disclosed in JP2009-029802A and JP2009-0119199A. However, JP 2009-029802 A aims to obtain a polymerizable compound having a fluorine atom at the α-position of the carboxyl group. Japanese Patent Application Laid-Open No. 2009-011999 aims to obtain a polymerizable compound having a fluorine atom at the α-position of the acid dissociable carboxylic acid ester. Further, in any document, a polymer using a compound represented by the following formula (4) as a raw material has not been synthesized, and is merely disclosed as an intermediate for synthesizing a target compound in Examples. It is.

  Further, the compound represented by the formula (5) is a compound disclosed in Journal of the American Chemical Society, 70, 527 (1948), but it is disclosed that a specific compound is obtained by utilizing a thermal decomposition reaction. This is the main purpose. Although there is a description that the polymer was prepared using the obtained compound, it merely disclosed properties such as hardness and color. Accordingly, all of these documents are compounds of the present invention aimed at obtaining a raw material compound of a polymer capable of changing water repellency by reacting with an alkali developer as a component of a radiation-sensitive resin composition for immersion exposure. It is not motivated.

In the compound (m-1-2), R ³¹ is a group represented by R ²¹ , R ² is a single bond, and X ¹ is a group represented by the following general formula (6). Preferably there is. That is, the compound (m-1-2) is a compound represented by the following general formula (m-1-2a) (hereinafter may be referred to as “compound (m-1-2a)”). Is preferred. Incidentally, in the general formula (m-1-2a), ^{R 9} and R have the same meanings as described in formula ^{(m-1-2), R 21} is synonymous with ^{R 21} that have already been described in the ^{R 31} is there.

  In General Formula (6) and (m-1-2a), Rf is a fluorine atom or a C1-C10 perfluoroalkyl group mutually independently. This Rf may be a linear perfluoroalkyl group or a branched perfluoroalkyl group. N2 is an integer of 1 to 4. That is, the group represented by the general formula (6) is a perfluorinated divalent hydrocarbon group having 1 to 4 carbon atoms in the main chain portion.

More specifically, a compound in which n2 is an integer of 1 to 2 and Rf is a fluorine atom or a trifluoromethyl group is preferable. Among them, n2 is an integer of 1 to 2, and Rf is a fluorine atom (that is, a compound in which the group represented by the general formula (6) is a group represented by the following formula (7)) or n2 Is more preferably a compound in which Rf is a trifluoromethyl group (that is, a compound in which the group represented by the general formula (6) is a group represented by the following general formula (8)). .

  In general formula (8), n3 is an integer of 1-2. That is, the group represented by the general formula (8) is a difluoromethylene group or a tetrafluoroethylene group.

In the compound (m-1-2), R ³¹ is a group represented by —R ²¹ —O—CO—, and X ¹ is a group represented by the following general formula (6). And a compound represented by the following general formula (m-1-2b) (hereinafter may be referred to as “compound (m-1-2b)”). In general formula (m-1-2b), R ⁹ , R ^2, and R have the same meaning as in the description of general formula (m-1-2).

  Examples of the compound (m-1-2b) include compounds in which n2 is 0, that is, compounds having no perfluorinated divalent hydrocarbon group represented by the general formula (6).

化合物（ｍ−１−２）は、例えば、下記一般式（ｍ−２−３）で表される化合物と、下記一般式（ｍ−２−４−１）〜（ｍ−２−４−３）のいずれかで表される化合物とを反応させることによって得ることができる。 Specific examples of the compound (m-1-2a) or the compound (m-1-2b) include compounds represented by the following general formula. In the following formulas, R and ^{R 9} are as defined description of the general formula (m-1-2).

The compound (m-1-2) includes, for example, a compound represented by the following general formula (m-2-3) and the following general formulas (m-2-4-1) to (m-2-4-3). It can obtain by making it react with the compound represented by either.

In general formula (m-2-3), X ¹ , R ² , R ³¹ and R have the same meaning as in the description of general formula (m-1-2). R ⁹¹ represents a hydroxyl group or a halogen atom.

Formula (m-2-4-1) and the general formula (m-2-4-2) ^{in, R} 10 of ^R 10, m1 and m2 are the general formula (1) and (2), m1, m2 It is synonymous with. In general formula (m-2-4-1), R ⁹² represents a halogen atom, preferably Cl. In general formula (m-2-4-2), R ⁹³ represents a halogen atom, preferably Br.

  The compound (m-1-2) can also be obtained by reacting a compound represented by the following general formula (m-2-5) with a compound represented by the following formula (m-2-6). be able to.

一般式（ｍ−２−５）中、Ｒ^９、Ｘ^１、Ｒ^２、Ｒ^３１及びＲは、一般式（ｍ−２−１）の説明と同義である。Ｒｈは水酸基又はハロゲン原子を示す。

In general formula (m-2-5), R ⁹ , X ¹ , R ² , R ^31, and R have the same definitions as in general formula (m-2-1). Rh represents a hydroxyl group or a halogen atom.

  The method for obtaining the compound represented by the general formula (m-2-5) is not particularly limited. For example, it can be obtained according to the method described in paragraphs [0112] to [0123] of JP2009-19199A. Can do.

[2] Second embodiment of the compound of the present invention:
2nd Embodiment of the compound of this invention is a compound represented by the following general formula (m-1-1a) (henceforth "compound (m-1-1a)" may be described). In General Formula (m-1-1a), R ² and R ³¹ have the same meanings as in the description of General Formula (m-1-2), and Rf is the same as that in General Formula (m-1-2a). It is synonymous with explanation.

In General Formula (m-1-1a), R ⁸ is a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

  Examples of the fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms include all the hydrogen atoms of a linear or branched alkyl group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, a group having a structure in which a part is substituted with a fluorine atom can be exemplified.

  Examples of the alkyl group include, in addition to a methyl group, carbon numbers such as ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, and the like. Examples thereof include an alkyl group having a structure in which one hydrogen atom is removed from 2 to 10 linear or branched hydrocarbons.

Examples of the alicyclic hydrocarbon group include cyclopropyl group, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5. .2.1.0 ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . And a group having a structure in which one hydrogen atom is removed from a cycloalkane such as 0 ^2,7 ] dodecane.

R ⁸ is more preferably a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and particularly preferably a trifluoromethyl group.

Moreover, in general formula (m-1-1a), n1 is an integer of 0-4. That is, the compound (m-1-1a) does not have the group represented by the general formula (9) or the group represented by the general formula (9) has 1 to 1 carbon atoms in the main chain portion. 4 is a wholly fluorine-substituted divalent hydrocarbon group.

[3] A third embodiment of the compound of the present invention:
A third embodiment of the compound of the present invention is a compound represented by the following general formula (m-1-1b) (hereinafter may be referred to as “compound (m-1-1b)”). In General Formula (m-1-1b), R ² has the same meaning as in the description of General Formula (m-1-2), and Rf has the same meaning as in the description of General Formula (m-1-2a). And R ⁸ and n 1 have the same meaning as in the description of the general formula (m-1-1a).

In General Formula (m-1-1b), R ³² is a linear or branched trivalent hydrocarbon group having 1 to 10 carbon atoms or a trivalent cyclic hydrocarbon group having 4 to 20 carbon atoms.

  Examples of the trivalent hydrocarbon group include methine group, ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, and the like. And a group having a structure in which three hydrogen atoms are removed from a linear or branched hydrocarbon having 2 to 10 carbon atoms.

  Examples of the trivalent cyclic hydrocarbon group include groups having a structure in which three hydrogen atoms are removed from an alicyclic hydrocarbon or aromatic hydrocarbon having 4 to 20 carbon atoms.

Specific examples of the alicyclic hydrocarbon include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1.0. ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane, tetracyclo [6.2.1.1 ^3,6 . And cycloalkanes such as 0 ^2,7 ] dodecane. Specific examples of the aromatic hydrocarbon include benzene and naphthalene.

In the general formula (m-1-1b), the group represented by R ³² has at least one hydrogen atom of these groups as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms such as n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group, hydroxyl group, cyano group, carbon number 1 In addition, those substituted with one or more of 10 to 10 hydroxyalkyl groups, carboxyl groups, oxygen atoms and the like are also included.

Oxygen atom R ³² the end of the ^{R 2} side, a sulfur atom, an imino group, a carbonyl group, the points also include those of -CO-O- or -CO-NH- is bound structure, with the ^{R 31} It is the same.

In the general formula (m-1-1a) or the general formula (m-1-1b), it is preferable that all R ⁸ are trifluoromethyl groups. That is, the compound (m-1-1a) or the compound (m-1-1b) is preferably a compound in which all R ⁸ are trifluoromethyl groups.

Specific examples of the compound (m-1-1a) or the compound (m-1-1b) include compounds represented by the following general formula. In the following general formulas, R has the same meaning as described in the general formula (m-1-2), ^{R 8} has the same meaning as described in the general formula (m-1-1a).

The compound (m-1-1a) or the compound (m-1-1b) is, for example, a compound represented by the following general formula (m-2-1) and the following general formula (m-2-2). It can be obtained by reacting the compound represented.

In the general formula (m-2-1), X ¹ , R ² and R are as defined in the general formula (m-1-2). R ⁸ has the same meaning as described for the general formula (m-1-1a). R ³ represents R ^{31 in the} general formula (m-1-2) or R ³² in the general formula (m-1-1b). When R ³ is the R ³¹ , n = 1, R ^{When 3} is R ³² , n = 2. R ⁸¹ represents a hydroxyl group, a halogen atom or —O—CO—R ⁸ .

[2] Polymer using the compound of the present invention:
Since the compound of the present invention is a (meth) acrylic compound, it can be made into a polymer by a conventionally known polymerization method. For example, a polymer can be obtained by using the compound of the present invention as a monomer and polymerizing in a suitable solvent in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent. In this case, as the “radical polymerization initiator”, hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds and the like can be used.

  Examples of the solvent include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane. Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide and chlorobenzene; ethyl acetate, n-butyl acetate, i-acetate Saturated carboxylic acid esters such as butyl and methyl propionate; ethers such as tetrahydrofuran, dimethoxyethane and diethoxyethane. These solvents can be used alone or in combination of two or more. Moreover, reaction temperature is 40-120 degreeC normally, Preferably it is 50-90 degreeC. The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

  Radiation sensitivity comprising a polymer using the compound of the present invention as a monomer (hereinafter sometimes referred to as “polymer (C)”) and a polymer (A) having an acid-dissociable group described later. In the resin composition, when the resist film is formed, the distribution of the polymer (C) tends to be high on the surface of the resist film due to the oil repellency of the polymer (C). That is, the polymer (A) is unevenly distributed in the coating surface layer. Therefore, it is not necessary to separately form an upper layer film for the purpose of blocking the photoresist film from the immersion medium, and can be suitably used for the immersion exposure method.

  In addition, a repeating unit derived from the compound of the present invention (hereinafter sometimes referred to as “repeating unit (c-1)”) generates a polar group by dissociating an alkali-dissociable group by hydrolysis during alkali development. Therefore, the water repellency of the resist coating surface can be reduced. Therefore, it is considered that development defects occurring in the resist film after alkali development can be suppressed. In addition, a photoresist film having an excellent pattern shape after development can be formed as compared with a case where a phenolic hydroxyl group is generated during alkali development.

[2-1] Repeating unit (c-1a-2):
By using the compound (m-1-2) as a monomer, a polymer (C) having a repeating unit represented by the following general formula (c-1a-2) can be obtained. In the following general formula (c-1a-2), R ⁹ , X ¹ , R ² , R ³¹ and R are as defined in the general formula (m-1-2).

More specifically, a polymer having a repeating unit represented by the following general formula (c-1a-2a) can be obtained by using the compound (m-1-2a) as a monomer. Similarly, by using the compound (m-1-2b) as a monomer, a polymer having a repeating unit represented by the following general formula (c-1a-2b) can be obtained. In the following general formula (c-1a-2a), R ⁹ , Rf, n2, R ²¹ and R are as defined in the general formula (m-1-2a), and the following general formula (c-1a) -B), R ⁹ , Rf, n 2, R ²² , R ²¹ and R are as defined in the general formula (m-1-2b).

  In the general formula (c-1a-2a) and the general formula (c-1a-2b), those in which n2 is 1 or more have a fluorine atom or a perfluoroalkyl group at the α-position of the carbonyloxy group. It is thought that the reactivity with respect to aqueous alkali solution becomes high. Moreover, the pKa of the COOH group generated by hydrolysis of the alkali dissociable group is also low, which is preferable from the viewpoint of improving hydrophilicity.

Examples of the repeating unit represented by the general formula (c-1a-2a) include those represented by the following general formulas (c-1a-2c) to (c-1a-2i). Examples of the repeating unit represented by the general formula (c-1a-2b) include those represented by the following general formulas (c-1a-2j) to (c-1a-2k).

[2-2] Repeating unit (c-1a-1a):
By using the compound (m-1-1a) as a monomer, a polymer (C) having a repeating unit represented by the following general formula (c-1a-1a) can be obtained. In addition, in the following general formula (c-1a-1a), R ⁸ , Rf, n1, R ² , R ³¹ and R have the same meaning as in the description of the general formula (m-1-1a).

Examples of the repeating unit represented by the general formula (c-1a-1a) include those represented by the following general formulas (c-1a-1c) to (c-1a-1f).

  In the general formula (c-1a-1a) and the general formula (c-1a-1b) described later, those having n1 of 1 or more are OH having a fluorine atom or a perfluoroalkyl group at the α-position by reaction with an aqueous alkaline solution. A group is formed. Such an OH group has a low pKa value as compared with an alcoholic OH group, and thus is preferable from the viewpoint of improving hydrophilicity.

[2-3] Repeating unit (c-1a-1b):
By using the compound (m-1-1b) as a monomer, a polymer (C) having a repeating unit represented by the following general formula (c-1a-1b) can be obtained. In the following general formula (c-1a-1b), R ⁸ , Rf, n1, R ² , R ³² and R are as defined in the general formula (m-1-1b).

Examples of the repeating unit represented by the general formula (c-1a-1b) include those represented by the following general formulas (c-1a-1f) to (c-1a-1g).

[2-4]: Repeating unit (c-2)
The polymer (C) is preferably a polymer having a repeating unit (c-2) represented by the following general formula (c-2) in addition to the repeating unit (c-1).

In general formula (c-2), R has the same meaning as in the description of general formula (c-1a-2). G is a single bond, oxygen atom, sulfur atom, —CO—O—, —SO ₂ —O—NH—, —CO—NH—, —O—CO—NH—, and R ⁴ is at least one hydrogen atom. Is a fluorine-substituted chain hydrocarbon group having 1 to 6 carbon atoms in which is substituted with a fluorine atom or a fluorine-substituted cyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

  Examples of the monomer that gives the repeating unit (c-2) include 2,2,2-trifluoroethyl (meth) acrylic acid ester and 2- (1,1,1,3,3,3-hexafluoro. Propyl) (meth) acrylic acid ester and the like.

[2-5]: Repeating unit (c-3)
The polymer (C) is preferably a polymer having a repeating unit (c-3) represented by the following general formula (c-3) in addition to the repeating unit (c-1).

In general formula (c-3), R is synonymous with the description of general formula (c-1a-2). R ⁶ has the general formula and ^{R 2} of (c-1a-2), and ^{R 31} of ^{R 5} of the general formula (c-1a-2), X 2 and ^{X 1} in formula (c-1a-2) Are synonymous with each other. A is an oxygen atom (excluding those directly bonded to an aromatic ring, a carbonyl group and a sulfoxyl group), an imino group, —CO—O— * or —SO ₂ —O— * (“*” is bonded to R ⁷ . Shows the bond to be performed.).

In general formula (c-3), R ⁷ is a hydrogen atom or an acid dissociable group. The “acid-dissociable group” refers to a group that substitutes a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group and dissociates in the presence of an acid.

  Specifically, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, (thiotetrahydropyranylsulfanyl) methyl group, (thiotetrahydrofuranylsulfanyl) methyl group, alkoxy-substituted methyl group, alkylsulfanyl-substituted methyl group Etc. In addition, as an alkoxyl group (substituent) in an alkoxy substituted methyl group, there exists a C1-C4 alkoxyl group, for example. Examples of the alkyl group (substituent) in the alkylsulfanyl-substituted methyl group include an alkyl group having 1 to 4 carbon atoms. Moreover, as an acid dissociable group, group represented by general formula (i) described in the term of the repeating unit (c-4) mentioned later may be sufficient.

In general formula (c-3), m represents an integer of 1 to 3. Accordingly, 1 to 3 R ⁷ are introduced into the repeating unit (c-3). When m is 2 or 3, R ⁶ , R ⁷ , X ² and A are independent of each other. That is, when m is 2 or 3, the plurality of R ⁷ may have the same structure or different structures. When m is 2 or 3, a plurality of R ⁶ may be bonded to the same carbon atom of R ⁵ or may be bonded to different carbon atoms.

Specific examples of the repeating unit (c-3) include repeating units represented by general formulas (c-3a) to (c-3c).

In the general formulas (c-3a) to (c-3c), R ¹⁶ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and L represents a methylene group substituted with a fluorine atom, or a carbon number of 2 20 represents a linear or branched fluorine-substituted divalent hydrocarbon group, and R ²⁰ represents a hydrogen atom or an acid-dissociable group. In the general formulas (c-3a) and (c-3b), R ¹⁹ is a single bond or a divalent linear, branched or cyclic, saturated or unsaturated carbon atom having 1 to 20 carbon atoms. Indicates a hydrogen group. Furthermore, q represents the integer of 1-3 in general formula (c-3c). However, when q is 2 or 3, L and R ²⁰ are independent of each other.

Specific examples of the monomer that gives the repeating unit (c-3) include compounds represented by general formulas (c-3-1) to (c-3-6).

In the general formulas (c-3-1) to (c-3-6), R ¹⁶ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ²⁰ independently of each other represents a hydrogen atom or an acid. A dissociable group is shown.

[2-6]: Repeating unit (c-4)
In addition to the repeating unit (c-1), the polymer (C) may have a repeating unit (c-4) represented by the following general formula (c-4). When the fluorine-containing polymer contains the repeating unit (c-4), the shape of the resist pattern after development can be further improved.

  In general formula (c-4), R is synonymous with the description of general formula (c-1a-2). Y represents an acid dissociable group.

Y in general formula (c-4) is preferably a group represented by general formula (i).

In the general formula (i), R ¹³ represents an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and R ¹⁴ and R ¹⁵ are independently of each other, 2 to 4 carbon atoms having a carbon number of 1 to 4 or alicyclic hydrocarbon groups having a carbon number of 4 to 20 or formed together with carbon atoms bonded to each other. A valent alicyclic hydrocarbon group is shown. Among these, a group having a cycloalkane skeleton is preferable in that the shape of the resist pattern after development can be further improved.

  As the monomer for constituting the repeating unit (c-4), (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-ethyladamantan-2-yl ester, (meth) ) Acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic Acid 2- (bicyclo [2.2.1] hept-2-yl) -2-methylethyl ester, (meth) acrylic acid 2- (adamantan-2-yl) -2-methylethyl ester, (meth) acrylic Acid 2-methyl-2-cyclopentyl ester, (meth) acrylic acid 2-ethyl-2-cyclopentyl ester, (meth) acrylic acid 2-methyl-2-cyclohexyl es Le, the (meth) 2-ethyl-2-cyclohexyl ester of acrylic acid.

  In addition, a polymer (C) may have a repeating unit (c-4) individually by 1 type or in combination of 2 or more types.

[2-7] Repeating unit (c-5):
In addition to the repeating unit (c-1), the polymer (C) has a repeating unit having an alkali-soluble group (hereinafter sometimes referred to as “repeating unit (c-5)”). May be. When the fluorine-containing polymer contains the repeating unit (c-5), the affinity for the developer can be improved.

The alkali-soluble group in the repeating unit (c-5) is preferably a functional group having a pKa of 4 to 11 hydrogen atoms. This is from the viewpoint of improving solubility in a developer. Specific examples of such functional groups include functional groups represented by general formula (ii) or general formula (iii).

In General Formula (ii), R ²³ represents a C 1-10 hydrocarbon group substituted with a fluorine atom.

In the general formula (ii), the hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom represented by R ²³ is such that one or more hydrogen atoms in the hydrocarbon group having 1 to 10 carbon atoms are fluorine atoms. Although it will not specifically limit if substituted by, For example, a trifluoromethyl group etc. are preferable.

  The main chain skeleton of the repeating unit (c-5) is not particularly limited, but is preferably a skeleton such as methacrylic acid ester, acrylic acid ester, or α-trifluoromethacrylic acid ester.

Examples of the repeating unit (c-5) include a repeating unit derived from a compound represented by the general formula (c-5-1) or (c-5-2).

In General Formula (c-5-1) or (c-5-2), R ²⁴ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ²⁵ represents a single bond or a carbon number of 1 to 20 A divalent linear, branched or cyclic, saturated or unsaturated hydrocarbon group. In General Formula (c-5-1), R ²³ represents a C 1-10 hydrocarbon group substituted with a fluorine atom.

In general formulas (c-5-1) and (c-5-2), the group represented by R ^{25 is the same} as R ² in general formula (c-1a-2). Further, in the general formula ^(c-5-1), with respect to the group represented by ^{R 23,} the same meaning as ^{R 23} in the general formula (ii).

[2-8]: Repeating unit (c-6)
In addition to the repeating unit (c-1), the polymer (C) may have a repeating unit (c-6) represented by the following general formula (c-6). When the fluorine-containing polymer contains the repeating unit (c-6), the affinity for the developer can be improved.

  In general formula (c-6), R is synonymous with the description of general formula (c-1a-2). Z represents a group having a lactone skeleton or a group having a cyclic carbonate structure.

[2-8a] Repeating unit (c-6a):
Among the repeating units (c-6), examples of the repeating unit having a group having a lactone skeleton include repeating units represented by general formulas (c-6a-1) to (c-6a-6).

In general formulas (c-6a-1) to (c-6a-6), R has the same meaning as in the description of general formula (c-1a-2). Moreover, in general formula (c-6a-1), R ^<a1> shows a hydrogen atom or the alkyl group which may have a C1-C4 substituent, and s1 shows the integer of 1-3. Furthermore, in the general formulas (c-6a-4) and (c-6a-5), R ^a4 represents a hydrogen atom or a methoxy group. In general formulas (c-6a-2) and (c-6a-3), R ^a2 represents a single bond, an ether group, an ester group, a carbonyl group, or a divalent chain hydrocarbon having 1 to 30 carbon atoms. A divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a divalent group obtained by combining these, s2 is 0 or 1. Furthermore, in the general formulas (c-6a-3) and (c-6a-5), R ^a3 represents an oxygen atom or a methylene group.

  Examples of the monomer that gives such a repeating unit include those described in paragraph [0043] of International Publication No. 2007/116664.

[2-8b] Repeating unit (c-6b):
As a repeating unit having a group having a cyclic carbonate structure, for example, there is a repeating unit represented by the general formula (c-6b).

In general formula (c-6b), R is as defined in formula (c-1a-2). D represents a trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Show. D may have an oxygen atom, a carbonyl group, or an imino group in its skeleton. D may have a substituent. However, in the general formula (c-6b), the following partial structure is necessarily formed.

In said formula, t shows the integer of 1-4. Examples of the substituent that D may have include the same groups as those described above for R ¹⁰ and hydroxyl groups.

  Monomers that give a repeating unit represented by the general formula (c-6b) are described in, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002), etc., and can be synthesized by a conventionally known method.

Particularly preferred examples of the repeating unit represented by the general formula (c-6b) include a repeating unit represented by the following general formula.

[2-9] Content ratio of each repeating unit:
The content ratio of the repeating unit (c-1) is preferably 10 mol% or more, and more preferably 50 mol% or more. When the content ratio of the repeating unit (c-1) is within the above range, it is particularly preferable from the viewpoint of ensuring water repellency at the time of immersion exposure and improving the affinity to the developer at the time of development.

  Moreover, it is preferable that the content rate of a repeating unit (c-2) or a repeating unit (c-3) is 20-90 mol%, It is more preferable that it is 20-80 mol%, It is 20-70 mol% Is particularly preferred. When the content ratio of the repeating unit (c-2) or the repeating unit (c-3) is within this range, it is said that both water repellency after coating and improved affinity for the developer after PEB are achieved. This is particularly effective from the viewpoint.

  Furthermore, the content of the repeating unit (c-4) is preferably 80 mol% or less, more preferably 20 to 80 mol%, and particularly preferably 30 to 70 mol%. When the content ratio of the repeating unit (c-4) is within this range, it is particularly effective from the viewpoint of improving the resist pattern shape after development.

  Furthermore, the content rate of a repeating unit (c-5) is 50 mol% or less normally, Preferably it is 5-30 mol%, More preferably, it is 5-20 mol%. When the content ratio of the repeating unit (c-5) is within this range, it is particularly effective from the viewpoint of ensuring water repellency after coating and increasing the contact angle with respect to the developer after PEB.

  Moreover, the content rate of a repeating unit (c-6) is 50 mol% or less normally, Preferably it is 5-30 mol%, More preferably, it is 5-20 mol%. When the content ratio of the repeating unit (D4) is within this range, it is particularly effective from the viewpoint of both ensuring water repellency after coating and increasing the contact angle with respect to the developer after PEB.

[2-10]: Fluorine atom content ratio:
In the said polymer (C), when the fluorine atom content rate makes the whole polymer 100 mass%, it is preferable that it is 5 mass% or more, and it is still more preferable that it is 5-50 mass%. It is especially preferable that it is -40 mass%. This fluorine atom content ratio can be measured by ¹³ C-NMR. When the fluorine atom content ratio in the polymer (C) is within the above range, the water repellency of the resist coating film surface formed by the radiation-sensitive resin composition containing the polymer (C) can be increased, There is no need to separately form an upper layer film during the immersion exposure.

[2-11] Physical property values:
The Mw of the polymer (C) is preferably 1,000 to 50,000, more preferably 1,000 to 40,000, and particularly preferably 1,000 to 30,000. When Mw is less than 1,000, there is a possibility that a resist film having a sufficient receding contact angle cannot be obtained. On the other hand, if it exceeds 50,000, the developability of the resist film may be lowered. Further, the ratio (Mw / Mn) of the polymer (C) Mw and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) by GPC method is preferably 1 to 5, preferably 1 to 4. More preferably it is.

  In addition, a polymer (C) is so preferable that there is little content of impurities, such as a halogen and a metal. When the content of such impurities is small, the sensitivity, resolution, process stability, pattern shape and the like of the resist film can be further improved.

[3] Radiation sensitive resin composition:
In addition to the polymer (C), the polymer (A) having an acid-dissociable group, the acid generator (B), and other optional components according to the purpose are mixed to obtain a radiation-sensitive resin composition. Can be prepared.

  When the polymer (C) is contained as an essential component in the radiation-sensitive resin composition, there is no need to separately form an upper layer film for the purpose of blocking the photoresist film and the immersion medium, and the immersion exposure method Can be suitably used.

  The polymer (C) is blended in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer (A) described later, ensuring water repellency of the resist coating film and the viewpoint of the resist pattern shape after development. To preferred. If the content of the polymer (C) is less than 0.1 parts by mass, the effect of adding the polymer (C) may not be obtained. If the content of the polymer (C) exceeds 20 parts by mass, the formed resist may have a T-top shape, or scum may occur, which may cause significant damage to patterning.

[3-1] Polymer (A):
An “acid-dissociable polymer” is a polymer having an acid-dissociable group. More specifically, it is a polymer that is insoluble or hardly soluble in alkali before the action of acid and becomes alkali-soluble when an acid-dissociable group is eliminated by the action of acid.

  “Alkali insoluble or hardly soluble in alkali” means that the resist is developed under alkaline development conditions employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the polymer (A). When a 100 nm thick film using only the polymer (A) is developed instead of the film, 50% or more of the initial film thickness remains after development.

[3-1-1] Fluorine atom content ratio:
The fluorine atom content ratio in the polymer (A) is less than 5% by mass, preferably 0 to 4.9% by mass, and more preferably 0 to 4% when the entire polymer (A) is 100% by mass. % By mass. In addition, this fluorine atom content rate can be measured by ¹³ C-NMR. When the fluorine atom content in the polymer (A) is within the above range, the water repellency of the resist coating surface formed by the radiation-sensitive resin composition containing the fluorine-containing polymer and the polymer (A) described above is improved. Therefore, it is not necessary to separately form an upper layer film during immersion exposure.

  As long as the polymer has the above properties, the specific structure of the polymer (A) is not particularly limited. However, the repeating unit represented by the general formula (c-3) (hereinafter referred to as “repeating unit (a-1)”) and the repeating unit represented by the general formula (c-6) (hereinafter referred to as “repeating unit”). (A-2) ") is preferable.

[3-1-2] Repeating unit (a-1):
In the polymer (A), the content of the repeating unit (a-1) is preferably 15 to 85 mol%, more preferably 25 to 75 mol%, and particularly preferably 35 to 60 mol%. . If it is less than 15 mol%, the contrast after dissolution is impaired, and the pattern shape may be lowered. On the other hand, if it exceeds 85 mol%, the adhesion to the substrate is insufficient and the pattern may be peeled off.

[3-1-3] Repeating unit (a-2):
In the polymer (A), the content of the repeating unit (a-2) is preferably 5 to 75 mol%, more preferably 15 to 65 mol%, and particularly preferably 25 to 55 mol%. . If it is less than 5 mol%, the resist may have insufficient adhesion to the substrate and the pattern may be peeled off. On the other hand, if it exceeds 75 mol%, the contrast after dissolution is impaired, and the pattern shape may be lowered.

[3-1-4] Other repeating units:
The polymer (A) may have other repeating units other than the repeating units (a-1) and (a-2) as long as it has the fluorine atom content. As the polymerizable unsaturated monomer constituting the other repeating unit, International Publication No. 2007 / 116664A, [0047] to [0048] paragraph, [0073] to [0077] paragraph, and [0079] to [0082] paragraph And monomers disclosed in (1).

  The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A) is usually 3,000 to 300,000, preferably 4,000 to 200. 1,000, more preferably 4,000 to 100,000. If the Mw is less than 3,000, the heat resistance as a resist may decrease. On the other hand, if it exceeds 300,000, developability as a resist may be lowered.

  The polymer (A) is preferably as less as possible as impurities such as halogen and metal from the viewpoint of improving the sensitivity, resolution, process stability, pattern shape and the like as a resist. Examples of the purification method of the polymer (A) include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation. is there. In addition, the radiation sensitive resin composition of this invention can mix | blend a polymer (A) individually by 1 type or in combination of 2 or more types.

[3-2] Acid generator (B):
The acid generator (B) generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”). The acid generator (B) dissociates the acid dissociable group present in the polymer (A) by the action of the acid generated by exposure, and makes the polymer (A) alkali-soluble. As a result, the exposed portion of the resist film becomes readily soluble in an alkali developer, and a positive resist pattern can be formed. Examples of such an acid generator (B) include compounds described in paragraphs [0080] to [0113] of JP2009-134088A.

  Specific examples of the acid generator (B) include diphenyliodonium trifluoromethanesulfonate. In addition, an acid generator (B) can be contained individually by 1 type or in combination of 2 or more types.

  The content of the acid generator (B) is preferably 0.1 to 30 parts by mass, more preferably 2 to 27 parts by mass, with respect to 100 parts by mass of the polymer (A). Particularly preferred is 25 parts by mass. If it is less than 0.1 parts by mass, the sensitivity and resolution as a resist film may be lowered. On the other hand, if it exceeds 30 parts by mass, the coatability and pattern shape as a resist film may be deteriorated.

[3-3] Other components:
When preparing the radiation-sensitive resin composition, if necessary, an acid diffusion controller, an alicyclic additive, a surfactant, a sensitizer, an antihalation agent, an adhesion aid, a storage stabilizer, Various additives such as an antifoaming agent can be blended.

（上記一般式（１０）中、Ｒ^４５〜Ｒ^４７は、相互に独立に、水素原子、置換されていてもよい、直鎖状、分岐状若しくは環状のアルキル基、アリール基、又はアラルキル基を示す。） [3-3-1] Acid diffusion controller (D):
Examples of the acid diffusion controller (D) include a compound represented by the general formula (10) (hereinafter referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). “Nitrogen-containing compound (II)”, compounds having 3 or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc. Can do. When an acid diffusion control agent is contained, the pattern shape and dimensional fidelity as a resist can be improved.

(In the general formula (10), R ^{45 to} R ⁴⁷ each independently represent a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, aryl group, or aralkyl group. Show.)

  Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline; Can be mentioned.

  As nitrogen-containing compound (II), ethylenediamine etc. can be mentioned, for example.

  Examples of the nitrogen-containing compound (III) include a polyethyleneimine polymer.

  Examples of the amide group-containing compound include formamide.

  As a urea compound, urea etc. can be mentioned, for example.

  Examples of the nitrogen-containing heterocyclic compound include pyridines such as pyridine, pyrazine and the like.

  Among these acid diffusion control agents, nitrogen-containing compounds (I), nitrogen-containing compounds (II), and nitrogen-containing heterocyclic compounds are preferable. In addition, an acid diffusion control agent can be used individually by 1 type or in combination of 2 or more types. The content of the acid diffusion controller is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A). When the content of the acid diffusion control agent is excessive, the sensitivity of the formed resist film tends to be remarkably lowered.

[3-3-2] Alicyclic additive:
An alicyclic additive is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Examples of such alicyclic additives include adamantane derivatives such as 1-adamantanecarboxylate t-butyl; deoxycholic acid esters such as t-butyl deoxycholic acid; lithocholic acid such as tert-butyl lithocholic acid; Examples include esters. These alicyclic additives can be used individually by 1 type or in mixture of 2 or more types. Content of an alicyclic additive is 50 mass parts or less normally with respect to 100 mass parts of polymers (A), Preferably it is 30 mass parts or less.

[3-3-3] Surfactant:
A surfactant is a component that exhibits an effect of improving coatability, developability, and the like. Examples of such surfactants include nonionic surfactants such as polyoxyethylene lauryl ether. These surfactants can be used individually by 1 type or in mixture of 2 or more types. The content of the surfactant is usually 2 parts by mass or less with respect to 100 parts by mass of the polymer (A).

[3-4] Preparation of composition solution:
The radiation-sensitive resin composition is usually dissolved in a solvent so that the total solid content is 1 to 50% by mass, preferably 3 to 25% by mass, and then, for example, a filter having a pore size of about 0.02 μm is used. The solution is prepared as a composition solution.

  Examples of the solvent used for the preparation of the composition solution include linear or branched ketones; cyclic ketones; propylene glycol monoalkyl ether acetates; 2-hydroxypropionic acid alkyls; Alkyl propionates;

  alcohols such as n-propyl alcohol; glycol ethers such as ethylene glycol monomethyl ether; aromatic compounds such as toluene; esters such as ethyl 2-hydroxy-2-methylpropionate; 3-methoxybutyl acetate and the like Acetates; acetoacetates such as methyl acetoacetate; pyruvates such as methyl pyruvate; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzylethyl ether, di -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, male It can be used diethyl ynoic acid, .gamma.-butyrolactone, ethylene carbonate, propylene carbonate and the like.

  These solvents can be used singly or in combination of two or more. Among these solvents, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates can be used. , Alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate and the like are preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples, comparative examples and preparation examples, “parts” and “%” are on a molar basis unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Measurement of receding contact angle]:
First, a film was formed on a substrate (wafer) with the radiation sensitive resin composition. Thereafter, the receding contact angle of the formed film was calculated in the following procedure using “DSA-10” manufactured by KRUS under an environment of room temperature 23 ° C., humidity 45%, and normal pressure.

  First, the wafer stage position is adjusted. Next, the wafer is set on the stage. Water is injected into the “DSA-10” needle. Next, the position of the needle is finely adjusted. Next, water is discharged from the needle to form a 25 μL water droplet on the wafer, and then the needle is once pulled out of the water droplet. Next, the needle is pulled down again to the finely adjusted position. Next, a water droplet is sucked with a needle at a speed of 10 μL / min for 90 seconds, and the contact angle is measured every second (total 90 times). Next, an average value is calculated for a total of 20 contact angles from the time when the contact angle is stabilized, and is set as the receding contact angle (°).

  A substrate with a film thickness of 110 nm was formed on an 8-inch silicon wafer with a radiation-sensitive resin composition, and the substrate was subjected to soft baking (SB) at 120 degrees for 60 seconds. "

  A film having a film thickness of 110 nm was formed on an 8-inch silicon wafer with a radiation-sensitive resin composition, and soft baking (SB) was performed at 120 degrees for 60 seconds. Thereafter, the substrate was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and the receding contact angle of the dried substrate was defined as “the receding contact angle after development”.

[Development defects]:
First, a coating having a film thickness of 110 nm is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which an underlayer antireflection film (“ARC66”, manufactured by Nissan Chemical Co., Ltd.) is formed, and soft baking is performed at 120 degrees for 60 seconds. (SB) was performed. Next, this film is exposed through a mask pattern using an ArF excimer laser immersion exposure apparatus (“NSR S610C”, manufactured by NIKON) under the conditions of NA = 1.3, ratio = 0.800, Dipole. did.

  After the exposure, post-baking (PEB) was performed at 95 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount for forming a line and space having a width of 45 nm was determined as the optimum exposure amount. With this optimum exposure amount, a line and space having a line width of 45 nm was formed on the entire surface of the wafer to obtain a defect inspection wafer. A scanning electron microscope (“CC-4000”, manufactured by Hitachi High-Technologies Corporation) was used for length measurement.

  Thereafter, the number of defects on the defect inspection wafer was measured using “KLA2810” manufactured by KLA-Tencor. Furthermore, the defects measured by “KLA2810” were classified into those judged to be resist-derived and foreign matters derived from the outside. After classification, if the total number of defects determined from the resist film (number of defects) was less than 100 pieces / wafer, “good”, if 100 to 500 pieces / wafer, “slightly good” When exceeding 500 pieces / wafer, it was determined as “bad”.

[Pattern shape of pattern]:
First, a coating having a film thickness of 110 nm is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which an underlayer antireflection film (“ARC66”, manufactured by Nissan Chemical Co., Ltd.) is formed, and soft baking is performed at 120 degrees for 60 seconds. (SB) was performed. Next, this film is exposed through a mask pattern using an ArF excimer laser immersion exposure apparatus (“NSR S610C”, manufactured by NIKON) under the conditions of NA = 1.3, ratio = 0.800, Dipole. did.

  After the exposure, post-baking (PEB) was performed at 95 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern.

  The cross-sectional shape of the formed pattern is observed with “S-4800” manufactured by Hitachi High-Technologies Corporation, and the line width Lb in the middle part of the film in the thickness direction of the film and the line width La on the film surface are measured. did. Thereafter, the formula: (La−Lb) / Lb is calculated, and when the calculated value is 0.90 <(La−Lb), “T-top” is set, and (La−Lb) <1.1. In this case, the top round was selected. When 0.90 ≦ (La−Lb) ≦ 1.1, it was determined as “good”. Further, when melted residue was generated in the exposed portion, it was determined as “scum”.

[Mask error factor (MEEF)]
First, a coating having a film thickness of 110 nm is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which an underlayer antireflection film (“ARC66”, manufactured by Nissan Chemical Co., Ltd.) is formed, and soft baking is performed at 120 degrees for 60 seconds. (SB) was performed. Next, this film is exposed through a mask pattern using an ArF excimer laser immersion exposure apparatus (“NSR S610C”, manufactured by NIKON) under the conditions of NA = 1.3, ratio = 0.800, Dipole. did.

  After the exposure, post-baking (PEB) was performed at 95 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount for forming a line and space having a width of 45 nm was determined as the optimum exposure amount. In the above Eop, LS patterns with a pitch of 90 nm were formed using mask patterns with target sizes of 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, and 50 nm, respectively.

  At this time, the slope of the straight line when the target size (nm) was plotted on the horizontal axis and the line width (nm) formed on the resist film using each mask pattern was plotted on the vertical axis was calculated as MEEF. As the MEEF (straight line) is closer to 1, the reproducibility of the mask is better. When the value is 1.10 ≦ MEEF <1.25, “good” is set, and 1.25 ≦ MEEF <1. The case of 50 was “slightly good”, and 1.50 ≦ MEEF was “bad”. The results obtained are shown in the table.

Example 1
2- (2,2,2-trifluoroacetoxy) ethyl methacrylate (compound represented by the following formula (M-16)) was synthesized.

  After replacing the reactor sufficiently dried by vacuum heating with dry nitrogen, 130.14 g (1.0 mol) of 2-hydroxyethyl methacrylate and 500 mL of methyl isobutyl ketone (MIBK) were placed in the reactor. added. The mixture was cooled to 0 ° C. in an ice bath, and 231.03 g (1.1 mol) of trifluoroacetic anhydride was added over 30 minutes while stirring.

  Then, what melt | dissolved 92.41 g (1.1 mol) of sodium hydrogencarbonate in 500 mL of water was added, stirring well. Thereafter, the MIBK layer was separated, and the aqueous layer was extracted again with MIBK to obtain an extract. This extract was combined with the MIBK layer, washed with saturated saline, and then dried over sodium sulfate (desiccant). Thereafter, the desiccant was filtered off with a Buchner funnel, the organic solvent was distilled off, and the residue was distilled under reduced pressure under 2 mmHg. In this way, 2- (2,2,2-trifluoroacetoxy) ethyl methacrylate (207.34 g (yield 92%)) was obtained.

In addition, ¹ H-NMR data of 2- (2,2,2-trifluoroacetoxy) ethyl methacrylate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.95 (s, 3H, C—CH ₃ ), 4.45 (m, 3H, CH ₂ ), 4.62 (m, 3H, CH ₂ ), 5. 62 (s, 1H, C = CH ₂ ), 6.13 (s, 1H, C = CH ₂ )

(Example 2)
A compound represented by the following formula (M-17) was synthesized.

  In a nitrogen atmosphere at 0 ° C., 5,5,5-trifluoro-4-hydroxy-4- (trifluoromethyl) pentan-2-yl methacrylate 29.42 g (100 mmol) and 4-methyl-2-pentanone 200 mL Was added. Thereafter, 23.10 g (100 mmol) of trifluoroacetic anhydride was added dropwise over 30 minutes. Then, after stirring at room temperature for 2 hours, an aqueous sodium hydrogen carbonate solution was added to stop the reaction. 4-Methyl-2-pentanone was added to the reaction solution for extraction three times, and the obtained organic layer was washed once with water and saturated brine, and dried over anhydrous sodium sulfate. Then, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography, and 5,5,5-trifluoro-4- (2,2,2) represented by the above formula (M-17). 17.29 g of 2-trifluoroacetoxy) -4- (trifluoromethyl) pentan-2-yl methacrylate was obtained (44% yield).

In addition, ¹ H- of 5,5,5-trifluoro-4- (2,2,2-trifluoroacetoxy) -4- (trifluoromethyl) pentan-2-yl methacrylate obtained in this example. NMR data is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.35 (d, 3H, CH ₃ ), 1.92 (s, 3H, CH ₃ ), 2.70-2.90 (m, 2H, CH ₂ ), 5.11-5.22 (m, 1H, O—CH), 5.47 (s, 1H, C═CH ₂ ), 6.10 (s, 1H, C═CH ₂ )

Example 3
A compound represented by the following formula (M-18) was synthesized.

  Under a nitrogen atmosphere, 400 mL of dehydrated methylene chloride and 11.13 g (110 mmol) of triethylamine were added to 11.51 g (50 mmol) of 4-[(2-methacryloyloxy) ethoxy] -4-oxobutyric acid at 0 ° C. Thereafter, 17.06 g (100 mmol) of benzyl chloroformate was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), an aqueous sodium hydrogen carbonate solution was added to stop the reaction.

  Thereafter, ethyl acetate was added to the reaction solution to perform extraction three times. The obtained organic layer was washed once with water and saturated brine, and dried over anhydrous sodium sulfate. Then, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography to obtain 11.21 g of benzyl 2- (methacryloyloxy) ethyl succinate represented by the formula (M-19). (Yield 70%).

The ¹ H-NMR data of ¹ -benzyl 2- [2- (methacryloyloxy) ethyl] cyclohexane-1,2-dicarboxylate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.94 (s, 3H, C—CH ₃ ), 2.55-2.71 (m, 4H, C (═O) CH ₂ ), 4.26-4 .45 (m, 4H, O—CH ₂ ), 5.12-5.28 (m, 2H, Ar—CH ₂ ), 5.59 (s, 1H, C═CH ₂ ), 6.12 (s _{, 1H, C = CH 2)} , 7.28-7.49 (m, 5H, Ar)

Example 4
A compound represented by the following formula (M-19) was synthesized.

  Under a nitrogen atmosphere, at 0 ° C., 400 mL of dehydrated methylene chloride and 11.13 g (110 mmol) of triethylamine were added to 28.43 g (100 mmol) of 2-{[2- (methacryloyloxy) ethoxy] carbonyl} cyclohexanecarboxylic acid. Thereafter, 17.06 g (100 mmol) of benzyl chloroformate was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), an aqueous sodium hydrogen carbonate solution was added to stop the reaction. Thereafter, ethyl acetate was added to the reaction solution to perform extraction three times. The obtained organic layer was washed once with water and saturated brine, and dried over anhydrous sodium sulfate. Then, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography, and 1-benzyl 2- [2- (methacryloyloxy) ethyl] cyclohexane- represented by the above formula (M-19). 26.66 g of 1,2-dicarboxylate was obtained (yield 71%).

The ¹ H-NMR data of ¹ -benzyl 2- [2- (methacryloyloxy) ethyl] cyclohexane-1,2-dicarboxylate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.31-2.26 (m, 8H, CH ₂ ), 1.92 (s, 3H, CH ₃ ), 2.87-2.91 (m, 2H, _{CH), 4.18-4.42 (m, 4H} , O-CH 2), 5.17-5.30 (m, 2H, Ar-CH 2), 5.59 (s, 1H, C = CH _{2), 6.11 (s, 1H} , C = CH 2), 7.29-7.51 (m, 5H, Ar)

(Example 5)
(1,3-Dioxoisoindoline-2-yl) methyl 2- (methacryloyloxy) ethyl succinate (compound represented by the following formula (M-20)) was synthesized.

  After replacing the reactor sufficiently dried by vacuum heating with dry nitrogen, 11.51 g (0.05 mol) of 4-[(2-methacryloyloxy) ethoxy] -4-oxobutyric acid was added to the reactor. ), 6.07 g (0.06 mol) of triethylamine, and 150 mL of dimethylformamide (DMF) were added. A solution prepared by dissolving 12.00 g (0.05 mol) of N- (bromomethyl) phthalimide in 100 mL of DMF was added over 15 minutes while stirring at 65 ° C. in an oil bath.

  After stirring for 1 hour, DMF was distilled off with a rotary evaporator, and the residue was extracted with ethyl acetate to obtain an extract. This extract was washed three times with water, then washed successively with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over sodium sulfate (desiccant). Thereafter, the desiccant was filtered off with a Buchner funnel, and then the organic solvent was distilled off. Thus, (1,3-dioxoisoindoline-2-yl) methyl 2- (methacryloyloxy) ethyl succinate (13.95 g (yield 72%)) represented by the formula (M-20) was obtained. Got.

The ¹ H-NMR data of (1,3-dioxoisoindoline-2-yl) methyl 2- (methacryloyloxy) ethyl succinate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.94 (s, 3H, C—CH ₃ ), 2.57-2.74 (m, 4H, C (═O) CH ₂ ), 4.26-4 .43 (m, 4H, O—CH ₂ ), 5.59 (s, 1H, C═CH ₂ ), 5.66-5.78 (m, 2H, CH ₂ —N), 6.12 (s _{, 1H, C = CH 2)} , 7.71-7.83 (m, 2H, Ar), 7.84-7.98 (m, 2H, Ar)

(Example 6-1)
Benzyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (a compound represented by the following formula (M-21)) was synthesized.

  After replacing the reactor sufficiently dried by vacuum heating with dry nitrogen, 22.22 g (0.1 mol) of 2,2-difluoro-3- (methacryloyloxy) pentanoic acid was placed in the reactor. Then, 11.13 g (0.11 mol) of triethylamine and 250 mL of methylene chloride were added. The mixture was cooled to 0 ° C. in an ice bath, and 17.06 g (0.1 mol) of benzyl chloroformate was added over 10 minutes while stirring.

  Thereafter, the temperature of the reactor was raised to room temperature, and after stirring for 2 hours, 300 g of a saturated aqueous sodium hydrogen carbonate solution was added with good stirring. Thereafter, the methylene chloride layer was separated, and the aqueous layer was extracted again with methylene chloride to obtain an extract. The extract was combined with the methylene chloride layer and washed with saturated brine, and then dried over sodium sulfate (desiccant). Thereafter, the desiccant was filtered off with a Buchner funnel, the organic solvent was distilled off, and the residue was purified by silica gel column chromatography. Thus, benzyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (23.14 g (yield 74%)) represented by the formula (M-21) was obtained.

In addition, ¹ H-NMR data of benzyl 2,2-difluoro-3- (methacryloyloxy) pentanoate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 0.95 (t, 3H, CH ₂ —CH ₃ ), 1.75-1.89 (m, 2H, CH ₂ —CH ₃ ), 1.87 (s, _{3H, CH 3 -C), 5.24} (s, 2H, Ph-CH 2), 5.34-5.39 (m, 1H, CH-CF 2), 5.55 (s, 1H, C = _{CH 2), 6.06 (s,} 1H, C = CH 2), 7.33-7.42 (m, 5H, Ar)

(Example 6-2)
The compound represented by the formula (M-21) could also be obtained by the following method.

  In a nitrogen atmosphere at 0 ° C., 1.60 g of potassium tert-butoxy was mixed with 140 mL of benzyl alcohol and 1200 mL of hexane in which 20.30 g (0.1 mol) of ethyl 2-bromo-2,2-difluoroacetate was dissolved. 14 mmol) was added. Thereafter, the mixture was stirred at 0 ° C. for 1 hour. After confirming the disappearance of the raw material by thin layer chromatography (TLC), 120 mL of concentrated hydrochloric acid was added to stop the reaction.

Thereafter, each was washed twice with water and saturated brine, dried over anhydrous sodium sulfate. Thereafter, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography to obtain 15.37 g of benzyl 2-bromo-2,2-difluoroacetate represented by the following formula (yield: 58%). ).

  Under a nitrogen atmosphere, 100 mL of dehydrated THF was added to 3.79 g (58.0 mmol) of activated metal zinc. Thereafter, the mixture was heated until THF was refluxed. After warming, 15.37 g (58.0 mmol) of benzyl 2-bromo-2,2-difluoroacetate was added followed by 2.81 g (48.3 mmol) of propionaldehyde. Thereafter, the mixture was stirred for 15 minutes. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to room temperature, and an aqueous sodium hydrogen sulfate solution was added to stop the reaction.

Thereafter, ethyl acetate was added to the reaction solution and extraction was performed three times. The obtained organic layer was washed once each with an aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over anhydrous sodium sulfate. Then, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography to obtain 9.32 g of benzyl 2,2-difluoro-3-hydroxypentanoate represented by the following formula (yield 79). %).

  Benzyl 2,2-difluoro-3-hydroxypentanoate 9.32 (38.2 mmol) at room temperature under nitrogen atmosphere, 50 mL of dehydrated THF, 4.63 g (45.8 mmol) of triethylamine, 466 mg (3.82 mmol) of dimethylaminopyridine ) Was added. Thereafter, 4.39 g (42.0 mmol) of methacrylic acid chloride was added dropwise over 10 minutes. The mixture was then stirred for 2 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), an aqueous sodium hydrogen carbonate solution was added to stop the reaction.

Thereafter, ethyl acetate was added to the reaction solution to perform extraction three times. The obtained organic layer was washed once with water and saturated brine, and dried over anhydrous sodium sulfate. Then, the product obtained by distilling off the solvent under reduced pressure was purified by column chromatography to obtain 6 benzyl 2,2-difluoro-3- (methacryloyloxy) pentanoate represented by the following formula (M-21). .20 g was obtained (52% yield).

(Example 7)
Propyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (a compound represented by the following formula (M-24)) was synthesized.

  After replacing the reactor sufficiently dried by vacuum heating with dry nitrogen, 22.22 g (0.1 mol) of 2,2-difluoro-3- (methacryloyloxy) pentanoic acid was placed in the reactor. P-Toluenesulfonic acid monohydrate 19.02 g (0.01 mol) and n-propanol 500 mL were added. Thereafter, the temperature was raised until n-propanol was refluxed, and the mixture was stirred for 2 hours. Thereafter, the reactor was cooled to room temperature, and 300 g of a saturated aqueous sodium hydrogen carbonate solution and 500 mL of ethyl acetate were added. Thereafter, the organic layer was separated to obtain an extract. The extract was washed with saturated brine and then dried over sodium sulfate (desiccant). Thereafter, the desiccant was filtered off with a Buchner funnel, the organic solvent was distilled off, and the residue was purified by silica gel column chromatography. In this way, propyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (18.99 g (yield 72%)) represented by the formula (M-24) was obtained.

In addition, ¹ H-NMR data of propyl 2,2-difluoro-3- (methacryloyloxy) pentanoate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 0.91 (t, 3H, CH ₂ —CH ₃ ), 0.93 (t, 3H, CH ₂ —CH ₃ ), 1.59-1.89 (m, _{4H, CH 2 -CH 3),} 1.87 (s, 3H, CH 3 -C), 4.13-4.22 (m, 2H, CH 2 -O), 5.34-5.39 (m , 1H, CH—CF ₂ ), 5.55 (s, 1H, C═CH ₂ ), 6.06 (s, 1H, C═CH ₂ )

(Example 8)
Methyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (a compound represented by the following formula (M-26)) was synthesized.

  Under a nitrogen atmosphere, 100 g of ethyl 2,2-difluoro-3- (methacryloyloxy) pentanoate is dissolved in 1000 g of dehydrated methanol, and 0.1 g of N, N-dimethylaminopyridine (DMAP) is added thereto for 5 hours. It was heated to return. The reaction solution was evaporated, dissolved again in 1000 g of dehydrated methanol, and heated for 5 hours. The solvent of the reaction solution was distilled off, and the residue was dissolved in 300 g of n-hexane. The solution was filtered through 50 g of silica gel to remove DMAP, thereby obtaining 89.7 g of methyl 2,2-difluoro-3- (methacryloyloxy) pentanoate (M-26) (yield 95%).

In addition, ¹ H-NMR data of methyl 2,2-difluoro-3- (methacryloyloxy) pentanoate obtained in this example is shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.00 (t, 3H, CH ₃ ), 1.70-1.90 (m, 2H, CH ₂ ), 1.95 (s, 3H, CH ₃ ), _{3.85 (s, 3H, CH 3} -O), 5.30-5.45 (m, 1H, CH-CF 2), 5.65 (s, 1H, C = CH 2), 6.17 ( s, 1H, C = CH ₂ )

(Comparative Example 1)
A compound represented by the following formula (M-25) was synthesized with reference to Example 10 of JP-A-2009-139909.

(Preparation of polymer (A))
A polymer (A) was synthesized using the compound shown below.

(Synthesis Example A-1)
Compound (M-1) 10.40 g (0.062 mol), compound (M-11) 2.01 g (0.015 mol) and compound (M-7) 13.74 g (0.062 mol) were added to 2-butanone 60 g. And a monomer solution charged with 1.27 g of dimethyl 2,2′-azobis (2-methylpropionate) was prepared. 3.84 g (0.015 mol) of the compound (M-5) was put into a 500 mL three-necked flask, 30 g of 2-butanone was added and dissolved, purged with nitrogen for 30 minutes, and then stirred at 80 ° C. while stirring the reaction kettle. The monomer solution prepared in advance was added dropwise using a dropping funnel over 3 hours. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.

After completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or lower, and poured into 600 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was dispersed in methanol to form a slurry, washed, and then filtered off twice, followed by drying at 60 ° C. for 15 hours to obtain a white powder copolymer (yield 23 g, yield). (76.7% rate). This copolymer has Mw of 5500 and Mw / Mn = 1.43, and as a result of ¹³ C-NMR analysis, compound (M-1), compound (M-5), and compound (M-11). The content (mol%) of repeating units derived from the compound (M-7) was 39.8: 8.6: 11.1: 40.5, respectively. This copolymer is referred to as “resin (A-1)”.

(Synthesis Examples A-2 to A-4)
Resins (A-2) to (A-4) were prepared in the same manner as in Synthesis Example 1 except that the compounding recipe of the compounds was shown in Table 2. Table 3 shows the physical properties of the resins (A-1) to (A-4).

(Synthesis of polymer (C))
A polymer (C) was synthesized using the compounds shown in Table 1.

(Synthesis Example C-1)
Compound (M-16) (5.0 g, 0.022 mol) is dissolved in 2-butanone (10 g), and dimethyl 2,2′-azobis (2-methylpropionate) (0.25 g) is added to a 200 mL three-necked flask. After purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring. The start of heating was set as the polymerization start time, and the polymerization reaction was carried out for 4 hours. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling. The polymerization solution was concentrated under reduced pressure using an evaporator until the weight of the polymerization solution became 7.5 g.

Thereafter, the concentrated solution was poured into a mixed solution of 50 g of methanol and 50 g of water to precipitate a slime-like white solid. The liquid part was removed by decantation, and a mixed solution of 50 g of methanol and 50 g of water was added again to wash the slime-like white solid twice. The collected solid was vacuum-dried at 60 degrees for 15 hours to obtain 3.1 g of white powder (yield 62%). Mw of this polymer was 7000 and Mw / Mn was 1.48. As a result of ¹³ C-NMR analysis, the content of the repeating unit derived from the compound (M-16) was 100 mol%. This copolymer is referred to as “polymer (C-1)”.

(Synthesis Examples C-2 to C-21)
Polymers (C-3) to (C-21) were synthesized in the same manner as in Synthesis Example C-2 except that the compounding recipe of the compounds was shown in Table 4. Table 5 shows the physical property values of the polymers (C-1) to (C-21).

(Acid generator (B))
Hereinafter, the acid generator (B) used in the preparation examples is shown in Table 6.

(Acid diffusion control agent (D))
The structural formula of the acid diffusion controller (D-1) used in the preparation examples is shown below.

(Solvent (E))
Hereinafter, the solvent (E) used in the preparation examples is shown.
(E-1): propylene glycol monomethyl ether acetate,
(E-2): Cyclohexanone.

  In addition, γ-butyrolactone was used as an additive.

(Preparation Example 1)
100 parts of polymer (A-2), 5 parts of polymer (C-1) prepared in Synthesis Example C-1, 9.9 parts of acid generator (B-1), acid diffusion controller (D-1) 1.5 parts, 100 parts of γ-butyrolactone as an additive, 1500 parts of solvent (E-1) and 650 parts of (E-2) were mixed to prepare a composition solution of a radiation sensitive resin composition.

(Preparation Examples 2 to 30)
A composition solution of each radiation-sensitive resin composition was prepared in the same manner as in Preparation Example 1, except that the formulation shown in Table 7 was used.

  The evaluation results are shown in Table 8.

  The compound of the present invention can be suitably used for synthesizing a polymer component of a chemically amplified resist for manufacturing a semiconductor device, particularly a resist for immersion exposure.

Claims (3)

The compound represented by the following general formula (m-1-1a).

[In General Formula (m-1-1a), R ⁸ represents a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Rf is a fluorine atom or a C1-C10 perfluoroalkyl group mutually independently, n1 shows the integer of 0-4. R ² represents a single bond, a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. R ³¹ represents a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an oxygen atom or sulfur at the terminal on the R ² side. A structure in which an atom, an imino group, a carbonyl group, —CO—O— or —CO—NH— is bonded is also included. R represents a hydrogen atom, a methyl group or a trifluoromethyl group. ] The compound represented by the following general formula (m-1-1b).

[In General Formula (m-1-1b), R ⁸ represents a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Rf is independently a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms, and n1 is independently an integer of 0 to 4. R ² represents a single bond, a methylene group, a linear or branched divalent hydrocarbon group having 2 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms. R ³² represents a linear or branched trivalent hydrocarbon group having 1 to 10 carbon atoms or a trivalent cyclic hydrocarbon group having 4 to 20 carbon atoms, and an oxygen atom, a sulfur atom, and an imino group at the terminal on the R ² side. A structure in which a group, a carbonyl group, —CO—O— or —CO—NH— is bonded is also included. R represents a hydrogen atom, a methyl group or a trifluoromethyl group. ] In the general formula (m-1-1a) or the general formula (m-1-1b), a compound of claim 1 or claim 2 ^{R 8} are all trifluoromethyl groups.