WO2016125585A1 - Acrylic acid ester derivative, mixture, polymer compound, and photoresist composition - Google Patents

Abstract

　Provided are a photoresist composition that can form high-resolution photoresist patterns having improved LWR, a polymer compound that can produce the photoresist composition, and a compound and mixture that can produce the polymer compound. The compound is, specifically, an acrylic acid ester derivative represented by general formula (1). (In general formula (1): R¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group; R² represents a hydrogen atom, an alkyl group or a cycloalkyl group; X¹ represents -S(=O)- or -S(=O)₂-; X² represents -O-, -S(=O)- or -S(=O)₂-; U¹ and U² each independently represents a single bond, or an alkylene group selected from the group consisting of a methylene group and an ethylene group, and said alkylene group may be substituted by at least one substituent group selected from the group consisting of an alkyl group and a cycloalkyl group; U³ represents a cycloalkylene group, or an alkylene group selected from the group consisting of a methylene group, an ethylene group, a trimethylene group and a tetramethylene group, and said cycloalkylene group or alkylene group may be substituted by at least one substituent group selected from the group consisting of an alkyl group and a cycloalkyl group; A¹ represents a single bond or a linear aliphatic hydrocarbon group; A² represents a linear aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and said alicyclic hydrocarbon group may be substituted by an alkyl group; and k represents an integer of 0-2.)

Description

Acrylic acid ester derivatives, mixtures, polymer compounds and photoresist compositions

The present invention relates to an acrylate derivative, a mixture, a polymer compound and a photoresist composition.

In recent years, in the field of electronic device manufacturing typified by integrated circuit element manufacturing, there has been an increasing demand for higher integration of electronic devices, and thus a photolithography technique for forming a fine pattern is required.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started. In addition, studies have been made on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like having shorter wavelengths than these excimer lasers.
Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.

As a resist material satisfying such requirements, a chemically amplified resist containing a base material component 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. . As a base component of the chemically amplified resist, a resin (hereinafter referred to as a base resin) is mainly used.
For example, a positive chemically amplified resist contains, as a base resin, a resin whose solubility in an alkaline developer is increased by the action of an acid. When a photoresist pattern is formed, an acid is generated from an acid generator by exposure. The solubility of the base resin in an alkaline developer is increased by the action of the acid (see, for example, Patent Document 1).
Further, as the negative chemically amplified resist, a base resin that contains a resin soluble in an alkali developer (alkali-soluble resin) and further contains a crosslinking agent is generally used. In such a resist composition, when an acid is generated from an acid generator by exposure at the time of forming a photoresist pattern, the base resin reacts with the crosslinking agent by the action of the acid, and the solubility of the base resin in an alkaline developer is lowered. (For example, see Non-Patent Documents 1 and 2).

Currently, as a resist base resin 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 (acrylic resin) is excellent in transparency near a wavelength of 193 nm. Resin) is mainly used.
Further, as a polymer compound for a photoresist composition, a polymer compound formed from a structural unit having a norbornane lactone skeleton or a norbornane sultone skeleton through a linking group from an acryloyloxy group has also been proposed (Patent Literature). 2 and 3).

JP 2003-241385 A JP 2001-188346 A International Publication No. 2010/001913

As described above, in recent years, in the manufacture of a semiconductor device or a liquid crystal display device, pattern miniaturization has rapidly progressed due to advances in lithography technology. Therefore, development of a resist material that can improve various lithography properties such as resolution and line width roughness (LWR) more than ever is eagerly desired. Therefore, development of a novel compound that can be a structural unit of a polymer compound to be contained in a photoresist composition is important.
Accordingly, an object of the present invention is to provide a photoresist composition that can improve the LWR and form a high-resolution photoresist pattern, and to provide a polymer compound that can produce the photoresist composition. Another object of the present invention is to provide an acrylate derivative and a mixture capable of producing the polymer compound.

As a result of intensive studies, the present inventors have found that a photoresist composition containing a polymer compound having a structural unit derived from an acrylate derivative having a specific structure or a mixture thereof has improved LWR and high resolution. It has been found that a photoresist pattern is formed.

The present invention relates to the following [1] to [15].
[1] The following general formula (1)

(In the general formula (1), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Represents.
X ¹ represents —S (═O) — or —S (═O) ₂ —, and X ² represents —O—, —S (═O) — or —S (═O) ₂ —.
U ¹ and U ² each independently represent a single bond or an alkylene group selected from the group consisting of a methylene group and an ethylene group, and the alkylene group has an alkyl group having 1 to 10 carbon atoms and a carbon number It may be substituted with at least one substituent selected from the group consisting of 3 to 10 cycloalkyl groups.
U ³ represents an alkylene group selected from the group consisting of a methylene group, an ethylene group, a trimethylene group and a tetramethylene group, or a cycloalkylene group having 3 to 10 carbon atoms, and the alkylene group and the cycloalkylene group have It may be substituted with at least one substituent selected from the group consisting of 1 to 10 alkyl groups and cycloalkyl groups having 3 to 10 carbon atoms.
A ¹ represents a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms.
A ² represents a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the alicyclic hydrocarbon group is an alkyl group having 1 to 10 carbon atoms. May be substituted.
k represents an integer of 0-2. )
An acrylic ester derivative represented by

[2] The following general formula (2)

(In General Formula (2), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in [1] above.
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
The acrylate derivative of the above-mentioned [1] represented by

[3] The following general formula (2-1)

(In the general formula (2-1), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in the above [1].)
An acrylate derivative of the above-mentioned [2] represented by

[4] The following general formula (3)

(In General Formula (3), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in [1] above.
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
The acrylate derivative of the above-mentioned [1] represented by

[5] The following general formula (3-1)

(In general formula (3-1), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in [1] above.)
The acrylic ester derivative of the above-mentioned [4] represented by

[6] The acrylate derivative according to any one of [1] to [5] above, wherein X ¹ is —S (═O) ₂ — and X ² is —O—.
[7] The acrylic ester derivative according to any one of the above [1] to [6], wherein k is 0.

[8] The following general formula (2)

(In General Formula (2), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in [1] above.
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
And the following general formula (3):

(In General Formula (3), R ¹ , R ² , X ¹ , X ² , A ² and k are as described in [1] above.
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
A mixture of acrylic ester derivatives represented by

[9] The mixing ratio [(2) :( 3)] of the acrylic ester derivative represented by the general formula (2) and the acrylic ester derivative represented by the general formula (3) is 50: The mixture of [8] above, which is 50 to 95: 5.
[10] In both of the above general formulas (2) and (3), X ¹ is —S (═O) ₂ — and X ² is —O—. blend.
[11] The mixture according to any one of [8] to [10], wherein k is 0 in both of the general formulas (2) and (3).
[12] A polymer compound having a structural unit derived from the acrylate derivative of any one of [1] to [7].
[13] A polymer compound having two or more structural units derived from the acrylate derivative of any one of [1] to [7].
[14] A polymer compound having a structural unit derived from the mixture of any one of [8] to [11].
[15] A photoresist composition comprising a photoacid generator, a solvent, and a polymer compound of any one of the above [12] to [14].

According to the photoresist composition containing a polymer compound having a structural unit derived from the acrylate derivative of the present invention or a mixture thereof, LWR is improved and a high-resolution photoresist pattern is formed.

[Acrylic acid ester derivatives]
The acrylic ester derivative of the present invention is represented by the following general formula (1). Hereinafter, the acrylic ester derivative represented by the general formula (1) is referred to as an acrylic ester derivative (1).
As described below, the acrylate derivative (1) has a ring structure containing a specific polar group at the molecular end. If a photoresist composition using a polymer compound obtained by using the acrylate derivative (1) (that is, a polymer compound having a structural unit derived from the acrylate derivative (1)), the LWR is An improved and high resolution photoresist pattern is formed.
This effect is caused is not clear that express, acrylic acid ester derivatives of the present invention, X ¹ in the ring structure is not adjacent to X ^2, attached via an X ² and alkylene or cycloalkylene group As a result, the solubility in an alkali developer is improved, the polar group in the cyclic structure and the acid generated from the photoacid generator are likely to interact, and the diffusion length of the acid is appropriately shortened. It is estimated that this is the cause.

(In the general formula (1), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Represents.
X ¹ represents —S (═O) — or —S (═O) ₂ —, and X ² represents —O—, —S (═O) — or —S (═O) ₂ —.
U ¹ and U ² each independently represent a single bond or an alkylene group selected from the group consisting of a methylene group and an ethylene group, and the alkylene group has an alkyl group having 1 to 10 carbon atoms and a carbon number It may be substituted with at least one substituent selected from the group consisting of 3 to 10 cycloalkyl groups.
U ³ represents an alkylene group selected from the group consisting of a methylene group, an ethylene group, a trimethylene group and a tetramethylene group, or a cycloalkylene group having 3 to 10 carbon atoms, and the alkylene group and the cycloalkylene group have It may be substituted with at least one substituent selected from the group consisting of 1 to 10 alkyl groups and cycloalkyl groups having 3 to 10 carbon atoms.
A ¹ represents a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms.
A ² represents a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the alicyclic hydrocarbon group is an alkyl group having 1 to 10 carbon atoms. May be substituted.
k represents an integer of 0-2. )

R ¹ is preferably a hydrogen atom or a methyl group.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ² include, for example, a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched chains, the same shall apply hereinafter). ), Various butyl groups, various hexyl groups, various octyl groups, various decyl groups, and the like. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ² include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclodecyl group. The cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, more preferably a cycloalkyl group having 4 to 6 carbon atoms.
Among these, R ² is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom from the viewpoint of resolution and LWR. .
X ¹ is preferably —S (═O) ₂ — from the viewpoint of resolution and LWR. X ² is preferably —O— or —S (═O) ₂ — from the viewpoint of resolution and LWR. Further, from the viewpoint of resolution and LWR, ^{X 1} is -S (= _{O) 2} - and is, and ^{X 2} is -O -, - S (= O ) 2 - is preferably, ^{X 1} is -S More preferably, (═O) ₂ — and X ² is —O—.

As described above, the alkylene group represented by U ¹ and U ² is substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. May be. Examples of the alkyl group and cycloalkyl group as the substituent include the same as the alkyl group and cycloalkyl group represented by R ² , and the preferred ones are also the same.
U ¹ is preferably an alkylene group selected from the group consisting of a methylene group and an ethylene group, and more preferably a methylene group, from the viewpoints of resolution and LWR.
U ² is preferably a single bond or a methylene group, more preferably a single bond, and more preferably a methylene group.

Examples of the cycloalkylene group having 3 to 10 carbon atoms represented by U ³ include 1,2-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclooctylene. Group, 1,2-cyclodecylene group and the like.
As described above, the alkylene group and cycloalkylene group represented by U ³ are substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. May be. Examples of the alkyl group and cycloalkyl group as the substituent include the same as the alkyl group and cycloalkyl group represented by R ² , and the preferred ones are also the same.
U ³ is preferably an alkylene group selected from the group consisting of a methylene group, an ethylene group, a trimethylene group and a tetramethylene group from the viewpoint of resolution and LWR, and an alkylene group selected from the group consisting of a methylene group and an ethylene group. More preferred is an ethylene group. Further, these are preferably substituted with an alkyl group having 1 to 10 carbon atoms, more preferably substituted with a methyl group, but these are also preferably unsubstituted.

Examples of the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by A ¹ and A ² include a methylene group, an ethylene group, a 1-methylethylene group, a trimethylene group, and an isopropylidene group. The chain aliphatic hydrocarbon group may be linear or branched. The chain aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, more preferably a chain aliphatic hydrocarbon group having 1 to 3 carbon atoms, and still more preferably a methylene group.
Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by A ² include a cyclobutylidene group, 1,2-cyclobutylene group, cyclopentylidene group, 1,2-cyclopentylene group, cyclohexylene, and the like. Den group, 1,2-cyclohexylene group, 1,4-cyclohexylene group and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 4 to 6 carbon atoms. Further, the alicyclic hydrocarbon group may be substituted with an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group as the substituent include the same alkyl groups represented by R ² above. The preferred ones are the same.
Among these, A ¹ is preferably a single bond, a methylene group, or a 1-methylethylene group, more preferably a single bond or a methylene group, still more preferably a single bond, and even more preferably a methylene group.
K represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
The term “single bond” means that they are directly bonded without any group. For example, when A ¹ is a single bond, the acrylate derivative represented by the general formula (1) Is represented by the following general formula (1 ′).

(In the general formula (1 ′), R ¹ , R ² , X ¹ , X ² , U ¹ , U ² , U ³ , A ² and k are the same as those in the general formula (1). .)

Among the acrylic ester derivatives (1) of the present invention, from the viewpoint of resolution and LWR, an acrylic ester derivative represented by the following general formula (2) or (3) is more preferable, and the following general formula (2-1) ) Or (3-1) is more preferred.

(In the general formula (2), R ¹ , R ² , X ¹ , X ² , A ² and k are the same as those in the general formula (1).
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
Preferable ones of R ¹ , R ² , X ¹ , X ² , A ² and k in the general formula (2) are the same as those described in the general formula (1).
The alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms represented by R ³ to R ¹⁰ are both an alkyl group and a cycloalkyl group represented by R ² in the general formula (1) The same thing is mentioned, A preferable thing is also the same.
R ³ to R ¹⁰ are each preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹¹ and R ¹² include a methyl group, an ethyl group, and various propyl groups. Among these, an alkyl group having 1 or 2 carbon atoms is preferable, and a methyl group is more preferable.
R ¹¹ and R ¹² are preferably a hydrogen atom.
z is preferably 0.

(In the general formula (3), R ¹ , R ² , X ¹ , X ² , A ² and k are the same as those in the general formula (1).
R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
z represents 0 or 1; )
Preferable ones of R ¹ , R ² , X ¹ , X ² , A ² and k in the general formula (3) are the same as those described in the general formula (1).
The alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms represented by R ³ to R ¹⁰ are both an alkyl group and a cycloalkyl group represented by R ² in the general formula (1) The same thing is mentioned, A preferable thing is also the same.
R ³ to R ¹⁰ are each preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹¹ and R ¹² include a methyl group, an ethyl group, and various propyl groups. Among these, an alkyl group having 1 or 2 carbon atoms is preferable, and a methyl group is more preferable.
R ¹¹ and R ¹² are preferably a hydrogen atom.
z is preferably 0.

(In general formula (2-1), R ¹ , R ² , X ¹ , X ² , A ² and k are the same as those in general formula (1).)
Preferable ones of R ¹ , R ² , X ¹ , X ² , A ² and k in the general formula (2-1) are the same as those described in the general formula (1).

(In general formula (3-1), R ¹ , R ² , X ¹ , X ² , A ² and k are the same as those in general formula (1).)
Preferable R ¹ , R ² , X ¹ , X ² , A ² and k in the general formula (3-1) are the same as those described in the general formula (1).

[blend]
The present invention also provides a mixture obtained by mixing two or more of the acrylate derivative (1). The mixture includes an acrylic ester derivative represented by the general formula (2) [hereinafter referred to as an acrylic ester derivative (2). ] And an acrylate derivative represented by the general formula (3) [hereinafter referred to as an acrylate derivative (3). And a mixture thereof is preferred. Furthermore, in each of the acrylic ester derivative (2) and the acrylic ester derivative (3), preferred groups are as described above. In particular, in both the acrylic ester derivative (2) and the acrylic ester derivative (3), a mixture in which X ¹ is —S (═O) ₂ — and X ² is —O— is preferable. Moreover, the mixture whose k is 0 is preferable in both the acrylic ester derivative (2) and the acrylic ester derivative (3).
The mixing ratio of the acrylate derivative (2) and the acrylate derivative (3) [acrylate derivative (2): acrylate derivative (3)] is preferably a molar ratio from the viewpoint of resolution and LWR. Is 50:50 to 95: 5, more preferably 60:40 to 95: 5, still more preferably 60:40 to 90:10, and particularly preferably 70:30 to 90:10.
If the photoresist composition uses a polymer compound obtained by using the mixture (that is, a polymer compound having a structural unit derived from the mixture), the LWR is improved and a high-resolution photoresist pattern is formed. Is done. Here, the “structural unit derived from the mixture” refers to all the structural units derived from the acrylate derivative of the present invention contained in the mixture.

Specific examples of the acrylate derivative of the present invention are shown below, but are not particularly limited thereto.

(Method for producing acrylic ester derivative (1))
There is no restriction | limiting in particular in the manufacturing method of acrylic ester derivative (1) of this invention, A well-known chemical reaction can be utilized and applied.
For example, as shown in the following chemical reaction formula 1, an alcohol derivative (a) is oxidized with an oxidizing agent to form an alcohol derivative (b) [hereinafter, this reaction is referred to as reaction (i). Then, the alcohol derivative (b) and the ester derivative (c) are reacted [hereinafter, this reaction is referred to as reaction (ii). The acrylic ester derivative (1) can be produced.

In the chemical reaction formula 1, R ¹ , R ² , A ¹ , A ² , U ¹ , U ² , U ³ , X ¹ , X ² and k are the same as those in the general formula (1). The preferred ones are the same.
X ⁵ represents —O— or —S—. When X ⁵ in the alcohol derivative (a) is —O—, X ² in the alcohol derivative (b) is —O—. When X ⁵ in the alcohol derivative (a) is —S—, X ² in the alcohol derivative (b) is —S (═O) — or —S (═O) ₂ —.
Y ¹ represents a halogen atom, a hydroxyl group, or R ¹³ —C (═O) —O—. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of handling, a chlorine atom is preferable. R ¹³ represents an alkyl group having 1 to 10 (preferably 1 to 5) carbon atoms, a cycloalkyl group having 3 to 10 (preferably 4 to 6) carbon atoms, or an aryl having 6 to 12 (preferably 6) carbon atoms. Group, a halogen-substituted aryl group having 6 to 12 carbon atoms (preferably 6), a vinyl group, and an alkyl-substituted vinyl group (the carbon number of the alkyl group moiety is 1 to 10, preferably 1 to 5, more preferably 1 to 3) , A methoxy group or an ethoxy group. R ¹³ is preferably an alkyl group having 1 to 10 carbon atoms, a vinyl group, a 1-methylvinyl group, a methoxy group or an ethoxy group, and a t-butyl group, a vinyl group, a 1-methylvinyl group, a methoxy group or an ethoxy group. Is more preferable.

(Reaction (i))
Reaction (i) is a reaction in which the alcohol derivative (a) is oxidized with an oxidizing agent, and the alcohol derivative (b) is obtained.
Examples of the oxidizing agent used in the reaction (i) include peracids and peroxides. Examples of the peracid include organic peracids such as performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, and percarboxylic acids such as monoperoxyphthalic acid; inorganics such as permanganic acid Peracids; and their salts. Examples of the salt include alkali metal salts such as lithium salt, sodium salt and potassium salt.
When an organic peracid is used as the peracid, the organic peracid may use an equilibrium peracid such as equilibrium formic acid or equilibrium peracetic acid. When using an equilibrium peracid, for example, an acid corresponding to a desired peracid (for example, formic acid corresponding to performic acid, acetic acid corresponding to peracetic acid) and hydrogen peroxide are combined and reacted. What is necessary is just to add to a system. Thereby, a desired organic peracid (for example, performic acid, peracetic acid, etc.) is generated in the reaction system and functions as an oxidizing agent. Further, when an equilibrium peracid is used, a strong acid such as sulfuric acid may be used as a catalyst.
Examples of the peroxide include hydrogen peroxide, peroxide, hydroperoside, and peroxo acid and its salt. Hydrogen peroxide may be used as it is without being diluted. However, from the viewpoint of ease of handling, it is diluted with a suitable solvent (for example, water) and is diluted with, for example, 20 to 65% by mass of hydrogen peroxide, preferably 20 It can also be used as ˜40 mass% hydrogen peroxide solution.

When hydrogen peroxide is used as the peroxide, a metal compound is often used in combination. For specific forms in the case where a metal compound is used in combination with hydrogen peroxide (the type of metal compound and the amount used), refer to paragraphs [0036] to [0041] of JP-A-2007-31355 as appropriate. Can be done.
The oxidizing agent is preferably organic peracid, more preferably equilibrium peracid, and still more preferably formic acid obtained as equilibrium peracid.
The amount of the oxidizing agent used is not particularly limited, but from the viewpoint of economy and ease of post-treatment, it is preferably 0.5 to 10 moles, more preferably 0.8 moles per mole of the alcohol derivative (a). ~ 4 moles.

Reaction (i) can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, water; aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; halogens such as methylene chloride and dichloroethane. Hydrocarbons; ethers such as tetrahydrofuran and diisopropyl ether; carboxylic acids such as formic acid and acetic acid. A solvent may be used individually by 1 type and may use 2 or more types together.
When reaction (i) is carried out in the presence of a solvent, the amount of the solvent used is preferably 0.1 to 20 with respect to 1 part by mass of the alcohol derivative (a) from the viewpoint of economy and ease of post-treatment. Part by mass, more preferably 0.3 to 10 parts by mass. Moreover, when using equilibrium peracid as an oxidizing agent, it is preferable that a solvent contains water from a viewpoint of reaction rate and a yield, and it is more preferable to use water alone as a solvent.
The reaction temperature in the reaction (i) is not particularly limited, and can be appropriately determined in consideration of a desired reaction rate, reaction selectivity, type of oxidizing agent, etc., preferably −40 to 100 ° C., more preferably The temperature is 10 to 80 ° C, more preferably 15 to 50 ° C.

When using an equilibrium peracid as the oxidizing agent, an acid corresponding to the peracid (for example, formic acid corresponding to performic acid, acetic acid corresponding to peracetic acid) and an alcohol derivative (in the presence or absence of a solvent) A method of adding (preferably dropping) hydrogen peroxide into the mixed solution containing a) is preferable. As long as the temperature is not rapidly increased, the addition time (dropping time) is not particularly limited, and may be appropriately adjusted within a range of, for example, 30 minutes to 24 hours.
Although not particularly limited, it can be determined that the reaction (i) has been completed by confirming the disappearance of the alcohol derivative (a) by gas chromatography analysis.
Reaction (i) can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

After completion of the oxidation reaction of reaction (i), it is preferable to quench the remaining oxidizing agent without reacting by adding a reducing agent. The reducing agent is not particularly limited, and examples thereof include sulfites such as sodium sulfite and sodium bisulfite; sulfides such as dimethyl sulfide and diphenyl sulfide.
The amount of the reducing agent used for quenching the oxidant remaining without reacting is not particularly limited, but is preferably 1 to 5 equivalents with respect to the oxidant remaining in the reaction system.

(Reaction (ii))
Reaction (ii) is a reaction between the alcohol derivative (b) and the ester derivative (c), and the acrylate derivative (1) is obtained.
Specific examples of the ester derivative (c) used in the reaction (ii) include carboxylic acid halides such as acrylic acid chloride, methacrylic acid chloride, 2-trifluoromethylacrylic acid chloride; acrylic acid, methacrylic acid, 2-trifluoro Carboxylic acids such as methyl acrylic acid; acrylic acid anhydride, methacrylic acid anhydride, acrylic acid pivalic acid anhydride, acrylic acid 2,4,6-trichlorobenzoic acid anhydride, methacrylic acid pivalic acid anhydride, methacrylic acid 2, 4,6-trichlorobenzoic anhydride, 2-trifluoromethylacrylic anhydride, 2-trifluoromethylacrylic acid pivalic anhydride, 2-trifluoromethylacrylic acid 2,4,6-trichlorobenzoic anhydride And acid anhydrides.
The amount of the ester derivative (c) used is preferably from 0.8 to 5 mol, more preferably from 0.8 to 3 mol, based on 1 mol of the alcohol derivative (b), from the viewpoint of economy and ease of post-treatment. preferable.

Reaction (ii) is preferably carried out in the presence of an acidic compound or a basic compound.
Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrofluoric acid; formic acid, acetic acid, trichloroacetic acid, propionic acid, butanoic acid, chloroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethane Examples include organic acids such as sulfonic acid. Among these, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid are preferable. An acidic compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the basic compound include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium hydrogen and potassium hydrogen carbonate; Tertiary amines such as triethylamine, tributylamine and diazabicyclo [2.2.2] octane; Nitrogen-containing heterocyclic aromatics such as pyridine and 2,6-lutidine Group compounds and the like. Among these, alkali metal hydrides, alkali metal hydroxides, and tertiary amines are preferred, tertiary amines are more preferred, and triethylamine is even more preferred. A basic compound may be used individually by 1 type, and may use 2 or more types together.
The reaction (ii) is more preferably carried out in the presence of a basic compound.
The amount of the acidic compound and the basic compound used is preferably from 0.1 to 5 mol, more preferably from 0.1 to 3 mol, from the viewpoints of economy and post-treatment.

Reaction (ii) can be carried out in the presence or absence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; halogens such as methylene chloride and dichloroethane. Hydrocarbons; ethers such as tetrahydrofuran and diisopropyl ether; nitriles such as acetonitrile and benzonitrile; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, t-butanol, s-butanol, and cyclohexanol; dimethyl sulfoxide, dimethyl Examples include aprotic polar solvents such as formamide. These may be used individually by 1 type and may use 2 or more types together.
When the reaction (ii) is carried out in the presence of a solvent, the amount of the solvent used is 0.1 to 30 parts by mass with respect to 1 part by mass of the alcohol derivative (b) from the viewpoint of economy and ease of post-treatment. Preferably, 0.1 to 15 parts by mass is more preferable.

The reaction temperature in the reaction (ii) varies depending on the type of the alcohol derivative (b), but is preferably −50 to 150 ° C., more preferably −10 to 100 ° C., and further preferably −10 to 50 ° C. The reaction pressure is not particularly limited, but is usually preferably 0.01 to 0.1 MPa, more preferably normal pressure.

As a method for carrying out the reaction (ii), an ester derivative (c) is added to a solution containing an alcohol derivative (b) and, if necessary, an acidic compound or a basic compound in the presence or absence of a solvent ( The method of preferably dropping) is preferred. As long as the temperature is not rapidly increased, the addition time (dropping time) is not particularly limited, and may be appropriately adjusted within a range of, for example, 30 minutes to 24 hours.
Although not particularly limited, it can be determined that the reaction (ii) has been completed by confirming the disappearance of the alcohol derivative (b) by gas chromatography analysis.
Reaction (ii) can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

Reaction (ii) can be stopped by adding at least one selected from the group consisting of water and alcohol, if necessary, and it is preferable to do so. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol and the like. Examples of water include ion-exchanged water, distilled water, and RO (Reverse Osmosis) water, but are not particularly limited thereto.
When at least one selected from the group consisting of water and alcohol is added, the amount used remains when an excess of the ester derivative (c) is used relative to the alcohol derivative (b). It is preferable to use 1 mol or more per 1 mol of the ester derivative (c). By completely decomposing the ester derivative (c) remaining in the reaction system in this manner, the production of by-products can be suppressed.

The acrylate derivative (1) obtained by the reaction (ii) is preferably separated and purified by a conventional method as necessary.
For example, the reaction mixture can be washed with water, concentrated, and separated and purified by a method used for separation and purification of ordinary organic compounds such as distillation, silica gel column chromatography, and recrystallization. In addition, as necessary, a metal such as nitrotriacetic acid, ethylenediaminetetraacetic acid or other chelating agent treatment, or zeta plus (trade name; manufactured by 3M Japan Co., Ltd.) or protego (product name: manufactured by Nihon Microlith Co., Ltd.) It is also possible to reduce the metal content in the obtained acrylic ester derivative (1) by the removal filter treatment.
In addition, when the alcohol derivative (a) used as a raw material by the said reaction (i) is a 2 or more types of mixture, the acrylic ester derivative (1) obtained by the above also becomes a 2 or more types of mixture. If necessary, they may be used for the production of a polymer compound described later after separation, or may be used for the production of a polymer compound described later in a mixture.

(Method for obtaining and producing alcohol derivative (a))
Here, the acquisition method and manufacturing method of alcohol derivative (a) used as a raw material of the said reaction (i) are demonstrated.
There is no restriction | limiting in particular in the acquisition method of alcohol derivative (a) used in reaction (i). They may be obtained industrially or synthesized by utilizing and applying known chemical reactions.
For example, among the alcohol derivatives (a), a method for producing an alcohol derivative (g) and an alcohol derivative (h) represented by the following general formula is shown in the following chemical reaction formula 2. As shown in the following chemical reaction formula 2, the mercaptan derivative (d) and the epoxide derivative (e) are reacted [hereinafter, this reaction is referred to as a raw material synthesis reaction (I). ] To obtain a sulfide derivative (f), and then cyclize the sulfide derivative (f) [hereinafter, this reaction is referred to as a raw material synthesis reaction (II). The alcohol derivative (a) represented by the following alcohol derivative (g) and alcohol derivative (h) can be manufactured by this.

In the chemical reaction formula 2, R ² to R ¹² and z are the same as those in the general formulas (2) and (3), and preferred ones are also the same.
X ³ represents a sulfur atom or an oxygen atom. X ⁴ is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of handling, a chlorine atom is preferable.
X ⁵ represents —O— or —S—.

(Raw material synthesis reaction (I))
The raw material synthesis reaction (I) is a reaction between the mercaptan derivative (d) and the epoxide derivative (e), and the sulfide derivative (f) is obtained.
Examples of the mercaptan derivative (d) include 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-2-propanol, 3-mercapto-2-butanol, 4-mercapto-2-methyl-1-ol. 1,2-ethanedithiol, 1,3-propanedithiol and the like. Among these, 2-mercaptoethanol is preferable from the viewpoint of industrial availability and performance of the finally obtained photoresist composition (for example, dissolution rate in a developing solution and resolution).
Examples of the epoxide derivative (e) include 2- (chloromethyl) oxirane (also known as epichlorohydrin), 2- (bromomethyl) oxirane, 2- (chloromethyl) -2-chlorooxirane, and the like. . Among these, 2- (chloromethyl) oxirane (also known as epichlorohydrin) is preferable from the viewpoint of industrial availability.
The amount of the epoxide derivative (e) used is not particularly limited, but from the viewpoint of economy and ease of post-treatment, it is preferably 0.8 to 5 moles per mole of the mercaptan derivative (d), 0.8 ˜3 mol is more preferred.

The raw material synthesis reaction (I) is preferably carried out in the presence of an acidic compound or a basic compound.
Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrofluoric acid; formic acid, acetic acid, trichloroacetic acid, propionic acid, butanoic acid, chloroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethane Examples include organic acids such as sulfonic acid. Among these, hydrochloric acid and sulfuric acid are preferable. An acidic compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the basic compound include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium hydrogen and potassium hydrogen carbonate; Tertiary amines such as triethylamine, tributylamine and diazabicyclo [2.2.2] octane; Nitrogen-containing heterocyclic aromatics such as pyridine and 2,6-lutidine Group compounds and the like. Among these, alkali metal bicarbonates, tertiary amines, and nitrogen-containing heterocyclic aromatic compounds are preferable, nitrogen-containing heterocyclic aromatic compounds are more preferable, and pyridine is more preferable.
The raw material synthesis reaction (I) is more preferably carried out in the presence of a basic compound.
The amount of the acidic compound and basic compound used is not particularly limited, but from the viewpoint of economy and ease of post-treatment, 0.01 to 10 mol is preferable with respect to 1 mol of mercaptan derivative (d). More preferred is 01 to 1 mol.

The raw material synthesis reaction (I) can be carried out in the presence or absence of a solvent.
The solvent is not particularly limited as long as the reaction is not inhibited. For example, water; aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; methylene chloride, dichloroethane, and the like Halogenated hydrocarbons; ethers such as tetrahydrofuran and diisopropyl ether; nitriles such as acetonitrile and benzonitrile; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, t-butanol, s-butanol and cyclohexanol; dimethyl sulfoxide, Examples include aprotic polar solvents such as dimethylformamide. Among these, water, ether, alcohol, nitrile, and aprotic polar solvent are preferable. These may be used individually by 1 type and may use 2 or more types together.
When the raw material synthesis reaction (I) is carried out in the presence of a solvent, the amount of the solvent used is 0.1 to 20 with respect to 1 part by mass of the mercaptan derivative (d) from the viewpoint of economy and ease of post-treatment. Part by mass is preferable, and 0.1 to 10 parts by mass is more preferable.

The reaction temperature in the raw material synthesis reaction (I) varies depending on the type of mercaptan derivative (d), epoxide derivative (e) and solvent, but is preferably −50 to 100 ° C., more preferably −10 to 50 ° C., and still more preferably Is 0 to 40 ° C. The reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure because it is convenient.
As a method for carrying out the raw material synthesis reaction (I), an epoxide derivative (e) is added to a mixed solution of a mercaptan derivative (d) and an acidic compound or basic compound used as necessary in the presence or absence of a solvent. The method of adding (preferably dropping) is preferable. As long as the temperature is not rapidly increased, the addition time (dropping time) is not particularly limited, and may be appropriately adjusted within a range of, for example, 30 minutes to 24 hours.

The sulfide derivative (f) may be appropriately separated and purified from the reaction mixture containing the sulfide derivative (f) obtained in the raw material synthesis reaction (I), but the next raw material synthesis reaction ( It is also possible to use it as a raw material of II), and it is easier to do so and it is preferable from the viewpoint of production cost.

(Raw material synthesis reaction (II))
The raw material synthesis reaction (II) is a reaction for cyclizing the sulfide derivative (f).
The raw material synthesis reaction (II) is preferably carried out in the presence of an acidic compound or a basic compound. As the acidic compound and basic compound, the same compounds as the acidic compound and basic compound described in the raw material synthesis reaction (I) can be used. Each of the acidic compound and the basic compound may be used alone or in combination of two or more. Among these, alkali metal hydrides, alkali metal hydroxides, and tertiary amines are preferable, alkali metal hydroxides are more preferable, and sodium hydroxide is more preferable.
The amount of the acidic compound and basic compound used is not particularly limited, but from the viewpoint of economy and ease of post-treatment, 0.01 to 10 mol is preferable with respect to 1 mol of the sulfide derivative (f). More preferably, 01 to 3 moles.

The raw material synthesis reaction (II) can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as the reaction is not inhibited. Examples of the solvent include the same solvents as described in the raw material synthesis reaction (I). Among these, water, ether, alcohol, nitrile, and aprotic polar solvent are preferable, and water or alcohol is more preferable. These may be used individually by 1 type and may use 2 or more types together.
When the raw material synthesis reaction (II) is carried out in the presence of a solvent, the amount of the solvent used is 0.1 to 30 with respect to 1 part by mass of the sulfide derivative (f) from the viewpoint of economy and ease of post-treatment. Part by mass is preferable, and 0.1 to 15 parts by mass is more preferable.

The reaction temperature in the raw material synthesis reaction (II) varies depending on the type of the sulfide derivative (f) and the solvent, but is preferably −50 to 100 ° C., more preferably −10 to 70 ° C., still more preferably 15 to 70 ° C. Particularly preferred is 30 to 70 ° C. Moreover, there is no restriction | limiting in particular in reaction pressure, However, Implementing under a normal pressure is preferable.
As a method for carrying out the raw material synthesis reaction (II), a method in which the sulfide derivative (f) is added (preferably dropped) to a mixed solution of an acidic compound or a basic compound and a solvent is preferable. As long as the temperature is not rapidly increased, the addition time (dropping time) is not particularly limited, and may be appropriately adjusted within a range of, for example, 30 minutes to 24 hours.

Separation and purification of the alcohol derivative (g) and alcohol derivative (h) from the reaction mixture obtained by the raw material synthesis reaction (II) can be performed by a method generally used for separation and purification of organic compounds. For example, after completion of the reaction, it can be separated by adding water to the reaction mixture, extracting with an organic solvent, and concentrating the resulting organic layer. Further, if necessary, the alcohol derivative (g) and the alcohol derivative (h) can be obtained individually or as a mixture by purification by recrystallization, distillation, silica gel column chromatography or the like.

[Polymer compound]
The polymer obtained by polymerizing the acrylate derivative (1) of the present invention or the mixture of the present invention alone is useful as a polymer compound for a photoresist composition. Furthermore, a copolymer obtained by copolymerizing the acrylate derivative (1) of the present invention or the mixture of the present invention and another polymerizable compound is useful as a polymer compound for a photoresist composition.
The polymer compound of the present invention has a structural unit derived from the acrylate derivative of the present invention.
For example, the compound of the present invention has a structural unit (a1) represented by the following general formula (a1).

(In the formula, R ¹ , R ² , X ¹ , X ² , A ¹ , A ² , U ¹ , U ² , U ³ and k are the same as those in the general formula (1).)

The polymer compound of the present invention is preferably selected from the group consisting of a structural unit (a2) represented by the following general formula (a2) and a structural unit (a3) represented by the following general formula (a3). Having at least one species.

(Wherein R ¹ to R ¹² , X ¹ , X ² , A ² , k and z are the same as those in the general formulas (2) and (3)).

The polymer compound of the present invention is more preferably a structural unit (a2-1) represented by the following general formula (a2-1) and a structural unit (a3-1) represented by the following general formula (a3-1). At least one selected from the group consisting of:

(Wherein R ¹ , R ² , X ¹ , X ² , A ² and k are the same as those in the general formulas (a2) and (a3)).

The polymer compound of the present invention contains structural units derived from the acrylate derivative of the present invention [for example, structural units (a1), (a2), (a2-1), (a3) and (a3-1)]. From 0 to 100 mol%, from the viewpoint of resolution and LWR, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 30 to 70 mol%. As described above, the polymer compound of the present invention may have a structural unit derived from another polymerizable compound that can be copolymerized with the acrylate derivative (1).
Specific examples of other polymerizable compounds (hereinafter referred to as copolymerization monomers) that can be copolymerized with the acrylate derivative (1) include compounds represented by the following chemical formulas. However, it is not particularly limited to these.

In the above general formulas (I) to (IX), R ^3a represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and R ^4a represents a polymerizable group-containing group. . R ^5a represents a hydrogen atom or —COOR ^6a (R ^6a represents an alkyl group having 1 to 3 carbon atoms). m represents an integer of 1 to 5. Z represents a methylene group, an ethylene group or an oxygen atom.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^3a and R ^6a in the comonomer include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ^3a include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polymerizable group in the polymerizable group-containing group represented by R ^4a include an acryloyl group, a methacryloyl group, a vinyl group, and a vinylsulfonyl group. Examples of the polymerizable group-containing group represented by R ^4a include acryloyl group, methacryloyl group, α-fluoroacryloyl group, trifluoromethacryloyl group, 2- (acryloyloxy) acetyl group, 2- (methacryloyloxy) acetyl group, Examples include 2- (trifluoromethacryloyloxy) acetyl group, vinyl group, vinylsulfonyl group, 2- (vinylsulfonyloxy) acetyl group and the like.

Specific examples of the compound represented by the general formula (I) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (II) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (III) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (IV) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (V) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (VI) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (VII) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (VIII) are shown below, but are not particularly limited thereto.

Specific examples of the compound represented by the general formula (IX) are shown below, but are not particularly limited thereto.

As the above comonomer, one arbitrary comonomer can be selected, or two or more can be used in combination.
Among the above, as the comonomer, preferably a comonomer represented by the above general formula (I), (II), (IV), (V) or (IX), more preferably, A copolymer monomer represented by the above general formula (I) or (II), more preferably a copolymer monomer represented by the above general formula (I) and a copolymer monomer represented by the above formula (II). It is combined use with a polymerization monomer.

<< Manufacture of polymer compounds >>
The polymer compound of the present invention can be produced by radical polymerization according to a conventional method. In particular, a method for synthesizing a polymer compound having a small molecular weight distribution includes living radical polymerization.
A general radical polymerization method includes a radical polymerization initiator, a solvent, and, if necessary, one or more acrylic ester derivatives (1) and, if necessary, one or more of the above-mentioned copolymerization monomers. Accordingly, the polymerization is carried out in the presence of a chain transfer agent.
There is no restriction | limiting in particular in the implementation method of radical polymerization, For example, the usual method used when manufacturing acrylic resin, such as solution polymerization method, emulsion polymerization method, suspension polymerization method, block polymerization method, etc. can be used.

Examples of the radical polymerization initiator include hydroperoxide compounds such as t-butyl hydroperoxide and cumene hydroperoxide; di-t-butyl peroxide, t-butyl-α-cumyl peroxide, di-α- Dialkyl peroxide compounds such as cumyl peroxide; diacyl peroxide compounds such as benzoyl peroxide and diisobutyryl peroxide; 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, Examples include azo compounds such as dimethyl azobisisobutyrate.
The amount of the radical polymerization initiator used can be appropriately selected according to the polymerization conditions such as the acrylic ester derivative of the present invention used in the polymerization reaction, the comonomer, the chain transfer agent, the type and amount of the solvent, and the polymerization temperature. Is the total polymerizable compound [the total amount of the acrylate derivative of the present invention and the comonomer, and so on. The amount is usually preferably 0.005 to 0.2 mol, more preferably 0.01 to 0.15 mol per 1 mol.

The solvent is not particularly limited as long as it does not inhibit the polymerization reaction. For example, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, Glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, propyl acetate; acetone, methyl ethyl ketone, methyl ipropyl ketone, methyl Isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexa Ketones, such as emissions diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethers such as 1,4-dioxane.
The amount of the solvent used is usually preferably 0.5 to 20 parts by mass and more preferably 1 to 10 parts by mass from the viewpoint of economy with respect to 1 part by mass of the total polymerizable compound.

Examples of the chain transfer agent include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid. When a chain transfer agent is used, the amount used is usually preferably 0.005 to 0.2 mol, more preferably 0.01 to 0.15 mol, per 1 mol of all polymerizable compounds.

The polymerization temperature is usually preferably 40 to 150 ° C., and more preferably 60 to 120 ° C. from the viewpoint of the stability of the produced polymer compound.
The time for the polymerization reaction varies depending on the polymerization conditions such as the acrylic ester derivative (1), the comonomer, the polymerization initiator, the type and amount of the solvent used, and the temperature of the polymerization reaction. 48 hours, more preferably 1 to 24 hours.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

The polymer compound thus obtained can be isolated by ordinary operations such as reprecipitation. The isolated polymer compound can be dried by vacuum drying or the like.
Examples of the solvent used in the reprecipitation operation include aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene and xylene; methylene chloride, chloroform, chlorobenzene, Halogenated hydrocarbons such as dichlorobenzene; nitrated hydrocarbons such as nitromethane; nitriles such as acetonitrile and benzonitrile; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; ketones such as acetone and methyl ethyl ketone; acetic acid Carboxylic acids such as; esters such as ethyl acetate and butyl acetate; carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; methanol, ethanol, propanol, isopropyl Include water; alcohols, alcohols such as butanol. These may be used alone or in combination of two or more.
The amount of solvent used in the reprecipitation operation varies depending on the type of polymer compound and the type of solvent, but it is usually preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the polymer compound. From the viewpoint of properties, the amount is more preferably 1 to 50 parts by mass.

The weight average molecular weight (Mw) of the polymer compound is not particularly limited, but is preferably 500 to 50,000, more preferably 1,000 to 30,000, still more preferably 4,000 to 15,000, particularly preferably. When it is 4,000 to 10,000, it is highly useful as a component of a photoresist composition described later. The weight average molecular weight is a value in terms of standard polystyrene determined by gel permeation chromatograph (GPC) measurement.
The molecular weight distribution (Mw / Mn) of the polymer compound is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. It is highly useful as a component. Such Mw and Mn are values in terms of standard polystyrene determined by gel permeation chromatograph (GPC) measurement.

[Photoresist composition]
A photoresist composition is prepared by blending the polymer compound of the present invention, a photoacid generator and a solvent, and, if necessary, a basic compound, a surfactant and other additives. Hereinafter, each component will be described.

<Photo acid generator>
As the photoacid generator, known photoacid generators conventionally used for chemically amplified resists can be used without particular limitation. Examples of the photoacid generator include onium salt photoacid generators such as iodonium salts and sulfonium salts; oxime sulfonate photoacid generators; bisalkyl or bisarylsulfonyldiazomethane photoacid generators; Examples include photoacid generators; iminosulfonate photoacid generators; disulfone photoacid generators. These may be used individually by 1 type and may use 2 or more types together. Among these, an onium salt photoacid generator is preferable, and the following fluorine-containing onium salt containing a fluorine-containing alkyl sulfonate ion as an anion is preferable from the viewpoint that the strength of the generated acid is strong.

Specific examples of the fluorine-containing onium salt include, for example, diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; triphenylsulfonium trifluoro L-methanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate; trifluoromethane sulfonate of tri (4-methylphenyl) sulfonium, heptafluoropropane sulfonate or nonafluorobutane sulfonate; trifluoromethane sulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, hepta Fluoropropanesulfonate or nonafluorobut Sulfonate; monophenyldimethylsulfonium trifluoromethane sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate; diphenyl monomethylsulfonium trifluoromethane sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate; (4-methylphenyl) diphenylsulfonium Trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; tri (4-tert-butyl) phenylsulfonium trifluoromethane Sulfonates, such as heptafluoropropane or nonafluorobutanesulfonate thereof. These may be used individually by 1 type and may use 2 or more types together.
The blending amount of the photoacid generator is usually preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymer compound from the viewpoint of ensuring the sensitivity and developability of the photoresist composition. 0.5 to 10 parts by mass.

<Solvent>
Solvents blended in the photoresist composition include, for example, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monobutyl ether, ethylene Glycol ethers such as glycol monobutyl ether acetate and diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, and propyl acetate; acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, Cases such as cyclopentanone and cyclohexanone Emissions diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethers such as 1,4-dioxane. These may be used individually by 1 type and may use 2 or more types together.
The amount of the solvent is usually preferably 1 to 50 parts by mass, and preferably 2 to 25 parts by mass with respect to 1 part by mass of the polymer compound.

<Basic compound>
In order to improve the resolution by suppressing the acid diffusion rate in the photoresist film, a basic compound is added to the photoresist composition in an amount that does not impair the characteristics of the photoresist composition as necessary. be able to. Examples of such basic compounds include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (1-adamantyl) acetamide, benzamide, N- Acetylethanolamine, 1-acetyl-3-methylpiperidine, pyrrolidone, N-methylpyrrolidone, ε-caprolactam, δ-valerolactam, 2-pyrrolidinone, acrylamide, methacrylamide, t-butylacrylamide, methylenebisacrylamide, methylenebismethacryl Amides such as amide, N-methylolacrylamide, N-methoxyacrylamide, diacetoneacrylamide; pyridine, 2-methylpyridine, 4-methylpyridine, nicotine, quinoline, Kridine, imidazole, 4-methylimidazole, benzimidazole, pyrazine, pyrazole, pyrrolidine, Nt-butoxycarbonylpyrrolidine, piperidine, tetrazole, morpholine, 4-methylmorpholine, piperazine, 1,4-diazabicyclo [2.2.2 ] Amines such as octane, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine and triethanolamine can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
When a basic compound is blended, the blending amount varies depending on the type of the basic compound used, but is usually preferably 0.01 to 10 moles, more preferably 0.05 to 1 mole of the photoacid generator. ~ 1 mole.

<Surfactant>
In order to improve applicability, the photoresist composition may further contain a surfactant in an amount that does not impair the characteristics of the photoresist composition, if desired.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, and the like. These may be used individually by 1 type and may use 2 or more types together.
When the surfactant is blended, the blending amount is usually preferably 2 parts by mass or less with respect to 100 parts by mass of the polymer compound.

<Other additives>
Furthermore, in the photoresist composition, as other additives, a sensitizer, an antihalation agent, a shape improver, a storage stabilizer, an antifoaming agent, etc. are added in an amount that does not impair the characteristics of the photoresist composition. Can be blended.

(Photoresist pattern formation method)
The photoresist composition of the present invention is applied to a substrate, prebaked usually at 70 to 160 ° C. for 1 to 10 minutes, and irradiated (exposed) through a predetermined mask, preferably at 70 to 160 ° C. A photoresist pattern can be formed by forming a latent image pattern by post-exposure baking for 1 to 5 minutes and then developing with a developer. The shape of the photoresist pattern thus obtained is good and the LWR is improved. That is, a high-resolution photoresist pattern is formed by using the acrylate derivative of the present invention.

For exposure, various wavelengths of radiation, such as ultraviolet rays and X-rays, can be used. For semiconductor resists, excimer lasers such as g-line, i-line, XeCl, KrF, KrCl, ArF, and ArCl are usually used. However, among these, it is preferable to use an ArF excimer laser from the viewpoint of fine processing.
Exposure is preferably from 0.1 ~ 1000mJ / cm ^2, and more preferably 1 ~ 500mJ / cm ^2.

Examples of the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and aqueous ammonia; alkylamines such as ethylamine, diethylamine and triethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium Examples include alkaline aqueous solutions in which quaternary ammonium salts such as hydroxide and tetraethylammonium hydroxide are dissolved. Among these, it is preferable to use an alkaline aqueous solution in which a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide is dissolved.
The concentration of the developer is usually preferably from 0.1 to 20% by mass, and more preferably from 0.1 to 10% by mass.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these examples. The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured and the molecular weight distribution was calculated as follows.
(Measurement of Mw and Mn and calculation method of molecular weight distribution)
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) using a differential refractometer as a detector and tetrahydrofuran (THF) as an eluent under the following conditions. It calculated | required as a conversion value by the calibration curve created with the standard polystyrene. Further, the molecular weight distribution (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
GPC measurement: As a column, two “TSK-gel SUPER HZM-H” (trade name: manufactured by Tosoh Corporation, 4.6 mm × 150 mm) and “TSK-gel SUPER HZ2000” (trade name: manufactured by Tosoh Corporation, 4 .6 mm × 150 mm) were used, which were connected in series, and measured under conditions of a column temperature of 40 ° C., a differential refractometer temperature of 40 ° C., and an eluent flow rate of 0.35 mL / min.

<Synthesis Example 1> Synthesis of 1- (2-hydroxyethylthio) -3-chloro-2-propanol Into a 2 L four-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, 515 g of 2-mercaptoethanol ( 6.59 mol) and 105 g (1.33 mol) of pyridine were added. To this solution, 616 g (6.66 mol) of epichlorohydrin was added dropwise at room temperature over 2 hours.
After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to obtain 1240 g of a colorless solution. When this solution was analyzed by ¹ H-NMR, it contained 1100 g of the following 1- (2-hydroxyethylthio) -3-chloro-2-propanol (yield 97.8% based on mercaptoethanol). It was confirmed.

<Synthesis Example 2> Synthesis of 1,4-oxathiepan-6-ol and 1,4-oxathian-2-methanol 283 g (7. 7) of sodium hydroxide was added to a 5 L 4-neck flask equipped with a stirrer and a thermometer. 07 mol) and 1950 g of distilled water were added, and the internal temperature was adjusted to 50 ° C. while stirring.
From a dropping funnel, 1200 g of a colorless solution containing 1096 g (6.42 mol) of 1- (2-hydroxyethylthio) -3-chloro-2-propanol obtained in Synthesis Example 1 was added at an internal temperature of 45 to 55 ° C. It was added dropwise over time. After completion of the dropwise addition, the reaction mixture was stirred for 1 hour at 50 ° C. and analyzed by gas chromatography. As a result, 1- (2-hydroxyethylthio) -3-chloro-2-propanol was completely disappeared.
The reaction mixture was cooled to 25 ° C. and then neutralized with 20% aqueous hydrochloric acid. Extraction was performed twice with 4400 g of ethyl acetate, and the obtained organic layers were combined and concentrated under reduced pressure. The concentrated solution was simply distilled to obtain 392 g of a fraction.
^{According to 1} H-NMR and GC-MS analysis, this fraction was a mixture of the following 1,4-oxathiepan-6-ol and 1,4-oxathian-2-methanol, and its molar ratio (1,4-oxathiepane -6-ol: 1,4-oxathian-2-methanol) was confirmed to be 80:20.

(1,4-oxathiepan-6-ol)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm): 2.74-2.81 (2H, m), 2.77 (1H, dd, J = 4.8, 7.6 Hz), 2.92 (1H, dd, J = 4.0 Hz, 14.8 Hz), 3.04 (1H, d, J = 9.6 Hz), 3.83-3.93 (4H, m), 4.08 (1H, m)
GC-MS m / z: 134 (95), 116 (91), 90 (50), 75 (61), 60 (100), 46 (65), 45 (64)

(1,4-oxathian-2-methanol)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm): 2.26-2.30 (1H, m), 2.62-2.65 (1H, m), 2.70 (1H, dd, J = 2.8 Hz, 10.8 Hz), 2.83-2.87 (1H, m), 2.89-2.94 (1H, m), 3.53-3.59 (1H, m), 3 .67-3.73 (1H, m), 3.77 (1H, dd, J = 2.0 Hz, 11.6 Hz), 3.83 (1H, dd, J = 1.2 Hz, 10.0 Hz), 4.23-4.29 (1H, m)
GC-MS m / z: 134 (80), 103 (100), 75 (19), 59 (18), 46 (38)

Synthesis Example 3 Synthesis of 4,4-dioxa-1,4-oxathiepan-6-ol and 4,4-dioxa-1,4-oxathian-2-methanol An internal volume of 5 L equipped with a stirrer and a thermometer In a four-necked flask, 486 g (10.3 mol) of 98% formic acid, 466 g of distilled water and 350 g of a mixture of 1,4-oxathiepan-6-ol and 1,4-oxathian-2-methanol obtained in Synthesis Example 2 (mixing) Molar ratio 80:20, 2.59 mol in total) was added, and the internal temperature was adjusted to 25 ° C. with stirring. To this, 601 g (5.30 mol) of 30% aqueous hydrogen peroxide was added dropwise from an addition funnel at an internal temperature of 30 to 35 ° C. over 4 hours. After the completion of the dropwise addition, the mixture was stirred at 35 ° C. for 4 hours, and the reaction mixture was analyzed by gas chromatography. .
After cooling the reaction mixture to 25 ° C., saturated aqueous sodium sulfite was added dropwise to quench excess peroxide in the system, and then neutralized with potassium bicarbonate. Extraction was performed twice with 2800 g of 2-butanone, and the obtained organic layers were combined and concentrated under reduced pressure to obtain 284 g of a concentrated solution.
According to GC-MS analysis, the following 4,4-dioxa-1,4-oxathiepan-6-ol and 4,4-dioxa-1,4-oxathian-2-methanol were mixed in a molar ratio (4,4 -Dioxa-1,4-oxathiepan-6-ol: 4,4-dioxa-1,4-oxathian-2-methanol) 81:19.

(4,4-dioxa-1,4-oxathiepan-6-ol)
GC-MS m / z: 166 (1), 123 (100), 93 (91), 58 (94), 44 (93)

(4,4-dioxa-1,4-oxathian-2-methanol)
GC-MS m / z: 166 (1), 135 (100), 107 (80), 72 (60), 57 (29), 44 (65)

Example 1 Synthesis of 6-methacryloyloxy-4,4-dioxa-1,4-oxathiepane and 2-methacryloyloxymethyl-4,4-dioxa-1,4-oxathiane Stirrer, thermometer, and dropping funnel Into a 4 L flask having an internal volume of 3 L, 4,4-dioxa-1,4-oxathiepan-6-ol and 4,4-dioxa-1,4-oxathian-2-methanol obtained in Synthesis Example 3 275 g (mixing molar ratio = 81: 19, net amount 250 g, 1.50 mol), 251 g (2.48 mol) of triethylamine and 750 g of acetonitrile were added, and the internal temperature was adjusted to 25 ° C. with stirring. To this, 173 g (1.65 mol) of methacryloyl chloride was added dropwise from an addition funnel at an internal temperature of 25 to 30 ° C. over 3 hours. After completion of the dropwise addition, the mixture was stirred at 30 ° C. for 4 hours, and then the reaction mixture was analyzed by gas chromatography, and 4,4-dioxa-1,4-oxathiepan-6-ol and 4,4-dioxa-1,4 were analyzed. It was confirmed that -oxathian-2-methanol disappeared.
Next, 183 g of distilled water was added dropwise at an internal temperature of 25 to 30 ° C. over 1 hour while stirring the reaction solution. Extraction was performed twice with 1000 g of ethyl acetate, and the obtained organic layers were combined, washed with 300 g of 2% hydrochloric acid water and 300 g of distilled water, and then concentrated under reduced pressure to obtain 350 g of a concentrated solution. By distilling and purifying the concentrated solution, 180 g (0.768 mol, 51% yield) of 6-methacryloyloxy-4,4-dioxa-1,4-oxathiepan described below and 2-methacryloyloxymethyl-4,4- 45.0 g (0.192 mol, 13% yield) of dioxa-1,4-oxathiane was obtained.

(6-Methacryloyloxy-4,4-dioxa-1,4-oxathiepan)
¹ H-NMR (400 MHz, DMSO-d ₆ , TMS, ppm): 1.88 (3H, s), 3.40-3.47 (1H, m), 3.60-3.67 (1H, m ), 3.70-3.73 (2H, m), 3.77-3.82 (1H, m), 3.98 (1H, dd, J = 4.4, 13.6 Hz), 4.02 -4.06 (1H, m), 4.07 (1H, dd, J = 4.8, 13.6 Hz), 5.11 (1H, m), 5.73 (1H, brs), 6.07 (1H, brs)

(2-methacryloyloxymethyl-4,4-dioxa-1,4-oxathiane)
¹ H-NMR (400 MHz, DMSO-d ₆ , TMS, ppm): 1.89 (3H, s), 3.14-3.21 (2H, m), 3.22-3.27 (1H, m ), 3.29-3.34 (1H, m), 3.75-3.77 (1H, m), 3.83-3.87 (1H, m), 3.95-4.05 (1H) M), 4.09-4.12 (1H, m), 4.25-4.31 (1H, m), 5.71 (1H, brs), 6.09 (1H, brs)

<Example 2> Synthesis of polymer compound (a) In a three-necked flask having an internal volume of 50 ml equipped with a stirrer, a reflux condenser and a thermometer, 4.0 g (17.2 mmol) of 2-methacryloyloxy-2-methyladamantane, Charged with 1.4 g (6.0 mmol) of 3-hydroxy-1-yl methacrylate, 4.6 g (19.8 mmol) of 6-methacryloyloxy-4,4-dioxa-1,4-oxathiepan and 36.0 g of methyl ethyl ketone, Nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate is dried under reduced pressure (26.0 Pa) at 50 ° C. for 8 hours, and the following structural units (however, the numerical values described in the lower right of the parentheses represent the molar ratio of the structural units, and the same applies hereinafter). 6.0 g of the polymer compound (a) having. The obtained polymer compound (a) had a weight average molecular weight (Mw) of 6,200 and a molecular weight distribution of 1.60.

<Example 3> Synthesis of polymer compound (b) In a three-necked flask with an internal volume of 50 ml equipped with a stirrer, a reflux condenser and a thermometer, 4.0 g (17.2 mmol) of 2-methacryloyloxy-2-methyladamantane, Charged with 1.4 g (6.0 mmol) of 3-hydroxy-1-yl methacrylate, 4.6 g (19.8 mmol) of 2-methacryloyloxymethyl-4,4-dioxa-1,4-oxathiane and 36.4 g of methyl ethyl ketone Nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate was dried at 50 ° C. under reduced pressure (26.0 Pa) for 8 hours to obtain 6.5 g of a polymer compound (b) having the following structural units. The obtained polymer compound (b) had a weight average molecular weight (Mw) of 5,860 and a molecular weight distribution of 1.60.

<Example 4> Synthesis of polymer compound (c) In a three-necked flask with an internal volume of 50 ml equipped with a stirrer, a reflux condenser and a thermometer, 4.0 g (17.2 mmol) of 2-methacryloyloxy-2-methyladamantane, 3-Hydroxy-1-yl methacrylate 1.4 g (6.0 mmol), 6-methacryloyloxy-4,4-dioxa-1,4-oxathiepan 4.6 g (19.8 mmol), 2-methacryloyloxymethyl-4 , 4-dioxa-1,4-oxathianne (1.2 g, 5.0 mmol) and methyl ethyl ketone (37.3 g) were charged, and nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate was dried under reduced pressure (26.0 Pa) at 50 ° C. for 8 hours to obtain 7.1 g of a polymer compound (c) having the following structural units. The obtained polymer compound (c) had a weight average molecular weight (Mw) of 6,300 and a molecular weight distribution of 1.62.

<Comparative Synthesis Example 1> Synthesis of Polymer Compound (d) In a three-necked flask having an internal volume of 50 ml equipped with an electromagnetic stirrer, a reflux condenser and a thermometer, 4.0 g of 2-methacryloyloxy-2-methyladamantane (17. 2 mmol), 1.4 g (6.0 mmol) of 3-hydroxy-1-yl methacrylate, 4.4 g (19.8 mmol) of 5- (methacryloyloxy) -2,6-norbornanecarbolactone and 36.0 g of methyl ethyl ketone. Nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 8 hours to obtain 7.0 g of a polymer compound (d) having the following structural units. The obtained polymer compound (d) had a weight average molecular weight (Mw) of 6,100 and a molecular weight distribution of 1.58.

Comparative Synthesis Example 2 Synthesis of Polymer Compound (e) In a three-necked flask having an internal volume of 50 ml equipped with an electromagnetic stirrer, a reflux condenser and a thermometer, 4.0 g of 2-methacryloyloxy-2-methyladamantane (17. 2 mmol), 3-hydroxy-1-yl methacrylate 1.4 g (6.0 mmol), methacrylic acid = 2-oxo-4-oxahexahydro-3,5-methano-2H-cyclopenta [b] furan-6- 4.2 g (19.0 mmol) of yl and 36.0 g of methyl ethyl ketone were charged, and nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 8 hours to obtain 7.0 g of a polymer compound (e) having the following structural units. The obtained polymer compound (e) had a weight average molecular weight (Mw) of 5,950 and a molecular weight distribution of 1.70.

Comparative Synthesis Example 3 Synthesis of Polymer Compound (f) In a three-necked flask having an internal volume of 50 ml equipped with an electromagnetic stirrer, a reflux condenser and a thermometer, 4.0 g of 2-methacryloyloxy-2-methyladamantane (17. 2 mmol), 3-hydroxy-1-yl = methacrylate 1.4 g (6.0 mmol), 5- (methacryloyloxyacetoxy) -2,6-norbornane sultone 6.3 g (19.8 mmol) and methyl ethyl ketone 36.0 g. Preparation and nitrogen bubbling were performed for 10 minutes. Under a nitrogen atmosphere, 0.54 g (3 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
The obtained reaction mixture was added dropwise to 500 g of methanol with stirring at room temperature, and the generated precipitate was collected by filtration. The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 8 hours to obtain 6.5 g of a polymer compound (f) having the following structural units. The obtained polymer compound (f) had a weight average molecular weight (Mw) of 6,050 and a molecular weight distribution of 1.63.

<Examples 5 to 7 and Comparative Examples 1 to 3>
100 parts by mass of the polymer compounds (a) to (f) obtained in Examples 2 to 4 or Comparative Synthesis Examples 1 to 3, “TPS-109” (product name, component; nonafluoro-n—) as a photoacid generator 4.5 parts by mass of triphenylsulfonium butane sulfonate (manufactured by Midori Chemical Co., Ltd.) and 1896 parts by mass of a propylene glycol monomethyl ether acetate / cyclohexanone mixed solvent (mass ratio = 1: 1) as a solvent were mixed to prepare a photoresist composition. Prepared.
These photoresist compositions were filtered using a membrane filter having a pore size of 0.2 μm. A cresol novolak resin ("PS-6937" manufactured by Gunei Chemical Industry Co., Ltd.) was applied with a 6% by mass propylene glycol monomethyl ether acetate solution by spin coating, and baked on a hot plate at 200 ° C for 90 seconds. Each of the filtrates was applied by spin coating on a silicon wafer having a diameter of 10 cm on which an antireflection film (underlayer film) having a thickness of 100 nm was formed, and pre-baked on a hot plate at 130 ° C. for 90 seconds to have a thickness of 300 nm. The resist film was formed. This resist film was exposed by a two-beam interference method using an ArF excimer laser having a wavelength of 193 nm. Subsequently, post exposure baking was performed at 130 ° C. for 90 seconds, followed by development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds to form a 1: 1 line and space pattern. The developed wafer was cleaved and observed with a scanning electron microscope (SEM), and the pattern shape observation and line width variation (LWR) of the exposure amount obtained by resolving the line-and-space with a line width of 100 nm at 1: 1. Measurements were made.
In the LWR, the line width is detected at a plurality of positions in the measurement monitor, and the dispersion (3σ) of variations in the detected positions is used as an index. Moreover, the cross-sectional shape of the pattern was observed using a scanning electron microscope (SEM) and evaluated as “◯” when the rectangularity was high and “X” when the rectangularity was low. The results are shown in Table 2.

From the above, the resist composition using the polymer compound (polymer compounds (a) to (c)) obtained by polymerizing the raw material containing the acrylate derivative of the present invention is the acrylate ester of the present invention. Compared to resist compositions that use polymer compounds (polymer compounds (d) to (f)) obtained by polymerization without using derivatives, it is possible to form a photoresist pattern with a better shape, and to improve LWR Therefore, it was possible to achieve both formation of a high-resolution photoresist pattern and reduction of LWR.

The acrylic ester derivative of the present invention is useful as a raw material for a polymer compound for a photoresist composition with improved LWR and forming a high-resolution resist pattern, and is useful in the production of semiconductors and printed boards.

Claims (15)

1. The following general formula (1)
   

   

   
   (In the general formula (1), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Represents.
   X ¹ represents —S (═O) — or —S (═O) ₂ —, and X ² represents —O—, —S (═O) — or —S (═O) ₂ —.
   U ¹ and U ² each independently represent a single bond or an alkylene group selected from the group consisting of a methylene group and an ethylene group, and the alkylene group has an alkyl group having 1 to 10 carbon atoms and a carbon number It may be substituted with at least one substituent selected from the group consisting of 3 to 10 cycloalkyl groups.
   U ³ represents an alkylene group selected from the group consisting of a methylene group, an ethylene group, a trimethylene group and a tetramethylene group, or a cycloalkylene group having 3 to 10 carbon atoms, and the alkylene group and the cycloalkylene group have It may be substituted with at least one substituent selected from the group consisting of 1 to 10 alkyl groups and cycloalkyl groups having 3 to 10 carbon atoms.
   A ¹ represents a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms.
   A ² represents a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the alicyclic hydrocarbon group is an alkyl group having 1 to 10 carbon atoms. May be substituted.
   k represents an integer of 0-2. )
   An acrylic ester derivative represented by
2. The following general formula (2)
   

   

   
   (In the general formula (2), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1.
   R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
   z represents 0 or 1; )
   The acrylic ester derivative according to claim 1, which is represented by:
3. The following general formula (2-1)
   

   

   
   (In the general formula (2-1), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1)
   The acrylic ester derivative according to claim 2, which is represented by:
4. The following general formula (3)
   

   

   
   (In General Formula (3), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1.
   R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
   z represents 0 or 1; )
   The acrylic ester derivative according to claim 1, which is represented by:
5. The following general formula (3-1)
   

   

   
   (In the general formula (3-1), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1)
   The acrylic ester derivative according to claim 4, which is represented by:
6. The acrylic ester derivative according to any one of claims 1 to 5, wherein X ¹ is -S (= O) _2- and X ² is -O-.
7. The acrylic ester derivative according to any one of claims 1 to 6, wherein k is 0.
8. The following general formula (2)
   

   

   
   (In the general formula (2), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1.
   R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
   z represents 0 or 1; )
   And the following general formula (3):
   

   

   
   (In General Formula (3), R ¹ , R ² , X ¹ , X ² , A ² and k are as defined in claim 1.
   R ³ to R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
   z represents 0 or 1; )
   A mixture of acrylic ester derivatives represented by
9. The mixing ratio [(2) :( 3)] of the acrylic ester derivative represented by the general formula (2) and the acrylic ester derivative represented by the general formula (3) is 50:50 to 95 in molar ratio. The mixture of claim 8, wherein:
10. The mixture according to claim 8 or 9, wherein in both of the general formulas (2) and (3), X ¹ is -S (= O) _2- and X ² is -O-.
11. The mixture according to any one of claims 8 to 10, wherein k is 0 in both of the general formulas (2) and (3).
12. A polymer compound having a structural unit derived from the acrylate derivative according to any one of claims 1 to 7.
13. A polymer compound having two or more kinds of structural units derived from the acrylate derivative according to any one of claims 1 to 7.
14. A polymer compound having a structural unit derived from the mixture according to any one of claims 8 to 11.
15. A photoresist composition comprising a photoacid generator, a solvent, and the polymer compound according to any one of claims 12 to 14.