JP2013166960A - Compound and polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition suitable for immersion exposure, a method of forming a resist pattern using the same, and a fluorine-containing compound useful for an additive used in the same.SOLUTION: A compound is represented by general formula (c-1-1) or (c-1-2). In the formula: R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X is a specific organic group having no acid dissociable moiety; Ais an aromatic cyclic group which may have a substituent; Xis a single bond or a divalent bonding group; and Ris an organic group having a fluorine atom.

Description

  The present invention relates to a resist composition for liquid immersion lithography containing a fluorine-containing compound, a resist pattern forming method using the resist composition for liquid immersion exposure, and a fluorine-containing compound.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to light such as light or an electron beam through a mask on which a predetermined pattern is formed. And a development process is performed to form a resist pattern having a predetermined shape on the resist film.
Along with the miniaturization of semiconductor elements, the wavelength of the exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). A machine has been developed. Along with the shortening of the wavelength of the exposure light source, the resist material is required to be improved in lithography characteristics such as sensitivity to the exposure light source and resolution capable of reproducing a pattern with a fine dimension. As a resist material that satisfies such requirements, a chemically amplified resist containing a base resin whose solubility in an alkaline developer is changed by the action of an acid and an acid generator that generates an acid upon exposure is used.
At present, as a base resin of a chemically amplified resist used in ArF excimer laser lithography and the like, a resin having a structural unit derived from (meth) acrylic acid ester in the main chain because of its excellent transparency near 193 nm ( Acrylic resin) is generally used.
Here, “(meth) acrylic acid” means one or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position. “(Meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position. “(Meth) acrylate” means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position.

As one of the methods for further improving the resolution, exposure (immersion exposure) is performed by interposing a liquid (immersion medium) having a higher refractive index than air between the objective lens of the exposure machine and the sample. A so-called immersion lithography (hereinafter referred to as “immersion exposure”) is known (for example, see Non-Patent Document 1).
According to immersion exposure, even when a light source having the same exposure wavelength is used, the same high resolution as when using a light source with a shorter wavelength or using a high NA lens can be achieved, and the depth of focus can be reduced. It is said that there is no decline. Moreover, immersion exposure can be performed using an existing exposure apparatus. For this reason, immersion exposure is expected to be able to form resist patterns with low cost, high resolution, and excellent depth of focus. In particular, in terms of lithography characteristics such as resolution, the semiconductor industry is attracting a great deal of attention.
Immersion exposure is effective in forming all pattern shapes, and can be combined with super-resolution techniques such as the phase shift method and the modified illumination method that are currently under investigation. Currently, as an immersion exposure technique, a technique mainly using an ArF excimer laser as a light source is being actively researched. Currently, water is mainly studied as an immersion medium.

In recent years, with respect to fluorine-containing compounds, their water repellency, transparency and other characteristics have attracted attention, and research and development in various fields has been actively conducted. For example, in the field of resist materials, acid instability such as a methoxymethyl group, tert-butyl group, tert-butyloxycarbonyl group, etc. is added to a fluorine-containing polymer compound for use as a base resin of a positive chemically amplified resist. Introducing groups. However, when such a fluorine-based polymer compound is used as a base resin for a positive resist composition, there are disadvantages such as generation of a large amount of outgas after exposure and insufficient resistance to dry etching gas (etching resistance). is there.
Recently, a fluorine-containing polymer compound having an acid labile group containing a cyclic hydrocarbon group has been reported as a fluorine-containing polymer compound having excellent etching resistance (see, for example, Non-Patent Document 2).

Proceedings of SPIE, 5754, 119-128 (2005). Proceedings of SPIE, 4690, 76-83 (2002).

  In immersion exposure, in addition to normal lithography characteristics (sensitivity, resolution, etching resistance, etc.), a resist material having characteristics corresponding to the immersion exposure technique is required. For example, in immersion exposure, when the resist film and the immersion solvent come into contact with each other, elution of the substance in the resist film into the immersion solvent (substance elution) occurs. Substance elution causes phenomena such as alteration of the resist layer and change in the refractive index of the immersion solvent, thereby deteriorating the lithography properties. Since the amount of this substance elution is affected by the characteristics (for example, hydrophilicity / hydrophobicity) of the resist film surface, for example, the elution of the substance can be reduced by increasing the hydrophobicity of the resist film surface. In the case where the immersion medium is water, when immersion exposure is performed using a scanning immersion exposure machine as described in Non-Patent Document 1, the immersion medium follows the movement of the lens. Therefore, the water following ability to move is required. If the water followability is low, the exposure speed is lowered, and there is a concern that the productivity may be affected. This water followability is considered to be improved by increasing the hydrophobicity of the resist film.

Thus, it is considered that by increasing the hydrophobicity of the resist film surface, it is possible to solve problems peculiar to the immersion exposure technique such as reduction of substance elution and improvement of water followability. However, even if the resist film is simply hydrophobized, there is an adverse effect on lithography characteristics and the like. For example, when the hydrophobicity of the resist film is increased, there is a problem that defects (defects) are likely to occur in the resist film after alkali development. In particular, in the case of a positive resist composition, defects are likely to occur in unexposed areas.
The “defect” is a general defect detected when a developed resist film is observed from directly above, for example, by a surface defect observation apparatus (trade name “KLA”) manufactured by KLA Tencor. Examples of the defects include scum, bubbles, dust, bridges (bridge structures between resist patterns), color unevenness, precipitates, and residues after development.
It is presumed that these problems can be solved if the material is hydrophobic at the time of immersion exposure and hydrophilic at the time of development. However, at present, there are few known materials having such characteristics.

  The present invention has been made in view of the above circumstances, and is useful as a resist composition suitable for immersion exposure, a resist pattern forming method using the resist composition, and an additive used in the resist composition. It is an object to provide a simple fluorine-containing compound.

In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention is a compound represented by the following general formula (c-1-1) or (c-1-2).

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは直鎖状もしくは分岐鎖状の脂肪族炭化水素基、テトラシクロドデカニル基から水素原子を１つ除いた基、２価の芳香族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、カーボネート結合（−Ｏ−Ｃ（＝Ｏ）−Ｏ−）、−ＮＨ−、−ＮＲ^０４（Ｒ^０４はアルキル基）−、−ＮＨ−Ｃ（＝Ｏ）−、＝Ｎ−、又は、「直鎖状もしくは分岐鎖状の脂肪族炭化水素基、テトラシクロドデカニル基から水素原子を１つ除いた基、又は２価の芳香族炭化水素基」と「−Ｏ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、カーボネート結合（−Ｏ−Ｃ（＝Ｏ）−Ｏ−）、−ＮＨ−、−ＮＲ^０４（Ｒ^０４はアルキル基）−、−ＮＨ−Ｃ（＝Ｏ）−、又は＝Ｎ−」との組み合わせであり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[Wherein, R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a linear or branched aliphatic hydrocarbon group, a tetracyclododecanyl group to a hydrogen atom; , Divalent aromatic hydrocarbon group, —O—, —C (═O) —, —C (═O) —O—, carbonate bond (—O—C (═O) — O—), —NH—, —NR ⁰⁴ (R ⁰⁴ is an alkyl group) —, —NH—C (═O) —, ═N—, or “linear or branched aliphatic hydrocarbon group” , A group obtained by removing one hydrogen atom from a tetracyclododecanyl group, or a divalent aromatic hydrocarbon group ”and“ —O—, —C (═O) —, —C (═O) —O—, carbonate bond (-O-C (= O) -O -), - NH -, - NR 04 (R 04 is an alkyl group) -, - NH-C ( = O) Or = a combination of N- ", A _aryl is an aromatic cyclic group which may have a substituent, X ₀₁ is a single bond or a divalent linking group, R ² are each An organic group having a fluorine atom independently. ]

  The second aspect of the present invention is a polymer compound having a structural unit represented by the following general formula (c-1-3) or (c-1-4).

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは直鎖状もしくは分岐鎖状の脂肪族炭化水素基、テトラシクロドデカニル基から水素原子を１つ除いた基、２価の芳香族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、カーボネート結合（−Ｏ−Ｃ（＝Ｏ）−Ｏ−）、−ＮＨ−、−ＮＲ^０４（Ｒ^０４はアルキル基）−、−ＮＨ−Ｃ（＝Ｏ）−、＝Ｎ−、又は、「直鎖状もしくは分岐鎖状の脂肪族炭化水素基、テトラシクロドデカニル基から水素原子を１つ除いた基、又は２価の芳香族炭化水素基」と「−Ｏ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、カーボネート結合（−Ｏ−Ｃ（＝Ｏ）−Ｏ−）、−ＮＨ−、−ＮＲ^０４（Ｒ^０４はアルキル基）−、−ＮＨ−Ｃ（＝Ｏ）−、又は＝Ｎ−」との組み合わせであり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[Wherein, R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a linear or branched aliphatic hydrocarbon group, a tetracyclododecanyl group to a hydrogen atom; , Divalent aromatic hydrocarbon group, —O—, —C (═O) —, —C (═O) —O—, carbonate bond (—O—C (═O) — O—), —NH—, —NR ⁰⁴ (R ⁰⁴ is an alkyl group) —, —NH—C (═O) —, ═N—, or “linear or branched aliphatic hydrocarbon group” , A group obtained by removing one hydrogen atom from a tetracyclododecanyl group, or a divalent aromatic hydrocarbon group ”and“ —O—, —C (═O) —, —C (═O) —O—, carbonate bond (-O-C (= O) -O -), - NH -, - NR 04 (R 04 is an alkyl group) -, - NH-C ( = O) Or = a combination of N- ", A _aryl is an aromatic cyclic group which may have a substituent, X ₀₁ is a single bond or a divalent linking group, R ² are each An organic group having a fluorine atom independently. ]

In the present specification and claims, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified.
Further, the “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
The “structural unit” means a monomer unit (monomer unit) constituting a polymer compound (polymer, copolymer).
“Exposure” is a concept including general irradiation of radiation.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorine-containing compound useful as a resist composition suitable for immersion exposure, the resist pattern formation method using the said resist composition, and the additive used for the said resist composition can be provided.

It is a figure explaining advancing angle ((theta) ₁ ), receding angle ((theta) ₂ ), and falling angle ((theta) ₃ ).

≪Resist composition for immersion exposure≫
The resist composition for immersion exposure of the present invention generates a base component (A) (hereinafter referred to as “component (A)”) whose solubility in an alkaline developer is changed by the action of an acid, and generates an acid upon exposure. An acid generator component (B) (hereinafter referred to as “component (B)”) and a fluorine-containing compound (C) represented by the general formula (c-1) exhibiting degradability with respect to an alkaline developer (hereinafter referred to as “the acid generator component (B)”) "(C) component").

<(A) component>
As the component (A), organic compounds that are usually used as base material components for chemically amplified resists can be used singly or in combination of two or more.
Here, the “base material component” is an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film-forming ability is improved and a nano-level resist pattern is easily formed.
The organic compound having a molecular weight of 500 or more used as the substrate component is a low molecular weight organic compound (low molecular material) having a molecular weight of 500 or more and less than 2000, and a high molecular weight organic compound (polymer material) having a molecular weight of 2000 or more. It is roughly divided into As the low molecular weight material, a non-polymer is usually used. Resin (polymer, copolymer) is used as the polymer material, and the “molecular weight” is a polystyrene-reduced mass average molecular weight measured by GPC (gel permeation chromatography). Hereinafter, the term “resin” refers to a resin having a molecular weight of 2000 or more.
As the component (A), a resin whose alkali solubility is changed by the action of an acid can be used, and a low molecular weight material whose alkali solubility is changed by the action of an acid can also be used.

When the resist composition for immersion exposure of the present invention is a negative resist composition, as the component (A), a base material component that is soluble in an alkali developer is used, and a cross-linking agent is added to the negative resist composition. Blended.
In such a negative resist composition, when an acid is generated from the component (B) by exposure, the acid acts to cause crosslinking between the base material component and the crosslinking agent, resulting in poor solubility in an alkali developer. To do. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the negative resist composition on the substrate is selectively exposed, the exposed portion turns into poorly soluble in an alkaline developer, while unexposed. Since the portion remains soluble in the alkali developer and does not change, a resist pattern can be formed by alkali development.
As the component (A) of the negative resist composition, a resin that is soluble in an alkali developer (hereinafter referred to as an alkali-soluble resin) is usually used.
As the alkali-soluble resin, a resin having a unit derived from at least one selected from α- (hydroxyalkyl) acrylic acid or a lower alkyl ester of α- (hydroxyalkyl) acrylic acid is a good resist with little swelling. A pattern can be formed, which is preferable. Α- (Hydroxyalkyl) acrylic acid includes acrylic acid in which a hydrogen atom is bonded to the α-position carbon atom to which the carboxy group is bonded, and a hydroxyalkyl group (preferably having 1 carbon atom) in the α-position carbon atom. One or both of [alpha] -hydroxyalkylacrylic acids to which (5) hydroxyalkyl groups) are attached.
As the crosslinking agent, for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group because a good resist pattern with less swelling can be formed. It is preferable that the compounding quantity of a crosslinking agent is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin.

  When the resist composition for immersion exposure according to the present invention is a positive resist composition, as the component (A), a base material component whose solubility in an alkaline developer is increased by the action of an acid is used. The component (A) is hardly soluble in an alkali developer before exposure. When an acid is generated from the component (B) by exposure, the solubility in the alkali developer is increased by the action of the acid. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion changes from poorly soluble to soluble in an alkaline developer. On the other hand, since the unexposed portion remains hardly soluble in alkali and does not change, a resist pattern can be formed by alkali development.

In the resist composition of the present invention, the component (A) is preferably a base material component whose solubility in an alkaline developer is increased by the action of an acid. That is, the resist composition of the present invention is preferably a positive resist composition.
The component (A) may be a resin component (A1) (hereinafter sometimes referred to as “component (A1)”) whose solubility in an alkaline developer is increased by the action of an acid. It may be a low molecular weight material (A2) (hereinafter also referred to as “component (A2)”) whose solubility in a developer increases, or a mixture thereof.

[(A1) component]
As the component (A1), resin components (base resins) that are usually used as base components for chemically amplified resists can be used alone or in combination of two or more.
In the present invention, the component (A1) preferably contains a structural unit derived from an acrylate ester.
Here, in the present specification and claims, the “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid esters” include those in which a hydrogen atom is bonded to the carbon atom at the α-position, and those in which a substituent (atom or group other than a hydrogen atom) is bonded to the carbon atom in the α-position. Include concepts. Examples of the substituent include a lower alkyl group and a halogenated lower alkyl group.
Note that the α-position (α-position carbon atom) of a structural unit derived from an acrylate ester means a carbon atom to which a carbonyl group is bonded, unless otherwise specified.
In the acrylate ester, as the lower alkyl group as a substituent at the α-position, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, Examples include lower linear or branched alkyl groups such as isopentyl group and neopentyl group.
Specific examples of the halogenated lower alkyl group include groups in which part or all of the hydrogen atoms in the above-mentioned “lower alkyl group as a substituent at the α-position” are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
In the present invention, the α-position of the acrylate ester is preferably a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and is a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group. In view of industrial availability, a hydrogen atom or a methyl group is most preferable.

The component (A1) particularly preferably has a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
In addition to the structural unit (a1), the component (A1) preferably further has a structural unit (a2) derived from an acrylate ester containing a lactone-containing cyclic group.
The component (A1) is derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1) or in addition to the structural units (a1) and (a2). It is preferable to have a structural unit (a3).

-Structural unit (a1):
The acid dissociable, dissolution inhibiting group in the structural unit (a1) has an alkali dissolution inhibiting property that makes the entire component (A1) difficult to dissolve in an alkali developer before dissociation, and dissociates with an acid. This increases the solubility of the entire component in an alkaline developer, and those that have been proposed as acid dissociable, dissolution inhibiting groups for base resins for chemically amplified resists can be used. Generally, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group is widely known. .

Here, the “tertiary alkyl ester” is an ester formed by replacing a hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carbonyloxy group (—C (O)). A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom of -O-). In this tertiary alkyl ester, when an acid acts, a bond is cut between an oxygen atom and a tertiary carbon atom.
The chain or cyclic alkyl group may have a substituent.
Hereinafter, a group that is acid dissociable by constituting a carboxy group and a tertiary alkyl ester is referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
Examples of the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include an aliphatic branched acid dissociable, dissolution inhibiting group and an acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group.

“Aliphatic branched” means having a branched structure having no aromaticity. The structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
As the aliphatic branched acid dissociable, dissolution inhibiting group, a tertiary alkyl group having 4 to 8 carbon atoms is preferable, and specific examples include a tert-butyl group, a tert-pentyl group, and a tert-heptyl group. .

The “aliphatic cyclic group” means a monocyclic group or a polycyclic group having no aromaticity.
The “aliphatic cyclic group” in the structural unit (a1) may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.
The basic ring structure excluding the substituent of the “aliphatic cyclic group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. The “aliphatic cyclic group” is preferably a polycyclic group.
Examples of the aliphatic cyclic group include monocycloalkanes, bicycloalkanes, tricycloalkanes, tetracycloalkanes that may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group. And groups obtained by removing one or more hydrogen atoms from a polycycloalkane. More specifically, monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are exemplified. .

  Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group. Specifically, 2-methyl-2 -Adamantyl group, 2-ethyl-2-adamantyl group, etc. are mentioned. Alternatively, in the structural units represented by the following general formulas (a1 ″ -1) to (a1 ″ -6), an adamantyl group such as a group bonded to an oxygen atom of a carbonyloxy group (—C (O) —O—) An aliphatic cyclic group such as a cyclohexyl group, a cyclopentyl group, a norbornyl group, a tricyclodecanyl group, or a tetracyclododecanyl group, and a branched alkylene group having a tertiary carbon atom bonded thereto. Groups.

［式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基を示し；Ｒ^１５、Ｒ^１６はアルキル基（直鎖状、分岐鎖状のいずれでもよく、好ましくは炭素数１〜５である）を示す。］

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R ¹⁵ and R ^{16 each} represents an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms. Is). ]

  In the general formulas (a1 ″ -1) to (a1 ″ -6), the lower alkyl group or halogenated lower alkyl group of R is a lower alkyl group or halogenated lower alkyl which may be bonded to the α-position of the acrylate ester. It is the same as the alkyl group.

The “acetal-type acid dissociable, dissolution inhibiting group” is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, the acid acts to break the bond between the acetal acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal acid dissociable, dissolution inhibiting group is bonded.
Examples of the acetal type acid dissociable, dissolution inhibiting group include a group represented by the following general formula (p1).

［式中、Ｒ^１’，Ｒ^２’はそれぞれ独立して水素原子または低級アルキル基を表し、ｎは０〜３の整数を表し、Ｙは低級アルキル基または脂肪族環式基を表す。］

[Wherein, R ¹ ′ and R ² ′ each independently represents a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 3, and Y represents a lower alkyl group or an aliphatic cyclic group. ]

In the above formula, n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.
Examples of the lower alkyl group for R ¹ ′ and R ² ′ include the same lower alkyl groups as those described above for R. A methyl group or an ethyl group is preferable, and a methyl group is most preferable.
In the present invention, it is preferable that at least one of R ¹ ′ and R ² ′ is a hydrogen atom. That is, the acid dissociable, dissolution inhibiting group (p1) is preferably a group represented by the following general formula (p1-1).

［式中、Ｒ^１’、ｎ、Ｙは上記と同様である。］

[Wherein R ¹ ′, n and Y are the same as described above. ]

Examples of the lower alkyl group for Y include the same lower alkyl groups as those described above for R.
The aliphatic cyclic group for Y can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups that have been proposed in a number of conventional ArF resists. For example, the above “aliphatic ring” Examples thereof are the same as those in the formula group.

  Examples of the acetal type acid dissociable, dissolution inhibiting group also include a group represented by the following general formula (p2).

［式中、Ｒ^１７、Ｒ^１８はそれぞれ独立して直鎖状もしくは分岐鎖状のアルキル基または水素原子であり、Ｒ^１９は直鎖状、分岐鎖状または環状のアルキル基である。または、Ｒ^１７およびＲ^１９がそれぞれ独立に直鎖状または分岐鎖状のアルキレン基であって、Ｒ^１７の末端とＲ^１９の末端とが結合して環を形成していてもよい。］

[Wherein, R ¹⁷ and R ¹⁸ each independently represent a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ represents a linear, branched or cyclic alkyl group. Alternatively, R ¹⁷ and R ¹⁹ may be each independently a linear or branched alkylene group, and the end of R ^{17 and} the end of R ¹⁹ may be bonded to form a ring. ]

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, may be linear or branched, and is preferably an ethyl group or a methyl group, and most preferably a methyl group.
In particular, it is preferable that one of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is a methyl group.
R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.
When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
When R ¹⁹ is cyclic, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, are included. Examples include a group excluding a hydrogen atom. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
In the above formula, R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R ^{19 and} the end of R ¹⁷ And may be combined.
In this case, a cyclic group is formed by R ¹⁷ , R ¹⁹ , the oxygen atom to which R ¹⁹ is bonded, and the carbon atom to which the oxygen atom and R ¹⁷ are bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

  As the structural unit (a1), one or more selected from the group consisting of structural units represented by the following general formula (a1-0-1) and structural units represented by the following general formula (a1-0-2): Is preferably used.

［式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基を示し；Ｘ^１は酸解離性溶解抑制基を示す。］

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and X ¹ represents an acid dissociable, dissolution inhibiting group. ]

［式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基を示し；Ｘ^２は酸解離性溶解抑制基を示し；Ｙ^２はアルキレン基または脂肪族環式基を示す。］

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group. ]

In general formula (a1-0-1), the lower alkyl group or halogenated lower alkyl group for R is the same as the lower alkyl group or halogenated lower alkyl group that may be bonded to the α-position of the acrylate ester. .
X ¹ is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include the above-described tertiary alkyl ester type acid dissociable, dissolution inhibiting group and acetal type acid dissociable, dissolution inhibiting group. And tertiary alkyl ester type acid dissociable, dissolution inhibiting groups are preferred.

In general formula (a1-0-2), R is the same as defined above.
X ² is the same as X ¹ in formula (a1-0-1).
Y ² is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aliphatic cyclic group, and a group in which two or more hydrogen atoms are removed is used as the aliphatic cyclic group. Except for the above, the same “aliphatic cyclic group” as described above can be used.
When Y ² is an alkylene group having 1 to 10 carbon atoms, it is more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. .
When Y ² is a divalent aliphatic cyclic group, a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable. .

  More specifically, examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1) to (a1-4).

［式中、Ｘ’は第３級アルキルエステル型酸解離性溶解抑制基を表し、Ｙは炭素数１〜５の低級アルキル基、または脂肪族環式基を表し；ｎは０〜３の整数を表し；Ｙ^２はアルキレン基または脂肪族環式基を表し；Ｒは前記と同じであり、Ｒ^１’、Ｒ^２’はそれぞれ独立して水素原子または炭素数１〜５の低級アルキル基を表す。］

[Wherein, X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group; n represents an integer of 0 to 3] Y ² represents an alkylene group or an aliphatic cyclic group; R is the same as defined above, and R ¹ ′ and R ² ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. Represent. ]

Wherein, X 'include the same tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups as those described above for X ^{1.
R 1 ', R 2',} n, as the Y, respectively, ^{R 1} in the general formula listed in the description of "acetal-type acid dissociable, dissolution inhibiting group" described above ^{(p1) ', R 2'} , n, Y The same thing is mentioned.
The Y ^2, the same groups as those described above for ^{Y 2} in the general formula (a1-0-2).

  Specific examples of the structural units represented by the general formulas (a1-1) to (a1-4) are shown below.

Among the above, the structural unit represented by the general formula (a1-1) is preferable, specifically, the formulas (a1-1-1) to (a1-1-6) and (a1-1-35) to ( It is more preferable to use at least one selected from the group consisting of structural units represented by a1-1-41).
Furthermore, the structural unit (a1) is represented by the following general formula (a1-1-01) that includes the structural units represented by the formula (a1-1-1) to the formula (a1-1-4). And those represented by the following general formula (a1-1-02) including the structural units represented by formulas (a1-1-35) to (a1-1-41) are also preferable.

（式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基を示し、Ｒ^１１は低級アルキル基を示す。）

(In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹¹ represents a lower alkyl group.)

（式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基を示し、Ｒ^１２は低級アルキル基を示す。ｈは１〜３の整数を表す。）

(In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R ¹² represents a lower alkyl group, and h represents an integer of 1 to 3.)

In general formula (a1-1-01), R is the same as defined above.
The lower alkyl group for R ^{11 is the same as} the lower alkyl group for R, preferably a methyl group or an ethyl group, and most preferably a methyl group.
In general formula (a1-1-02), R is the same as defined above.
The lower alkyl group for R ^{12 is the same as} the lower alkyl group for R, preferably a methyl group or an ethyl group, and most preferably an ethyl group. h is preferably 1 or 2, and most preferably 2.

As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.
In the component (A1), the proportion of the structural unit (a1) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, more preferably 25 to 50 mol%, based on all structural units constituting the component (A1). Is more preferable. By setting it to the lower limit value or more, a pattern can be easily obtained when the resist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

Structural unit (a2):
The structural unit (a2) is a structural unit derived from an acrylate ester containing a lactone-containing cyclic group.
Here, the lactone-containing cyclic group refers to a cyclic group containing one ring (lactone ring) containing an —O—C (O) — structure. The lactone ring is counted as the first ring, and when it is only the lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
When the copolymer (A1) is used for forming a resist film, the lactone cyclic group of the structural unit (a2) is improved in the adhesion of the resist film to the substrate or has an affinity for a developer containing water. It is effective in improving the sex.

As the structural unit (a2), any unit can be used without any particular limitation.
Specifically, examples of the lactone-containing monocyclic group include groups in which one hydrogen atom has been removed from a monocyclic lactone such as γ-butyrolactone or mevalonic lactone. Examples of the lactone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring.

  More specifically, examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.

［式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基であり、Ｒ’は水素原子、低級アルキル基、炭素数１〜５のアルコキシ基または−ＣＯＯＲ”であり、前記Ｒ”は水素原子、または炭素数１〜１５の直鎖状、分岐鎖状もしくは環状のアルキル基であり、ｍは０または１の整数であり、Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子である。］

[Wherein, R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R ′ is a hydrogen atom, a lower alkyl group, an alkoxy group having 1 to 5 carbon atoms, or —COOR ″, wherein R ″ is A hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, m is an integer of 0 or 1, and A ″ is a carbon which may contain an oxygen atom or a sulfur atom. It is an alkylene group of formulas 1 to 5, an oxygen atom or a sulfur atom.]

R in the general formulas (a2-1) to (a2-5) is the same as R in the structural unit (a1).
The lower alkyl group for R ′ is the same as the lower alkyl group for R in the structural unit (a1).
When R ″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Or a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorinated alkyl group Specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Etc.
In general formulas (a2-1) to (a2-5), R ′ is preferably a hydrogen atom in view of industrial availability.
Specific examples of the alkylene group having 1 to 5 carbon atoms that may contain an oxygen atom or sulfur atom of A ″ include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, —O—CH ₂ —. _{, -CH 2 -O-CH 2 -} , - S-CH 2 -, - CH 2 -S-CH 2 - , and the like.
Below, the specific structural unit of the said general formula (a2-1)-(a2-5) is illustrated.

In the component (A1), as the structural unit (a2), one type may be used alone, or two or more types may be used in combination.
As the structural unit (a2), at least one selected from the group consisting of the structural units represented by the general formulas (a2-1) to (a2-5) is preferable, and the general formulas (a2-1) to ( More preferred is at least one selected from the group consisting of structural units represented by a2-3). Among them, chemical formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-2-9), (a2-2-10) ), (A2-3-1), (a2-3-2), (a2-3-9) and at least one selected from the group consisting of structural units represented by (a2-3-10) Is preferably used.

As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.
In the component (A1), the proportion of the structural unit (a2) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on the total of all the structural units constituting the component (A1). 50 mol% is more preferable. By making it the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by making it the upper limit value or less, it is possible to balance with other structural units.

-Structural unit (a3):
The structural unit (a3) is a structural unit derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group.
When the component (A1) has the structural unit (a3), the hydrophilicity of the component (A1) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved. Contributes to improvement.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. A hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group). It is done. As the polycyclic group, for example, a resin for a resist composition for ArF excimer laser can be appropriately selected from among many proposed ones. The polycyclic group preferably has 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

  The structural unit (a3) is derived from a hydroxyethyl ester of acrylic acid when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a3-1), a structural unit represented by (a3-2), (a3-3) ) Is preferable.

（式中、Ｒは前記と同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。）

(Wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, and l is an integer of 1 to 5) And s is an integer of 1 to 3.)

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
j is preferably 1, and a hydroxyl group bonded to the 3rd position of the adamantyl group is particularly preferred.
In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.
In formula (a3-3), t ′ is preferably 1. l is preferably 1. s is preferably 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.
In the component (A1), the proportion of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 25 mol% with respect to all the structural units constituting the component (A1). Is more preferable. By setting it to the lower limit value or more, the effect of containing the structural unit (a3) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

-Structural unit (a4):
The component (A1) may contain other structural units (a4) other than the structural units (a1) to (a3) as long as the effects of the present invention are not impaired.
The structural unit (a4) is not particularly limited as long as it is another structural unit that is not classified into the structural units (a1) to (a3) described above, and is for ArF excimer laser and KrF excimer laser (preferably ArF excimer). A number of hitherto known materials can be used for resist resins such as lasers.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing a non-acid-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those exemplified in the case of the structural unit (a1), and for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). A number of hitherto known materials can be used as the resin component of the resist composition.
In particular, at least one selected from a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include those represented by the following general formulas (a4-1) to (a4-5).

（式中、Ｒは前記と同じである。）

(In the formula, R is as defined above.)

  When the structural unit (a4) is contained in the component (A1), the proportion of the structural unit (a4) in the component (A1) is 1 to 30 with respect to the total of all the structural units constituting the component (A1). Mol% is preferable and 10 to 20 mol% is more preferable.

  In the present invention, the component (A1) preferably contains a copolymer having the structural units (a1), (a2) and (a3). Examples of the copolymer include copolymers composed of the structural units (a1), (a2) and (a3), copolymers composed of the structural units (a1), (a2), (a3) and (a4). Can be mentioned.

The component (A1) can be obtained by polymerizing a monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
Further, for the component (A1), in the polymerization, a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C (CF ₃ ) ₂ —OH is used in combination, so that the terminal A —C (CF ₃ ) ₂ —OH group may be introduced into the. As described above, a copolymer introduced with a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom reduces development defects and LER (line edge roughness: uneven unevenness of line side walls). It is effective in reducing

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (A1) is not particularly limited, but is preferably 2000 to 50000, more preferably 3000 to 30000, and 5000 to 20000. Most preferred. When it is smaller than the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist. When it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
Further, the dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. In addition, Mn shows a number average molecular weight.

[(A2) component]
As the component (A2), a low molecular compound having a molecular weight of 500 or more and less than 2000 and having an acid dissociable, dissolution inhibiting group and a hydrophilic group as exemplified in the description of the component (A1) above is preferable. Specifically, a compound in which a part of hydrogen atoms of a hydroxyl group of a compound having a plurality of phenol skeletons is substituted with the acid dissociable, dissolution inhibiting group can be mentioned.
The component (A2) is, for example, a part of the hydrogen atom of the hydroxyl group of a low molecular weight phenol compound known as a sensitizer in a non-chemically amplified g-line or i-line resist or a heat resistance improver. Those substituted with a soluble dissolution inhibiting group are preferred and can be arbitrarily used.
Examples of such low molecular weight phenol compounds include bis (4-hydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl). ) Propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, bis (4-hydroxy-) 3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyph Phenylmethane, bis (4-hydroxy-3-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl- 4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, Examples include 2, 3, 4 nuclei of formalin condensates of phenols such as phenol, m-cresol, p-cresol or xylenol. Of course, it is not limited to these.
The acid dissociable, dissolution inhibiting group is not particularly limited, and examples thereof include those described above.

As the component (A), one type may be used alone, or two or more types may be used in combination.
Among these, the component (A) is preferably a base material component whose solubility in an alkaline developer is increased by the action of an acid, and particularly preferably the component (A1).
In the resist composition of the present invention, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<(B) component>
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulfonyl) diazomethanes. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

  As the onium salt acid generator, for example, a compound represented by the following general formula (b-1) or (b-2) can be used.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”は、それぞれ独立に、アリール基またはアルキル基を表し；式（ｂ−１）におけるＲ^１”〜Ｒ^３”のうち、いずれか２つが相互に結合して式中のイオウ原子と共に環を形成してもよく；Ｒ^４”は、直鎖状、分岐鎖状または環状のアルキル基またはフッ素化アルキル基を表し；Ｒ^１”〜Ｒ^３”のうち少なくとも１つはアリール基を表し、Ｒ^５”〜Ｒ^６”のうち少なくとも１つはアリール基を表す。］

[Wherein, R ¹ ″ to R ³ ″ and R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group; among R ¹ ″ to R ³ ″ in formula (b-1), Any two may be bonded together to form a ring with the sulfur atom in the formula; R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group; R ¹ At least one of “˜R ³ ” represents an aryl group, and at least one of R ⁵ ”to R ⁶ ” represents an aryl group.]

In formula (b-1), R ¹ ″ to R ³ ″ each independently represents an aryl group or an alkyl group. In addition, any two of R ¹ ″ to R ³ ″ in formula (b-1) may be bonded to each other to form a ring together with the sulfur atom in the formula.
Further, at least one of R ¹ ″ to R ³ ″ represents an aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably aryl groups, and most preferably all R ¹ ″ to R ³ ″ are aryl groups.
The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups It may or may not be substituted with a group, a halogen atom, a hydroxyl group or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Is most preferred.
As the alkoxy group that may be substituted for the hydrogen atom of the aryl group, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, Most preferred is a tert-butoxy group.
The alkoxy group that may be substituted for the hydrogen atom of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
The halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, linear C1-10, branched or cyclic alkyl group, and the like. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
Among these, R ¹ ″ to R ³ ″ are most preferably a phenyl group or a naphthyl group, respectively.

When any two of R ¹ ″ to R ³ ″ in the formula (b-1) are bonded to each other to form a ring together with the sulfur atom in the formula, a 3 to 10 membered ring including the sulfur atom is formed. It is preferable that a 5- to 7-membered ring is formed.
When any two of R ¹ ″ to R ³ ″ in formula (b-1) are bonded to each other to form a ring together with the sulfur atom in the formula, the remaining one may be an aryl group preferable. Examples of the aryl group include the same aryl groups as those described above for R ¹ ″ to R ³ ″.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group is a cyclic group as indicated by R ¹ ″ and preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 carbon atoms. Most preferably, it is -10.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Particularly, all the hydrogen atoms are substituted with fluorine atoms. A fluorinated alkyl group (perfluoroalkyl group) is preferable because the strength of the acid is increased.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In formula (b-2), R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group. At least one of R ⁵ ″ to R ⁶ ″ represents an aryl group. It is preferable that all of R ⁵ ″ to R ⁶ ″ are aryl groups.
As the aryl group for R ⁵ ″ to R ⁶ ″, the same as the aryl groups for R ¹ ″ to R ³ ″ can be used.
Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″.
Among these, it is most preferable that R ⁵ ″ to R ⁶ ″ are all phenyl groups.
"The, ^{R 4} in the formula (b-1)" ^{R 4} in the In the formula (b-2) include the same as.

Specific examples of the onium salt acid generators represented by the formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-methylphenyl) sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptaful Lopropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate , Trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenyl (1- (4-methoxy) naphthyl) sulfonium, its heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, di (1-naphthyl) phenyl sulphonium trifluoromethane sulphonate, its heptafluoropropane sulphonate or its nonafluorobutane sulphonate; 1-phenyltetrahydrothiophenium trifluoromethane sulphonate, its heptafluoropropane sulphonate Or nonafluorobutanesulfonate thereof; 1- (4-methylphenyl) ) Tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropane sulfonate 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonaflu 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; 1-phenyltetrahydrothiopyranium trifluoromethanesulfonate , Its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (4-hydroxyphenyl) tetrahydrothiopyranium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (3,5-dimethyl -4-Hydroxyphenyl) tetrahydrothiopyranium trifluoromethanesulfonate, its heptafluoropropanes Honeto or nonafluorobutanesulfonate; 1- (4-methylphenyl) trifluoromethanesulfonate tetrahydrothiophenium Pila chloride, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, and the like.
In addition, onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

  In addition, in the general formula (b-1) or (b-2), an onium salt-based acid generator in which the anion moiety is replaced with an anion moiety represented by the following general formula (b-3) or (b-4). Can also be used (the cation moiety is the same as (b-1) or (b-2)).

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”、Ｚ”は、それぞれ独立に、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０のアルキル基を表す。］

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Most preferably, it has 3 carbon atoms.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably Has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible because the solubility in the resist solvent is good within the above carbon number range.
In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, as the number of hydrogen atoms substituted with fluorine atoms increases, the strength of the acid increases, and high-energy light or electron beam of 200 nm or less This is preferable because the transparency to the surface is improved.
The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. A perfluoroalkylene group or a perfluoroalkyl group.

  Moreover, the sulfonium salt which has a cation part represented by the following general formula (b-5) or (b-6) can also be used as an onium salt type | system | group acid generator.

［式中、Ｒ^４１〜Ｒ^４６はそれぞれ独立してアルキル基、アセチル基、アルコキシ基、カルボキシ基、水酸基またはヒドロキシアルキル基であり；ｎ_１〜ｎ_５はそれぞれ独立して０〜３の整数であり、ｎ_６は０〜２の整数である。］

[Wherein R ^{41 to} R ⁴⁶ are each independently an alkyl group, acetyl group, alkoxy group, carboxy group, hydroxyl group or hydroxyalkyl group; n _{1 to} n ₅ are each independently an integer of 0 to 3; There, _{n 6} is an integer of 0-2. ]

In R ^{41 to} R ⁴⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, n A butyl group or a tert-butyl group is particularly preferable.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
The hydroxyalkyl group is preferably a group in which one or more hydrogen atoms in the alkyl group are substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
When the codes n _{1 to} n ₆ attached to R ^{41 to} R ⁴⁶ are integers of 2 or more, the plurality of R ^{41 to} R ⁴⁶ may be the same or different.
n ₁ is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.
n ₂ and n ₃ are preferably each independently 0 or 1, more preferably 0.
n ₄ is preferably 0 to 2, more preferably 0 or 1.
n ₅ is preferably 0 or 1, more preferably 0.
n ₆ is preferably 0 or 1, more preferably 1.

The anion part of the sulfonium salt having a cation part represented by the formula (b-5) or (b-6) is not particularly limited, and is the same as the anion part of the onium salt acid generators proposed so far. It may be a thing. Examples of the anion moiety include fluorinated alkyl sulfonate ions such as the anion moiety (R ⁴ ″ SO ₃ ⁻ ) of the onium salt acid generator represented by the general formula (b-1) or (b-2). An anion moiety represented by the general formula (b-3) or (b-4), etc. Among them, a fluorinated alkyl sulfonate ion is preferable, and a fluorinated alkyl sulfonic acid having 1 to 4 carbon atoms. Ion is more preferable, and linear perfluoroalkylsulfonic acid ions having 1 to 4 carbon atoms are particularly preferable, and specific examples thereof include trifluoromethylsulfonic acid ions, heptafluoro-n-propylsulfonic acid ions, and nonafluoro-n. -Butyl sulfonate ion etc. are mentioned.

  In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation with radiation. is there. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ^31, a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned.
Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as “halogenated alkyl group”) is particularly preferable.
The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.

As the organic group for R ^32, a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は２または３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3.]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and carbon atoms. Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred.

As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³⁵ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred is the strength of the acid generated. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups as those having no substituent of R ³⁵ .
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), pamphlet of International Publication No. 04/074242, An oxime sulfonate-based acid generator disclosed in Examples 1 to 40) on pages 65 to 85 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

(B) As a component, these acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, as the component (B), it is preferable to use an onium salt acid generator having an anion of a fluorinated alkyl sulfonate ion which may have a substituent.
0.5-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component in the resist composition for immersion exposure of this invention, 1-10 mass parts is more preferable. By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(C) component>
In the present invention, the component (C) is a fluorine-containing compound represented by the following general formula (c-1) that is decomposable with respect to an alkaline developer.

［式中、Ｒ^１は有機基であって、重合性基を含んでいてもよい。ただし、当該重合性基は、炭素原子間の多重結合を有するものであって、その炭素原子のいずれもが、式（ｃ−１）における−Ｃ（＝Ｏ）−の炭素原子に直接結合しない基である。Ｒ^２はフッ素原子を有する有機基である。］

[Wherein R ¹ is an organic group and may contain a polymerizable group. However, the polymerizable group has a multiple bond between carbon atoms, and none of the carbon atoms is directly bonded to the carbon atom of —C (═O) — in formula (c-1). It is a group. R ² is an organic group having a fluorine atom. ]

In the resist composition for immersion exposure according to the present invention, by containing the component (C), in the formation of the resist pattern, the resist is hydrophobic during immersion exposure and hydrophilic during alkali development. A film can be formed.
In the present specification and claims, the phrase “degradable with respect to an alkali developer” means that it is decomposed by the action of an alkali developer (preferably 2.38% by mass of tetramethylammonium at 23 ° C. (Decomposes by the action of an aqueous hydroxide (TMAH) solution), which means that the solubility in an alkaline developer is increased. The component (C) is hardly soluble in an alkali developer before being decomposed, and when decomposed by the action of the alkali developer, a carboxy group which is a hydrophilic group is generated, and the solubility in an alkali developer is increased. A compound.

In the general formula (c-1), R ¹ is an organic group and may contain a polymerizable group.
The “polymerizable group” is a group that allows a compound having the polymerizable group to be polymerized by radical polymerization or the like.
However, the polymerizable group has a multiple bond between carbon atoms, and none of the carbon atoms is directly bonded to the carbon atom of —C (═O) — in formula (c-1). It is a group. That is, when R ¹ is an organic group containing a polymerizable group, R ¹ is between the carbon atom forming the multiple bond and the carbon atom of —C (═O) — in formula (c-1) And an organic group containing a group other than the polymerizable group.

The component (C) may be a high molecular weight high molecular compound (polymer, copolymer) composed of repeating structural units, or a low molecular weight low molecular compound (non-polymer).
Hereinafter, when the component (C) is a low molecular compound, the fluorine-containing compound (C) may be referred to as a fluorine-containing compound (C1). Moreover, when (C) component is a high molecular compound, this fluorine-containing compound (C) may be called fluorine-containing compound (C2).

[Fluorine-containing compound (C1)]
In the fluorine-containing compound (C1), R ¹ in the general formula (c-1) is preferably an organic group containing a polymerizable group. That is, R ¹ is preferably an organic group composed of a polymerizable group and a group other than the polymerizable group.

In R ¹ , as the organic group containing a polymerizable group, generally, an organic group containing a polymerizable group used in a monomer can be used, and has, for example, an ethylenically unsaturated double bond. Preferred is a group.
Examples of the group having an ethylenically unsaturated double bond include a group represented by CH _{2 ═CR} —A _aryl — (wherein A _aryl represents an aromatic cyclic group which may have a substituent). _{.), CH 2 = CR-} C (= O) groups represented by -O- and the like.
R is the same as R in the description of the component (A) and is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
Specific examples of the lower alkyl group for R include lower groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. A chain or branched alkyl group is exemplified.
Specific examples of the halogenated lower alkyl group for R include groups in which some or all of the hydrogen atoms of the lower alkyl group have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
R is more preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group, and even more preferably a hydrogen atom or a methyl group.
A _aryl represents an aromatic cyclic group which may have a substituent. Specific examples of A _aryl include a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring which may have a substituent.
The ring skeleton of the aromatic cyclic group in A _aryl preferably has 6 to 15 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Among these, a benzene ring or a naphthalene ring is particularly preferable.
In A _aryl , examples of the substituent that the aromatic cyclic group may have include a halogen atom, an alkyl group, an alkoxy group, a halogenated lower alkyl group, and an oxygen atom (═O). Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. The substituent that the aromatic cyclic group of A _aryl may have is preferably a fluorine atom.
The aromatic cyclic group of A _aryl may have no substituent, may have a substituent, and preferably has no substituent.
In A _aryl , when the aromatic cyclic group has a substituent, the number of substituents may be one, two or more, and one or two. Is preferable, and one is more preferable.

In R ¹ , an organic group containing a polymerizable group is also preferably an organic group composed of a group having an ethylenically unsaturated double bond and a group other than the polymerizable group.
Examples of the group having such an ethylenically unsaturated double bond, the _{above-described, CH 2 = CR-C (} = O) -O- , a group represented _{by, CH 2 = CR-A aryl} - , a group represented by ( However, A _aryl represents an aromatic cyclic group which may have a substituent.
R is preferably each independently a hydrogen atom or a methyl group. A _aryl is the same as above.
Examples of the group other than the polymerizable group include a divalent linking group, which is preferably a divalent organic group having no acid-dissociable portion. Good hydrocarbon groups, groups containing heteroatoms, etc. are preferred.
The “acid-dissociable part” means a part in the organic group that is dissociated by the action of an acid generated by exposure.

(Hydrocarbon group which may have a substituent)
In a group other than the polymerizable group, the hydrocarbon group “has a substituent” means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms. Means.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Such an aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

  More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and 2 Most preferred.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group, an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [— (CH ₂ ) ₃ -], tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - CH (CH 2 Alkylethylene groups such as CH ₃ ) CH ₂ —; alkyltrimethylene groups such as —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —; —CH (CH ₃ ) CH _{2 CH 2 CH 2 -, - CH} 2 CH (CH 3) CH 2 CH 2 - , etc. And alkyl alkylene groups such as Le Kill tetramethylene group. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The chain-like (straight chain or branched chain) aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (═O), and the like.

Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and the chain aliphatic aliphatic hydrocarbon group described above. Examples include a group bonded to the terminal of an aromatic hydrocarbon group or interposed in the middle of a chain aliphatic hydrocarbon group.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

Examples of the aromatic hydrocarbon group include aromatic monovalent aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A divalent aromatic hydrocarbon group obtained by removing one hydrogen atom from the hydrocarbon nucleus;
An aromatic hydrocarbon group in which a part of carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom;
Benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl group such as 2-naphthylethyl group, etc. Aromatic hydrocarbon groups and the like removed.
Among them, the divalent aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group in which one hydrogen atom is further removed from a phenyl group, and an aromatic hydrocarbon group in which one hydrogen atom is further removed from a naphthyl group are particularly preferable. preferable.
The number of carbon atoms in the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

Among the above, the hydrocarbon group which may have a substituent is preferably a linear, branched or cyclic aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon group, more preferably a methylene group. , An ethylene group, —CH (CH ₃ ) —, a group obtained by further removing one hydrogen atom from a tetracyclododecanyl group, and an aromatic hydrocarbon group obtained by further removing one hydrogen atom from a phenyl group are particularly preferred.

(Groups containing heteroatoms)
A heteroatom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
Examples of the group containing a hetero atom include -O-, -C (= O)-, -C (= O) -O-, carbonate bond (-O-C (= O) -O-), -NH. ^-, - NR ^{04 (R} 04 is an alkyl group) -, - NH-C ( = O) -, = N-, or a combination of the "these groups" with a divalent hydrocarbon group.
Examples of the divalent hydrocarbon group include the same hydrocarbon groups that may have a substituent as described above, and a linear or branched aliphatic hydrocarbon group is preferable.
Among them, the group containing a hetero atom is more preferably a combination of the “these groups” and a divalent hydrocarbon group. Specifically, the “these groups” and the aliphatic hydrocarbon group The combination of the above aliphatic hydrocarbon group, the above “these groups”, and the above aliphatic hydrocarbon group is particularly preferable.

In the general formula (c-1), R ² is an organic group having a fluorine atom.
The “organic group having a fluorine atom” refers to a group in which part or all of the hydrogen atoms in the organic group are substituted with fluorine atoms.
Preferred examples of R ² include a fluorinated hydrocarbon group that may or may not have a substituent. Of these, a fluorinated saturated hydrocarbon group or a fluorinated unsaturated hydrocarbon group is preferable, and a fluorinated saturated hydrocarbon group is particularly preferable.
R ² may be linear, branched or cyclic, and is preferably linear or branched.
In R ² , the number of carbon atoms is preferably 1-20, more preferably 1-15, particularly preferably 1-10, and most preferably 1-5.
Further, in the organic group having a fluorine atom of R ² , 25% or more of hydrogen atoms in the organic group are preferably fluorinated, more preferably 50% or more are fluorinated, and 60% or more. It is particularly preferable that is fluorinated since the hydrophobicity of the resist film during immersion exposure is increased.

  Among the above, suitable examples of the fluorine-containing compound (C1) include, for example, compounds represented by the following general formula (c-1-1) or (c-1-2) (hereinafter, these are collectively shown). "Compound (C1-1)").

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは酸解離性部位を有さない二価の有機基であり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[In the formula, each R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a divalent organic group having no acid-dissociable site, and A _aryl is a substituent. An aromatic cyclic group which may have, X ₀₁ is a single bond or a divalent linking group, and R ² is an organic group having a fluorine atom independently. ]

In the general formula (c-1-1) or (c-1-2), R and R ² are the same as described above.
R is more preferably a hydrogen atom or a methyl group.
R ² is preferably a fluorinated hydrocarbon group, more preferably a fluorinated hydrocarbon group having 1 to 5 carbon atoms, —CH ₂ —CF ₃ , —CH ₂ —CF ₂ —CF ₃ , —CH (CF ₃ ) ₂ , —CH ₂ —CF ₂ —CF ₂ —CF ₃ , —CH ₂ —CH ₂ —CF ₂ —CF ₂ —CF ₂ —CF ₃ are most preferred.

In the general formula (c-1-1), X is a divalent organic group having no acid dissociable portion.
Preferred examples of X include the above-described hydrocarbon groups that may have a substituent and groups containing a hetero atom.
In the general formula (c-1-2), A _aryl is the same as described above.
In general formula (c-1-2), X ₀₁ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, —O—, —C (═O) —, —C (═O) —O—, and a carbonate bond (—O—C (═O). -O-), -NH-C (= O)-, or a combination thereof may be mentioned, and a combination of -O- and an alkylene group having 1 to 12 carbon atoms is most preferable.
Examples of the alkylene group having 1 to 12 carbon atoms include linear, branched or cyclic alkylene groups, linear or branched alkylene groups having 1 to 5 carbon atoms, and 4 to 12 carbon atoms. A cyclic alkylene group is preferred.

  Especially, as a suitable thing of a compound (C1-1), the compound represented by the following general formula (c-1-10) or (c-1-11) is mentioned, for example.

［式中、ＲおよびＲ^２はそれぞれ前記と同じであり；ＡおよびＢはそれぞれ独立して置換基を有していてもよい２価の炭化水素基であり、Ｑ^１は酸素原子を含む２価の連結基であり、ｒは０又は１の整数であり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０２は単結合、−（Ｒ^７）_ａ０−Ｏ−［Ｃ（＝Ｏ）］_ｂ０−Ｒ^８−、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^９−である。］

[Wherein, R and R ² are the same as defined above; A and B are each independently a divalent hydrocarbon group which may have a substituent, and Q ¹ includes an oxygen atom 2 Is a valent linking group, r is an integer of 0 or 1, A _aryl is an aromatic cyclic group which may have a substituent, X ₀₂ is a single bond, — (R ⁷ ) _a0 — O— [C (═O)] _b0 —R ⁸ —, or —C (═O) —O—R ⁹ —. ]

In the general formula (c-1-10), R and R ² are the same as defined above.
In the general formula (c-1-10), A is a divalent hydrocarbon group which may have a substituent, and is a linear alkylene group, a branched alkylene group, or a cyclic alkylene. Group, an aromatic hydrocarbon group in the description of R ¹ is preferable, an ethylene group, —CH (CH ₃ ) —, a group obtained by further removing one hydrogen atom from a tetracyclododecanyl group, and a hydrogen atom from a phenyl group Further, an aromatic hydrocarbon group excluding one is particularly preferable.
In the general formula (c-1-10), B is a divalent hydrocarbon group which may have a substituent, and is preferably a linear alkylene group or a branched alkylene group. And the ethylene group is particularly preferred.
In the general formula (c-1-10), Q ¹ is a divalent linking group containing an oxygen atom, and —O—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, carbonate bond (—O—C (═O) —O—) and —NH—C (═O) — are preferred, —O—, —C (═O) —O. -And -OC (= O)-are particularly preferred.
In the general formula (c-1-10), r is an integer of 0 or 1.

In general formula (c-1-11), R, R ² and A _aryl are the same as defined above.
X ₀₂ is a single bond, — (R ⁷ ) _a0 —O— [C (═O)] _b0 —R ⁸ —, or —C (═O) —O—R ⁹ —.
R ⁷ , R ⁸ , and R ⁹ are each independently a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 1 to 5 carbon atoms. A cyclic alkylene group having 4 to 10 carbon atoms is preferred.
a0 is 0 or an integer of 1 to 5. b0 is an integer of 0 or 1.

  As the compound (C1-1), compounds represented by the following general formulas (c-1-12) to (c-1-20) are particularly preferable.

In the general formulas (c-1-12) to (c-1-20), R and R ² are the same as defined above; R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a lower alkyl group. A1, a2, a5, a7, a9 and a11 to a13 each independently represent an integer of 1 to 5; a4, a6, a8 and a10 each independently represents an integer of 0 or 1 to 5; ; b1-b5 are each independently an integer of 0 or 1; ^{R 5} is a substituent, e represents an integer of 0 to 2; _{a 1} is a cyclic alkylene group having 4 to 20 carbon atoms .

In the general formula (c-1-12), examples of the lower alkyl group for R ⁵¹ and R ⁵² include the same lower alkyl groups as those described above for R. A methyl group or an ethyl group is preferable, and a methyl group is the most preferable. preferable. In the present invention, it is preferable that at least one of R ⁵¹ and R ⁵² is a hydrogen atom.
In the general formula (c-1-12), a1 is preferably 1 to 3, and more preferably 1 or 2.
In the general formula (c-1-13), a2 and a3 are each independently preferably 1 to 3, and more preferably 1 or 2. b1 is 0 or 1.
In the general formula (c-1-14), a4 is preferably 0 or 1 to 3, more preferably 0 or 1 to 2, and most preferably 0 or 1. a5 is preferably 1 to 3, and more preferably 1 or 2. Examples of the substituent for R ⁵ include a halogen atom, a lower alkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogenated lower alkyl group, and an oxygen atom (═O). Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. e is preferably 0 or 1, and particularly preferably 0 from an industrial viewpoint. b2 is preferably 0.
In general formula (c-1-15), a6 is preferably 0 or 1 to 3, more preferably 0 or 1 to 2, and most preferably 0 or 1. a7 is preferably 1 to 3, and more preferably 1 or 2. b3 is preferably 0. R ⁵ and e are the same as defined above.
In the general formula (c-1-16), A ₁ is a cyclic alkylene group having 4 to 20 carbon atoms, preferably a cyclic alkylene group having 5 to 15 carbon atoms, and a cyclic alkylene group having 6 to 12 carbon atoms. Groups are more preferred. Specific examples include those exemplified for the “cyclic aliphatic hydrocarbon group” in the hydrocarbon group which may have a substituent described above.
In the general formula (c-1-17), a8 is preferably 0 or 1 to 3, more preferably 0 or 1 to 2, and most preferably 0 or 1. a9 is preferably 1 to 3, and more preferably 1 or 2. b4 is preferably 0. R ⁵ and e are the same as defined above.
In general formula (c-1-18), a10 is preferably 0 or 1 to 3, more preferably 0 or 1 to 2, and most preferably 0 or 1. a11 is preferably 1 to 3, and more preferably 1 or 2. b5 is preferably 0. R ⁵ and e are the same as defined above.
In the general formula (c-1-19), a12 is preferably 1 to 3, and more preferably 1 or 2. R ⁵ and e are the same as defined above.
In the general formula (c-1-20), a13 is preferably 1 to 3, and more preferably 1 or 2. R ⁵ and e are the same as defined above.

  Specific examples of the compounds represented by the general formulas (c-1-12) to (c-1-20) are shown below.

The fluorine-containing compound (C1) described above can be suitably used as it is as an additive for a resist composition for immersion exposure.
In addition, when the fluorine-containing compound (C1) is a compound containing a polymerizable group such as the compound (C1-1), the fluorine-containing compound (C1) is polymerized alone or by other polymerization. A high molecular compound can be obtained by copolymerizing with a functional compound. Similar to the fluorine-containing compound (C1), such a polymer compound can be suitably used as an additive for a resist composition for immersion exposure.
Among the above, the compound (C1-1) is also useful as a monomer for producing the fluorine-containing compound (C2) described later.

[Fluorine-containing compound (C2)]
Preferred examples of the fluorine-containing compound (C2) include polymer compounds having a structural unit derived from a compound in which R ¹ in the fluorine-containing compound (C1) is an organic group containing a polymerizable group.
As a preferable specific example, a high unit having a structural unit represented by the following general formula (c-1-3) or (c-1-4) (hereinafter collectively referred to as “structural unit (c1)”). Examples thereof include molecular compounds.

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは酸解離性部位を有さない二価の有機基であり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[In the formula, each R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a divalent organic group having no acid-dissociable site, and A _aryl is a substituent. An aromatic cyclic group which may have, X ₀₁ is a single bond or a divalent linking group, and R ² is an organic group having a fluorine atom independently. ]

In the general formulas (c-1-3) to (c-1-4), A _aryl , R, R ² , X and X ₀₁ are respectively represented by the general formulas (c-1-1) to (c— It is the same as A _aryl , R, R ² , X and X ₀₁ in 1-2).

  Preferred examples of the structural unit (c1) include those represented by the following general formulas (c-1-31) to (c-1-35) or (c-1-41) to (c-1-44). The structural unit is given.

In the general formulas (c-1-31) to (c-1-35), R, R ² , R ⁵¹ , R ⁵² , a1 to a7, b1 to b3, R ⁵ , e, and A ₁ are all , R, R ² , R ⁵¹ , R ⁵² , a1 to a7, b1 to b3, R ⁵ , e and A ₁ in the description of the fluorine-containing compound (C1).
In the general formulas (c-1-41) to (c-1-44), R, R ² , a8 to a13, b4, b5, R ⁵ and e are all about the fluorine-containing compound (C1). ^R in the description, R 2, a8~a13, the same as b4, b5, ^{R 5} and e.

  Specific examples of the structural units represented by general formulas (c-1-31) to (c-1-35) and general formulas (c-1-41) to (c-1-44) are shown below. .

  The structural unit (c1) is composed of structural units represented by the general formulas (c-1-31) to (c-1-35) and (c-1-41) to (c-1-44). Preferably, at least one selected from the group is represented by the general formulas (c-1-31) to (c-1-35), (c-1-41) and (c-1-42). At least one selected from the group consisting of units is more preferred, and a group consisting of structural units represented by the general formulas (c-1-31), (c-1-35) and (c-1-42) At least one selected from is particularly preferred.

In the fluorine-containing compound (C2), as the structural unit (c1), one type may be used alone, or two or more types may be used in combination.
In the fluorine-containing compound (C2), the proportion of the structural unit (c1) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on the total of all the structural units constituting the fluorine-containing compound (C2). , 40 to 100 mol% is more preferable, 50 to 100 mol% is particularly preferable, and 100 mol% may be used. When the proportion of the structural unit (c1) is equal to or more than the lower limit of the above range, in the resist pattern formation, characteristics that are hydrophobic during immersion exposure and hydrophilic during alkali development are further improved.

The fluorine-containing compound (C2) may have a structural unit other than the structural unit (c1) as long as the effects of the present invention are not impaired.
Such a structural unit is not particularly limited, but a structural unit derived from a compound copolymerizable with a compound that derives the structural unit (c1) [the compound (C1-1) or a precursor thereof or the like] is preferable. As such a structural unit, for example, the structural units (a1) to (a4) listed as the constituents that the resin component (A1) may have, a structural unit derived from hydroxystyrene, or derived from styrene. Examples thereof include a structural unit and a structural unit having a carboxy group.
Examples of the precursor of the compound (C1-1) include a compound (carboxylic acid compound) in which —O—R ² in the compound (C1-1) is substituted with —O—H.
Among these, as a structural unit other than the structural unit (c1) included in the fluorine-containing compound (C2), a structural unit containing an acid-dissociable group (hereinafter referred to as “structural unit (c2)”) or a carboxy group is included. It is preferably a structural unit (hereinafter referred to as “structural unit (c3)”).

-Structural unit (c2):
In the fluorine-containing compound (C2), the structural unit (c2) refers to a structural unit containing an acid dissociable group.
In the present specification and claims, the “acid-dissociable group” is an organic group that can be dissociated by the action of an acid.
The acid dissociable group contained in the structural unit (c2) is not particularly limited as long as it is an organic group that can be dissociated by the action of an acid. For example, acid dissociation properties of a base resin for a chemically amplified resist have hitherto been included. The thing proposed as a dissolution inhibitory group is mentioned. Specific examples include the same acid dissociable, dissolution inhibiting groups as mentioned above for the structural unit (a1). The structure of the main chain of the structural unit (c2) is not particularly limited, and examples thereof include a structural unit derived from styrene and a structural unit derived from (meth) acrylic acid.

  As a fluorine-containing copolymer (C2), it is preferable that a structural unit (c2) is a structural unit represented by the following general formula (c2-1).

［式中、Ｒは水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｑ^１’は単結合又は二価の連結基であり、Ｒ^３は酸解離性基である。］

[Wherein, R represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; Q ¹ ′ represents a single bond or a divalent linking group, and R ³ represents an acid dissociable group. ]

In the formula (c2-1), R represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group. Examples of the lower alkyl group and halogenated lower alkyl group for R ¹ include the same groups as those described above for R.
In formula (c2-1), Q ¹ ′ is a single bond or a divalent linking group. Examples of the divalent linking group for Q ¹ ′ include the same as X ₀₁ in formula (c-1-4) or a divalent aromatic hydrocarbon group. As a bivalent aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group is mentioned, The group remove | excluding two hydrogen atoms from benzene, naphthalene, and anthracene is mentioned.
In the structural unit (c2), as Q ¹ ′, a single bond or —C (═O) —O—R ^c — [R ^c is a straight chain having 1 to 10 carbon atoms which may contain an oxygen atom, or It is a branched alkylene group. The alkylene group may be fluorinated. It is preferable that it is a single bond.

In formula (c2-1), R ³ is an acid dissociable group.
The acid dissociable group for R ³ is not particularly limited as long as it is an organic group that can be dissociated by the action of an acid, and is a cyclic or chain tertiary alkyl ester type acid dissociable group; an alkoxyalkyl group And acetal type acid dissociable groups. Among these, R ³ is preferably a tertiary alkyl ester-type acid dissociable group, and more preferably a structural unit represented by the following general formula (IV-1).

［式中、複数のＲ^３０１はそれぞれ同じであっても異なっていてもよく、少なくとも１つは炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基であり；残りの２つのＲ^３０１は、それぞれ独立して炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、または炭素数４〜２０の１価の脂肪族環式基であるか、あるいは、前記残りの２つのＲ^３０１は相互に結合して、それぞれが結合している炭素原子と共に炭素数４〜２０の２価の脂肪族環式基を形成している。］

Wherein or different even multiple R ³⁰¹ are the same, respectively, at least one is linear or branched alkyl group having 1 to 4 carbon atoms; the remaining two R ³⁰¹ Are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent aliphatic cyclic group having 4 to 20 carbon atoms, or the remaining two R ³⁰¹ are bonded to each other to form a divalent aliphatic cyclic group having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded. ]

Examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms are selected from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclodecane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Excluded groups and the like. More specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like can be given.
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

As the acid dissociable group represented by the general formula (IV-1), a plurality of R ³⁰¹ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms. Examples thereof include a butyl group, a tert-pentyl group, and a tert-hexyl group.

As the acid dissociable group represented by the general formula (IV-1), at least one of the plurality of R ^{301 is} a linear or branched alkyl group having 1 to 4 carbon atoms, and the remaining two R ³⁰¹ Are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent aliphatic cyclic group having 4 to 20 carbon atoms, such as 1- (1-adamantyl) ) -1-methylethyl group, 1- (1-adamantyl) -1-methylpropyl group, 1- (1-adamantyl) -1-methylbutyl group, 1- (1-adamantyl) -1-methylpentyl group; 1 -(1-cyclopentyl) -1-methylethyl group, 1- (1-cyclopentyl) -1-methylpropyl group, 1- (1-cyclopentyl) -1-methylbutyl group, 1- (1-cyclopentyl) -1- Methylpentyl 1- (1-cyclohexyl) -1-methylethyl group, 1- (1-cyclohexyl) -1-methylpropyl group, 1- (1-cyclohexyl) -1-methylbutyl group, 1- (1-cyclohexyl)- 1-methylpentyl group, etc. are mentioned.

As the acid dissociable group represented by the general formula (IV-1), among the plurality of R ³⁰¹ , one R ³⁰¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, Examples of the group in which R ³⁰¹ is bonded to each other to form a divalent aliphatic cyclic group having 4 to 20 carbon atoms together with the carbon atom to which each is bonded include a 2-methyl-2-adamantyl group, 2-alkyl-2-adamantyl group such as 2-ethyl-2-adamantyl group, 2-isopropyl-2-adamantyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl Examples include 1-alkyl-1-cycloalkyl groups such as -1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 1-methyl-1-cyclooctyl group, and 1-ethyl-1-cyclooctyl group. .
Among these, as the acid dissociable group represented by the general formula (IV-1), among the plurality of R ³⁰¹ , one R ³⁰¹ is a linear or branched alkyl group having 1 to 4 carbon atoms. In which two R ³⁰¹ 's are bonded to each other to form a divalent aliphatic cyclic group having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded, particularly 2-methyl A 2-adamantyl group and a 2-isopropyl-2-adamantyl group are preferred.

Moreover, as long as the group represented by general formula (IV-1) can function as an acid dissociable group, each R ³⁰¹ may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom.

In formula (c2-1), examples of preferable structural units in which Q ¹ ′ is a single bond include structural units represented by general formulas (c2-1-1) to (c2-1-14) shown below. Can be mentioned.
In formula (c2-1), examples of preferable structural units in which Q ¹ ′ is —C (═O) —O—R ^c — include, for example, the following general formulas (c2-1-15) to (c2-1-1- 28), and the like. However, R in the following general formula is the same as the above R, and is preferably a hydrogen atom or a methyl group.

  The structural unit (c2) is preferably at least one selected from the group consisting of structural units represented by the general formulas (c2-1-1) to (c2-1-28). -1-1) to (c2-1-14) and at least one selected from the group consisting of structural units represented by (c2-1-25) is more preferred. It is particularly preferable that it is a structural unit represented by (c2-1-3), (c2-1-9), (c2-1-12) or (c2-1-25).

In the fluorine-containing compound (C2), as the structural unit (c2), one type may be used alone, or two or more types may be used in combination.
In the fluorine-containing compound (C2), the proportion of the structural unit (c2) is preferably smaller than the proportion of the structural unit (c1). For example, 1 mol% or more and less than 80 mol% is preferable with respect to the total of all the structural units which comprise a fluorine-containing compound (C2), 5-70 mol% is more preferable, and 10-60 mol% is further more preferable.

  When the fluorine-containing compound (C2) is a copolymer, the proportion of the structural unit (c1) in the fluorine-containing compound (C2) is 10 to 10% of the total of all the structural units constituting the fluorine-containing compound (C2). 90 mol% is preferable, 20-90 mol% is more preferable, 30-80 mol% is further more preferable, and 40-70 mol% is the most preferable.

-Structural unit (c3):
In the fluorine-containing compound (C2), the structural unit (c3) refers to a structural unit having a carboxy group.
Preferred examples of the structural unit (c3) include structural units represented by general formula (c3-1), (c3-2), or (c3-3) shown below.

［式中、Ｒは水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｑ^１’は単結合又は二価の連結基である。ＡおよびＢはそれぞれ独立して置換基を有していてもよい２価の炭化水素基であり、Ｑ^１は酸素原子を含む２価の連結基であり、ｒは０又は１の整数であり；Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０２は単結合、−（Ｒ^７）_ａ０−Ｏ−［Ｃ（＝Ｏ）］_ｂ０−Ｒ^８−、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^９−である。］

[Wherein, R represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; Q ¹ ′ represents a single bond or a divalent linking group. A and B are each independently a divalent hydrocarbon group which may have a substituent, Q ¹ is a divalent linking group containing an oxygen atom, and r is an integer of 0 or 1 A _aryl is an aromatic cyclic group which may have a substituent, X ₀₂ is a single bond, — (R ⁷ ) _a0 —O— [C (═O)] _b0 —R ⁸ —, or —C (═O) —O—R ⁹ —. ]

In the general formula (c3-1), R and Q ¹ ′ are the same as R and Q ¹ ′ in the formula (c2-1), respectively.
In formula (c3-2), R, A, B, Q 1 and r are each, R in the formula (c-1-10), A, B, is the same as ^{Q 1} and r.
In the general formula (c3-3), R, A _aryl and X ₀₂ are all the same as R, A _aryl and X ₀₂ in the formula (c-1-11).

Specific examples of the structural units represented by the general formulas (c3-1) to (c3-3) are shown below.
In general formulas (c3-1) to (c3-3), R is the same as described above, and is preferably a hydrogen atom or a methyl group.

The structural unit (c3) is preferably at least one selected from the group consisting of structural units represented by the general formulas (c3-1), (c3-2) and (c3-3). The structural unit represented by (c3-1) is particularly preferable.
As the structural unit (c3), more specifically, the general formulas (c3-1-1), (c-3-2-1) to (c3-2-6), and (c3-3-1) to At least one selected from the group consisting of structural units represented by (c3-3-3) is more preferred, with structural units represented by the general formula (c3-1-1) being most preferred.

In the fluorine-containing compound (C2), as the structural unit (c3), one type may be used alone, or two or more types may be used in combination.
In the fluorine-containing compound (C2), the proportion of the structural unit (c3) is preferably from 1 to 25 mol%, more preferably from 5 to 20 mol%, based on the total of all the structural units constituting the fluorine-containing compound (C2). 10 to 20 mol% is particularly preferable.

In the present invention, the fluorine-containing compound (C2) is preferably a polymer having the structural unit (c1).
Examples of the polymer include a polymer composed of the structural unit (c1); a copolymer composed of the structural units (c1) and (c2); a copolymer composed of the structural units (c1), (c2) and (c3). Etc.

Although the mass mean molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of a fluorine-containing compound (C2) is not specifically limited, 2000-100000 are preferable, 3000-100000 are more preferable, 4000- 50000 is more preferable, and 5000 to 50000 is most preferable. If it is below the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and if it is above the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
Further, the dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. In addition, Mn shows a number average molecular weight.

  The fluorine-containing compound (C2) described above can be suitably used as an additive for a resist composition for immersion exposure.

As the component (C), one of the above fluorine-containing compounds may be used alone, or two or more thereof may be used in combination.
In the resist composition for immersion exposure according to the present invention, the component (C) is preferably a fluorine-containing compound (C1) or a fluorine-containing compound (C2), more preferably a fluorine-containing compound (C2). It is particularly preferable to use a polymer compound having a structural unit (structural unit (c1)) represented by the general formula (c-1-3) or (c-1-4).
The content of the component (C) in the resist composition for immersion exposure according to the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the component (A). 0.5 to 30 parts by mass is particularly preferable, and 1 to 15 parts by mass is most preferable. The hydrophobicity of the resist film formed using the resist composition for immersion exposure is improved by setting it to the lower limit value or more of the above range, and the hydrophobicity suitable for immersion exposure is obtained. The hydrophilicity of the resist film due to contact with the developer becomes higher. When it is at most the upper limit value, the lithography properties are improved.

[Production method of fluorine-containing compound (C)]
As an example, the fluorine-containing compound (C) of the present invention introduces a group represented by R ² into —O—H of a compound represented by R ¹ —C (═O) —O—H (—O— The hydrogen atom of —H is substituted with R ² ).
Introduction of the group represented by R ² can be carried out using a conventionally known method. For example, a compound represented by the following general formula (I) (hereinafter referred to as “compound (I)”), A method of reacting the compound (II) represented by the following general formula (II) can be used.

［式中、Ｒ^１およびＲ^２はそれぞれ前記と同じである。］

[Wherein, R ¹ and R ² are the same as defined above. ]

The method of reacting compound (I) and compound (II) is not particularly limited, and examples thereof include a method of bringing compound (I) and compound (II) into contact in the reaction solvent in the presence of a base. .
As compound (I) and compound (II), a commercially available product or a synthesized product may be used.
Examples of the compound (I) include low molecular weight compounds derived from acrylate esters such as carboxyalkyl (meth) acrylate and succinic acid mono ((meth) acryloyloxyalkyl); structural units derived from acrylate esters. The high molecular compound etc. which have can be used.
As the compound (II), for example, a fluorinated alkyl alcohol can be used.
Any reaction solvent may be used as long as it can dissolve the starting compounds (I) and (II). Specifically, tetrahydrofuran (THF), acetone, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide ( DMSO), acetonitrile and the like.
Examples of the base include organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP) and pyridine; inorganic bases such as sodium hydride, K ₂ CO ₃ and Cs ₂ CO ₃ .
Examples of the condensing agent include carbodiimide reagents such as ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarboimide (DCC), diisopropylcarbodiimide, carbodiimidazole, tetraethylpyrophosphate, benzotriazole-N-hydroxytrisdimethylaminophosphonium hexa Fluorophosphide salt (Bop reagent) and the like.
Moreover, you may use an acid as needed. As the acid, those usually used in dehydration condensation and the like can be used. Specifically, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p- Organic acids such as toluenesulfonic acid can be mentioned. These may be used alone or in combination of two or more.
About 1-3 equivalent is preferable with respect to compound (I), and, as for the addition amount of compound (II), 1-2 equivalent is more preferable.
The reaction temperature is preferably -20 to 40 ° C, more preferably 0 to 30 ° C.
The reaction time varies depending on the reactivity of compound (I) and compound (II), the reaction temperature, etc., but is usually preferably 30 to 480 minutes, more preferably 60 to 360 minutes.

  When the component (C) is a polymer compound (for example, a fluorine-containing compound (C2)), the polymer compound is a monomer that induces a desired structural unit (for example, the compound (C1-1)). , Azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate and the like can be obtained by polymerization by a known radical polymerization using a radical polymerization initiator.

<Optional component>
In the resist composition for immersion exposure according to the present invention, a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) is further added as an optional component in order to improve the resist pattern shape, the stability over time. It is preferable to contain.
Since a wide variety of components (D) have already been proposed, any known one may be used. Among them, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are used. preferable. Here, the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of the aliphatic amine include an amine (alkyl amine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, etc .; diethanolamine, triethanolamine, diisopropanolamine Triisopropanolamine, di -n- octanol amines, alkyl alcohol amines tri -n- octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is preferable, and tri-n-pentylamine is more preferable.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.
These may be used alone or in combination of two or more.
In the present invention, it is particularly preferable to use an alkylamine as the component (D), and it is most preferable to use tri-n-pentylamine.
(D) component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

In the resist composition for immersion exposure according to the present invention, an organic carboxylic acid, a phosphorus oxoacid, and a phosphorus oxoacid can be used as optional components for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, stability over time, etc. At least one compound (E) selected from the group consisting of derivatives thereof (hereinafter referred to as “component (E)”) can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of phosphorus oxo acids and derivatives thereof include phosphoric acid, phosphonic acid, phosphinic acid and the like, and among these, phosphonic acid is particularly preferable.
Examples of the oxo acid derivative of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. 15 aryl groups and the like.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of the phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
(E) A component may be used individually by 1 type and may use 2 or more types together.
In the present invention, it is preferable to use an organic carboxylic acid as the component (E), and it is particularly preferable to use salicylic acid.
(E) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

  The resist composition for immersion exposure according to the present invention further contains miscible additives as desired, for example, additional resins for improving the performance of the resist film, surfactants for improving coating properties, and dissolution inhibition. An agent, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.

<Organic solvent (S)>
The resist composition for immersion exposure according to the present invention can be produced by dissolving a material in an organic solvent (hereinafter sometimes referred to as “(S) component”).
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one of known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Monohydric alcohols; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl of the polyhydric alcohols or compound having the ester bond Ether alkyl such as ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having a propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) among these]; cyclic ethers such as dioxane, methyl lactate, Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, Aromatic organics such as dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene A solvent etc. can be mentioned.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), EL, and γ-butyrolactone are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of the component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. In general, the solid content concentration of the resist composition is 2 -20% by mass, preferably 5-15% by mass.

  The dissolution of the material in the component (S) can be carried out, for example, by simply mixing and stirring each of the above components by a usual method, and if necessary, a disperser such as a dissolver, a homogenizer, or a three roll mill You may use and disperse and mix. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

≪Resist pattern formation method≫
The method for forming a resist pattern of the present invention includes a step of forming a resist film on a support using the resist composition for immersion exposure according to the first aspect of the present invention, a step of immersing the resist film, and A step of alkali-developing the resist film to form a resist pattern.

A preferred example of the method for forming a resist pattern of the present invention is shown below.
First, after applying the resist composition for immersion exposure of the present invention on a support with a spinner or the like, a resist film is formed by performing pre-baking (post-apply baking (PAB) treatment).

The support is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
Further, the support may be a substrate in which an inorganic and / or organic film is provided on the above-described substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include organic films such as an organic antireflection film (organic BARC) and a lower organic film in a multilayer resist method.
Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and the resist pattern formed on the upper resist film is used as a mask. This is a method of patterning a lower organic film, and it is said that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, the required thickness can be secured by the lower organic film, so that the resist film can be thinned and a fine pattern with a high aspect ratio can be formed.
In the multilayer resist method, basically, a method of forming a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and one or more intermediate layers between the upper resist film and the lower organic film And a method of forming a multilayer structure of three or more layers (metal thin film etc.) (three-layer resist method).

  After the resist film is formed, an organic antireflection film may be further provided on the resist film to form a three-layer laminate including a support, a resist film, and an antireflection film. The antireflection film provided on the resist film is preferably soluble in an alkali developer.

  The steps so far can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the resist composition for immersion exposure to be used.

Next, liquid immersion lithography is selectively performed on the resist film obtained above through a desired mask pattern. At this time, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than that of air, and exposure (immersion exposure) is performed in this state.
The wavelength used for the exposure is not particularly limited, and can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, or an F ₂ laser. The resist composition according to the present invention is effective for a KrF or ArF excimer laser, particularly an ArF excimer laser.

As the immersion medium, a solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film formed using the resist composition for immersion exposure of the present invention is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range.
Examples of the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
Specific examples of the fluorine-based inert liquid include a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as a main component. Examples thereof include liquids, and those having a boiling point of 70 to 180 ° C are preferable, and those having a boiling point of 80 to 160 ° C are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range since the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluorotributylamine ( Boiling point of 174 ° C.).
The resist composition for immersion exposure according to the present invention is not particularly adversely affected by water, and is excellent in lithography properties such as sensitivity and resist pattern shape. Therefore, in the present invention, water is preferably used as the immersion medium. . Water is also preferable from the viewpoints of cost, safety, environmental problems, and versatility.

  Next, after the immersion exposure step is completed, post-exposure heating (post-exposure baking (PEB)) is performed, and subsequently, development processing is performed using an alkaline developer composed of an alkaline aqueous solution. And preferably, water rinsing is performed using pure water. The water rinse is performed, for example, by dropping or spraying water on the surface of the support while rotating the support to wash away the developer on the support and the resist composition for immersion exposure dissolved by the developer. Can be implemented. Then, drying is performed to obtain a resist pattern in which the resist film (the coating film of the resist composition for immersion exposure) is patterned into a shape corresponding to the mask pattern.

≪Fluorine-containing compounds≫
The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following general formula (c-1), and component (C) in the description of the resist composition for immersion exposure according to the first aspect of the present invention. Is the same.

［式中、Ｒ^１は有機基であって、重合性基を含んでいてもよい。ただし、当該重合性基は、炭素原子間の多重結合を有するものであって、その炭素原子のいずれもが、式（ｃ−１）における−Ｃ（＝Ｏ）−の炭素原子に直接結合しない基である。Ｒ^２はフッ素原子を有する有機基である。］

[Wherein R ¹ is an organic group and may contain a polymerizable group. However, the polymerizable group has a multiple bond between carbon atoms, and none of the carbon atoms is directly bonded to the carbon atom of —C (═O) — in formula (c-1). It is a group. R ² is an organic group having a fluorine atom. ]

In the general formula (c-1), R ¹ and R ² are the same as R ¹ and R ² in the description of the component (C), respectively.

Especially, as a fluorine-containing compound represented by the said general formula (c-1), it is preferable that it is a compound represented by the following general formula (c-1-1) or (c-1-2).
Moreover, as a fluorine-containing compound represented by the said general formula (c-1), it is a high molecular compound which has a structural unit represented by the following general formula (c-1-3) or (c-1-4). Preferably there is. Preferred examples of the polymer compound include the fluorine-containing compound (C2) described above.

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは酸解離性部位を有さない二価の有機基であり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[In the formula, each R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a divalent organic group having no acid-dissociable site, and A _aryl is a substituent. An aromatic cyclic group which may have, X ₀₁ is a single bond or a divalent linking group, and R ² is an organic group having a fluorine atom independently. ]

［式中、Ｒはそれぞれ独立して水素原子、低級アルキル基、又はハロゲン化低級アルキル基であり；Ｘは酸解離性部位を有さない二価の有機基であり、Ａ_ａｒｙｌは置換基を有していてもよい芳香族環式基であり、Ｘ_０１は単結合又は二価の連結基であり、Ｒ^２はそれぞれ独立してフッ素原子を有する有機基である。］

[In the formula, each R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a divalent organic group having no acid-dissociable site, and A _aryl is a substituent. An aromatic cyclic group which may have, X ₀₁ is a single bond or a divalent linking group, and R ² is an organic group having a fluorine atom independently. ]

In the general formulas (c-1-1) to (c-1-4), R, R ² , A _aryl , X, and X ₀₁ are R, R ² , and R in the description of the component (C), respectively. Same as A _aryl , X and X ₀₁ .

The above-described fluorine-containing compound of the third aspect of the present invention is a novel compound that has not been conventionally known.
Such a fluorine-containing compound is useful as an additive for a resist composition, and a resist composition to which the fluorine-containing compound is added is suitable for immersion exposure.
The resist composition to which the fluorine-containing compound is added is not particularly limited as long as it is used for immersion exposure, and is a base material component whose solubility in an alkaline developer is changed by the action of an acid, and A chemically amplified resist composition containing an acid generator component that generates an acid upon exposure is suitable.
The fluorine-containing compound is particularly useful as an additive used in the resist composition for immersion exposure according to the first aspect of the present invention.

The resist composition for immersion exposure according to the first aspect of the present invention has good lithography characteristics and characteristics suitable for immersion exposure, which are characteristics required for a resist composition used for immersion exposure ( Therefore, it can be suitably used for immersion exposure.
That is, the resist film formed using the resist composition for immersion exposure according to the present invention contains the component (C) (that is, the fluorine-containing compound according to the third aspect of the present invention).
Since the component (C) has a fluorine atom and has high hydrophobicity, it has both properties of increasing hydrophilicity under basic conditions by having —C (═O) —O—R ^2. Have. This is because the ester bond [—C (═O) —O—] is decomposed (hydrolyzed) by the action of a base (alkaline developer) to produce a hydrophilic group [—C (═O) —OH]. is there.
Therefore, the resist film formed using the resist composition for immersion exposure according to the present invention in which the component (C) is blended with the component (A) and the component (B) is contacted with an alkali developer (for example, While having a high hydrophobicity during immersion exposure, the hydrophilicity is increased by contact with an alkaline developer.
Thus, since the hydrophobicity at the time of immersion exposure is high, the resist film formed using the resist composition for immersion exposure according to the present invention has a scanning type as described in Non-Patent Document 1. It is very excellent in water followability required when immersion exposure is performed using an immersion exposure machine.
Moreover, since hydrophilicity increases at the time of alkali development, according to the resist composition for immersion exposure of the present invention, defects in immersion exposure can be effectively reduced. That is, in the immersion exposure, when immersion exposure is performed on the resist film, the solubility of the exposed portion in the alkaline developer changes. For example, in the case of the positive type, the solubility of the exposed portion in the alkaline developer increases, and in the case of the negative type, the solubility of the exposed portion in the alkaline developer decreases. Then, by performing alkali development, in the case of the positive type, the exposed portion is removed, and in the case of the negative type, the unexposed portion is removed to form a resist pattern.
At this time, the surface of the resist film where the radiation is not irradiated by immersion exposure (for example, the unexposed portion in the case of a positive type) is subjected to a defect (watermark defect) after the alkali development and the influence of an immersion medium such as water. However, the resist film formed using the resist composition for immersion exposure according to the present invention has increased hydrophilicity during alkali development, so that the occurrence of defects can be reduced.

Moreover, by using the resist composition for immersion exposure of the present invention, substance elution from the resist film during immersion exposure can be suppressed.
That is, as described above, the immersion exposure is performed by exposing the portion between the lens and the resist film on the wafer, which is conventionally filled with an inert gas such as air or nitrogen, at a time higher than the refractive index of air. This is a method including a step of performing exposure (immersion exposure) in a state filled with a solvent (immersion medium) having a large refractive index. In immersion exposure, when the resist film and the immersion solvent come into contact with each other, elution (substance elution) of substances ((B) component, (D) component, etc.) in the resist film into the immersion solvent occurs. Substance elution causes phenomena such as alteration of the resist layer and change in the refractive index of the immersion solvent, thereby deteriorating the lithography properties.
The amount of this substance elution is affected by the characteristics of the resist film surface (for example, hydrophilicity / hydrophobicity). Therefore, for example, it is presumed that elution of the substance is reduced by increasing the hydrophobicity of the resist film surface.
Since the resist film formed using the resist composition for immersion exposure according to the present invention contains a component (C) having a fluorine atom, exposure and alkali development are performed as compared with the case where the component (C) is not included. High hydrophobicity before performing. Therefore, according to the resist composition for immersion exposure of the present invention, substance elution during immersion exposure can be suppressed.
Since elution of the substance can be suppressed, the use of the resist composition for immersion exposure according to the present invention can suppress the alteration of the resist film and the change in the refractive index of the immersion solvent in the immersion exposure. A resist pattern having a good shape and the like can be formed by suppressing fluctuations in the refractive index of the immersion solvent. Further, the contamination of the lens of the exposure apparatus can be reduced, and therefore, it is not necessary to take protective measures against these, and it is possible to contribute to the simplification of the process and the exposure apparatus.
In addition, since the resist film formed from the resist composition for immersion exposure according to the present invention hardly swells with water, a fine resist pattern can be formed with high accuracy.
Furthermore, the resist composition for immersion exposure of the present invention has good lithography properties such as sensitivity, resolution and etching resistance, and forms a resist pattern without any practical problems when used as a resist in immersion exposure. it can. For example, by using the resist composition for immersion exposure according to the present invention, a fine resist pattern having a dimension of 100 nm or less can be formed.

The hydrophobicity of the resist film includes the contact angle with water, for example, the static contact angle (the angle between the surface of the water droplet on the resist film in the horizontal state and the resist film surface), and the dynamic contact angle (the tilted resist film). The contact angle when the water droplet starts to fall (fall angle), the contact angle (advance angle) at the front end point of the water drop direction, the contact angle (retreat angle) at the rear end point of the drop direction), etc. It can be evaluated by measuring. For example, the higher the hydrophobicity of the resist film, the larger the static contact angle, advancing angle, and receding angle, while the falling angle becomes smaller.
Here, as shown in FIG. 1, when the plane 2 on which the droplet 1 is placed is gradually inclined, the advance angle starts to move (drop) on the plane 2 when the droplet 1 is gradually inclined. Is the angle θ ₁ formed by the surface of the droplet at the lower end 1 a of the droplet 1 and the plane 2. At this time (when the droplet 1 starts moving (falling) on the plane 2), the angle θ2 formed by the droplet surface at the upper end 1b of the droplet 1 and the plane ₂ is the receding angle, The inclination angle θ _{3 of the} plane 2 is the falling angle.
In this specification, the advancing angle, the receding angle, and the falling angle are measured as follows.
First, a resist composition solution is spin-coated on a silicon substrate, and then heated at 110 ° C. for 60 seconds to form a resist film.
Next, with respect to the resist film, DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.), AUTO SLIDING ANGLE: SA-30DM (product name, manufactured by Kyowa Interface Science Co., Ltd.), AUTO DISPENSER: AD-31 ( It can be measured using a commercially available measuring device such as a product name (manufactured by Kyowa Interface Science Co., Ltd.).

In the resist composition for immersion exposure according to the present invention, it is preferable that the measured value of the receding angle before exposure and alkali development in a resist film obtained using the resist composition is 50 degrees or more, and 50 to 150 Is more preferred, 50 to 130 degrees is particularly preferred, and 53 to 100 degrees is most preferred. When the receding angle is greater than or equal to the lower limit, the substance elution suppression effect during immersion exposure is improved. The reason for this is not clear, but one of the main factors may be related to the hydrophobicity of the resist film. That is, since the immersion medium is water-based, such as water, it has high hydrophobicity. Therefore, after immersion exposure is performed, the immersion medium is quickly removed from the resist film surface after the immersion medium is removed. It is presumed that the fact that it can be removed has an effect. Further, when the receding angle is not more than the upper limit value, the lithography characteristics and the like are good.
For the same reason, the resist composition for immersion exposure according to the present invention has a measured value of a static contact angle of 60 degrees or more before performing exposure and alkali development in a resist film obtained using the resist composition. It is preferably 63 to 99 degrees, and particularly preferably 65 to 98 degrees.
In the resist composition for immersion exposure according to the present invention, it is preferable that the measured value of the falling angle before exposure and alkali development in a resist film obtained using the resist composition is 36 degrees or less. It is more preferably ˜36 degrees, particularly preferably 7 to 30 degrees, and most preferably 14 to 27 degrees. When the sliding angle is less than or equal to the upper limit value, the substance elution suppression effect during immersion exposure is improved. Further, when the sliding angle is at least the lower limit value, the lithography properties and the like are good.
The above-mentioned various angles (dynamic contact angle (advance angle, receding angle, sliding angle, etc.), static contact angle) are determined depending on the composition of the resist composition for immersion exposure, for example, the type and composition of component (C). The amount can be adjusted by adjusting the type of component (A). For example, as the content of the component (C) increases, the hydrophobicity of the resulting resist composition increases, the advancing angle, the receding angle, and the static contact angle increase, and the sliding angle decreases.

As described above, the resist composition for immersion exposure according to the present invention is sufficiently provided with various properties required for resist materials in immersion exposure, and can be suitably used for immersion exposure.
The component (C) is useful as an additive for use in a resist composition for immersion exposure.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Synthesis of fluorinated compound (C)>
As shown in the following Examples 1-42, the fluorine-containing compound was synthesize | combined by each synthesis example.

Example 1
Synthesis example of compound (1):
In a 500 ml three-necked flask, under a nitrogen atmosphere, 11.5 g (76.4 mmol) of fluoroalcohol (C ₂ F ₅ CH ₂ OH), 16 g (83.3 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride and dimethylamino 200 ml of tetrahydrofuran (THF) solution of 0.4 g (3.5 mmol) of pyridine (DMAP) was added, and 16.0 g (83.3 mmol) of 2-carboxyethyl acrylate was added thereto, followed by stirring for 4 hours.
After confirming the disappearance of the raw material by thin layer chromatography (TLC), water was added to stop the reaction. The reaction solvent was concentrated under reduced pressure, and the organic layer obtained by extraction three times with ethyl acetate was washed three times with water. The product obtained by distilling off the solvent under reduced pressure was dried to obtain 12.5 g of compound (1) which is an ester compound.

¹ H-NMR of the obtained compound (1) was measured. The results are shown below.
¹ H-NMR data (1) (solvent: CDCl ₃ , 400 MHz, internal standard: tetramethylsilane)
δ 6.40 d 1H Ha, 6.12 dd 1H Hb, 5.74 d 1H Hc, 4.59 t 2H Hd, 4.42 t 2H He, 2.77 t 2H Hf
From the results described above, it was confirmed that the compound (1) had a structure shown below.

(Example 2)
Synthesis example of compound (2):
In a 500 ml three-necked flask, under a nitrogen atmosphere, 11.5 g (76.4 mmol) of fluoroalcohol (C ₂ F ₅ CH ₂ OH), 16 g (83.3 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride and dimethylamino 200 ml of THF solution of 0.4 g (3.5 mmol) of pyridine (DMAP) was added, and 15.0 g (69.4 mmol) of succinic acid mono (2-acryloyloxyethyl) was added thereto and stirred for 4 hours.
After confirming the disappearance of the raw material by thin layer chromatography (TLC), water was added to stop the reaction. The reaction solvent was concentrated under reduced pressure, and the organic layer obtained by extraction three times with ethyl acetate was washed three times with water. The product obtained by distilling off the solvent under reduced pressure was dried to obtain 21.24 g of Compound (2).

About the obtained compound (2), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (CDCl ₃ ) 6.48-6.43 (d, 1H, Ha), 6.20-6.12 (dd, 1H, Hb), 5.90-5.87 (d, 1H, Ha), 4.57 (m, 2H, Hg), 4.38-4.33 (m, 4H, He, Hf), 2.76-2.69 (m, 4H, Hc, Hd)
From the results described above, it was confirmed that the compound (2) had a structure shown below.

(Example 3)
Synthesis example of polymer compound (3):
In a 100 ml three-necked flask connected with a thermometer and a reflux tube, 4.00 g (14.49 mmol) of the compound (1) obtained in Example 1 was placed, and then 22.67 g of tetrahydrofuran was added and dissolved. . To this solution, 0.58 mmol of dimethyl azobisisobutyrate (trade name: V-601) was added as a polymerization initiator and dissolved.
The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization liquid was concentrated under reduced pressure, then dropped into a large amount of methanol / water mixed solvent, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the target product was obtained. A polymer compound (3) 1.5 g represented by the following formula (3) was obtained.
With respect to this polymer compound (3), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 4500, and the molecular weight dispersity (Mw / Mn) was 1.31.

Example 4
Synthesis example of polymer compound (4):
In a 300 ml three-necked flask connected with a thermometer and a reflux tube, 9.00 g (25.86 mmol) of the compound (2) obtained in Example 2 was placed, and then 51.00 g of tetrahydrofuran was added and dissolved. . To this solution, 0.52 mmol of dimethyl azobisisobutyrate (trade name: V-601) was added as a polymerization initiator and dissolved.
The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization liquid was concentrated under reduced pressure, then dropped into a large amount of methanol / water mixed solvent, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the target product was obtained. There was obtained 7.2 g of a polymer compound (4) represented by the following formula (4).
With respect to this polymer compound (4), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5300, and the molecular weight dispersity (Mw / Mn) was 1.41.

(Example 5)
Synthesis example of polymer compound (5): Polymer compound (5) was obtained by performing the following steps 1 to 4.
[Step 1]
To a 500 ml three-necked flask, under a nitrogen atmosphere, 16.04 g (90 mmol) of 4-hydroxyphenyl methacrylate, 15.20 g (110 mmol) of potassium carbonate and 100 ml of acetone were added, and tert-butyl bromoacetate was maintained at 0 ° C. 20 g (102.53 mmol) was added and reacted at room temperature for 10 hours. After completion of the reaction, suction filtration was performed, the filtrate was concentrated under reduced pressure, acetone was removed, extraction was performed with water / ethyl acetate, and the resulting organic layer was washed with water three times. Then, the organic layer was concentrated under reduced pressure to obtain 20.1 g of compound (5-1).

About the obtained compound (5-1), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR data (6) (solvent: CDCl ₃ , 400 MHz, internal standard: tetramethylsilane)
δ 7.04 d 2H Ha, 6.90 d 2H Hb, 6.32 s 1H Hc, 5.73 s 1H Hd, 4.50 s 2H He, 2.05 s 3H Hf, 1.49 s 9H Hg
From the results shown above, it was confirmed that the compound (5-1) had a structure shown below.

[Step 2]
Under a nitrogen atmosphere, 15.00 g (51.37 mmol) of the compound (5-1) was placed in a 300 ml three-necked flask, and then 85.00 g of tetrahydrofuran was added and dissolved. To this solution, 7.70 mmol of dimethyl azobisisobutyrate (trade name: V-601) was added and dissolved as a polymerization initiator.
The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization liquid was concentrated under reduced pressure, dropped into a large amount of methanol / water mixed solvent, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the following formula ( 6.5 g of the polymer compound (5-2) shown in 5-2) was obtained.
With respect to the polymer compound (5-2), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 17300, and the molecular weight dispersity (Mw / Mn) was 1.68.

[Step 3]
Under a nitrogen atmosphere, 6.17 g of the polymer compound (5-2) was dissolved in 100 g of THF in a 500 ml three-necked flask, and 9.5 g (50 mmol) of p-toluenesulfonic acid hydrate was added thereto. In addition, the mixture was heated to reflux for 24 hours. After completion of the reaction, the reaction solution was returned to room temperature, THF was removed by concentration under reduced pressure, and extraction with water / ethyl acetate and washing with pure water were performed three times.
Thereafter, the organic layer was concentrated under reduced pressure to obtain 3.0 g of a polymer compound (5-3) represented by the following formula (5-3).
With respect to this polymer compound (5-3), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 12500, and the molecular weight dispersity (Mw / Mn) was 1.70.

[Step 4]
In a 500 ml three-necked flask, under a nitrogen atmosphere, 2.1 g (13.97 mmol) of fluorine alcohol (C ₂ F ₅ CH ₂ OH), 2.68 g (13.97 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride and Add 100 ml of THF solution of 0.08 g (0.64 mmol) of dimethylaminopyridine (DMAP), add 3.0 g of the polymer compound (5-3), stir for 4 hours, and stop the reaction by adding water. did. The reaction solvent was concentrated under reduced pressure, extracted three times with ethyl acetate, and the resulting organic layer was washed three times with water and concentrated under reduced pressure. The obtained solid was dispersed and washed with 100 ml of heptane, suction filtered, and the solid obtained on the filter paper was dried to obtain 3.1 g of a polymer compound (5) represented by the following formula (5). .
With respect to the polymer compound (5), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 16,500, and the molecular weight dispersity (Mw / Mn) was 1.71.

(Example 6)
Synthesis example of compound (6):
Under a nitrogen atmosphere at 0 ° C., 45 g (333 mmol) of potassium carbonate and 45 g (296 mmol) of methyl bromoacetate were added to 450 ml of an acetone solution of 46 g (269 mmol) of 2-vinylnaphthol, and the mixture was returned to room temperature and stirred for 3 hours. . After confirming the disappearance of the raw material by thin layer chromatography (TLC), the reaction solution was filtered, and the solvent was distilled off from the obtained filtrate under reduced pressure. Then, water was added and extracted three times with ethyl acetate. The obtained organic layer was washed twice with water, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by recrystallization (n-heptane-ethyl acetate) to obtain 54 g of Compound (6) -1 as a colorless solid (yield 83%).
Next, 200 ml of a 25 mass% TMAH aqueous solution was added to 450 ml of a THF solution of 54 g (222 mmol) of Compound (6) -1 at 0 ° C. in a nitrogen atmosphere, and the mixture was stirred at room temperature for 3 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), the THF solvent was distilled off under reduced pressure. At 0 ° C., 55 ml of 10N hydrochloric acid was added to the resulting aqueous reaction solution to adjust to acidity, and then extracted three times with ethyl acetate. The organic layer was washed twice with water, and the solvent was distilled off under reduced pressure to obtain 50 g of Compound (6) -2 as a colorless solid (yield 98%).
Next, at 0 ° C. in a nitrogen atmosphere, 33 g (222 mmol) of 2,2,3,3,3-pentafluoro-1-propanol, 51 g (266 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dimethylaminopyridine (DMAP) ) 50 g (222 mmol) of the compound (6) -2 was added to 400 ml of 1 g (11 mmol) in THF, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. Then, it extracted 3 times with ethyl acetate and the organic layer was wash | cleaned twice with water. The crude product obtained by distilling off the solvent under reduced pressure was purified by recrystallization (heptane-ethyl acetate) to obtain 59 g of Compound (6) as a colorless solid (yield 74%).

¹ H-NMR for the compounds (6) -1, (6) -2, and (6) was measured. The results are shown below.

Spectrum data of compound (6) -1
¹ H-NMR (CDCl ₃ ) 7.75-7.60 (m, 4H, Hc), 7.25-7.10 (m, 2H, Hc), 6.85 (dd, 1H, Hb), 5 .80 (d, 1H, Ha), 5.30 (d, 1H, Ha), 4.75 (s, 2H, Hd), 3.83 (s, 3H, He)

Spectrum data of compound (6) -2
¹ H-NMR (DMSO-d6) 13.15 (br, 1H, He), 7.95-7.75 (m, 4H, Hc), 7.30-7.20 (m, 2H, Hc), 6.85 (dd, 1H, Hb), 5.90 (d, 1H, Ha), 5.25 (d, 1H, Ha), 4.75 (s, 2H, Hd)

Spectrum data of compound (6)
¹ H-NMR (DMSO-d6) 7.86-7.69 (m, 4H, Hc), 7.32 (d, 1H, Hc), 7.23 (dd, 1H, Hc), 6.86 ( dd, 1H, Hb), 5.92 (d, 1H, Ha), 5.33 (d, 1H, Ha), 5.10 (s, 2H, Hd), 5.97 (t, 2H, He)

(Example 7)
Synthesis example of polymer compound (8):
In a three-necked flask connected with a thermometer and a reflux tube, 3.50 g (9.71 mmol) of the compound (6) and 1.93 g (12.36 mmol) of the compound (7) were added, and 30.77 g of tetrahydrofuran was added. In addition, it was dissolved. To this solution, 0.88 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 2.10 g of compound (8) was obtained.
With respect to this polymer compound (8), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 11,600, and the dispersity (Mw / Mn) was 1.35. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 56.7 / 43. 3.

(Example 8)
Synthesis example of polymer compound (9):
Into a three-necked flask connected with a thermometer and a reflux tube, 5.25 g (14.57 mmol) of compound (6) and 2.78 g (17.81 mmol) of compound (7) were placed, and 45.50 g of tetrahydrofuran was added. In addition, it was dissolved. To this solution, 4.86 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 3.20 g of compound (9) was obtained.
With respect to this polymer compound (9), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6700, and the dispersity (Mw / Mn) was 1.26. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 57.8 / 42. 2. The polymer compound (9) is represented by the same chemical formula as the polymer compound (8).

Example 9
Synthesis example of polymer compound (11):
In a three-necked flask connected with a thermometer and a reflux tube, 5.25 g (14.57 mmol) of compound (6) and 3.28 g (17.81 mmol) of compound (10) were placed, and 48.34 g of tetrahydrofuran was added. In addition, it was dissolved. To this solution, 1.29 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 1.70 g of compound (11) was obtained.
With respect to this polymer compound (11), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 11700, and the dispersity (Mw / Mn) was 1.27. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 63.0 / 37. 0.

(Example 10)
Synthesis example of polymer compound (13):
To a three-necked flask connected with a thermometer and a reflux tube, 3.00 g (8.33 mmol) of compound (6) and 2.95 g (10.60 mmol) of compound (12) were added, and 40 g of tetrahydrofuran was added. Dissolved. To this solution, 1.14 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 2.57 g of compound (13) was obtained.
With respect to this polymer compound (13), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 11900, and the dispersity (Mw / Mn) was 1.33. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 59.0 / 41. 0.

(Example 11)
Synthesis example of polymer compound (15):
In a three-necked flask connected with a thermometer and a reflux tube, 5.00 g (13.88 mmol) of compound (6), 1.84 g (11.80 mmol) of compound (7), and 0.65 g of compound (14) ( 9.02 mmol), and 42.44 g of tetrahydrofuran was added and dissolved. To this solution, 1.73 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 2.57 g of compound (15) was obtained.
With respect to this polymer compound (15), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 11000, and the dispersity (Mw / Mn) was 1.32. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m / n = 53.5 / It was 28.6 / 17.9.

(Example 12)
Synthesis example of compound (16):
Under a nitrogen atmosphere at 0 ° C., 61 g (600 mmol) of triethylamine and 64 g (418 mmol) of methyl bromoacetate were added to 300 ml of a THF solution of 30 g (348 mmol) of methacrylic acid, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), the reaction solution was evaporated under reduced pressure. Water was added to the obtained reaction product, and extracted with ethyl acetate three times. The organic layer was washed twice with water, and the solvent was distilled off under reduced pressure to obtain 47 g of Compound (16) -1 as a colorless liquid (yield 85%).
Next, 700 ml of a 2.38 mass% TMAH aqueous solution was added to 700 ml of a THF solution of 30 g (190 mmol) of the compound (16) -1 at 0 ° C. in a nitrogen atmosphere, followed by stirring at room temperature for 3 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), the THF solvent was distilled off under reduced pressure. To the resulting aqueous reaction solution, 50 ml of 10N hydrochloric acid was added at 0 ° C. to adjust the acidity, followed by extraction three times with ethyl acetate. The obtained organic layer was washed twice with water, and the solvent was distilled off under reduced pressure to obtain 26 g of Compound (16) -2 as a colorless liquid (yield 95%).
Next, at 0 ° C. in a nitrogen atmosphere, 27 g (177 mmol) of 2,2,3,3,3-pentafluoro-1-propanol, 37 g (195 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dimethylaminopyridine (DMAP) ) Compound (16) -2 (17 g, 118 mmol) was added to 0.6 ml (5 mmol) in THF (100 ml), and the mixture was warmed to room temperature and stirred for 3 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel filtration (ethyl acetate) to obtain 19 g of Compound (16) as a colorless liquid (yield 58%).

¹ H-NMR of compound (16) -1, compound (16) -2, and compound (16) was measured. The results are shown below.

Spectrum data of compound (16) -1
¹ H-NMR (CDCl ₃ ) 6.23 (s, 1H, Hb), 5.67 (d, 1H, Hb), 4.13 (s, 2H, Hc), 3.78 (s, 3H, Hd) ), 2.00 (s, 3H, Ha)

Spectrum data of compound (16) -2
¹ H-NMR (CDCl ₃ ) 6.23 (s, 1H, Hb), 5.67 (d, 1H, Hb), 4.69 (s, 2H, Hc), 2.00 (s, 3H, Ha )

Spectrum data of compound (16)
¹ H-NMR (CDCl ₃ ) 6.14 (s, 1H, Hb), 5.80 (d, 1H, Hb), 4.90 (s, 4H, Hc, Hd), 1.92 (s, 3H , Ha)

(Example 13)
Synthesis example of polymer compound (17):
In a three-necked flask connected with a thermometer and a reflux tube, 3.50 g (12.67 mmol) of compound (16), 0.82 g (5.28 mmol) of compound (7), and 0.23 g of compound (14) ( 3.17 mmol) was added and 25.78 g of tetrahydrofuran was added and dissolved. To this solution, 1.27 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 3.40 g of compound (17) was obtained.
With respect to this polymer compound (17), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 14000, and the dispersity (Mw / Mn) was 1.67. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m / n = 62.3 / It was 25.6 / 12.1.

(Example 14)
Synthesis example of polymer compound (18):
In a three-necked flask connected with a thermometer and a reflux tube, 4.00 g (14.48 mmol) of the compound (16) and 1.51 g (9.67 mmol) of the compound (7) were added, and 31.5 g of tetrahydrofuran was added. In addition, it was dissolved. To this solution, 1.21 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 3.12 g of compound (18) was obtained.
With respect to this polymer compound (18), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 15300, and the dispersity (Mw / Mn) was 1.50. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 61.4 / 38. 6.

(Example 15)
Synthesis example of polymer compound (19):
In a three-necked flask connected with a thermometer and a reflux tube, 4.00 g (14.48 mmol) of the compound (16) and 1.78 g (9.66 mmol) of the compound (10) were added, and 33.0 g of tetrahydrofuran was added. In addition, it was dissolved. To this solution, 1.21 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 0.82 g of compound (19) was obtained.
With respect to this polymer compound (19), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 13900, and the dispersity (Mw / Mn) was 1.30. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 69.1 / 30. It was 9.

(Example 16)
Synthesis example of polymer compound (20):
To a three-necked flask connected with a thermometer and a reflux tube, 4.15 g (15.03 mmol) of the compound (16) was added, and 23.52 g of tetrahydrofuran was added and dissolved. To this solution, 0.30 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 0.82 g of compound (20) was obtained.
With respect to this polymer compound (20), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 23000, and the dispersity (Mw / Mn) was 1.80.

(Example 17)
Synthesis example of polymer compound (21): Polymer compound (21) was obtained by performing the following steps 1 to 4.
[Step 1]
25 g of ethyl lactate and 200 g of tetrahydrofuran were mixed at 0 ° C. in a nitrogen atmosphere, and then 30.4 g of triethylamine was added with stirring. Thereafter, 20.9 g of methacryloyl chloride was added dropwise, and the mixture was returned to room temperature and reacted for 10 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove tetrahydrofuran. Thereafter, extraction with water / ethyl acetate was performed, and the organic layer was concentrated under reduced pressure to obtain 31 g of the intended ester compound (21) -1.

¹ H-NMR of the obtained compound (21) -1 was measured. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 6.20 (s, 1H, Ha), 5.62 (s, 1H, Hb), 5.12 (q, 1H, Hc), 4.21 (q, 2H) , Hd), 1.97 (s, 3H, He), 1.53 (d, 3H, Hf), 1.28 (t, 3H, Hg)
From the results shown above, it was confirmed that the compound (21) -1 had a structure shown below.

[Step 2]
Into a 1 L, three-necked flask, 10 g of compound (21) -1 and 205.7 g of tetrahydrofuran were added, stirred at room temperature, and maintained at 0 ° C. 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution 205.7g was dripped, it was made to react for 1 hour, returning to room temperature. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove tetrahydrofuran, the system was acidified with 1N HCl, and extracted with water / ethyl acetate. The obtained ethyl acetate solution was concentrated under reduced pressure to obtain 7.2 g of compound (21) -2.

About the obtained compound (21) -2, ¹ H-NMR was measured. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 6.12 (s, 1H, Ha), 5.63 (s, 1H, Hb), 5.17 (q, 1H, Hc), 1.97 (s, 3H , Hd), 1.59 (d, 3H, He)
From the results shown above, it was confirmed that the compound (21) -2 had a structure shown below.

[Step 3]
At 0 ° C. under a nitrogen atmosphere, 8.0 g (53.11 mmol) of 2,2,3,3,3-pentafluoro-1-propanol (fluoroalcohol), 12.7 g of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride (66 .39 mmol) and 7.0 g (44.26 mmol) of compound (21) -2 were added to 100 ml of THF solution of 0.27 g (0.02 mmol) of dimethylaminopyridine (DMAP), returned to room temperature, and stirred for 3 hours. . After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The reaction solution was concentrated under reduced pressure to remove THF, then extracted three times with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, dissolved in heptane, suction filtered, and the filtrate was concentrated again under reduced pressure to obtain 8.1 g of Compound (21) -3 (yield 74%).

About the obtained compound (21) -3, ¹ H-NMR was measured. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ6.21 (s, 1H, Ha), 5.67 (s, 1H, Hb), 5.20 (q, 1H, Hc), 4.69 (q, 1H) , Hd), 4.51 (q, 1H, He), 1.98 (s, 3H, Hf), 1.58 (d, 3H, Hg)
From the results shown above, it was confirmed that the compound (21) -3 had a structure shown below.

[Step 4]
In a three-necked flask connected with a thermometer and a reflux tube, 8.10 g (27.93 mmol) of compound (21) -3 was added to 45.90 g of tetrahydrofuran and dissolved. To this solution, 1.40 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature.
The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 5.3 g of compound (21) was obtained.
With respect to this polymer compound (21), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 18900, and the molecular weight dispersity (Mw / Mn) was 1.55.

(Example 18)
Synthesis example of polymer compound (22):
Under a nitrogen atmosphere at 0 ° C., 0.88 g (5.26 mmol) of 1,1,1,3,3,3-hexafluoro-2-propanol, 1.30 g (81.42 mmol) of ethyldiisopropylaminocarbodiimide (EDCl) hydrochloride ) And dimethylaminopyridine (DMAP) 52 mg (0.43 mmol) in 15 ml of THF, 1.0 g (4.38 mmol) of the compound (6) -2 was added, and the mixture was allowed to warm to room temperature and stirred for 24 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The solvent was distilled off under reduced pressure to obtain 1.4 g of Compound (22) -1 as a colorless liquid (yield 84%).

¹ H-NMR of the obtained compound (22) -1 was measured. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) 7.82-7.05 (m, 6H, Hc), 6.83 (q, 1H, Hb), 5.85 (m, 1H, He), 5.80 (D, 1H, Ha), 5.32 (d, 1H, Ha), 4.96 (s, 2H, Hd)
From the results shown above, it was confirmed that the compound (22) -1 had a structure shown below.

In a three-necked flask connected with a thermometer and a reflux tube, 1 g (2.65 mmol) of compound (22) -1 was added to 5.67 g of tetrahydrofuran and dissolved. To this solution, 0.13 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. Compound (22) 0.5g was obtained.
With respect to this polymer compound (22), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 18,800, and the molecular weight dispersity (Mw / Mn) was 1.25.

(Example 19)
Synthesis example of polymer compound (24):
At 0 ° C. under a nitrogen atmosphere, 5.29 g (35.28 mmol) of 2,2,3,3,3-pentafluoro-1-propanol, 15.60 g (81.42 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride and To 100 ml of a THF solution of 0.17 g (1.36 mmol) of dimethylaminopyridine (DMAP) was added 15.00 g (27.14 mmol) of the compound (23), and the mixture was returned to room temperature and stirred for 24 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The solvent was distilled off under reduced pressure to obtain 26 g of Compound (24) -1 as a colorless liquid (yield 95%).

About the obtained compound (24) -1, < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) 6.37 (d, 1 H, Ha), 6.05 (t, 1 H, Hb), 5.78 (d, 1 H, Ha), 5.01, 4.63 -4.40 (m, 3H, Hc, Hd), 2.86-1.02 (m, 15H, He)
From the results shown above, it was confirmed that the compound (24) -1 had a structure shown below.

In a three-necked flask connected with a thermometer and a reflux tube, 4.00 g (9.80 mmol) of Compound (24) -1 was added to 26.67 g of tetrahydrofuran and dissolved. To this solution, 0.404 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 1.4 g of compound (24) was obtained.
With respect to this polymer compound (24), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5700, and the molecular weight dispersity (Mw / Mn) was 2.47.

(Example 20)
Synthesis example of compound (25):
At 0 ° C. under a nitrogen atmosphere, 95.0 g (360.8 mmol) of 3,3,4,4,5,5,6,6,6-nonafluorohexanol, 79.8 g of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride (416.0 mmol) and 40 g (277.5 mmol) of the compound (16) -2 were added to 350 ml of THF solution of 1.7 g (13.8 mmol) of dimethylaminopyridine (DMAP), and the mixture was returned to room temperature and stirred for 3 hours. . After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel filtration (ethyl acetate) to obtain 99.6 g of Compound (25) as a colorless liquid.

About the obtained compound (25), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (CDCl ₃ ) 6.22 (s, 1H, Hb), 5.69 (s, 1H, Hb), 4.70 (s, 2H, Hc), 4.50 (t, 2H, Hd) ), 2.56-2.44 (m, 2H, He), 2.00 (s, 3H, Ha)
From the results shown above, it was confirmed that the compound (25) had a structure shown below.

(Example 21)
Synthesis example of compound (26):
2,0,3,3,4,4,4-heptafluorobutanol 33.3 g (167 mmol), ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride 38.3 g (200 mmol), dimethylaminopyridine at 0 ° C. under nitrogen atmosphere (DMAP) 20 g (139 mmol) of the compound (16) -2 was added to 200 ml of 0.85 g of THF solution, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel filtration (ethyl acetate) to obtain 23 g of Compound (26) as a colorless liquid.

About the obtained compound (26), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (CDCl ₃ ) 6.24 (s, 1H, Hb), 5.70 (s, 1H, Hb), 4.79 (s, 2H, Hc), 4.60-4.66 (t , 2H, Hd), 1.99 (s, 3H, Ha)
From the results shown above, it was confirmed that the compound (26) had a structure shown below.

(Example 22)
Synthesis example of compound (27):
Under nitrogen atmosphere at 0 ° C., 2,2,2-trifluoroethanol 23.48 g (234.5 mmol), ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride 51.9 g (270.6 mmol), dimethylaminopyridine (DMAP) 0 26 g (180.39 mmol) of the compound compound (16) -2 was added to 200 ml of a THF solution of .11 g (0.9 mmol), and the mixture was returned to room temperature and stirred for 3 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel filtration (ethyl acetate) to obtain 25 g of Compound (27) as a colorless liquid.

About the obtained compound (27), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (CDCl ₃ ) 6.24 (s, 1H, Hb), 5.70 (s, 1H, Hb), 4.80 (s, 2H, Hc), 4.60-4.51 (m , 2H, Hd), 1.99 (s, 3H, Ha)
From the results shown above, it was confirmed that the compound (27) had a structure shown below.

(Example 23)
Synthesis example of compound (28):
At 0 ° C. under a nitrogen atmosphere, 30.3 g (180.4 mmol) of 1,1,1,3,3,3-hexafluoro-2-propanol, 39.9 g of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride (208 0.1 mmol) and 20 g (138.8 mmol) of the compound (16) -2 were added to 200 ml of THF solution of 0.08 g (0.7 mmol) of dimethylaminopyridine (DMAP), and the mixture was returned to room temperature and stirred for 3 hours. After confirming the disappearance of the raw materials by thin layer chromatography (TLC), the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. The organic layer obtained by extraction three times with ethyl acetate was washed twice with water. The crude product obtained by evaporating the solvent under reduced pressure was purified by silica gel filtration (ethyl acetate) to obtain 25 g of Compound (28) as a colorless liquid.

About the obtained compound (28), < ¹ > H-NMR was measured. The results are shown below.
¹ H-NMR (CDCl ₃ ) 6.21 (s, 1H, Hb), 5.83-5.76 (m, 1H, Hd), 5.70 (s, 1H, Hb), 4.89 (s) , 2H, Hc), 2.00 (s, 3H, Ha)
From the results shown above, it was confirmed that the compound (28) had a structure shown below.

(Example 24)
Synthesis example of polymer compound (30):
To a three-necked flask connected with a thermometer and a reflux tube, 71.80 g (259.99 mmol) of compound (16) and 19.41 g (86.66 mmol) of compound (29) were added with 136.82 g of tetrahydrofuran. Dissolved. To this solution, 20.80 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was added dropwise to 76.00 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (30) as the target product 32 g was obtained.
With respect to this polymer compound (30), the standard polystyrene equivalent weight average molecular weight (Mw) determined by GPC measurement was 25,500, and the dispersity (Mw / Mn) was 1.56. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 77.3 / 22. 7.

(Example 25)
Synthesis example of polymer compound (31):
To a three-necked flask connected with a thermometer and a reflux tube was added 70.00 g (253.48 mmol) of compound (16), 22.08 g (98.58 mmol) of compound (29), and 38.12 g of tetrahydrofuran. Dissolved. To this solution, 70.41 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This was added dropwise to 76.73 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization liquid was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (31) which was the target product 53 g was obtained.
With respect to this polymer compound (31), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 13,100, and the dispersity (Mw / Mn) was 1.31. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 76.6 / 23. 4. The structure of the polymer compound (31) is the same as that of the polymer compound (30).

(Example 26)
Synthesis example of polymer compound (32):
To a three-necked flask connected with a thermometer and a reflux tube, 20.00 g (72.42 mmol) of compound (16) and 24.33 g (108.63 mmol) of compound (29) were added with 66.50 g of tetrahydrofuran. Dissolved. To this solution, 36.21 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was dropwise added to 36.94 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (32) which was the target product 22 g was obtained.
With respect to this polymer compound (32), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 11,900, and the dispersity (Mw / Mn) was 1.44. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 41.3 / 58. 7. The structure of the polymer compound (32) is the same as that of the polymer compound (30).

(Example 27)
Synthesis example of polymer compound (33):
To a three-necked flask connected with a thermometer and a reflux tube was added 15.00 g (54.32 mmol) of compound (16), 4.06 g (18.11 mmol) of compound (29) and 28.59 g of tetrahydrofuran. Dissolved. To this solution, 1.09 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This was added dropwise to 15.88 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (33) which was the target product 3 g was obtained.
With respect to the polymer compound (33), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 87,100, and the dispersity (Mw / Mn) was 1.62. Further, the copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 76.3 / 23. 7. The structure of the polymer compound (33) is the same as that of the polymer compound (30).

(Example 28)
Synthesis example of polymer compound (34):
To a three-necked flask connected with a thermometer and a reflux tube, 12.35 g (44.72 mmol) of compound (16) and 6.68 g (29.81 mmol) of compound (29) were added with 28.55 g of tetrahydrofuran. Dissolved. To this solution, 5.22 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This was added dropwise to 15.85 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (34) which was the target product 6 g was obtained.
With respect to this polymer compound (34), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 28,300, and the dispersity (Mw / Mn) was 1.41. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 59.5 / 40. It was 5. The structure of the polymer compound (34) is the same as that of the polymer compound (30).

(Example 29)
Synthesis Example of Polymer Compound (35) In a three-necked flask connected with a thermometer and a reflux tube, 15.00 g (54.32 mmol) of compound (16), 5.21 g (23.28 mmol) of compound (29) 114.52 g of tetrahydrofuran was added and dissolved. To this solution, 4.66 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed, and dried, and then the target polymer. 5.57 g of compound (35) was obtained.
With respect to this polymer compound (35), the standard polystyrene equivalent mass average molecular weight (Mw) determined by GPC measurement was 15,000, and the molecular weight dispersity (Mw / Mn) was 1.37. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 74.5 / 25. It was 5. The structure of the polymer compound (35) is the same as that of the polymer compound (30).

(Example 30)
Synthesis example of polymer compound (36):
To a three-necked flask connected with a thermometer and a reflux tube, 15.00 g (38.44 mmol) of compound (25), 3.69 g (16.47 mmol) of compound (29) was added to 105.91 g of tetrahydrofuran. Dissolved. To this solution, 3.30 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane or n-heptane and isopropanol mixed solution, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed and dried. As a result, 4.26 g of the target polymer compound (36) was obtained.
With respect to this polymer compound (36), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 16,000, and the molecular weight dispersity (Mw / Mn) was 1.38. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 77.2 / 22. It was 8.

(Example 31)
Synthesis example of polymer compound (37):
To a three-necked flask connected with a thermometer and a reflux tube was added 14.82 g (41.13 mmol) of compound (6), 4.96 g (22.15 mmol) of compound (29) and 112.69 g of tetrahydrofuran. Dissolved. To this solution, 3.16 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. The reaction solution was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature. The obtained reaction polymerization solution is concentrated under reduced pressure, then dropped into a large amount of n-heptane or n-heptane and isopropanol mixed solution, and an operation for precipitating the polymer is performed. The precipitated polymer compound is filtered, washed and dried. Thus, 3.75 g of the target polymer compound (37) was obtained.
With respect to this polymer compound (37), the standard polystyrene equivalent weight average molecular weight (Mw) determined by GPC measurement was 15,100, and the molecular weight dispersity (Mw / Mn) was 1.27. Further, the copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 75.0 / 25. 0.

(Example 32)
Synthesis example of polymer compound (38):
To a three-necked flask connected with a thermometer and a reflux tube, 20.00 g (88.44 mmol) of compound (27) and 6.60 g (29.48 mmol) of compound (29) were added with 39.90 g of tetrahydrofuran. Dissolved. To this solution, 23.58 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was added dropwise to 22.17 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered off, washed and dried, and the desired polymer compound (38) 13 g was obtained.
With respect to this polymer compound (38), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 13,800, and the dispersity (Mw / Mn) was 1.50. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 77.6 / 22. 4.

(Example 33)
Synthesis example of polymer compound (39):
To a three-necked flask connected with a thermometer and a reflux tube, 13.65 g (60.36 mmol) of compound (27), 10.20 g (45.53 mmol) of compound (29) and 35.78 g of tetrahydrofuran were added. Dissolved. To this solution, 21.18 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was added dropwise to 19.87 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (39) which was the target product 14 g was obtained.
With respect to this polymer compound (39), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 14,100, and the dispersity (Mw / Mn) was 1.39. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 60.3 / 39. 7. The structure of the polymer compound (39) is the same as that of the polymer compound (38).

(Example 34)
Synthesis example of polymer compound (40):
To a three-necked flask connected with a thermometer and a reflux tube, 20.00 g (61.32 mmol) of compound (26), 5.34 g (23.85 mmol) of compound (29) and 38.01 g of tetrahydrofuran were added. Dissolved. To this solution, 17.03 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This was added dropwise to 21.17 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (40) which was the target product 14 g was obtained.
With respect to this polymer compound (40), the standard polystyrene equivalent mass average molecular weight (Mw) determined by GPC measurement was 17,100, and the dispersity (Mw / Mn) was 1.35. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 75.5 / 24. It was 5.

(Example 35)
Synthesis example of polymer compound (41):
To a three-necked flask connected with a thermometer and a reflux tube was added 10.45 g (32.04 mmol) of compound (26), 5.41 g (24.17 mmol) of compound (29), and 23.79 g of tetrahydrofuran. Dissolved. To this solution, 11.24 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This was dropwise added to 13.22 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization liquid was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (41) which was the target product 3 g was obtained.
With respect to this polymer compound (41), the standard polystyrene equivalent weight average molecular weight (Mw) determined by GPC measurement was 23,700, and the dispersity (Mw / Mn) was 1.51. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 60.5 / 39. It was 5. The structure of the polymer compound (41) is the same as that of the polymer compound (40).

(Example 36)
Synthesis example of polymer compound (42):
To a three-necked flask connected with a thermometer and a reflux tube was added 15.00 g (50.99 mmol) of compound (28), 3.81 g (17.00 mmol) of compound (29) and 28.22 g of tetrahydrofuran. Dissolved. To this solution, 13.60 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was dropwise added to 15.67 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (42) which was the target product 10 g was obtained.
With respect to this polymer compound (42), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 19,500, and the dispersity (Mw / Mn) was 1.45. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 76.9 / 23. 1

(Example 37)
Synthesis example of polymer compound (43):
To a three-necked flask connected with a thermometer and a reflux tube was added 10.30 g (35.02 mmol) of compound (28), 5.92 g (26.42 mmol) of compound (29), and 24.33 g of tetrahydrofuran. Dissolved. To this solution, 12.29 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was added dropwise to 13.52 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature. The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered, washed and dried, and the polymer compound (43) which was the target product 1 g was obtained.
With respect to this polymer compound (43), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 38,600, and the dispersity (Mw / Mn) was 1.57. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 61.7 / 38. 3. The structure of the polymer compound (43) is the same as that of the polymer compound (42).

(Example 38)
Synthesis example of polymer compound (44):
In a flask connected with a thermometer, a reflux tube, and a nitrogen introduction tube, 5.00 g (22.12 mmol) of the compound (27) was dissolved in 11.67 g of tetrahydrofuran. To this solution, 1.1 mmol of dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd .: V-601) was added and dissolved as a polymerization initiator. This was subjected to a polymerization reaction at 67 ° C. in a nitrogen atmosphere over 3 hours. After completion of the predetermined time, the reaction solution was cooled to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and the polymer was precipitated. The precipitated polymer compound was filtered off, washed with a mixed solvent of heptane / IPA (isopropanol) and dried. As a result, 5 g of the target polymer compound (44) was obtained.
With respect to this polymer compound (44), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 32,000, and the molecular weight dispersity (Mw / Mn) was 2.78.

(Example 39)
Synthesis example of polymer compound (45):
In a flask connected with a thermometer, a reflux tube, and a nitrogen introduction tube, 15.00 g (66.37 mmol) of the compound (27) was dissolved in 35 g of tetrahydrofuran. To this solution, 16.6 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. This was subjected to a polymerization reaction at 67 ° C. in a nitrogen atmosphere over 3 hours. After completion of the predetermined time, the reaction solution was cooled to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered off, washed with a heptane / IPA mixed solvent, dried, and the target product. As a result, 12 g of the polymer compound (45) was obtained.
With respect to this polymer compound (45), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 15,000, and the molecular weight dispersity (Mw / Mn) was 2.06.

(Example 40)
Synthesis example of polymer compound (47):
In a separable flask connected with a thermometer, a reflux tube, and a nitrogen introduction tube, 15.00 g (66.37 mmol) of compound (27) and 5.18 g (22.12 mmol) of compound (46) Dissolved in 27 g of tetrahydrofuran. To this solution, 4.4 mmol of dimethyl azobisisobutyrate (V-601) was added as a polymerization initiator and dissolved. This was added dropwise to 16.82 g of tetrahydrofuran heated to 67 ° C. in a nitrogen atmosphere over 3 hours to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then the reaction solution was cooled to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered off, washed with a heptane / IPA mixed solvent, dried, and the target product. 17 g of the polymer compound (47) was obtained.
With respect to this polymer compound (47), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 28,000, and the molecular weight dispersity (Mw / Mn) was 2.35.
The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was 1 / m = 76.9 / 23. 1

(Example 41)
Synthesis example of polymer compound (49):
In a separable flask connected with a thermometer, a reflux tube, and a nitrogen introduction tube, 36.84 g (163 mmol) of the compound (27) was dissolved in 79.63 g of PGMEA. To this solution, 8.6 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. A PGMEA solution of the compound (48) heated to 80 ° C. in a nitrogen atmosphere for 3 hours, that is, 22 g (83.97 mmol) of the compound (48) in 22 g of PGMEA (in a mass ratio, the compound (48): The solution was added dropwise to the solution dissolved in PGMEA = 1: 1) to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered off, washed with a heptane / IPA mixed solvent, dried, and the target product. 16 g of the polymer compound (49) was obtained.
With respect to this polymer compound (49), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 19,800, and the molecular weight dispersity (Mw / Mn) was 1.80.
The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 73.1 / 2.26. It was 9.

(Example 42)
Synthesis example of polymer compound (50):
In a separable flask connected with a thermometer, a reflux tube, and a nitrogen introduction tube, 19.58 g (86.65 mmol) of compound (27) was dissolved in 46.32 g of PGMEA. To this solution, 5.8 mmol of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator. A PGMEA solution of the compound (48) heated to 80 ° C. for 3 hours under a nitrogen atmosphere, that is, 38 g (145.04 mmol) of the compound (48) in 38 g of PGMEA (in a mass ratio, the compound (48): The solution was added dropwise to the solution dissolved in PGMEA = 1: 1) to carry out a polymerization reaction. After completion of dropping, the reaction solution was heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature.
The obtained reaction polymerization solution was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated polymer compound was filtered off, washed with a heptane / IPA mixed solvent, dried, and the target product. As a result, 8 g of the polymer compound (50) was obtained.
With respect to this polymer compound (50), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 18600, and the molecular weight dispersity (Mw / Mn) was 1.44.
The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) is 1 / m = 53.9 / 46. 1

<Degradability test for alkaline developer>
Using the compound (1), the compound (2), and the polymer compound (5), which are ester compounds obtained in the above synthesis examples, a decomposability test for an alkali developer was performed by the following method.
[When compound (1) is used]
To the screw tube, 0.1 g of compound (1), 4.9 g of tetrahydrofuran, and 5 g of a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution were added and reacted at room temperature for 1 minute. Thereafter, the mixture was neutralized with 1N-HCl, and the tetrahydrofuran was removed by concentration under reduced pressure, followed by extraction with water / ethyl acetate, and the organic layer was concentrated under reduced pressure to obtain a product. And the decomposability | degradability with respect to an alkali developing solution was evaluated by confirming the structure of the obtained product by < ¹ > H-NMR.
As a result, it was confirmed that 2-carboxyethyl acrylate was produced.

[When compound (2) is used]
In the method using the above compound (1), except that the compound (2) was used instead of the compound (1), the method for the alkaline developer was performed in the same manner as in the method using the compound (1). Degradability was evaluated.
As a result, it was confirmed that succinic acid mono (2-acryloyloxyethyl) was produced.

[When using high molecular compound (5)]
To the screw tube, 0.1 g of the polymer compound (5), 4.9 g of tetrahydrofuran, and 5 g of a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution were added and reacted at room temperature for 10 hours. Thereafter, the mixture was neutralized with 1N-HCl, and the tetrahydrofuran was removed by concentration under reduced pressure, followed by extraction with water / ethyl acetate, and the organic layer was concentrated under reduced pressure to obtain a product. And the decomposability | degradability with respect to an alkali developing solution was evaluated by confirming the structure of the obtained product by < ¹ > H-NMR.
As a result, it was confirmed that the polymer compound (5-3) was produced.

As is clear from the above results, the compound (1), the compound (2) and the polymer compound (5) are all decomposed by “—O—CH ₂ —CF ₂ —CF ₃ ” in the molecule. It was confirmed that “—C (═O) —OH” was generated in the molecule, that is, the decomposition reaction was caused by the action of the alkaline developer.
Further, the compounds (25) to (28) and the polymer compounds (30) to (45), (47), (49), and (50) were also tested in the same manner as described above. It was confirmed that a decomposition reaction occurred.

<Preparation of resist composition>
(Examples 43 to 68, Comparative Example 1)
The components shown in Table 1 below were mixed and dissolved to prepare a positive resist composition.

In Table 1, each abbreviation indicates the following, and the numerical value in [] is the blending amount (part by mass).
(A) -1: a copolymer of Mw7000 and Mw / Mn1.8 represented by the following chemical formula (A) -1. In the formula, the numerical value on the lower right of () indicates the ratio (mol%) of each structural unit.

(B) -1: (4-methylphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate.
(C) -1: the polymer compound (3).
(C) -2: The polymer compound (4).
(C) -3: The polymer compound (5).
(C) -4: The polymer compound (8).
(C) -5: the polymer compound (9).
(C) -6: The polymer compound (11).
(C) -7: The polymer compound (13).
(C) -8: the polymer compound (15).
(C) -9: the polymer compound (17).
(C) -10: the polymer compound (18).
(C) -11: the polymer compound (19).
(C) -12: the polymer compound (20).
(C) -13: the polymer compound (21).
(C) -14: the polymer compound (22).
(C) -15: the polymer compound (24).
(D) -1: tri-n-pentylamine.
(E) -1: salicylic acid.
(S) -1: γ-butyrolactone.
(S) -2: Mixed solvent of PGMEA / EL = 8/2 (mass ratio).

<Measurement of contact angle in resist film>
Next, the resist compositions of Examples 43 to 68 and Comparative Example 1 were each applied onto an 8-inch silicon wafer subjected to hexamethyldisilazane (HMDS) treatment using a spinner, and 110 ° C. on a hot plate. The resist film having a film thickness of 120 nm was formed by pre-baking for 60 seconds and drying.
Water was dropped on the surface of the resist film (resist film before exposure), and the contact angle (static contact angle) was measured using DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.). (Measurement of contact angle: 2 μL of water). This measured value was defined as “contact angle before development (°)”.
The wafer after the contact angle measurement was subjected to alkali development treatment for 30 seconds and 60 seconds with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C., and then using pure water for 15 seconds. After rinsing with water, the contact angle was measured in the same manner as described above. The respective measured values were defined as “contact angle after 30 seconds development (°)” and “contact angle after 60 seconds development (°)”.
Further, in Examples 43 to 68 and Comparative Example 1, the difference between the contact angle before development and the contact angle after 60 seconds development was determined and set as “Δ contact angle (°)”. These results are shown in Table 2.

From the results of Table 2, the resist film formed using the resist compositions of Examples 43 to 68 containing the fluorine-containing compound according to the present invention is the resist composition of Comparative Example 1 that does not contain the fluorine-containing compound. It was confirmed that the contact angle before development was higher than the resist film formed by using the resist film.
This shows that the hydrophobicity of the resist film is increased by containing the fluorine-containing compound. This is expected to improve both the scan followability and the elution reduction effect during the immersion scan exposure.

In addition, from the results of Table 2, the resist films formed using the resist compositions of Examples 43 to 68 have contact angles after development for 30 seconds and after development for 60 seconds to be contact angles before development. It was confirmed that it was lower than that.
From this, it can be seen that the hydrophilicity of the resist film is increased by the alkali development treatment by containing the fluorine-containing compound. Thereby, it is expected that the effect of reducing the defect due to immersion is improved.

  As described above, the resist films formed using the resist compositions of Examples 43 to 68 are higher in hydrophobicity than the resist film formed using the resist composition of Comparative Example 1 during immersion exposure. It was confirmed that the alkali development has a characteristic that the hydrophilicity is higher than that before the development.

<Formation of resist pattern>
Next, an organic antireflection film composition “ARC29A” (trade name, manufactured by Brewer Science) is applied onto a 12-inch silicon wafer using a spinner and baked on a hot plate at 205 ° C. for 60 seconds. Then, an organic antireflection film having a film thickness of 89 nm was formed.
Then, each of the resist compositions is applied onto the antireflection film using a spinner, prebaked (PAB) on a hot plate at 110 ° C. for 60 seconds, and dried to obtain a film thickness. A 100 nm resist film was formed.
Next, an ArF excimer laser (193 nm) is applied to the resist film through a mask pattern using an ArF immersion exposure apparatus NSR-S609B (manufactured by Nikon; NA (numerical aperture) = 1.07, σ0.97). ) Was selectively irradiated. Then, PEB processing is performed at 110 ° C. for 60 seconds, and further development processing is performed for 30 seconds with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C., and then pure water is used for 30 seconds. Rinse with water and shake off to dry.
As a result, in each example, a line and space pattern having a line width of 55 nm and a pitch of 110 nm was formed on the resist film.

From the above results, it was confirmed that the resist compositions of Examples 43 to 68 according to the present invention were suitable for immersion exposure.
Moreover, it has confirmed that the fluorine-containing compound of Examples 1-42 which concerns on this invention was useful as an additive used for the resist composition for immersion exposure.

DESCRIPTION OF SYMBOLS 1 ... Droplet, 1a ... Lower end, 1b ... Upper end, 2 ... Plane, [theta] ₁ ... Advance angle, [theta] ₂ ... Receding angle, [theta] ₃ ... Falling angle

Claims (2)

The compound represented by the following general formula (c-1-1) or (c-1-2).

[Wherein, R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a linear or branched aliphatic hydrocarbon group, a tetracyclododecanyl group to a hydrogen atom; , Divalent aromatic hydrocarbon group, —O—, —C (═O) —, —C (═O) —O—, carbonate bond (—O—C (═O) — O—), —NH—, —NR ⁰⁴ (R ⁰⁴ is an alkyl group) —, —NH—C (═O) —, ═N—, or “linear or branched aliphatic hydrocarbon group” , A group obtained by removing one hydrogen atom from a tetracyclododecanyl group, or a divalent aromatic hydrocarbon group ”and“ —O—, —C (═O) —, —C (═O) —O—, carbonate bond (-O-C (= O) -O -), - NH -, - NR 04 (R 04 is an alkyl group) -, - NH-C ( = O) Or = a combination of N- ", A _aryl is an aromatic cyclic group which may have a substituent, X ₀₁ is a single bond or a divalent linking group, R ² are each An organic group having a fluorine atom independently. ] The high molecular compound which has a structural unit represented by the following general formula (c-1-3) or (c-1-4).

[Wherein, R is independently a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; X is a linear or branched aliphatic hydrocarbon group, a tetracyclododecanyl group to a hydrogen atom; , Divalent aromatic hydrocarbon group, —O—, —C (═O) —, —C (═O) —O—, carbonate bond (—O—C (═O) — O—), —NH—, —NR ⁰⁴ (R ⁰⁴ is an alkyl group) —, —NH—C (═O) —, ═N—, or “linear or branched aliphatic hydrocarbon group” , A group obtained by removing one hydrogen atom from a tetracyclododecanyl group, or a divalent aromatic hydrocarbon group ”and“ —O—, —C (═O) —, —C (═O) —O—, carbonate bond (-O-C (= O) -O -), - NH -, - NR 04 (R 04 is an alkyl group) -, - NH-C ( = O) Or = a combination of N- ", A _aryl is an aromatic cyclic group which may have a substituent, X ₀₁ is a single bond or a divalent linking group, R ² are each An organic group having a fluorine atom independently. ]

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