JP2009196944A - New acrylate derivative, and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound showing slight swelling during its development that constitutes a photoresist composition, and a new acrylate derivative useful as a raw material for producing the polymer compound. <P>SOLUTION: Disclosed is an acrylate derivative represented by formula (1). In the formula; R<SP>1</SP>and R<SP>2</SP>each represents a linear, branched or cyclic alkyl group, or R<SP>1</SP>and R<SP>2</SP>together represent a linear, branched or cyclic alkylene group; R<SP>3</SP>and R<SP>4</SP>each represents a hydrogen atom, a hydroxy group, an alkoxy group, or a linear, branched or cyclic alkyl group, or R<SP>3</SP>and R<SP>4</SP>together represent a linear, branched or cyclic alkylene group, an oxygen atom or a sulfur atom; R<SP>5</SP>represents a hydrogen atom, a methyl group, or a trifluoromethyl group; W represents a linear, branched or cyclic alkylene group; and n represents 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel acrylate derivative and a method for producing the same. The acrylic ester derivative obtained in the present invention is a novel compound and is useful as a material for a polymer compound for a photoresist composition.

In the field of electronic device manufacturing typified by integrated circuit element manufacturing, there is an increasing demand for high integration of devices, and therefore a photolithography technique for forming a fine pattern is required. For this reason, development of a photoresist composition corresponding to photolithography in which radiation having a wavelength of 200 nm or less such as ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm) or the like has been actively performed, Chemically amplified photoresist composition comprising a polymer compound having an acid-dissociable functional group and a compound that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) (hereinafter referred to as “photoacid generator”) Many have been proposed. This polymer compound having an acid-dissociable functional group basically has a structure in which a part of the alkali-soluble part of the alkali-soluble polymer compound is protected with an appropriate acid-dissociable functional group. The selection of the group is very important in adjusting the function as a photoresist composition.
As existing acid dissociable functional groups, 1) those having an adamantane structure (see Non-Patent Document 1 and Patent Document 1), and 2) a photoresist composition comprising as a component a polymer compound containing a structural unit having a lactone ring Is known (see Patent Document 2).

In recent years, under the circumstances where further miniaturization of pattern rules of electronic devices is required, a photo comprising a polymer compound containing a structural unit having a lactone-based protecting group, with improved sensitivity, resolution, dry etching resistance, etc. A resist composition has been proposed (see Patent Document 3 and Patent Document 4). However, it is difficult to say that these photoresist compositions still have sufficient performance. The biggest problem is the line width variation of the formed pattern called line width roughness (LWR), which is required to be less than 8% of the allowable line width. (Non-patent document 2). In order to improve LWR, it is necessary to suppress pattern deformation due to swelling. In order to suppress pattern deformation due to swelling, it is necessary that the polymer compound as the resist composition component is difficult to swell. However, a polymer compound prepared with a conventionally known combination of polymerizable compounds does not necessarily have a satisfactory level of performance. For this reason, development of the polymer compound for photoresists which is harder to swell is still anxious.
JP-A-9-73173 JP 2004-46206 A JP 11-223950 A JP 2000-267287 A Journal of Photopolymer Science and Technology (Journal of Photopolymer Science and Technology), Vol. 9, No, 3,475-487 (1996) ITRS 2006 Lithography, page 7

  Accordingly, an object of the present invention is to provide a polymer compound constituting a photoresist composition with small swelling during development, a novel acrylate derivative useful as a material thereof, and an efficient production method thereof. It is in.

  As a result of intensive studies on the relationship between the characteristics of various polymer compounds for photoresist and the swelling property during development of the photoresist composition, the present inventors have 1) dissolution of the exposed portion in the developer. Swelling can be suppressed by using a high-speed polymer compound for a photoresist composition, and 2) a specific acid useful as a raw material for a polymer compound having a specific repeating structure with a high dissolution rate in a developing solution of an exposed portion. A compound having a dissociative functional group was found and the present invention was completed.

That is, the present invention
1. The following general formula (1)

(In the formula, each of R ¹ and R ² represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² are combined together at any position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom, wherein R ³ and R ⁴ are each a hydrogen atom, a hydroxyl group, an alkoxy group or a carbon number of 1; Represents a linear, branched, or cyclic alkyl group of 1 to 10, or R ³ and R ⁴ together may contain an oxygen atom or a sulfur atom at an arbitrary position, 1 carbon atom 10 to 10 linear, branched or cyclic alkylene groups, oxygen atoms, or sulfur atoms.
R ⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
W represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms.
n represents 0 or 1. )
An acrylic ester derivative represented by (hereinafter referred to as an acrylic ester derivative (1));
2. Acrylate derivative (1) wherein W is a methylene group or a 1,1-ethanediyl group;
3. acrylic ester derivative (1) wherein n is 0;
4). Acrylic ester derivative (1) wherein R ³ and R ⁴ are hydrogen atoms;
5. An acrylate derivative (1) wherein R ³ and R ⁴ are hydrogen atoms and W is a methylene group or a 1,1-ethanediyl group;
6). An acrylate derivative (1) wherein R ³ and R ⁴ are hydrogen atoms and n is 0;
7). The following general formula (2)

(Wherein R ³ and R ⁴ are as defined above.)
A sulfolane derivative (hereinafter referred to as sulfolane derivative (2)) represented by the following general formula (3)

(In the formula, R ¹ and R ² are as defined in the previous term.)
The following general formula (4) is obtained by reacting a ketone compound represented by the formula (hereinafter referred to as ketone compound (3)).

(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
And then reacting the tertiary alcohol (4) with the polymerizable group-introducing agent, or the tertiary alcohol (4). ) And a linking group introducing agent, and then reacting with a polymerizable group introducing agent; and a method for producing an acrylate derivative (1),
8). Sulfolane derivative (2) and the following general formula (5)

Wherein R ^{1 ′} and R ^{2 ′} are
1) R ^{1 ′} represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. R ^{2 ′} represents a linear, branched, or cyclic alkyl group having 2 to 10 carbon atoms; or 2) R ^{1 ′} and R ^{2 ′} are combined to form an oxygen atom or a sulfur atom at an arbitrary position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms, which may contain
One of them.
The following general formula (6), characterized by reacting with a ketone compound represented by formula (hereinafter referred to as ketone compound (5)):

(Wherein R ³ , R ⁴ , R ^{1 ′} and R ^{2 ′} are as defined above.)
A method for producing a tertiary alcohol represented by (hereinafter referred to as tertiary alcohol (6)).
9. Tertiary alcohol (6);
10. Tertiary alcohol (6) wherein R ³ and R ⁴ are hydrogen atoms;
11. A polymer compound obtained by polymerizing the acrylate derivative (1) as at least one of raw materials (hereinafter referred to as polymer compound (7));
Is achieved by providing

  According to the present invention, there are provided a polymer compound constituting a photoresist composition having an improved LWR with small swelling during development, a novel acrylate derivative as a raw material, and an efficient production method thereof. Can do.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and isobutyl. Group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like. Examples of the linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom at an arbitrary position represented by R ¹ and R ² together include 1 , 2-ethanediyl group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, (cyclopentane-1 ′, 3′-diyl) methyl group , (2 ′, 2 ′, 3′-trimethylcyclopentane-1 ′, 3′-diyl) methyl group, bicyclo [3.3.1] nonane-3,7-diyl group, 2-oxabutane-1,4 A diyl group, 2-oxapentane-1,5-diyl group, 3-oxapentane-1,5-diyl group and the like can be mentioned. When R ¹ and R ² together represent an alkylene group, the alkylene group forms a ring structure together with the carbon atoms to which it is bonded. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornane ring, a camphor ring, an adamantane ring, a tetrahydrofuran ring, and a tetrahydropyran ring.

Examples of the alkoxy group represented by R ³ and R ⁴ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and isobutyl. Group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, and the like. Examples of the linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom at an arbitrary position represented by R ³ and R ⁴ together include, for example, 1, 4-butanediyl group, cyclopentane-1,3-diyl group, tetrahydrofuran-2,5-diyl group and the like can be mentioned. When R ³ and R ⁴ together represent an alkylene group, the alkylene forms a ring structure with the carbon atoms to which it is bonded. Examples of the ring structure include a cyclohexane ring, a norbornane ring, and an oxanorbornane ring.

  Examples of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms represented by W include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, and propane-1,1. -Diyl group, propane-1,2-diyl group, propane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,1-diyl group, cyclohexane-1,4-diyl group, etc. Can be mentioned. Of these, a methylene group and an ethane-1,1-diyl group are preferred.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ^{1 ′} include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like.

Examples of the linear, branched, or cyclic alkyl group having 2 to 10 carbon atoms represented by R ^{2 ′} include, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- A butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, tetrahydropyran-4-yl group and the like can be mentioned.
Examples of the linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom at an arbitrary position represented by R ^{1 ′} and R ^{2 ′} together include: 1,2-ethanediyl group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, (cyclopentane-1 ′, 3′-diyl) Methyl group, (2 ′, 2 ′, 3′-trimethylcyclopentane-1 ′, 3′-diyl) methyl group, bicyclo [3.3.1] nonane-3,7-diyl group, 2-oxabutane-1 , 4 diyl group, 2-oxapentane-1,5-diyl group, 3-oxapentane-1,5-diyl group and the like. When R ^{1 ′} and R ^{2 ′} together represent an alkylene group, the alkylene group forms a ring structure with the carbon atoms to which it is attached. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornane ring, a camphor ring, an adamantane ring, a tetrahydrofuran ring, and a tetrahydropyran ring.

  Specific examples of the acrylate derivative (1) include the following formulas (1-a) to (1-aa), but are not limited thereto.

  The acrylic ester derivative (1) is produced, for example, by reacting the sulfolane derivative (2) with the ketone compound (3) to produce the tertiary alcohol (4) in the first step), and the second step) the tertiary alcohol (4). ) And a polymerizable group introducing agent, or by reacting the tertiary alcohol (4) with a linking group introducing agent and then reacting with the polymerizable group introducing agent. It is not limited.

(Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are as defined above.)

  Hereinafter, each step will be described.

There is no restriction | limiting in particular in the manufacturing method of the sulfolane derivative | guide_body (2) used at a 1st process, A sulfolane derivative | guide_body (2) can be manufactured by derivatizing the sulfolene obtained by reacting sulfurous acid gas and butadiene. In addition, after reducing the acid anhydride, the resulting alcohol is protected with a leaving group and treated with sodium sulfide to obtain a cyclic sulfide, which can then be oxidized (Non-Patent Document). 3). Commercial products can also be used as they are.
Tetrahedron Letters (Tetrahedron Letters), Vol. 23, 3277-3280 (1982)

  As the method of the first step, the tertiary alcohol (4) can be synthesized by generating an enolate of sulfolane in the presence of a base and nucleophilic addition to a ketone compound.

  Examples of the base used in the first step include, but are not limited to, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide alkali; sodium hydride, potassium hydride, and the like. Alkali metal hydrides such as calcium hydride; organic alkali metal compounds such as methyl lithium, ethyl lithium, butyl lithium, sec-butyl lithium, tert-butyl lithium; organic alkaline earth Metallic compounds; organic Grignard reagents such as methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesiummagnesium; organometallic compounds of monovalent copper salts and alkali metals or alkaline earth metals; lithium diisopropylamide, etc. Or organic amines such as triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene; These bases can be used alone or in admixture of two or more bases. Although the usage-amount of a base has the preferable range of 0.5 mol-10 mol with respect to a sulfolane derivative (2), the range of 0.7-1.5 mol is more preferable from a viewpoint of a by-product.

  The reaction in the first step is usually carried out in a solvent, and any solvent may be used as long as it does not adversely affect the reaction, but an aromatic hydrocarbon solvent such as toluene or benzene; diethyl ether , Ethers such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; alcohols such as methanol, ethanol, isopropyl alcohol and tert-butyl alcohol; N, N-dimethylformamide; It is carried out in an aprotic polar solvent such as dimethyl sulfoxide; or a mixed solvent thereof.

  The reaction temperature in the first step varies depending on the solvent, base, sulfolane derivative (2), and ketone compound (3) used, but is usually within the range of the reflux temperature of the solvent used from -20 ° C.

  The reaction time of the first step varies depending on the solvent, base, sulfolane derivative (2), and ketone compound (3) used, but is usually preferably in the range of 0.5 to 48 hours, and in the range of 1 to 24 hours. Is more preferable.

  In the reaction in the first step, the tertiary alcohol (4) can be usually obtained by neutralization. If necessary, it can be isolated by operations used for isolating organic compounds such as solvent extraction, distillation, column chromatography, and recrystallization.

Of the tertiary alcohol (4) thus obtained, the tertiary alcohol (4) in which R ² is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms is a tertiary alcohol. Equal to (6). Tertiary alcohol (6) is a novel compound.

  Next, the second step will be described.

When n of the acrylate derivative (1) is 0, the tertiary alcohol (3) obtained in the first step and the formula CH ₂ = CHR ⁵ COX (wherein R ⁵ is as defined above), Formula (CH ₂ = CHR ⁵ CO) ₂ O (wherein R ⁵ is as defined above), Formula CH ₂ = CHR ⁵ COOC (= O) R ⁶ (wherein R ⁵ is as defined above, R ⁶ represents a t-butyl group or a 2,4,6-trichlorophenyl group), or the formula CH ₂ = CHR ⁵ COOSO ₂ R ⁷ (wherein R ⁵ is as defined above, and R ⁷ is methyl Or a p-tolyl group) (hereinafter these compounds are referred to as polymerizable group introducing agent A) in the presence of a basic substance (hereinafter referred to as second step-A). To do. When n of the acrylic ester derivative (1) is 1, the tertiary alcohol (3) obtained in the first step and the formula X—W—COX (W is as defined above, and X is a chlorine atom) , Bromine atom or iodine atom), formula (X—W—CO) ₂ O (wherein X and W are as defined above), formula X—W—COOC (═O) R ⁷ (wherein X and W are as defined above, R ⁸ represents a t-butyl group or a 2,4,6-trichlorophenyl group), or a formula XW-COOSO ₂ R ⁹ ( In the formula, X and W are as defined above, and R ⁹ represents a methyl group or a p-tolyl group) (hereinafter, these compounds are referred to as a linking group introducing agent B1) as a base. It reacted presence of sex material (hereinafter, a second step referred to as -B-1), then the formula _CH 2 = ^CHR 5 CO M (wherein, R ⁵ are as defined above, M represents a sodium atom or a potassium atom.) The compound represented by (hereinafter, these compounds will be referred to as a polymerizable group-introducing agent B2) and reacting (Hereinafter referred to as second step-B-2). Hereinafter, 2nd process-A-2nd process-B are demonstrated in order.

  Specific examples of the n = 0 acrylate derivative (1) produced by the second step-A include (1-a) to (1-u), for example.

Among the polymerizable group-introducing agent A used in the second step-A, examples of the compound represented by the formula CH ₂ ═CHR ⁵ COX include acrylic acid chloride, methacrylic acid chloride, and 2-trifluoromethylacrylic acid chloride. Examples of the compound represented by the formula (CH ₂ ═CHR ⁵ CO) ₂ O include acrylic anhydride, methacrylic anhydride, 2-trifluoromethylacrylic anhydride, and the like, and the formula CH ₂ ═CHR ⁵ COOC (= O) Compounds represented by R ⁶ include acrylic acid pivalic acid anhydride, acrylic acid 2,4,6-trichlorobenzoic acid anhydride, methacrylic acid pivalic acid anhydride, methacrylic acid 2,4,6-trichlorobenzoic acid. Anhydride, 2-trifluoromethylacrylic acid pivalic acid anhydride, 2-trifluoromethylacrylic acid 2,4,6-trichloro And benzoic anhydride. Examples of the compound represented by the formula ^{_{CH 2 = CHR 5 COOSO 2 R}} 7, methanesulfonic anhydride acrylate, p- toluenesulfonic anhydride acrylic acid, methanesulfonic acid methacrylic anhydride Methacrylic acid p-toluenesulfonic acid anhydride, 2-trifluoromethylacrylic acid methanesulfonic acid anhydride, 2-trifluoromethylacrylic acid p-toluenesulfonic acid anhydride, and the like. The amount of the polymerizable group-introducing agent A used is preferably in the range of 0.8-fold to 7-fold moles with respect to the tertiary alcohol (4) from the viewpoint of economy and ease of post-treatment, The range of 0.8 to 5 times mole is more preferable.

  The basic substance used in the second step-A includes sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine, tributylamine, diazabicyclo [2.2.2. ] And octane. The amount of the basic substance used is preferably in the range of 0.8 to 20 moles relative to the tertiary alcohol (3) from the viewpoint of economy and ease of post-treatment, More preferably, it is in the range of 10 to 10 mol.

  The second step-A can be carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as the reaction is not inhibited, and aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; halogenated carbonization such as methylene chloride and dichloroethane. Hydrogen; ethers such as tetrahydrofuran and diisopropyl ether; nitriles such as acetonitrile and benzonitrile are preferred. These solvents may be used alone or in combination of two or more. The amount used when using a solvent is preferably in the range of 0.1 to 10 times by mass with respect to the tertiary alcohol (4) from the viewpoint of economy and ease of post-treatment. More preferably, it is in the range of 1 to 5 times by mass.

  The reaction temperature of the second step-A varies depending on the type of the polymerizable group-introducing agent A, tertiary alcohol (4) and basic substance used, but is generally in the range of −50 ° C. to 80 ° C. preferable.

  The reaction of the second step-A can be stopped by adding water or alcohol. Examples of the alcohol include methanol, ethanol, n-propanol, and i-propanol. It is also possible to use a mixture of water and alcohol. The amount of water or alcohol used may be 1 mole or more with respect to the excess polymerizable group introducing agent A. If the amount used is small, the excess polymerizable group introducing agent A cannot be completely decomposed and a by-product may be produced.

  Next, 2nd process-B is demonstrated. Specific examples of the n = 1 acrylate derivative (1) produced by the second step-B include (1-v) to (1-aa).

Of the linking group introducing agent B1 used in the second step-B-1, the compound represented by the formula XW-COX includes chloroacetic acid chloride, 2-chloropropionic acid chloride, 2-bromo-2-methylpropion. Examples of the compound represented by the formula X—W—COOC (═O) R ⁸ include chloroacetic acid pivalic anhydride, chloroacetic acid 2,4,6-trichlorobenzoic anhydride, 2-chloro Examples include propionic acid pivalic acid anhydride, 2-chloropropionic acid 2,4,6-trichlorobenzoic acid anhydride and the like, and the compound represented by the formula X—W—COOSO ₂ R ⁹ includes chloroacetic acid methanesulfonic acid anhydride. , Chloroacetic acid p-toluenesulfonic acid anhydride, 2-chloropropionic acid methanesulfonic acid anhydride, 2-chloropropionic acid p-toluenesulfonic acid Anhydrous and the like, and examples of the formula (X-W-CO) a compound represented by the 2 _O, chloroacetic acid anhydride, and the like anhydrous 2-chloropropionic acid. The amount of the linking group introducing agent B1 used is preferably in the range of 0.8 times to 7 times the mol of the tertiary alcohol (4) from the viewpoints of economy and ease of post-treatment. More preferably, it is in the range of 8 times mol to 5 times mol.

  As the basic substance used in the second step-B-1, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine, tributylamine, diazabicyclo [2.2 .2] octane and the like. The amount of the basic substance used is preferably in the range of 0.8 to 20 moles relative to the tertiary alcohol (3) from the viewpoint of economy and ease of post-treatment, It is more preferable that it is in the range of 10 mol to 10 mol.

  The second step-B-1 can be carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as the reaction is not inhibited, and aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; halogenated carbonization such as methylene chloride and dichloroethane. Hydrogen; ethers such as tetrahydrofuran and diisopropyl ether; nitriles such as acetonitrile and benzonitrile are suitable. These solvents may be used alone or in combination of two or more. When using a solvent, the amount used is preferably in the range of 0.1 to 10 times by mass with respect to the tertiary alcohol (3) from the viewpoint of economy and ease of post-treatment, The range of 0.1 to 5 times the mass is more preferable.

  The reaction temperature in the second step -B-1 varies depending on the type of the linking group introducing agent B1, tertiary alcohol (3) and basic substance used, but is generally in the range of -50 ° C to 80 ° C. Is preferred.

  The reaction of the second step-B-1 can be stopped by adding water or alcohol. Examples of the alcohol include methanol, ethanol, n-propanol, i-propanol and the like. It is also possible to use a mixture of water and alcohol. The amount of water or alcohol used may be an amount of 1 mol or more with respect to the excess linking group introducing agent B1. If the amount used is small, the excess linking group introducing agent B1 may not be completely decomposed and a by-product may be produced.

  As the polymerizable group introducing agent B2 used in the second step-B-2, sodium acrylate, potassium acrylate, sodium methacrylate, potassium methacrylate, sodium 2-trifluoromethyl acrylate, 2-trifluoromethyl acrylic Examples include potassium acid. The amount of the polymerizable group-introducing agent B2 used is in the range of 0.8-fold to 5-fold moles relative to the product of the third step-B-1 from the viewpoint of economy and ease of post-treatment. Is preferable, and the range of 0.8 to 3 times mol is more preferable.

  In the second step-B-2, it is preferable to use potassium iodide, sodium iodide, tetrabutylammonium iodide, tetrabutylammonium bromide, or the like as an activator as necessary. When the activator is used, the amount used is preferably in the range of 0.001 to 0.5 mol times the product of the third step-B-1, and the ease of post-treatment and From the economical viewpoint, it is more preferably in the range of 0.005 mol times to 0.3 mol times.

  The second step-B-2 can be carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as the reaction is not inhibited, and aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and cymene; halogenated carbonization such as methylene chloride and dichloroethane. Hydrogen; ethers such as tetrahydrofuran and diisopropyl ether; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. When using a solvent, the amount of use should be in the range of 0.1 to 10 times the product of the third step-B-1 from the viewpoint of economy and ease of post-treatment. Is preferable, and the range of 0.1 to 5 times by mass is more preferable.

  The reaction temperature of the second step-B-2 varies depending on the type of the polymerizable group-introducing agent B2 to be used, the product of the second step-B-1, and the basic substance, but is generally -50 ° C to 80 ° C. A range is preferable.

  Thus, the acrylic ester derivative (1) obtained through the second step-A or the second step B-1 and B-2 is preferably separated and purified by a conventional method as necessary. For example, the reaction mixture can be washed with water, concentrated, and purified by a method used for separation and purification of ordinary organic compounds such as distillation, column chromatography, or recrystallization. In addition, if necessary, after addition of a chelating agent such as nitrilotriacetic acid or ethylenediaminetetraacetic acid, metal such as filtration or zeta plus (trade name: manufactured by Cuno Co., Ltd.) or protego (product name: manufactured by Nihon Microlith Co., Ltd.) It is also possible to reduce the metal content in the obtained acrylate derivative (1) by treating with a removal filter.

  The polymer compound (7) is obtained by polymerizing the acrylic ester derivative (1) alone or by copolymerizing the acrylic ester derivative (1) with another polymerizable compound. The structural unit based on the acid ester derivative (1) exceeds 0 mol% and is 100 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%. Specific examples of the structural unit based on the acrylate derivative (1) include those represented by the following formulas (1′-a) to (1′-aa), but are not limited thereto.

As other polymerizable compounds to be copolymerized (hereinafter referred to as copolymerization monomers), the following formulas (I) to (X) (wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a group represented by CH ₂ ═CHR ¹⁹ CO— (R ¹⁹ represents a hydrogen atom, a methyl group or a trifluoromethyl group), and R ¹³ represents H or COOR ²⁰ (R ²⁰ represents an alkyl group such as a methyl group, an ethyl group, and an n-propyl group, and a cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, and a 2-adamantyl group). However, it is not limited to these. Only one type of comonomer can be used, or two or more types can be mixed and used as necessary.

Specific examples of the polymer compound (7) include, but are not limited to, the following polymer compounds (A-1) to (A-24). (R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are as defined above. L, m, and n represent constituent unit molar ratios.)

  Although there is no restriction | limiting in particular in the weight average molecular weight (Mw) of a high molecular compound (7), The polymer for photoresists as Mw by the following measuring methods is the range of 500-50000, Preferably it is 1000-30000. It is useful as a raw material for the composition. The Mw is measured by gel permeation chromatography (GPC method) using two TSK-gel SUPER HZM-H (trade name, 4.6 mm × 150 mm, manufactured by Tosoh Corporation) and TSK-gel SUPER HZ2000 (Tosoh Corporation). (Manufactured by the company, 4.6 mm x 150 mm) using a series of 1 piece, using tetrahydrofuran as a solvent, column temperature 40 ° C, RI temperature 40 ° C, eluent flow rate 0.35 ml / min. Calculated as a conversion value using a calibration curve prepared with standard polystyrene. Further, the dispersity (Mw / Mn) is determined by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

  The degree of dispersion of the polymer compound (7) is preferably in the range of 1.0 to 2.5, and more preferably in the range of 1.0 to 2.0.

  The polymer compound (7) is a radical polymerization reaction by supplying an acrylic ester derivative (1), a polymerization initiator, and, if necessary, one or more kinds of comonomer, a solvent and a chain transfer agent to a reactor. Obtained. Hereinafter, such a polymerization reaction will be described.

  In the production of the polymer compound (7), the monomeric acrylate derivative (1) and the comonomer are polymerized according to the corresponding constituent unit molar ratio in the polymer compound (7). Let That is, in the same manner as in a general radical polymerization reaction, the polymerization is performed in consideration of the polymerization rate ratio of each monomer and the molar ratio of the corresponding structural unit in the desired polymer compound (7). By appropriately adjusting the molar ratio of the acrylic ester derivative (1) to be subjected to the reaction and the comonomer, a polymer compound (7) having a desired molar ratio of structural units can be obtained.

  The polymerization initiator used for the production of the polymer compound (7) includes hydroperoxide compounds such as t-butyl hydroperoxide; dialkyl peroxide compounds such as di-t-butyl peroxide; diacyl peroxide compounds such as benzoyl peroxide; 2 , 2′-azobisisobutyronitrile, azo compounds such as dimethyl 2,2′-azobisisobutyrate, and the like. Among these, it is preferable to use azo compounds such as 2,2'-azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate. The amount of the polymerization initiator used is preferably in the range of 0.5 mol% to 20 mol%, more preferably in the range of 1 to 15 mol%, based on the total number of moles of the polymerizable compound. Similar to the general radical polymerization reaction, the molecular weight of the polymer compound (7) can be adjusted by the amount of the polymerization initiator used.

  In the production of the polymer compound (7), a chain transfer agent may be used as necessary. Examples of the chain transfer agent include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid. These may be used alone or in admixture of two or more. When using a chain transfer agent, the amount used is preferably in the range of 0.5 mol% to 20 mol%, more preferably in the range of 1 to 15 mol%, based on the total number of moles of the polymerizable compound.

  The production of the polymer compound (7) is preferably carried out in a solvent. The solvent to be used is not particularly limited as long as the polymerization reaction is not inhibited. Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Glycol ethers such as acetate; Esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, and propyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; Ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane And the like ether of. These may be used alone or in combination of two or more. The amount of the solvent used is usually preferably in the range of 0.5 to 20 times by mass with respect to the total mass of the polymerizable compound from the viewpoint of economy and ease of post-treatment, and 1 to 10 times by mass. A range of mass times is more preferable.

  In the production of the polymer compound (7), the polymerization method is not particularly limited, and a known method used for producing an acrylic polymer such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method is used. Among them, it is preferable to use a solution polymerization method.

  The polymerization temperature in the production of the polymer compound (7) is in the range of 40 ° C. to 150 ° C. and 60 ° C. to 120 ° C. from the viewpoint of the stability of the acrylic ester derivative (1) and the polymer compound (7). It is preferable that it is the range of these.

  The polymer compound (7) thus obtained can be isolated by ordinary operations such as gel permeation chromatography and reprecipitation. The molecular weight and the degree of dispersion can be adjusted by ordinary operations such as gel permeation chromatography and reprecipitation. Furthermore, the metal content can be reduced by operations such as chelating agent treatment and metal removal filter treatment as necessary.

  Examples of the solvent used as the reprecipitation solvent include aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene and xylene; methylene chloride, chloroform, chlorobenzene, di- Halogenated hydrocarbons such as chlorobenzene; 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 and the like Carboxylic acids; acetates such as ethyl acetate and butyl acetate; carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; methanol, ethanol, propanol, isopropyl Alcohol, alcohol such as butanol. One of these solvents may be used alone, or two or more thereof may be mixed and used.

  The polymer compound (7) can be used as a component of a photoresist composition (hereinafter referred to as photoresist compound (8)) containing the polymer compound (7). The photoresist composition (8) comprises a polymer compound (7), a solvent described later, a photoacid generator, and a basic substance and additives as necessary.

  Examples of the solvent used in the photoresist composition (8) include propylene glycol monoethyl ether, propylene glycol monomethyl 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 methyl acetate 3-methoxypropionate, ethyl acetate, propyl acetate; acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone , Methyl amyl ketone, Ropentanon, ketones such as cyclohexanone diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethers such as 1,4-dioxane.

  A solvent may be used individually or may be used in mixture of 2 or more types. The usage-amount of a solvent is the range of 1 mass times-50 mass times normally with respect to a high molecular compound (7), and it is preferable that it is the range of 2 mass times-25 mass times.

  As a photo-acid generator used for a photoresist composition (8), the conventionally well-known compound which produces | generates an acid efficiently by exposure can be used. Examples of the photoacid generator used include sulfonium salts such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethylmethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate; diphenyliodohexafluorosulfone; Iodonium salts such as fate; disulfones such as diphenyldisulfone and ditolyldisulfone; triazines such as 1-methyl-3,5-bistrichloromethyltriazine and 1,3,5-tristrichloromethyltriazine; bis (cyclohexylsulfonyl) diazomethane; Diazomethane such as bis (phenylsulfonyl) diazomethane; (2′-nitrophenyl) methyl-p-toluenesulfonate Sulfonic acid ester such as (2 ′, 6′-dinitrophenyl) methyl-p-toluenesulfonate, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane; diazonaphthoquinone; benzoin tosylate, etc. Is mentioned. These photoacid generators can be used alone or in admixture of two or more. The amount of the photoacid generator used can be selected according to the strength of the acid generated by radiation irradiation and the amount of the acrylate derivative (1) in the polymer compound (7). It is 0.1 mass%-30 mass%, Preferably it is the range of 0.5 mass%-10 mass%.

  The photoresist composition (8) may further contain a basic substance if necessary. Basic substances 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, methylenebismethacrylamide, N -Amides such as methylolacrylamide, N-methoxyacrylamide, diacetoneacrylamide; pyridine, 2-methylpyridine, 4-methylpyridine, nicotine, quinoline, acridine, imida Sol, 4-methylimidazole, benzimidazole, pyrazine, pyrazole, pyrrolidine, piperidine, tetrazole, morpholine, 4-methylmorpholine, piperazine, 1,4-diazabicyclo [2.2.2] octane, tributylamine, tripentylamine, Examples of the amine include trihexylamine, triheptylamine, trioctylamine, and triethanolamine. These basic substances may be used alone or in combination of two or more. When a basic substance is used, the amount used varies depending on the type of the basic substance, but it is generally used in a range of 0.01 mol times to 10 mol times with respect to the photoacid generator, and 0.05 mol times. It is preferably used in the range of ˜1 mol times.

  The photoresist composition (8) may further contain various additives such as a surfactant, a sensitizer, an antihalation agent, a storage stabilizer, and an antifoaming agent, if necessary.

  After the photoresist composition (8) is applied to the substrate, it is pre-baked at a temperature of about 70 ° C. to 160 ° C., irradiated with radiation, particularly ArF excimer laser, and then post-treated at a temperature of 70 ° C. to 160 ° C. for 30 seconds or more. The pattern can be formed by baking and then treating with water or an alkaline developer.

For exposure of the photoresist composition (8), various wavelengths of radiation, such as ultraviolet rays and X-rays, can be used. For semiconductor resists, g-line, i-line, XeCl, KrF, KrCl, ArF, ArCl Excimer lasers such as F ₂ are used. Exposure energy is preferably in the range of 0.1~1000mJ / cm ^2, the range of 1 to 500 mJ / cm ² is more preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by this Example.
The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by standard polystyrene using gel permeation chromatography (GPC) measurement using a differential refractometer as a detector and tetrahydrofuran (THF) as an eluent. It was calculated | required as a conversion value by the calibration curve created in (1).
GPC measurement: 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) as columns ) Using one connected in series, measurement was performed under the conditions of a column temperature of 40 ° C., a differential refractometer temperature of 40 ° C., and an eluent flow rate of 0.1 mL / min.

<Example 1>
Synthesis of 2- (1′-hydroxycyclopentane-1′-yl) -tetrahydrothiophene-1,1-dioxide

  Into a 1 L 4-neck flask equipped with a thermometer, three-way cock, and dropping funnel, 235 ml of ethylmagnesium bromidetetrahydrofuran 1 mol / l solution was added in a nitrogen atmosphere, and then a mixture of 24 g of sulfolane and 125 g of tetrahumanlofuran was mixed. The reaction solution was added dropwise so that the internal temperature was 35 ° C. or lower. Thereafter, the reaction solution was heated in an oil bath and refluxed and stirred for 2 hours. To this reaction solution, 16 g of cyclopentanone was added dropwise over 2 hours, and then stirred at room temperature for 2 hours. To the reaction mixture, 500 g of 25% aqueous ammonium chloride solution was dropped, and the organic layer and the aqueous layer were separated. The organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/2) to give 2- (1-hydroxy-) having the following physical properties. 12 g of 1-cyclopentyl) -tetrahydrothiophene-1,1-dioxide was obtained (purity 99%, yield 30%).

¹ H-NMR (300 MHz, CDCl ₃ , TMS, ppm) δ: 1.4-1.91 (6H, m), 2.01-2.46 (4H, m), 3.0 (2H, m) 3.16 (1H, m)

<Example 2>
Synthesis of 2- (1′-methacryloyloxycyclohexane-1′-yl) -tetrahydrothiophene-1,1-dioxide

  2- (1′-Hydroxycyclopentane-1′-yl) -tetrahydro obtained by the method of Example 1 under a nitrogen atmosphere in a 200 ml four-necked flask equipped with a thermometer, a three-way cock and a dropping funnel 11 g of thiophene-1,1-dioxide, 33 g of methylene chloride, 0.7 g of dimethylaminopyridine, and 40.5 g of triethylamine were charged. Subsequently, 23 g of methacryloyl chloride was added dropwise so that the internal temperature of the reaction solution was 35 ° C. or lower. Then, it stirred at room temperature for 7 hours. Ethanol (5 g) was added dropwise to the reaction mixture, and then water (50 g) was added and stirred for 15 minutes. The organic layer and the aqueous layer were separated, and the organic layer was washed with 50 g of water and then concentrated under reduced pressure. Purification by silica gel column chromatography gave 10 g of 2- (1′-methacryloyloxycyclohexane-1′-yl) -tetrahydrothiophene-1,1-dioxide having the following physical properties (purity 99%, yield). 70%).

¹ H-NMR (300 MHz, CDCl ₃ , TMS, ppm) δ: 1.60-1.79 (4H, m), 1.95 (3H, s), 2.00-2.155 (4H, m) 2.18-2.53 (4H, m), 2.99 (1H, m), 3.17 (1H, m), 4.34 (1H, t, J = 7.4 Hz), 5.56 (1H, s), 6.11 (1H, s)

<Synthesis Example 1>
Synthesis of 2- (2′-hydroxybutane-2′-yl) -tetrahydrothiophene-1,1-dioxide

  125 ml of ethylmagnesium bromide tetrahydrofuran 1 mol / l solution was charged in a 1 L 4-neck flask with a thermometer, three-way cock and dripping funnel in a nitrogen atmosphere, and then mixed with 15 g of sulfolane and 75 g of tetrahumanlofuran. The reaction solution was added dropwise so that the internal temperature was 35 ° C. or lower. Thereafter, the reaction solution was heated in an oil bath and stirred for 2 hours under reflux. To this reaction solution, 7 g of acetone was dropped over 2 hours, and then stirred at room temperature for 2 hours. To the reaction mixture, 500 g of 25% aqueous ammonium chloride solution was dropped, and the organic layer and the aqueous layer were separated. The organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/2) to give 2- (2′-hydroxy) having the following physical properties. 6 g of butane-2′-yl) -tetrahydrothiophene-1,1-dioxide was obtained (purity 99%, yield 28%).

¹ H-NMR (300 MHz, CDCl ₃ , TMS, ppm) δ: 1.58 (3H, s), 1.68-1.78 (2H, m), 1.93 (3H, s), 2.20 (2H, d, J = 9.6 Hz), 3.61-3.78 (4H, m), 5.54 (1H, s), 6.07 (1H, s)

<Example 3>
Synthesis of 2- (2′-methacryloyloxybutane-2′-yl) -tetrahydrothiophene-1,1-dioxide

  2- (2′-Hydroxybutane-2′-yl) -thiophene-obtained by the method of Synthesis Example 1 under a nitrogen atmosphere in a 50-ml four-necked flask equipped with a thermometer, a three-way cock, and a dropping funnel 1,2-dioxide 2g was charged. 6 g of methylene chloride, 137 g of dimethylaminopyridine, and 3.3 g of triethylamine were charged. Subsequently, 2.3 g of methacryloyl chloride was added dropwise so that the internal temperature of the reaction solution was 35 ° C. or lower. Then, it stirred at room temperature for 7 hours. To the reaction mixture, 350 mg of ethanol was added dropwise, and then 30 g of water was added and stirred for 15 minutes. The organic layer and the aqueous layer were separated, and the organic layer was washed with 30 g of water and then concentrated under reduced pressure. By purifying by silica gel column chromatography, 1.7 g of 2- (2′-methacryloyloxybutane-2′-yl) -tetrahydrothiophene-1,1-dioxide having the following physical properties was obtained (purity 99% , Yield 70%). In addition, logP which is a log value of an octanol / water partition coefficient and SP which is a solubility parameter were calculated using Hamiltonian PM5 of calculation software CAChe (trade name; Fujitsu Limited).

¹ H-NMR (300 MHz, CDCl ₃ , TMS, ppm) δ: 1.74 (3H, s), 1.77 (3H, m), 1.92 (3H, s), 1.99-2.34 (4H, d, m), 2.98 (1H, m), 3.19 (1H, m), 3.64 (1H, t, J = 7.6 Hz), 5.55 (1H, s), 6.11 (1H, s)
logP1.71
SP20.8 (J / mol)

[Synthesis of polymer compounds]

<Example 4> Synthesis of polymer compound a

  Under a nitrogen atmosphere, 2- (1′-methacryloyloxycyclohexane-1′-yl) -tetrahydrothiophene-1,1-dithione was added to a 200-ml round bottom flask equipped with a magnetic stirrer, a reflux condenser and a thermometer. 10 g (48.83 mmol) of oxide, 11.5 g (48.83 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, 160 g of propylene glycol monomethyl ether and 1.4 g (8.5 mmol) of 2,2′-azobisisobutyronitrile And polymerization reaction was carried out at 80 to 85 ° C. for 4 hours. The obtained reaction mixture was added dropwise with stirring to about 20 times the mass of methanol at room temperature with stirring, and the resulting precipitate was collected by filtration. The precipitate was dried at 60 ° C. under reduced pressure (26.7 Pa) for 12 hours to obtain 7 g of a polymer compound b consisting of the following repeating units. The obtained polymer compound b had an Mw of 15917 and a dispersity of 1.57.

<Example 5> Synthesis of polymer compound b

  Under a nitrogen atmosphere, a 2- (2′-methacryloyloxybutane-2′-yl) -tetrahydrothiophene-1,1-dithione was added to a 200 ml round bottom flask equipped with a magnetic stirrer, reflux condenser and thermometer. 12 g (48.83 mmol) of oxide, 11.5 g (48.83 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, 177.0 g of propylene glycol monomethyl ether and 1.4 g of 2,2′-azobisisobutyronitrile (8 0.5 mmol), and a polymerization reaction was carried out at 80 to 85 ° C. for 4 hours. The obtained reaction mixture was added dropwise with stirring to about 20 times the mass of methanol at room temperature with stirring, and the resulting precipitate was collected by filtration. The precipitate was dried under reduced pressure (26.7 Pa) at 60 ° C. for 12 hours to obtain 8 g of a polymer compound b consisting of the following repeating units. The obtained polymer compound b had an Mw of 13240 and a dispersity of 1.47.

<Example 6> Synthesis of polymer compound c

  To a round bottom flask having an internal volume of 100 ml equipped with a magnetic stirrer, a reflux condenser and a thermometer, 5.09 g of 2- (1′-methacryloyloxycyclohexane-1′-yl) -tetrahydrothiophene-1,1-dioxide was added. (18.7 mmol), 1.96 g (12.5 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, 3.18 g (18.7 mmol) of α-methacryloyloxy-γ-butyrolactone, 60.0 g of methyl ethyl ketone, and nitrogen bubbling For 10 minutes. Under a nitrogen atmosphere, 2,6'-azobisisobutyronitrile (0.66 g, 4.0 mmol) was charged, and a polymerization reaction was performed at 80 ° C for 4 hours. The obtained reaction mixture was dropped into methanol of about 20 times mass at room temperature while stirring to obtain a white precipitate. The precipitate was collected by filtration and dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 6.63 g of a polymer compound a consisting of the following repeating units. The obtained polymer compound a had an Mw of 8000 and a dispersity of 2.0.

<Example 7> Synthesis of polymer compound d

  To a round bottom flask having an internal volume of 100 ml equipped with a magnetic stirrer, a reflux condenser and a thermometer, 4.60 g of 2- (2′-methacryloyloxybutane-2′-yl) -tetrahydrothiophene-1,1-dioxide was added. (18.7 mmol), 1.96 g (12.5 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, 3.18 g (18.7 mmol) of α-methacryloyloxy-γ-butyrolactone, 61.0 g of methyl ethyl ketone, and nitrogen bubbling For 10 minutes. Under a nitrogen atmosphere, 2,6'-azobisisobutyronitrile (0.66 g, 4.0 mmol) was charged, and a polymerization reaction was performed at 80 ° C for 4 hours. The obtained reaction mixture was dropped into methanol of about 20 times mass at room temperature while stirring to obtain a white precipitate. The precipitate was collected by filtration and dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 6.45 g of a polymer compound b consisting of the following repeating units. Mw of the obtained polymer compound b was 8300, and the degree of dispersion was 1.90.

<Synthesis Example 2> Synthesis of polymer compound e

  Under a nitrogen atmosphere, 10.0 g (42.3 mmol) of 2-methacryloyloxy-2-methyladamantane, 1-hydroxy-3-butene was added under a nitrogen atmosphere to a round bottom flask equipped with a magnetic stirrer, a reflux condenser and a thermometer. First, 10.0 g (42.7 mmol) of methacryloyloxyadamantane, 80.0 g of propylene glycol monomethyl ether, and 1.40 g (8.53 mmol) of 2,2′-azobisisobutyronitrile were charged at 81 to 87 ° C. for 2 hours. A polymerization reaction was performed. The obtained reaction mixture was added dropwise with stirring to about 20 times the mass of methanol at room temperature with stirring, and the resulting precipitate was collected by filtration. A solution obtained by dissolving the precipitate in 100.0 g of THF was dropped into methanol of the same mass as above while stirring, and the resulting precipitate was collected by filtration and washed with methanol of the same mass as above to obtain a white precipitate. Obtained. The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 13.2 g of a polymer compound h composed of the following repeating units. The obtained polymer compound h had an Mw of 16,100 and a dispersity of 1.68.

<Synthesis Example 3> Synthesis of Polymer Compound f

  In Synthesis Example 2, the same procedure as in Example 10 except that 7.39 g (42.7 mmol) of 2-methacryloyloxytetrahydropyran was used instead of 10.0 g (42.3 mmol) of 2-methacryloyloxy-2-methyladamantane. The polymerization reaction was carried out with the charged amount and conditions. The obtained reaction mixture was added dropwise with stirring to about 20 times the mass of methanol at room temperature with stirring, and the resulting precipitate was collected by filtration. A solution obtained by dissolving the precipitate in 100.0 g of THF was dropped into methanol of the same mass as above while stirring, and the resulting precipitate was collected by filtration and washed with methanol of the same mass as above to obtain a white precipitate. Obtained. The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 9.96 g of a polymer compound i having the following repeating units. The obtained polymer compound i had Mw of 13,200 and a dispersity of 1.71.

<Synthesis Example 4> Synthesis of polymer compound g

  Under a nitrogen atmosphere, 9.14 g (50.2 mmol) of 1-methacryloyloxy-1-methylcyclohexane, 1-hydroxy-3-methylcyclohexane was added to a 200 ml round bottom flask equipped with a magnetic stirrer, a reflux condenser and a thermometer. 11.82 g (50.0 mmol) of methacryloyloxyadamantane, 101.4 g of 1,4-dioxane, and 1.24 g (7.55 mmol) of 2,2′-azobisisobutyronitrile were charged at 5 ° C. at 80 to 82 ° C. A time polymerization reaction was carried out. The obtained reaction mixture was dropped into a water-methanol mixed solution (weight ratio water: methanol = 1: 3) of about 20 times mass with respect to the reaction mixture at room temperature while stirring, and a precipitate formed. Filtered. A solution obtained by dissolving the precipitate in 140.0 g of THF was dropped into a water-methanol mixed solution (weight ratio water: methanol = 1: 3) having the same mass as above while stirring, and the generated precipitate was collected by filtration. A white precipitate was obtained by washing with a water-methanol mixed solution having the same mass as above (weight ratio water: methanol = 1: 3). The precipitate was dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 11.8 g of a polymer compound j consisting of the following repeating units. Mw of the obtained polymer compound j was 12600, and the degree of dispersion was 1.83.

<Synthesis Example 5> Synthesis of polymer compound h

  To a round bottom flask having an internal volume of 100 ml equipped with a magnetic stirrer, a reflux condenser and a thermometer, 4.39 g (18.7 mmol) of 2-methacryloyloxy-2-methyladamantane, 1-hydroxy-3-methacryloyloxyadamantane 2 .96 g (12.5 mmol), α-methacryloyloxy-γ-butyrolactone 3.18 g (18.7 mmol), and methyl ethyl ketone 60.5 g were charged, and nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 2,6'-azobisisobutyronitrile (0.66 g, 4.0 mmol) was charged, and a polymerization reaction was performed at 80 ° C for 4 hours. The obtained reaction mixture was dropped into methanol of about 20 times mass at room temperature while stirring to obtain a white precipitate. The precipitate was collected by filtration and dried at 50 ° C. under reduced pressure (26.7 Pa) for 10 hours to obtain 6.06 g of a polymer compound c consisting of the following repeating units. The obtained polymer compound c had an Mw of 9800 and a dispersity of 1.53.

<Evaluation of dissolution characteristics in developer by QCM method>
100 parts by mass of polymer compounds a to h obtained in Examples 4 to 7 and Synthesis Examples 2 to 5, 3 parts by mass of TPS-109 (product name, manufactured by Midori Chemical Co., Ltd.) as a photoacid generator, A solvent (a mixed solvent of propylene glycol monomethyl ether acetate / ethyl lactate = 1/1) was mixed to prepare four types of photoresist compositions having a polymer compound concentration of 12% by mass. These photoresist compositions were filtered using a filter [made of tetrafluoroethylene resin (PTFE), pore size 0.2 μm], and then spinned onto a 1-inch quartz substrate having a gold electrode vacuum-deposited on the surface. It was applied by a coating method to form a photosensitive layer having a thickness of about 300 nm. The quartz substrate on which these photosensitive layers are formed is pre-baked at 110 ° C. for 90 seconds on a hot plate, and then exposed using an ArF excimer laser (wavelength: 193 nm) at an exposure amount of 100 mJ / cm ² , followed by 110 ° C. And post-exposure bake for 90 seconds. The quartz substrate was set in a quartz vibrator microbalance device “RQCM” (trade name; manufactured by Maxtek), and developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 120 seconds. The change in frequency of the quartz substrate during development is monitored over time, and the obtained change in frequency is converted into a change in film thickness. From the increase in film thickness, the maximum swelling amount and from the change in film thickness are dissolved. The speed was calculated. The results are shown in Table 1.

<Two-beam interferometry exposure evaluation>
100 parts by mass of polymer compounds a to h obtained in Examples 4 to 7 and Synthesis Examples 2 to 5, 3 parts by mass of TPS-109 (product name, manufactured by Midori Chemical Co., Ltd.) as a photoacid generator, A solvent (a mixed solvent of propylene glycol monomethyl ether acetate / ethyl lactate = 1/1) was mixed to prepare four types of photoresist compositions having a polymer compound concentration of 12% by mass. These photoresist compositions were filtered using a filter [made of tetrafluoroethylene resin (PTFE), pore size 0.2 μm]. A cresol novolak resin (PS-6937 manufactured by Gunei Chemical Co., Ltd.) is coated with a 6% by weight propylene glycol monomethyl ether acetate solution by a spin coating method, and baked on a hot plate at 200 ° C. for 90 seconds to obtain a film thickness of about 100 nm. Each of the filtrates is applied by spin coating on a silicon wafer having a diameter of 10 cm on which an antireflection film (undercoat film) is formed, and is pre-baked on a hot plate at 130 ° C. for 90 seconds to form a resist having a thickness of about 300 nm. A 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, the film was post-exposure baked at 130 ° C. for 90 seconds, and then developed with a 2.38% by 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 (hereinafter referred to as LWR) at an exposure amount obtained by resolving a line and space with a line width of 100 nm at 1: 1. Measured). 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. The results are shown in Table 2.

  From the above results, in the case of the polymer compound containing the acrylate derivative (1) of the present invention in the repeating unit (polymer compounds a, b, c, d), the polymer compound not containing (polymer compound e) , F, g, h), the dissolution rate in the alkaline developer used in the development process when producing a photoresist is very high, the maximum swelling during development is very small, and the LWR is improved. Therefore, it can be seen that it is useful as a chemically amplified resist for manufacturing semiconductor devices.

Claims (11)

The following general formula (1)

(In the formula, each of R ¹ and R ² represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² are combined together at any position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom, wherein R ³ and R ⁴ are each a hydrogen atom, a hydroxyl group, an alkoxy group or a carbon number of 1; Represents a linear, branched, or cyclic alkyl group of 1 to 10, or R ³ and R ⁴ together may contain an oxygen atom or a sulfur atom at an arbitrary position, 1 carbon atom Represents a linear, branched or cyclic alkylene group of from 10 to 10, an oxygen atom, or a sulfur atom, R ⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and W represents a straight chain having 1 to 10 carbon atoms. Chain, branched, or cyclic al .n representing the alkylene group represents 0 or 1.)
An acrylic ester derivative represented by   The acrylic ester derivative according to claim 1, wherein W is a methylene group or a 1,1-ethanediyl group.   The acrylic ester derivative according to claim 1, wherein n is 0. The acrylic ester derivative according to claim 1, wherein R ³ and R ⁴ are hydrogen atoms. The acrylic ester derivative according to claim 1, wherein R ³ and R ⁴ are hydrogen atoms, and W is a methylene group or a 1,1-ethanediyl group. The acrylic ester derivative according to claim 1, wherein R ³ and R ⁴ are hydrogen atoms, and n is 0. The following general formula (2)

(Wherein R ³ and R ⁴ each represent a hydrogen atom, a hydroxyl group, an alkoxy group, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or R ³ and R ^4. Together represent a C1-C10 linear, branched or cyclic alkylene group, oxygen atom or sulfur atom which may contain an oxygen atom or a sulfur atom at any position.
And the following general formula (3)

(In the formula, each of R ¹ and R ² represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² are combined together at any position. (Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom.)
By reacting the ketone compound represented by the following general formula (4)

(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
And then reacting with the tertiary alcohol and the polymerizable group introducing agent, or reacting the tertiary alcohol with the linking group introducing agent and then reacting with the polymerizable group introducing agent. The following general formula (1)

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are as defined above. R ⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. W is a straight chain having 1 to 10 carbon atoms, Represents a branched or cyclic alkylene group, and n represents 0 or 1.)
The manufacturing method of the acrylic ester derivative shown by these. The following general formula (2)

(Wherein R ³ and R ⁴ each represent a hydrogen atom, a hydroxyl group, an alkoxy group, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or R ³ and R ^4. Together represent an oxygen atom or a C1-C10 linear, branched or cyclic alkylene group, oxygen atom or sulfur atom which may contain a sulfur atom at any position. Sulfolane derivative and the following general formula (5)

Wherein R ^{1 ′} and R ^{2 ′} are
1) R ^{1 ′} represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. R ^{2 ′} represents a linear, branched, or cyclic alkyl group having 2 to 10 carbon atoms; or 2) R ^{1 ′} and R ^{2 ′} are combined to form an oxygen atom or a sulfur atom at an arbitrary position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms, which may contain
One of them. )
The following general formula (6), characterized by reacting a ketone compound represented by

(Wherein R ³ , R ⁴ , R ^{1 ′} and R ^{2 ′} are as defined above.)
The manufacturing method of the tertiary alcohol shown by these. The following general formula (6)

Wherein R ^{1 ′} and R ^{2 ′} are
1) R ^{1 ′} represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. R ^{2 ′} represents a linear, branched, or cyclic alkyl group having 2 to 10 carbon atoms; or 2) R ^{1 ′} and R ^{2 ′} are combined to form an oxygen atom or a sulfur atom at an arbitrary position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms, which may contain
One of them. R ³ and R ⁴ each represent a hydrogen atom, a hydroxyl group, an alkoxy group, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or R ³ and R ⁴ are combined together Represents a C1-C10 linear, branched or cyclic alkylene group, an oxygen atom or a sulfur atom which may contain an oxygen atom or a sulfur atom at an arbitrary position. )
A tertiary alcohol represented by The tertiary alcohol according to claim 9, wherein R ³ and R ⁴ are hydrogen atoms. The following general formula (1)

(In the formula, each of R ¹ and R ² represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² are combined together at any position. Represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms which may contain an oxygen atom or a sulfur atom, wherein R ³ and R ⁴ are each a hydrogen atom, a hydroxyl group, an alkoxy group or a carbon number of 1; Represents a linear, branched, or cyclic alkyl group of 1 to 10, or R ³ and R ⁴ together may contain an oxygen atom or a sulfur atom at an arbitrary position, 1 carbon atom Represents a linear, branched or cyclic alkylene group of from 10 to 10, an oxygen atom, or a sulfur atom, R ⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and W represents a straight chain having 1 to 10 carbon atoms. Chain, branched, or cyclic al .n representing the alkylene group represents 0 or 1.)
A polymer compound obtained by polymerizing at least one of the acrylate derivatives represented by formula (1) as a raw material.