JP2009286720A - alpha-SUBSTITUTED ACRYLATE DERIVATIVE, AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new &alpha;-substituted acrylate derivative useful as a raw material for a polymer compound for use in a photoresist composition excellent in its dissolution-rate controllability while maintaining its high transparency in the vicinity of the wavelength of 193 nm, and an efficient method of producing the same. <P>SOLUTION: The &alpha;-substituted acrylate derivative is represented by formula (I) (in the formula, R<SP>1</SP>represents a hydrogen atom, a 1-5C alkyl group or a 1-5C fluorinated alkyl group; R<SP>2</SP>and R<SP>3</SP>each independently represents a hydrogen atom, an alkyl group that may contain an oxygen atom on an optional position thereof, a cycloalkyl group that may contain an oxygen atom on an optional position thereof or they may combine together to represent an alkylene group; and W represents a cycloalkylene group that may contain an oxygen atom on an optional position thereof). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an α-substituted acrylate derivative and a method for producing the same. The α-substituted acrylate derivative obtained by the present invention is a novel compound and is useful as a raw material for a polymer compound for 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 devices, and therefore, 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 F2 excimer lasers having shorter wavelengths than these excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like.
Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern 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. . Resin (base resin) is mainly used as the base component of the chemically amplified resist.
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 resist 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 upon exposure at the time of forming a resist pattern, the base resin and the crosslinking agent react due to the action of the acid, and the solubility of the base resin in an alkaline developer decreases. (For example, refer nonpatent literature 1-2.).
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. 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.
JP 2003-241385 A SPIE Advances in Resist Technology and Processing XIV, Vol. 3333, p417-424 (1998) SPIE Advances in Resist technology and Processing XIX, Vol. 4690 p94-100 (2002)

  However, the conventional acrylic resin used as a photoresist composition for ArF shows a high acidity of about 4 pKa because carboxylic acid is used as a soluble group, and phenol with about 10 pKa is used as a soluble group. Since the dissolution rate in an alkaline developer is faster than that of the photoresist composition for KrF, pattern swelling and pattern collapse have become prominent problems when forming a fine pattern.

  Thus, an object of the present invention is to provide a novel α-substituted acrylic acid that is useful as a material for a polymer compound for a photoresist composition having excellent control of dissolution rate while maintaining high transparency in the vicinity of a wavelength of 193 nm. An object is to provide an ester derivative and an efficient production method thereof.

  As a result of intensive studies to solve the problems of the background art described above, the present inventors have introduced a sulfamoyloxy group having acidity equivalent to that of phenol into an α-substituted acrylate derivative. Thus, the polymer compound obtained by polymerizing the compound as a structural unit has moderate alkali solubility while maintaining high transparency in the vicinity of a wavelength of 193 nm, and the dissolution rate can be controlled. It has been found that it is useful as a component of a photoresist composition that can prevent pattern collapse and can form a pattern with excellent resolution.

That is, the present invention
[1] The following general formula (I)

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, R ² and R ³ are each independently a hydrogen atom, oxygen at an arbitrary position; An alkyl group that may contain an atom, or a cycloalkyl group that may contain an oxygen atom at any position, or an alkylene group bonded to each other to represent an alkylene group, W represents an oxygen atom at any position Represents a cyclic alkylene group which may be contained.)
An α-substituted acrylate derivative represented by the formula [hereinafter referred to as α-substituted acrylate derivative (I). ],
[2] General formula (II)

(Wherein R ¹ and W are as defined above.)
The alcohol derivative (II) shown below [hereinafter referred to as the alcohol derivative (II). ] And the general formula XSO ₂ NR ² R ³
(In the formula, X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R ² and R ³ are as defined above.)
The sulfamoyl halide derivative shown below [Hereinafter referred to as a sulfamoyl halide derivative. And a method for producing an α-substituted acrylate derivative (I).

  According to the present invention, the novel α-substituted acrylate derivative (I), which is a material of a polymer compound for a photoresist composition excellent in controlling the dissolution rate while maintaining high transparency in the vicinity of a wavelength of 193 nm, and A manufacturing method thereof can be provided.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the fluorinated alkyl group having 1 to 5 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, and a perfluoro group. Examples thereof include a butyl group, a perfluoroisobutyl group, a perfluoro-tert-butyl group, a perfluoropentyl group, a perfluoroisopentyl group, and a perfluoroneopentyl group. Among these, a hydrogen atom, a methyl group, or a trifluoromethyl group is preferable, and a hydrogen atom or a methyl group is more preferable in terms of industrial availability.

Examples of the alkyl group that may contain an oxygen atom at any position represented by R ² and R ³ include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. T-butyl group, 2-methyl-2-butyl group, 3-methyl-2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, methoxymethyl group, 1-ethoxyethyl group, etc. Examples of the cycloalkyl group that may contain an oxygen atom at any position include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, Cyclohexyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, cycloheptyl group, 1-methyl-1-cycloheptyl group, 1- Til-1-cycloheptyl group, cyclooctyl group, 1-methyl-1-cyclooctyl group, 1-ethyl-1-cyclooctyl group, bicyclo [2.2.1] hept-2-yl group, 1-adamantyl Group, 2-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, tetrahydrofuran-2-yl group, tetrahydropyran-2-yl group and the like, and R ² and R ³ are Examples of the alkylene group represented by bonding include an ethanediyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

  X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Examples of the cyclic alkylene group which may contain an oxygen atom at an arbitrary position represented by W include a cyclopropanediyl group, a cyclobuta-1,2-diyl group, a cyclobuta-1,3-diyl group, and a cyclopenta-1 , 2-diyl group, cyclopenta-1,3-diyl group, cyclohexa-1,2-diyl group, cyclohexa-1,3-diyl group, cyclohexa-1,4-diyl group, bicyclo [2.2.1 ] Hepta-2,3-diyl group, bicyclo [2.2.1] hepta-2,5-diyl group, 7-oxabicyclo [2.2.1] hepta-2,5-diyl group, bicyclo [2] 2.1] hepta-2,6-diyl group, 7-oxabicyclo [2.2.1] hepta-2,6-diyl group, adamanta-1,3-diyl group, adamanta-1,2-diyl Groups and the like.

The α-substituted acrylate derivative (I) of the present invention is useful as a component of a polymer compound suitably used as a resin component of a negative photoresist composition or a positive photoresist composition. The α-substituted acrylate derivative (I), in which either one or both of R ² and R ³ are hydrogen atoms, is a component (hereinafter referred to as “component”) that reacts with a crosslinking agent in the polymer compound for a negative photoresist composition. It is referred to as a negative-type constituent). In addition, the α-substituted acrylate derivative (I) in which both of R ² and R ³ are an alkyl group, a cycloalkyl group, or an alkylene group is used as a substrate in a polymer compound for negative and positive photoresist compositions. It is useful as a component for imparting adhesion, a component that increases the affinity with a developer, and a component for adjusting dissolution rate (hereinafter referred to as a negative / positive component). Either R ² or R ^{3 is} an alkyl group which may contain an oxygen atom at any position or a cyclic alkylene group which may contain an oxygen atom at any position, or both The α-substituted acrylate derivative (I) which is an alkylene group is a constituent that becomes soluble in an alkali developer upon exposure of the polymer compound for positive photoresist composition (hereinafter referred to as a positive constituent). Useful as.

  Hereinafter, the α-substituted acrylate derivative (I) useful as a negative component, a negative / positive component, and a positive component will be described.

In the α-substituted acrylate derivative (I) useful as a negative component, either one or both of R ² and R ³ are preferably hydrogen atoms, and more preferably both are hydrogen atoms.

The α-substituted acrylate derivative (I) useful as a negative / positive-type component is such that R ² and R ³ are an alkyl group, a cycloalkyl group, or a hydrogen atom, or R ² and R ³ are bonded An alkylene group is preferable.

The α-substituted acrylate derivative (I) useful as a positive component is an alkyl group or an arbitrary position in which either one or both of R ² and R ³ may contain an oxygen atom. It is preferably a cyclic alkylene group which may contain an oxygen atom, or a combination thereof and an alkylene group, preferably a tertiary group such as a tert-butyl group, a tert-pentyl group or a tert-heptyl group. Alkyl group; 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 1-methyl-1-cyclopentyl group, 1- A tertiary cycloalkyl group such as ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group; Alkoxy such as xymethyl group, ethoxymethyl group, 1-methoxyethyl group, methoxyethoxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, adamantyloxymethyl group, tetrahydropyran-2-yl group, tetrahydrofuran-2-yl group An alkyl group is more preferred.

  Specific examples of the α-substituted acrylate derivative (I) include the following (I-1) to (I-75), but are not limited thereto.

  Although there is no restriction | limiting in particular in the manufacturing method of (alpha) -substituted acrylic ester (I) of this invention, For example, it can manufacture by the method of making alcohol derivative (II) react with a sulfamoyl halide derivative.

  Hereinafter, the production method of the α-substituted acrylate derivative (I) will be described.

(In the formula, R ¹ , R ² , R ³ , X and W are as described above.)

There is no restriction | limiting in particular in the manufacturing method of alcohol derivative (II) which is a raw material, Commercially available 3-hydroxyadamantyl methacrylate, 3-hydroxyadamantyl acrylate, etc. can be used as it is.
Although there is no restriction | limiting in particular in the manufacturing method of a sulfamoyl halide derivative, For example, it can manufacture by making chlorosulfonyl isocyanate and formic acid react in presence of solvents, such as hexane.

  Hereinafter, the manufacturing method of said (alpha) -substituted acrylate derivative (I) is demonstrated in detail.

  The amount of the sulfamoyl halide derivative used is preferably in the range of 0.8 to 10 moles relative to the alcohol derivative (II), and in the range of 1 to 5 moles from the viewpoint of economy and ease of post-treatment. Further preferred.

The reaction 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, aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide, N, Amides such as N-dimethylacetamide and N-methylpyrrolidone; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more.
The amount of the solvent used is preferably 100 times by mass or less, more preferably 50 times by mass or less, still more preferably 20 times by mass or less based on the alcohol derivative (II).

  Although reaction temperature changes with kinds of alcohol derivative (II) and sulfamoyl halide derivative to be used, the range of -20-100 degreeC is preferable, and it is -20-80 degreeC from a viewpoint of side reaction suppression, such as superposition | polymerization. A range is more preferred.

  The reaction time varies depending on the type and amount of the alcohol derivative (II) and sulfamoyl halide derivative used, and the reaction temperature. Usually, the range is 0.5 to 48 hours, preferably 0.5 to 24 hours. A range is further preferred.

  The reaction is preferably carried out in the presence of a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and for example, quinone compounds such as hydroquinone, methoxyphenol, benzoquinone, tolquinone, p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol And alkylphenol compounds such as 2-tert-butyl-4,6-dimethylphenol; amine compounds such as phenothiazine. One type of polymerization inhibitor may be used, or two or more types may be used in combination. When using a polymerization inhibitor, the amount used is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, based on the mass of the entire reaction mixture.

  There is no restriction | limiting in particular in reaction operation, The charging method and order of alcohol derivative (II), a sulfamoyl halide derivative, and a solvent may be arbitrary. As a specific reaction operation, for example, a method in which a sulfamoyl halide derivative and a solvent are charged into a batch reactor and the alcohol derivative (II) is added is preferable.

  Isolation and purification of the α-substituted acrylate derivative (I) from the reaction mixture obtained by the method of the present invention can be carried out by methods generally used for isolation and purification of organic compounds. For example, after completion of the reaction, the α-substituted acrylate derivative (I) can be isolated by adding water to the reaction mixture, extracting with an organic solvent, and concentrating the resulting organic layer. If necessary, the α-substituted acrylate derivative (I) having a high purity can be obtained by purification by recrystallization, distillation, silica gel column chromatography or the like. Furthermore, the metal content in the α-substituted acrylate derivative (I) can be reduced by treating with a chelating agent, a demetallizing filter or the like, if necessary.

≪Synthesis of polymer compound≫

  Polymer compound obtained by polymerizing α-substituted acrylate derivative (I) or polymer compound obtained by copolymerizing α-substituted acrylate derivative (I) with other polymerizable compound [hereinafter, both These are collectively referred to as polymer compound (A1). ] Is useful as a polymer compound for photoresist compositions. The polymer compound (A1) is a structural unit (a0-1) based on the α-substituted acrylate derivative (I) [hereinafter referred to as a structural unit (a0-1). ] Is more than 0 mol% and 100 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%. Specific examples of the structural unit (a0-1) include those represented by the following formulas (a0-1-10) to (a0-1-87).

In the polymer compound (A1), as the structural unit (a0-1), one type of structural unit may be used, or two or more types may be used in combination.
The polymer compound (A1) may be a polymer composed of only one type of structural unit (a0-1), or may be a copolymer composed of two or more types of structural units (a0-1). Further, it may be a copolymer containing other structural units.
When the polymer compound (A1) is a copolymer containing other structural units other than the structural unit (a0-1), the proportion of the structural unit (a0-1) in the polymer compound (A1) 10-80 mol% is preferable with respect to all the structural units which comprise a compound (A1), 15-80 mol% is more preferable, 20-70 mol% is further more preferable, and 20-60 mol% is especially 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.

  When the polymer compound (A1) is a copolymer containing other structural units other than the structural unit (a0-1), examples of the other structural units include the following structural units (a1) and structural units (a2). ), Structural unit (a3), structural unit (a4), and the like. As the structural unit (a3), the following structural unit (a′3), structural unit (a ″ 3), and the like can be given.

[Structural unit (a1)]
The structural unit (a1) is a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group. The acid dissociable, dissolution inhibiting group has an alkali dissolution inhibiting property that makes the entire polymer compound (A1) insoluble in an alkaline developer before dissociation when forming a resist pattern as a resist composition, It is dissociated by an acid generated by exposure from a generator component to increase the solubility of the entire polymer compound (A1) in an alkaline developer. Up to now, the acid dissociation property of a base resin for a chemically amplified resist What was proposed as a dissolution inhibiting group can be used.

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

(In the above formula, 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; M represents 0 or 1; R is the same as defined above; R ¹ ′ and R ² ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.)

[Structural unit (a2)]
The structural unit (a2) is a structural unit derived from an acrylate ester containing a lactone-containing cyclic group.

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

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 or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1. And A is an alkylene group having 1 to 5 carbon atoms or an oxygen atom.)

[Structural unit (a3)]
The structural unit (a3) is a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group, which does not correspond to the structural unit (a0).

  More specifically, examples of the structural unit (a3) include structural units represented by general formulas (a′3-1) and (a ″ 3-1) shown below.

(In the formula, R is the same as above, R ^{4 is a} hydrogen atom or a hydroxyalkyl group, and j is an integer of 1 to 3).

Wherein R ⁵ is a hydrogen atom, an alkyl group, a halogenated alkyl group or a hydroxyalkyl group; R ⁶ is a hydrogen atom, an alkyl group or a hydroxyalkyl group, provided that at least one of R ⁵ and R ⁶ is It is a hydroxyalkyl group.)

Wherein R is the same as above, k is an integer of 1 to 3, t ′ is an integer of 1 to 3, l is an integer of 1 to 5, and s is an integer of 1 to 3. .)

[Structural unit (a4)]
The structural unit (a4) is a structural unit derived from (meth) acrylic acid cyclic alkyl ester.

  Specific examples of the structural unit (a4) include those represented by the following general formulas (a4-1) to (a4-5).

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

[Other structural units]
The polymer compound (A1) may have other structural units (a4) other than the structural units (a0) 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 not classified into the above structural units (a0) to (a3), and is not limited to 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.

Preferred copolymers as the polymer compound (A1) include the following copolymers (A1-1) to (A1-5).
Copolymer (A1-1): A copolymer having at least two types of structural units, including the structural units (a0) and (a1).
Copolymer (A1-2): a copolymer having at least two types of structural units, including the structural units (a0) and (a2).
Copolymer (A1-3): a copolymer having at least two types of structural units, including the structural units (a0) and (a3).
Copolymer (A1-4): a copolymer having at least three types of structural units, including the structural units (a0), (a1), and (a2).
Copolymer (A1-5): A copolymer having at least three structural units, including the structural unit (a0) and two structural units (a3).

The mass average molecular weight (Mw) of the polymer compound (A1) (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but when used as a base component of a negative resist composition, 1000-8000 are preferable, 2000-7000 are more preferable, and 2500-6500 are the most preferable. Moreover, when using as a base-material component of a positive resist composition, 3000-50000 are preferable, 4000-30000 are more preferable, 4000-20000 are the most preferable. When Mw is smaller than the upper limit of these ranges, there is sufficient solubility in a resist solvent to be used as a resist. When Mw is larger than the lower limit of these ranges, dry etching resistance and resist pattern cross-sectional shape are good. is there.
The dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and most preferably 1.2 to 3.8. In addition, Mn shows a number average molecular weight.

[Production of polymer compound (A1)]
In the polymer compound (A1), a monomer for deriving each structural unit was used, for example, a radical polymerization initiator such as dimethyl-2,2-azobis (2-methylpropionate) or azobisisobutyronitrile. It can be obtained by polymerization by known radical polymerization or the like.

  The polymer compound (A1) is a group of a so-called chemically amplified resist composition containing a base material component whose solubility in an alkali developer is changed by the action of an acid and an acid generator component that generates an acid upon exposure. It is useful as a material component. For example, according to a resist composition containing the polymer compound (A1) as a base component, a resist pattern having excellent resolution can be formed. Hereinafter, the resist composition using the polymer compound (A1) as a base component will be described. The resist composition can be prepared by blending the polymer compound (A1), an acid generator component that generates an acid upon exposure, a crosslinking agent component, an organic solvent, and other optional components.

  The resist pattern forming method using the resist composition includes a step of forming a resist film on the support using the resist composition, a step of exposing the resist film, and an alkali developing of the resist film. It can be performed by a method including a step of forming a resist pattern.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited at all by these Examples.

Example 1 Synthesis of 3-sulfamoyloxyadamantyl acrylate

  A 5 L four-necked flask equipped with a thermometer, a dropping funnel and a stirrer was charged with nitrogen, and 980 g of heptane and 334 g (2.4 mol) of chlorosulfonyl isocyanate were charged from the dropping funnel. After cooling the internal temperature to 5 ° C., 110 g (2.4 mol) of formic acid was added dropwise from a dropping funnel at such a rate as to maintain the internal temperature of 5-8 ° C. After completion of dropping, the internal temperature was raised to 20 ° C. and stirred for 10 hours. A solution of 175 g (0.79 mol) of 3-hydroxyadamantyl acrylate, 525 g of N-methylpyrrolidone, 2.1 g of 4-methoxyphenol and 2.1 g of phenothiazine can be maintained at an internal temperature of 20 ° C. or less from the dropping funnel. It was dripped at a speed. After stirring at an internal temperature of 20 to 25 ° C. for 3 hours, the reaction mixture was transferred to a separatory funnel and the upper layer was discarded. To the resulting lower layer, 890 g of ethyl acetate and 700 g of water were added, stirred, allowed to stand, and then separated. 890 g of ethyl acetate was added to the aqueous layer and re-extracted. Two ethyl acetate layers were mixed and then washed five times with 900 g of water. Subsequently, it was washed with 400 g of 7% by mass-aqueous sodium hydrogen carbonate solution and 400 g of water. After the washing, the organic layer was concentrated under reduced pressure to 500 g, and then 630 g of toluene was added. After heating to an internal temperature of 55 ° C., the mixture was cooled to 3 ° C. and recrystallized. The obtained suspension was filtered to obtain 145 g (0.48 mol) of 3-sulfamoyloxyadamantyl acrylate as crystals (yield = 61%).

¹ H-NMR (300 MHz, DMSO-d ₆ , TMS, ppm) δ: 7.44 (2H, s), 6.26 (1H, m), 6.07 (1H, m,), 3.34 ( 1H, s), 2.48 (3H, s), 2.34 (2H, s), 2.04 (6H, m), 1.52 (2H, s)

Example 2 Synthesis of 3-sulfamoyloxyadamantyl methacrylate

  The same operation as in Example 1 was carried out except that 186.7 g (0.79 mol) of 3-hydroxyadamantyl methacrylate was used instead of 175 g (0.79 mol) of 3-hydroxyadamantyl acrylate, and 3-sulfamoyl was obtained. 159.5 g (0.51 mol) of oxyadamantyl methacrylate was obtained (yield = 64%).

¹ H-NMR (300 MHz, DMSO-d ₆ , TMS, ppm) δ: 7.43 (2H, s), 5.96 (1H, s), 5.62 (1H, s), 2.48 (2H , S), 2.35 (3H, br), 2.23 (1H, s), 2.04 (6H, m), 1.84 (3H, s) 1.52 (2H, s)

<Synthesis Example 1>
After charging 13.0 g of propylene glycol monomethyl ether into a 100 ml four-necked flask equipped with a thermometer, a nitrogen introducing tube, a dropping funnel, and a stirring device, nitrogen was bubbled through the nitrogen introducing tube for 15 minutes. Next, after the internal temperature was raised to 80 ° C., 7.0 g (mmol) of 3-sulfamoyloxyadamantyl acrylate, 0.05 g (0.3 mmol) of azobisisobutyronitrile and propylene glycol monomethyl ether were added from a dropping funnel. 22.6 g of solution was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred at 80 to 83 ° C. for 3 hours, cooled to 25 ° C., and the reaction solution was dropped into 309 g of diisopropyl ether. The resulting precipitate was filtered using a glass filter, and the obtained powder was dissolved in 28 g of propylene glycol monomethyl ether and dropped into a mixed solvent of 136 g of diisopropyl ether and 15 g of ethyl acetate. The resulting precipitate was filtered using a glass filter, and the obtained powder was dried at 40 ° C. under reduced pressure for 8 hours. 5.6 g of the following polymer compound having a mass average molecular weight = 6100 and a molecular weight dispersity = 1.35 was obtained (yield = 80%).

<Synthesis Example 2>
14.8 g of propylene glycol monomethyl ether was charged into a 100 ml four-necked flask equipped with a thermometer, a nitrogen introducing tube, a dropping funnel, and a stirring device, and then nitrogen was bubbled through the nitrogen introducing tube for 15 minutes. Next, after raising the internal temperature to 80 ° C., 4.0 g (13.3 mmol) of 3-sulfamoyloxyadamantyl acrylate, 2.9 g (13.1 mmol) of 3-hydroxyadamantyl acrylate, azobis from the dropping funnel. A solution of 0.06 g (0.3 mmol) of isobutyronitrile and 26.6 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred at 80 to 83 ° C. for 3 hours, and then the reaction solution was dropped into 204 g of diisopropyl ether. The resulting precipitate was filtered using a glass filter, and the obtained powder was redissolved in 20 g of propylene glycol monomethyl ether. The solution was dropped into a mixed solvent of 117 g of diisopropyl ether and 13 g of ethyl acetate, the resulting precipitate was filtered using a glass filter, and the obtained solid was dried under reduced pressure to obtain a mass average molecular weight of 5600 and a dispersity of 1 .40 high molecular weight compound (5.0 g) was obtained (yield 72%).

<Synthesis Example 3>
After charging 33.2 g of propylene glycol monomethyl ether into a 200 ml four-necked flask equipped with a thermometer, a nitrogen introducing tube, a dropping funnel, and a stirring device, nitrogen was bubbled through the nitrogen introducing tube for 15 minutes. Next, after raising the internal temperature to 78 ° C., 6.10 g (20.2 mmol) of 3-sulfamoyloxyadamantyl acrylate and 2.79 g (13.5 mmol) of azobisisobutyronitrile from the dropping funnel A solution of 0.22 g (1.35 mmol) and 33.2 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After the completion of dropping, the mixture was stirred at 78 to 80 ° C. for 2 hours, and then the reaction solution was dropped into 300 g of n-hexane. The filtrate was removed by decantation, and the resulting precipitate was redissolved in 27.6 g of propylene glycol monomethyl ether. The solution was dropped into a mixed solvent of 360 g of n-hexane and 40 g of isopropyl alcohol, the filtrate was removed by decantation, and the obtained solid was dried under reduced pressure to give a high mass average molecular weight of 3800 and a dispersity of 1.48. 6.2 g of molecular weight compound was obtained (yield 70%).

<Synthesis Example 4>
After charging 23.3 g of propylene glycol monomethyl ether into a 200 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, a dropping funnel, and a stirrer, nitrogen was bubbled through the nitrogen inlet tube for 15 minutes. Next, after raising the internal temperature to 78 ° C., 6.10 g (20.2 mmol) of 3-sulfamoyloxyadamantyl acrylate and 2.79 g (13.5 mmol) of azobisisobutyronitrile from the dropping funnel A solution of 0.14 g (0.85 mmol) and 42.0 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After the completion of dropping, the mixture was stirred at 78 to 80 ° C. for 2 hours, and then the reaction solution was dropped into 300 g of n-hexane. The filtrate was removed by decantation, and the resulting precipitate was redissolved in 23.4 g of propylene glycol monomethyl ether. The solution was dropped into a mixed solvent of 270 g of n-hexane and 30 g of isopropyl alcohol, the filtrate was removed by decantation, and the obtained solid was dried under reduced pressure to obtain a high mass average molecular weight of 6040 and a dispersity of 1.37. 3.7 g of a molecular weight compound was obtained (42% yield).

<Synthesis Example 5>
After charging 37.0 g of propylene glycol monomethyl ether into a 200 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube, a dropping funnel, and a stirrer, nitrogen was bubbled through the nitrogen introduction tube for 15 minutes. Next, after raising the internal temperature to 80 ° C., 9.0 g (29.9 mmol) of 3-sulfamoyloxyadamantyl acrylate, 1.54 g (7.5 mmol) of adamantyl acrylate, azobisisobutyro A solution of 0.17 g (1.9 mmol) of nitrile and 69.6 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After completion of dropping, the mixture was stirred at 80 ° C. for 2 hours, and then the reaction solution was dropped into 2200 g of diisopropyl ether. The resulting precipitate was filtered using a glass filter, and the obtained solid was dried under reduced pressure to obtain 7.7 g of a high molecular weight compound having a mass average molecular weight of 4300 and a dispersity of 1.31 (yield 73%). .

<Synthesis Example 6>
After charging 14.0 g of propylene glycol monomethyl ether into a 100 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube, a dropping funnel, and a stirrer, nitrogen was bubbled through the nitrogen introduction tube for 15 minutes. Next, after raising the internal temperature to 80 ° C., 6.1 g (20.1 mmol) of 3-sulfamoyloxyadamantyl acrylate, 2.4 g (20.4 mmol) of 2-hydroxyethyl acrylate, azobis from the dropping funnel A solution of 0.08 g (0.5 mmol) of isobutyronitrile and 22.0 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred at 80 to 83 ° C. for 3 hours, and then the reaction solution was dropped into 204 g of diisopropyl ether. The resulting precipitate was filtered using a glass filter, and the obtained powder was redissolved in 20 g of propylene glycol monomethyl ether. The solution was dropped into a mixed solvent of 117 g of diisopropyl ether and 13 g of ethyl acetate, the resulting precipitate was filtered using a glass filter, and the resulting solid was dried under reduced pressure to obtain a weight average molecular weight of 7000 and a molecular weight dispersion of 1 5.9 g of a high molecular weight compound of .50 was obtained (yield = 70%).

<Reference Examples 1-5>
Each component shown in Table 1 was mixed and dissolved to prepare a negative resist composition.

Each abbreviation in Table 1 has the following meaning. Moreover, the numerical value in [] is a compounding quantity (mass part).
(A) -1: the polymer compound (1).
(A) -2: the polymer compound (2).
(A) -4: The polymer compound (4).
(A) -5: The polymer compound (5).
(A) -6: the polymer compound (6).
(A) -1 ′: a polymer having a mass average molecular weight of 5000 represented by the above formula (1).
(B) -2: Triphenylsulfonium trifluoromethanesulfonate.
(C) -1: A compound represented by the following chemical formula (C) -1 (tetramethoxymethylated glycoluril, product name: Nicalac MX-270, manufactured by Sanwa Chemical Co., Ltd.).
(D) -1: Triisopropanolamine.
(S) -1: Propylene glycol monomethyl ether (PGME).

The following evaluation was performed using the obtained resist composition.
[Evaluation of residual film properties]
An organic antireflective coating composition “ARC29” (trade name, manufactured by Brewer Science Co., Ltd.) is uniformly applied on an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a thickness of 77 nm was formed.
The resist composition is applied onto the organic antireflection film using a spinner, pre-baked (PAB) at 90 ° C. for 60 seconds on a hot plate, and dried to obtain a film thickness. A 160 nm resist film was formed.
An ArF excimer laser (193 nm) was applied to the resist film with an ArF exposure apparatus NSR-S302 (product name, manufactured by Nikon; NA (numerical aperture) = 0.60, 2/3 annular illumination). It exposed with the exposure amount of 30 mJ / cm < ² >. Thereafter, a post-exposure heating (PEB) treatment was performed at 110 ° C. for 60 seconds, followed by development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 60 seconds, followed by washing with water for 30 seconds and drying. did.
At this time, a residual film curve was obtained from the change in the residual film ratio (unit:%, resist film thickness after development / resist film thickness during film formation (before exposure) × 100) due to the change in exposure amount. As a result, all the resist compositions of Reference Examples 1 to 6 showed good contrast. Moreover, the maximum remaining film rate (convergence value of the remaining film rate) is respectively Reference Example 1 (73%), Reference Example 2 (96%), Reference Example 3 (99.6%), and Reference Example 4 (60%). ), Reference Example 5 (100%), and Reference Example 6 (70%).
From the above results, it was confirmed that the resist compositions of Reference Examples 1 to 6 were excellent in residual film characteristics and functioned as negative resist compositions.

[Evaluation of lithography properties]
An organic antireflective coating composition “ARC29” (trade name, manufactured by Brewer Science Co., Ltd.) is uniformly applied on an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a thickness of 77 nm was formed.
On the organic antireflection film, the resist composition of Reference Example 2 was applied using a spinner, prebaked (PAB) at 90 ° C. for 60 seconds on a hot plate, and dried to form a film. A resist film having a thickness of 160 nm was formed.
An ArF excimer laser (193 nm) is applied to the resist film by using an ArF exposure apparatus NSR-S302 (product name, manufactured by Nikon; NA (numerical aperture) = 0.60, 2/3 annular illumination) as a mask pattern. Selectively irradiated. Thereafter, PEB treatment was carried out at 110 ° C. for 60 seconds, followed by development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 60 seconds, followed by washing with water for 30 seconds and drying.
As a result, the resolution of a line-and-space resist pattern (LS pattern) having a line width of 250 nm and a pitch of 500 nm was confirmed.
At this time, the optimum exposure dose Eop (mJ / cm ² ) at which an LS pattern having a line width of 250 nm and a pitch of 500 nm was formed was determined as “sensitivity”. As a result, the Eop of Reference Example 2 was 35 mJ / cm ² .
In addition, as “resolution”, the limit resolution (nm) in the Eop was determined using a length measurement SEM (scanning electron microscope) S-9220 (manufactured by Hitachi). As a result, the limit resolution of Reference Example 2 was 150 nm.

  From the above results, it was confirmed that the polymer compound of the present invention was useful as a base component of the resist composition.

Claims (4)

The following general formula (I)

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, R ² and R ³ are each independently a hydrogen atom, oxygen at an arbitrary position; Represents an alkyl group which may contain an atom or a cycloalkyl group which may contain an oxygen atom at any position, or a combination of them together to represent an alkylene group, and W represents an oxygen atom at any position. Represents a cyclic alkylene group that may be present.)
An α-substituted acrylate derivative represented by the formula: The α-substituted acrylate derivative according to claim 1, wherein R ² and R ³ are each a hydrogen atom. The α-substituted acrylate derivative according to claim 1, wherein R ² and R ³ are each a hydrogen atom, and W is a cyclic alkylene group having 5 to 10 carbon atoms. The following general formula (II)

(Wherein R ¹ and W are as defined above.)
And an alcohol derivative represented by the general formula XSO ₂ NR ² R ³
(In the formula, X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R ² and R ³ are as defined above.)
The method for producing an α-substituted acrylate derivative according to claim 1, wherein the sulfamoyl halide derivative represented by formula (1) is reacted.