Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
  • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

• the present invention relates to a polymer, a resist composition containing the polymer, a method for producing a substrate on which a pattern is formed using the resist composition, (meth) acrylic acid ester, and production of the (meth) acrylic acid ester. Regarding the method.
• the present application claims priority based on Japanese Patent Application No. 2019-059909, Japanese Patent Application No. 2019-059910, and Japanese Patent Application No. 2019-060490 filed in Japan on March 27, 2019, the contents of which are incorporated herein by reference. To do.
• a (meth) acrylic acid ester containing a sulfonyl group (hereinafter, may be referred to as a "sulfonyl group-containing (meth) acrylic acid ester”) is known as a sulfur-containing monomer.
• a polymer obtained by homopolymerizing a sulfonyl group-containing (meth) acrylic acid ester or a copolymer obtained by copolymerizing with another monomer may be, for example, a material having a high dielectric constant, a material having a high refractive index, or an anti-inflammatory material. It is used as an effective medical adhesive.
• Patent Document 1 As a method for producing such a sulfonyl group-containing (meth) acrylic acid ester, a method by transesterification reaction between a (meth) acrylic acid ester and an alcohol is known (for example, Patent Document 1).
• the wavelength has been shortened, and as the next-generation exposure light source, an ArF excimer laser having a wavelength of 193 nm and EUV (extreme ultraviolet) having a higher energy wavelength of 13.5 nm were used.
• EUV extreme ultraviolet
• Mass production of semiconductor elements is progressing. It is desirable that the resist polymer applied to these contains a polar group from the viewpoint of adhesion to a substrate and affinity for a polar solvent.
• a (meth) acrylic acid ester containing a lactone group has been widely used as a monomer containing such a polar group.
• the sulfonyl group-containing (meth) acrylic acid ester has high polarity and is expected to be applicable as a monomer (raw material monomer) constituting a polymer for resist.
• a chemically amplified resist composition is known as a resist composition that can suitably cope with shortening the wavelength of irradiation light and miniaturizing a pattern in a lithography technique.
• the chemically amplified resist composition contains a resist polymer from which an acid-eliminating group is eliminated by the action of an acid, and a photoacid generator.
• pattern miniaturization has progressed rapidly, and it is desired to develop a resist material capable of further improving various lithography characteristics such as sensitivity, pattern formability, and line widow roughness (LWR).
• the monomer represented by the formula (a1-1-2) the monomer represented by the formula (a2-1-1): the formula (a3-1-1).
• Represented monomer A polymer obtained by polymerizing a mixture containing the monomer represented by the formula (I-2) in a molar ratio of 30:20:40:10 is described. .. Further, when a resist pattern was formed using a resist composition containing this polymer and an acid generator, it was shown that the side surface of the pattern was roughened and the line widow sloughness (LWR) was inferior.
• the sulfonyl group-containing (meth) acrylic acid ester is highly polymerizable, and when exposed to a high temperature in the transesterification reaction, it is a high molecular weight substance due to the polymerization of the sulfonyl group-containing (meth) acrylic acid ester.
• Patent Document 1 describes that the product is purified by recrystallization, washing, or the like, but the high molecular weight substance cannot be sufficiently removed by such a method.
• the present invention provides a polymer having excellent developer solubility, a resist composition containing the polymer, a method for producing a substrate on which a pattern is formed using the resist composition, and a reduction in high molecular weight substances. It is an object of the present invention to provide a modified (meth) acrylic acid ester, or to provide a method for producing a (meth) acrylic acid ester having a reduced high molecular weight.
• R 1 represents a hydrogen atom or a methyl group
• a 1 represents a linking group or a single bond containing an ester bond, where A 1 has no tertiary carbon atom
• Z 1 is , Represents an atomic group forming a sulfur-containing ring-type hydrocarbon group having 3 to 6 carbon atoms including a carbon atom bonded to A 1 and -SO 2- .
• the polymer of the above [1] further containing a structural unit (2) having an acid-eliminating group.
• Step 1 A (meth) acrylic acid ester represented by the following formula (1x) by a transesterification reaction between an alcohol represented by the following formula (2x) and a (meth) acrylic acid ester represented by the following formula (3x).
• Step 2 A step of adding a poor solvent to the solution containing the (meth) acrylic acid ester (1x) obtained in the step 1 to precipitate a high molecular weight substance and removing the high molecular weight substance.
• R 11 represents a hydrogen atom or a methyl group
• a 11 represents a linking group or a single bond containing an ester bond, where A 11 has no tertiary carbon atom
• Z 11 is , carbon atoms and -SO 2 which is bound to a 11 - represents an atomic group necessary for forming a including sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms.
• Z 11 is a carbon atom and -SO 2 bonded with hydroxy group - represents an atomic group necessary for forming a including sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms.
• R 11 represents a hydrogen atom or a methyl group
• R 12 represents a linear or branched alkyl group having 1 to 10 carbon atoms.
• R 11 represents a hydrogen atom or a methyl group
• a 11 represents a linking group or a single bond containing an ester bond, where A 11 has no tertiary carbon atom
• Z 11 is , carbon atoms and -SO 2 which is bound to a 11 - represents an atomic group necessary for forming a including sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms.
• the present invention it is possible to provide a polymer having good developer solubility, a resist composition containing the polymer, and a method for producing a substrate in which a pattern is formed using the resist composition. According to the present invention, it is possible to provide a sulfonyl group-containing (meth) acrylic acid ester having a reduced high molecular weight.
• (meth) acrylic acid means one or both of acrylic acid and methacrylic acid.
• the "constituent unit” means an atomic group formed by a polymerization reaction of monomers.
• the monomer represented by the formula (1) may be referred to as the monomer (1).
• the compound represented by the formula (1) may be referred to as the compound (1).
• the polymer of the present embodiment (hereinafter, also referred to as “polymer A”) contains a structural unit (1) based on the monomer (1) represented by the following formula (1).
• the content of the structural unit based on the monomer having a polycyclic structure is 35 mol% or less with respect to all the structural units of the polymer A.
• the polymer A preferably further contains one or more of the structural units (2) having an acid-eliminating group.
• the polymer A may contain one or more structural units other than the structural units (1) and (2).
• Polymer A is suitable as a resist polymer.
• the structural unit (1) is a structural unit formed by cleaving the ethylenic double bond of the monomer (1).
• R 1 is a hydrogen atom or a methyl group.
• the A 2 and A 3 are divalent chain hydrocarbon groups having 1 to 5 carbon atoms. The chain hydrocarbon groups as A 2 and A 3 may be linear or branched. A 2 and A 3 are preferably alkylene groups having 1 to 3 carbon atoms. A 2 and A 3 do not contain a tertiary carbon atom.
• Z 1 is an atomic group that forms a sulfur-containing cyclic hydrocarbon group (4-membered ring to 7-membered ring) having 3 to 6 carbon atoms including a carbon atom bonded to A 1 and -SO 2-. is there.
• the sulfur-containing cyclic hydrocarbon group preferably has 4 to 6 carbon atoms.
• a substituent may be bonded to the carbon atom constituting the sulfur-containing cyclic hydrocarbon group ring. Examples of the substituent include a linear or branched alkyl group, hydroxy group, amino group, aldehyde group, chloro group, bromo group and iodo group having 1 to 10 carbon atoms.
• the monomer (1) has an embodiment in which a substituent is not bonded to a carbon atom constituting a sulfur-containing ring-type hydrocarbon group ring, or an alkyl group having 1 to 6 carbon atoms is bonded as a substituent. Is preferable.
• the monomer of this embodiment is represented by the following formula (1').
• R 1, A 1 is the same as R 1, A 1 in the formula (1).
• n represents an integer of 1 to 4.
• the heterocycle bonded to A 1 is, for example, a 4-membered ring when n is 1 and a 7-membered ring when n is 4. In terms of stability and ease of synthesis, n is preferably 2.
• R 2 represents a substituent attached to a carbon atom constituting the hetero ring. However, R 2 does not bond to the carbon atom bonded to A 1 .
• the m R 2 each independently represent an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched.
• R 2 there are a plurality in one molecule may be identical to one another or may be different.
• m is an integer of 0 or more (n + 1) or less, an integer of 0 or more and n or less is preferable, 0 or 1 is more preferable, and 0 is most preferable.
• Examples of the groups bonded to A 1 include the groups represented by the following formulas (1a) to (1d). * In the formula represents the bond with A 1 .
• R 1 is a hydrogen atom or a methyl group
• a 1 is a single bond
• any of the groups represented by the above formulas (1a) to (1d) is bonded to A 1. It is preferable to use the above mode.
• the group represented by the formula (1a) to (1d) is particularly preferable in terms of stability and ease of synthesis.
• the structural unit (1) contained in the polymer A may be one kind or two or more kinds.
• the structural unit (1) is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, based on all the structural units of the polymer A.
• the upper limit is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less from the viewpoint of sensitivity and resolution.
• the structural unit (1) is preferably 15 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 25 to 60 mol%, and 25 to 50 mol% with respect to all the structural units of the polymer A. Is particularly preferable.
• the structural unit (2) is a structural unit based on a monomer having an acid-eliminating group (hereinafter, also referred to as a monomer (2)).
• the acid-eliminating group is a group having a bond that cleaves by the action of an acid, and a part or all of the acid-eliminating group is eliminated from the polymer by the cleavage of the bond.
• the acid desorbing group of the polymer reacts with the acid to be desorbed in the exposed portion by heating after the exposure, and becomes soluble in the alkaline developer.
• the monomer (2) is preferably a (meth) acrylic acid ester compound.
• the monomer (2) preferably contains a (meth) acrylic acid ester compound having an acid-eliminating group containing an alicyclic hydrocarbon group in terms of dry etching resistance in the lithography process.
• the alicyclic hydrocarbon group may be monocyclic or polycyclic.
• the alicyclic hydrocarbon group may contain a hetero atom.
• the hetero atom is preferably one or more selected from the group consisting of O, S and N.
• the number of atoms constituting the ring is preferably 5 to 22.
• an acrylic acid ester having a tertiary carbon atom at a bond site with an oxygen atom constituting an ester bond of the acrylic acid ester is more preferable.
• Specific examples include the monomers (2-1) to (2-4) of the following formulas.
• the monomer (2-4) is more preferable in that the effect of improving the solubility of the developing solution can be easily obtained when combined with the structural unit (1).
• R 31 , R 32 , R 33 , and R 34 each independently represent a hydrogen atom or a methyl group.
• R 21 , R 24 , and R 25 each independently represent an alkyl group having 1 to 5 carbon atoms.
• the alkyl group may be linear or branched.
• R 22 and R 23 each independently represent an alkyl group having 1 to 3 carbon atoms.
• the alkyl group may be linear or branched.
• R 331 , R 332 , R 333 , and R 334 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the alkyl group may be linear or branched.
• X 1 , X 2 , X 3 , and X 4 each independently represent an alkyl group having 1 to 6 carbon atoms.
• the alkyl group may be linear or branched.
• n1, n2, n3, and n4 each independently represent an integer of 0 to 4.
• n1, n2, when the n3 or n4 is 2 or more, X 1, X 2, X 3 or X 4 is more present in one molecule may be identical to one another or may be different.
• Z 2 and Z 3 independently represent -O-, -S-, -NH- or- (CH 2 ) k-, respectively.
• k represents an integer from 1 to 6.
• q represents 0 or 1.
• r represents an integer from 0 to 3.
• the structural unit (2) contained in the polymer A may be one kind or two or more kinds.
• the structural unit (2) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, based on all the structural units of the polymer A. If it is at least the lower limit of the above range, good sensitivity can be easily obtained, and if it is at least the upper limit, a good balance as a resist can be easily obtained, and good adhesion to the substrate can be easily obtained.
• the structural unit (2) preferably includes a structural unit (2i) having an acid-eliminating group containing an alicyclic hydrocarbon group.
• the alicyclic hydrocarbon group may be monocyclic or polycyclic.
• the alicyclic hydrocarbon group may contain a hetero atom.
• the hetero atom is preferably one or more selected from the group consisting of O, S and N.
• the number of atoms constituting the ring is preferably 5 to 22.
• the content of the structural unit (2i) is preferably 25 mol% or more, more preferably 35 mol% or more, further preferably 50 mol% or more, and 75 mol% or more with respect to the total number of moles of the structural unit (2). Especially preferable. It may be 100 mol%.
• the content of the structural unit (2i) is at least the above lower limit value, the effect of improving the solubility of the developing solution can be easily obtained when combined with the structural unit (1).
• the structural unit (2) includes a structural unit (2ii) having an acid-eliminating group containing a monocyclic alicyclic hydrocarbon group. It is preferable that the monocyclic alicyclic hydrocarbon group does not contain a hetero atom.
• the number of atoms constituting the ring of the monocyclic alicyclic hydrocarbon group is more preferably 5 to 8, and even more preferably 5 to 6.
• a structural unit based on the monomer (2-4) is more preferable.
• the content of the structural unit (2ii) is preferably 25 mol% or more, more preferably 35 mol% or more, further preferably 50 mol% or more, and 75 mol% or more with respect to the total number of moles of the structural unit (2). Especially preferable. It may be 100 mol%. When the content of the structural unit (2ii) is at least the above lower limit value, the effect of improving the solubility of the developing solution can be easily obtained when combined with the structural unit (1).
• the content of the structural unit based on the monomer having a polycyclic structure is 35 mol% or less, more preferably 30 mol% or less, based on all the structural units of the polymer A.
• the structural unit having a polycyclic structure is 35 mol% or less, the polymer A is excellent in developer solubility.
• a structural unit known in the chemically amplified resist composition can be used as another structural unit.
• a structural unit having a lactone skeleton and a structural unit having a hydrophilic group can be mentioned.
• the lactone backbone is preferably a 4- to 20-membered ring, more preferably a 5- to 10-membered ring.
• the lactone skeleton may be a monocycle having only a lactone ring, or an aromatic or non-aromatic hydrocarbon ring or heterocycle may be condensed on the lactone ring.
• a (meth) acrylic acid ester compound is preferable.
• a (meth) acrylic acid ester having a substituted or unsubstituted ⁇ -valerolactone ring and a (meth) acrylic acid ester having a substituted or unsubstituted ⁇ -butyrolactone ring from the viewpoint of excellent adhesion to a substrate or the like.
• At least one selected from the group consisting of is preferable, and a monomer having an unsubstituted ⁇ -butyrolactone ring is particularly preferable.
• the monomer having a lactone skeleton examples include ⁇ - (meth) acryloyloxy- ⁇ -methyl- ⁇ -valerolactone, 4,4-dimethyl-2-methylene- ⁇ -butyrolactone, and ⁇ - (meth) acryloyl.
• the content thereof is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and further 30 to 50 mol% with respect to all the constituent units of the polymer A. preferable. Within the above range, the effect of improving the adhesion to the substrate can be easily obtained.
• hydrophilic group is one or more selected from the group consisting of -C (CF 3 ) 2- OH, hydroxy group, cyano group, methoxy group, carboxy group and amino group.
• a (meth) acrylic acid ester compound and a styrene derivative having a hydroxy group are preferable.
• the monomer having a hydrophilic group examples include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-n (meth) acrylate.
• 3-hydroxyadamantyl (meth) acrylate, 3,5-dihydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl- 2-adamantyl (meth) acrylate and the like are preferable.
• the hydrophilic unit contained in the polymer A may be one kind or two or more kinds.
• the structural unit having a hydrophilic group contributes to the improvement of the wettability of the polymer A to the developing solution.
• the content of the structural unit having a hydrophilic group is preferably 0 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 20 mol% with respect to all the structural units of the polymer A. Within the above range, a good balance as a resist can be easily obtained.
• Preferred embodiments of the polymer A include the following embodiments (i) to (iv).
• the total of the unit (1) and the lactone unit is 25 to 85 mol%
• the constituent unit (2) is 20 to 80 mol%
• the total of the constituent unit (1), the constituent unit (2) and the lactone unit are the following embodiments (i) to (iv).
• the total of the constituent unit (1) and the hydrophilic unit is 15 to 80 mol%
• the constituent unit (2) is 20 to 80 mol%
• the constituent unit (1), the constituent unit (2) and the hydrophilicity A polymer in which the total with the unit is 35 to 100 mol%.
• the hydrophilic unit is 0 to 40 mol%, the total of the constituent unit (1), the lactone unit and the hydrophilic unit is 25 to 85 mol%, and the constituent unit (2) is 25 to 80 mol%.
• a polymer in which the total of the structural unit (1), the structural unit (2), the lactone unit, and the hydrophilic unit is 50 to 100 mol%.
• the polymer A can be produced, for example, by a solution polymerization method in which a monomer is radically polymerized using a polymerization initiator in the presence of a polymerization solvent.
• the weight average molecular weight of the polymer A is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000.
• the resist composition of the present embodiment preferably contains the polymer A, a resist solvent, and a compound that generates an acid by irradiation with active light or radiation.
• the polymer A may be used alone or in combination of two or more.
• the content of the polymer A with respect to the resist composition (excluding the solvent) is not particularly limited, but is preferably 70 to 99.9% by mass.
• the resist solvent examples include cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like.
• the resist solvent may be used alone or in combination of two or more.
• the amount of the resist solvent used depends on the thickness of the resist film to be formed, but is preferably in the range of 100 to 10,000 parts by mass with respect to 100 parts by mass of the polymer A.
• the compound that generates an acid by irradiation with active light or radiation can be arbitrarily selected from those that can be used as a photoacid generator in the chemically amplified resist composition.
• a photoacid generator one type may be used alone, or two or more types may be used in combination.
• the photoacid generator include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, diazomethane compounds and the like.
• the amount of the photoacid generator used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer A.
• the resist composition may contain nitrogen-containing compounds, acid compounds (organic carboxylic acids, oxo acids of phosphorus or derivatives thereof), surfactants, other quenchers, sensitizers, antihalation agents, and storage stabilizers, if necessary. , Various additives such as antifoaming agent may be contained. As the additive, those known in the field of resist composition can be used.
• the resist composition is applied by spin coating or the like on the surface (processed surface) of a substrate to be processed such as a silicon wafer. Then, the substrate to be processed to which the resist composition is applied is dried by a baking process (pre-baking) or the like to form a resist film on the substrate. Then, the resist film is irradiated with light having a wavelength of 250 nm or less via a photomask to form a latent image (exposure).
• the irradiation light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, the EUV excimer laser Preferably, ArF excimer laser is particularly preferable.
• immersion is performed by irradiating light with a high refractive index liquid such as pure water, perfluoro-2-butyl tetrahydrofuran, or perfluorotrialkylamine interposed between the resist film and the final lens of the exposure apparatus. Exposure may be performed.
• inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, di-n-butylamine and the like.
• Tertiary amines such as triethylamine and methyldiethylamine
• Alcoholic amines such as dimethylethanolamine and triethanolamine
• Tertiary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide
• examples thereof include aqueous solutions of cyclic amines such as pihelidine
• the (meth) acrylic acid ester of the present embodiment is a sulfonyl group-containing (meth) acrylic acid ester (compound (1x)) represented by the following formula (1x) and contains a high molecular weight substance having a molecular weight of 5000 or more. Is 0.1% by mass or less.
• R 11 represents a hydrogen atom or a methyl group
• a 11 represents a linking group or a single bond containing an ester bond, where A 11 has no tertiary carbon atom
• Z 11 is , carbon atoms and -SO 2 which is bound to a 11 - represents an atomic group necessary for forming a including sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms.
• the (meth) acrylic acid ester of the present embodiment in which the content of the high molecular weight substance having a molecular weight of 5000 or more is defined is not "(meth) acrylic acid ester" but "(meth) acrylic acid ester composition”.
• a high molecular weight substance having a molecular weight of 5000 or more (hereinafter, may be simply referred to as a “high molecular weight substance”) is 0.1% by mass or less. It is contained in a very small amount, or its content is below the detection limit and is hardly contained.
• the high molecular weight body content of the high molecular weight body is 0.1% by mass or less, the product is regarded as a "(meth) acrylic acid ester product" and is used for various purposes. Therefore, in the present embodiment, the high molecular weight is thus obtained.
• a (meth) acrylic acid ester containing a very small amount or almost no body is referred to as a "(meth) acrylic acid ester".
• the high molecular weight body content of 0.1% by mass or less is below the detection limit in the analysis of the high molecular weight body and substantially includes the high molecular weight body content of 0% by mass.
• a 11 is a linking group or a single bond containing an ester bond. However, A 11 does not have a tertiary carbon atom.
• the linking group containing the ester bond as A 11 is the same as the linking group containing the ester bond as A 1 .
• a 11 is preferably a single bond from the viewpoint of easy availability of raw materials and ease of synthesis.
• R 11 is a hydrogen atom or a methyl group, preferably a methyl group.
• Z 11 is an atomic group forming a sulfur-containing cyclic hydrocarbon group (4-membered ring to 7-membered ring) having 3 to 6 carbon atoms including a carbon atom bonded to A 11 and -SO 2-. is there.
• the sulfur-containing cyclic hydrocarbon group preferably has 4 to 6 carbon atoms.
• a substituent may be bonded to the carbon atom constituting the sulfur-containing cyclic hydrocarbon group ring. Examples of the substituent include a linear or branched alkyl group, hydroxy group, amino group, aldehyde group, chloro group, bromo group and iodo group having 1 to 10 carbon atoms.
• the sulfur-containing cyclic hydrocarbon group is more preferably a 2-sulfolane or 3-sulfolane structure having a 5-membered ring containing a sulfonyl group, and among them, 3 -Sulfolane structure is most preferred.
• 3-sulfolanyl methacrylate is most preferable.
• the content of the high molecular weight substance in the (meth) acrylic acid ester can be analyzed by the method described in the section of Examples described later, and the detection limit is 0.03% by mass or less.
• the high molecular weight compound in the (meth) acrylic acid ester of the present embodiment has a sulfonyl group which is a target product (compound (1x)) in step 1 of the method for producing (meth) acrylic acid ester described later (meth).
• Acrylic acid ester, or the compound (3x) described later, which is a raw material for producing the compound (1x) is a high molecular weight compound produced by polymerization or copolymerization due to its high polymerizable property. Its molecular weight is 5000 or more, weight average molecular weight measured by the method described in the Examples section below (Mw) of a 3 ⁇ 10 5 ⁇ 6 ⁇ 10 about 5.
• the content of the high molecular weight substance in the (meth) acrylic acid ester of the present embodiment is preferably 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably 0.03% by mass or less. Most preferably, it is below the detection limit.
• the (meth) acrylic acid ester of the present embodiment in which the content of the high molecular weight substance is reduced in this manner can be produced by the method for producing the (meth) acrylic acid ester of the present embodiment described later.
• the (meth) acrylic acid ester of the present embodiment having a reduced high molecular weight substance content can exhibit the original excellent properties of the sulfonyl group-containing (meth) acrylic acid ester without being affected by the high molecular weight substance.
• it is useful in a wide range of applications such as plastic raw materials, paints, and adhesives.
• the sulfonyl group-containing (meth) acrylic acid ester of the present embodiment is useful as a monomer constituting a resist application, for example, a polymer for ArF resist.
• a monomer having a reduced high molecular weight substance content the lithography characteristics of the resist polymer can be improved.
• the solubility and developability of the resist polymer can be improved, and defects during development due to the high molecular weight substance can be prevented.
• it is derived from the sulfonyl group and can improve the adhesion to the substrate and the affinity to the polar solvent.
• the sulfonyl group-containing (meth) acrylic acid ester of the present embodiment can be suitably used as the monomer (1) constituting the polymer A.
• the method for producing a (meth) acrylic acid ester of the present embodiment is a method for producing a (meth) acrylic acid ester represented by the above formula (1x), and includes the following steps 1 and 2.
• Step 1 (Meta) acrylic acid represented by the formula (1x) by a transesterification reaction between an alcohol represented by the following formula (2x) and a (meth) acrylic acid ester represented by the following formula (3x). The step of obtaining a solution containing an ester.
• Z 11 is a carbon atom and -SO 2 bonded with hydroxy group - represents an atomic group necessary for forming a including sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms.
• R 11 represents a hydrogen atom or a methyl group
• R 12 represents a linear or branched alkyl group having 1 to 10 carbon atoms.
• Step 2 A step of adding a poor solvent to the solution containing the (meth) acrylic acid ester represented by the formula (1x) obtained in Step 1 to precipitate a high molecular weight substance and removing the high molecular weight substance.
• step 1 the compound (1x) is obtained by reacting the alcohol compound (2x) represented by the formula (2x) with the (meth) acrylic acid ester compound (3x) represented by the formula (3x).
• Z 11 is an atomic group that forms a sulfur-containing cyclic hydrocarbon group having 3 to 6 carbon atoms including a carbon atom bonded to a hydroxy group and —SO 2- .
• the sulfur-containing cyclic hydrocarbon group preferably has 4 to 6 carbon atoms.
• a substituent may be bonded to a carbon atom constituting the ring of the sulfur-containing cyclic hydrocarbon group. Examples of the substituent include a linear or branched alkyl group, hydroxy group, amino group, aldehyde group, chloro group, bromo group and iodo group having 1 to 10 carbon atoms.
• the sulfur-containing cyclic hydrocarbon group is more preferably a 2-sulfolane or 3-sulfolane structure having a 5-membered ring containing a sulfonyl group.
• the 3-sulfolane structure is the most preferable.
• the compound (2x) 3-hydroxysulfolane is most preferable.
• R 11 is a hydrogen atom or a methyl group, preferably a methyl group.
• R 12 is a linear or branched alkyl group having 1 to 10 carbon atoms.
• linear or branched alkyl groups having 1 to 10 carbon atoms methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, t-butyl group, normal pentyl group, normal hexyl group, 2 -Ethylhexyl group and the like can be mentioned. Since it is necessary to remove the alcohol derived from the raw material ester by distillation in the transesterification reaction, it is preferable that the boiling point of the by-product alcohol produced in the transesterification reaction is low. From this point of view, R 12 is preferably a methyl group. That is, as the compound (3x), methyl acrylate or methyl methacrylate is preferable.
• step 1 the compound (1x) is produced by a transesterification reaction.
• the conditions of the transesterification reaction are not particularly limited, and a known method may be used.
• Japanese Patent Application Laid-Open No. 2007-153763 discloses a method for obtaining 3-sulfolanyl methacrylate by reacting 3-hydroxysulfolane with methyl methacrylate.
• compound (2x) In order to obtain compound (1x) in good yield, it is preferable to dehydrate compound (2x) before use.
• a method of dehydration a method in which the compound (2x) is dissolved in an organic solvent, heated, and water is removed by azeotropic boiling of the organic solvent and water is preferable.
• the azeotropic organic solvent benzene, toluene, ethylbenzene, methylethylketone, 1,4-dioxane, hexane, cyclohexane and the like can be used.
• the compound (3x) When the compound (3x) is azeotropically heated with water, the compound (2x) can be dissolved in the compound (3x) and dehydrated by azeotropic boiling.
• a catalyst may or may not be used in the transesterification reaction. It is preferable to use a catalyst in order to obtain the compound (1x) in good yield.
• a catalyst a titanium catalyst or a tin catalyst can be used.
• the titanium catalyst include tetramethoxytitanium, tetraethoxytitanium, tetranormal propoxytitanium, tetraisopropoxytitanium, tetranormalbutoxytitanium, tetraisobutoxytitanium and the like.
• tin catalyst examples include dinormal butyl tin oxide, dinormal octyl tin oxide, di-2-ethylhexyl tin oxide and the like. It is preferable to use a titanium catalyst from the viewpoint of catalyst removability after the reaction.
• the amount of the catalyst used is preferably 0.001 mol or more, more preferably 0.01 mol or more, based on 1 mol of the compound (2x), from the viewpoint of efficiently obtaining the compound (1x).
• the amount of the catalyst used is preferably 0.05 mol or less, more preferably 0.03 mol or less, relative to 1 mol of the compound (2x), from the viewpoint of catalyst removability and cost.
• the transesterification catalyst may be added all at once or may be added in portions.
• the amount of the catalyst used is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0.03 mol, based on 1 mol of the compound (2x).
• the amount of the compound (3x) used in the transesterification reaction is not particularly limited, but from the viewpoint of obtaining the compound (1x) in good yield, 0.5 mol or more per mol of the compound (2x) is preferable, and 0.8 mol or more is preferable. Is more preferable, and 1.0 mol or more is further preferable.
• the by-product alcohol is removed by azeotrope with the compound (3x)
• the amount of the compound (3x) used is small, the by-product alcohol cannot be sufficiently removed, so that the reaction rate may decrease. There is.
• the amount of the compound (3x) used is preferably 12 mol or less, preferably 10 mol or less, per 1 mol of the compound (2x). More preferably, 8 mol or less is further preferable.
• the amount of the compound (3x) to be used is preferably 0.5 to 12 mol, more preferably 0.8 to 10 mol, still more preferably 1 to 8 mol, per 1 mol of the compound (2x).
• a polymerization inhibitor In order to suppress the polymerization of compound (3x) and compound (1x), it is preferable to add a polymerization inhibitor to the reaction system.
• the type of the polymerization inhibitor is not particularly limited, and one type may be used or two or more types may be used.
• polymerization inhibitor examples include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-tert-butyl-4-methylphenol, tert-butylcatechol, and 2,6-di-tert.
• Phenolic compounds such as -butyl-4-methylphenol, N, N-diiropropyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N, N-di Amine compounds such as -2-naphthylparaphenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine- N-oxyl, 4-acetamide-2,2,6,6-tetramethylpiperidin-N-oxyl, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the like.
• -Oxyl compounds and the like can be mentioned.
• the amount of oxygen-containing gas to be introduced can be set as appropriate. It is particularly preferable to use air as the oxygen-containing gas.
• the temperature of the transesterification reaction is not particularly limited, but is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, in order to remove by-product alcohol and improve the reaction rate. Further, in order to suppress the polymerization of compound (3x) and compound (1x), the temperature is preferably 160 ° C. or lower, more preferably 140 ° C. or lower. For example, the temperature of the transesterification reaction is preferably 30 to 160 ° C, more preferably 60 to 140 ° C.
• the time of the transesterification reaction is preferably 0.5 hours or more, more preferably 1 hour or more, from the viewpoint of efficiently obtaining the compound (1x). Further, in order to suppress the polymerization of the compound (3x) and the compound (1x), 50 hours or less is preferable, and 30 hours or less is more preferable.
• the transesterification reaction time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours.
• a catalyst When a catalyst is used as a post-treatment after the reaction, an operation of inactivating the catalyst may be performed.
• the compound (1x) when used for resist, it is preferable to reduce metal contamination as much as possible. Therefore, when a metal is used as the catalyst, it is preferable to deactivate and remove the catalyst.
• the method include the following methods. That is, after cooling the reaction solution to about 70 ° C. or lower with stirring, the same amount or more of water as the added catalyst, an adsorbent, and Celite as a filtration aid are added to turn the catalyst into a metal oxide and lose it. Let it live and precipitate. After the addition is completed, stirring is continued for about 1 to 5 hours. The precipitated metal oxide can be removed by pressure filtration, vacuum filtration or the like.
• Step 2 Purification step
• step 2 a poor solvent is added to the solution containing the compound (1x) produced in step 1 to precipitate a high molecular weight substance, and the precipitated high molecular weight substance is removed.
• the precipitation of the high molecular weight substance by the poor solvent in this step 2 is to precipitate the high molecular weight substance without precipitating the compound (1x), and the cleaning operation and the recrystallization operation described later in which the high molecular weight substance is not precipitated. Is different.
• the poor solvent to be added is not particularly limited, and hydrocarbon solvents such as pentane, hexane, heptane, cyclopentane, cyclohexane, octane, toluene and xylene, diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane and the like are used.
• hydrocarbon solvents such as pentane, hexane, heptane, cyclopentane, cyclohexane, octane, toluene and xylene, diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane and the like are used.
• Examples thereof include ether solvents, ester solvents such as ethyl acetate, butyl acetate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and butyl methacrylate, and alcohol solvents such as methanol, ethanol and 2-propanol.
• ester solvents such as ethyl acetate, butyl acetate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and butyl methacrylate
• alcohol solvents such as methanol, ethanol and 2-propanol.
• One type of poor solvent may be used alone, or two or more types may be mixed and used. It is more preferable to use a hydrocarbon solvent having a low solubility of the high molecular weight substance.
• saturated hydrocarbon solvents having 5 to 7 carbon atoms such as pentane, hexane, and heptane are more preferable because they can
• the amount of the poor solvent added can be appropriately determined depending on the amount of the high molecular weight substance and the solubility.
• the mass of the compound (2x) used in the reaction is preferably 0.2 times by mass or more, more preferably 0.5% by mass or more. Further, from the viewpoint of economy and pot efficiency, the mass of the compound (2x) used in the reaction is preferably 5 times by mass or less, more preferably 3 times by mass or less.
• the amount of the poor solvent added is preferably 0.2 to 5 times by mass, more preferably 0.5 to 3 times by mass, based on the mass of the compound (2x) used in the reaction.
• the method for removing the precipitated high molecular weight substance is not particularly limited, and examples of the distillation residue include separation, pressure filtration, vacuum filtration, and centrifugation.
• An appropriate method may be appropriately used in consideration of the boiling point, properties, scale, amount of high molecular weight substance, etc. of the compound (1x). It is desirable to use pressure filtration, vacuum filtration, and centrifugation, which are non-heating methods, in order to prevent the formation of high molecular weight substances again in the process of removal. After the high molecular weight substance is separated, it may be concentrated by vacuum distillation or the like to remove the poor solvent.
• Step 2 may include a purification operation of compound (1x), if necessary.
• Examples of the method for purifying the compound (1x) include washing, heat treatment, filtration, distillation, recrystallization and the like. These may be carried out alone or in combination of two or more.
• the purification may be carried out before or after the high molecular weight molecular precipitation step, or may be carried out both before and after.
• the compound (2x) Since the compound (2x) has a sulfonyl group, it has high polarity and is easily dissolved in water. Therefore, the compound (2x) can be removed to the aqueous layer by washing with water or an aqueous solution in which 5 to 30% by mass of an inorganic salt such as sodium chloride, ammonium sulfate, or sodium sulfate is dissolved as a cleaning solution.
• the number of washings can be appropriately determined. It is preferable to include a step of washing with water from the viewpoint of reducing the mixing of the metal into the compound (1x).
• the washing may be carried out without adding a solvent, or may be diluted with a solvent.
• a solvent is not particularly limited, and hydrocarbon solvents such as pentane, hexane, heptane, cyclopentane, cyclohexane, octane, toluene and xylene, and ether solvents such as diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran and dioxane are used.
• Solvents such as ethyl acetate, butyl acetate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate and the like can be used.
• One of these solvents may be used alone, or two or more of these solvents may be mixed and used.
• the amount of the solvent used can be appropriately determined according to the solubility of the compound (1x) and the amount of the washing liquid.
• the compound (1x) is purified by distillation, it is preferable to add a polymerization inhibitor and appropriately introduce an oxygen-containing gas such as air at a vacuum degree of 1.3 kPa (10 mmHg) or less. In particular, since there is little heat history, it is preferable to carry out by a method such as thin film distillation.
• a solvent is used in which the compound (1x) is dissolved between room temperature and 40 ° C. and cooled to room temperature or lower to precipitate crystals.
• the solvent used for recrystallization include alcohol solvents such as methanol, ethanol, isopropanol and butanol, ester solvents such as ethyl acetate, butyl acetate and methyl methacrylate, diethyl ether, diisopropyl ether and t-butyl methyl ether.
• the ether solvent can be used alone or in combination.
• a hydrocarbon solvent such as hexane, octane or heptane, which is difficult to dissolve crystals
• a halogen solvent such as chloroform, dichloroethane or dichloromethane, water or the like
• the alcohol solvent can also be used by mixing with an ester solvent or the ether solvent. It is preferable to use the alcohol solvent alone because the solvent can be easily reused. Further, a mixed solvent of an alcohol solvent and a hydrocarbon solvent is more preferable in terms of making the slurry concentration at the time of crystal precipitation appropriate and improving the recovery rate.
• the slurry concentration is preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of suppressing an increase in viscosity and improving process passability. Further, from the viewpoint of economy and pot efficiency, 5% by mass or more is preferable, and 10% by mass or more is more preferable. For example, the slurry concentration is preferably 5 to 25% by mass, more preferably 10 to 20% by mass.
• the compound (1x) it is preferable to dissolve the compound (1x) in a solvent at 30 ° C. or higher, gradually cool it, and add seed crystals when the internal temperature reaches 5 to 10 ° C. to promote crystallization.
• the internal temperature rises due to latent heat, but when it is cooled and the internal temperature becomes 10 ° C. or less, the crystals are separated.
• Crystal separation can be performed using a centrifugal filter, a pressure filter or the like. After the crystals are separated, they are washed with a solvent.
• the composition ratio (unit: mol%) of the structural unit based on each monomer was determined by 1 H-NMR measurement.
• an ECS-400 type superconducting FT (Fourier conversion) -NMR device manufactured by JEOL Ltd. was used, and a sample solution of about 5% by mass (solvent was deuterated chloroform) was placed in a sample tube having a diameter of 5 mm ⁇ .
• the integration was performed 64 times in a single pulse mode with an observation frequency of 400 MHz.
• the measurement temperature was 60 ° C.
• turbidity Th (80) is an index of solubility in a low-polarity organic solvent
• Tm (80) is an index of solubility in a highly polar organic solvent. The higher the turbidity, the lower the solubility in organic solvents. In other words, the higher the turbidity, the higher the polarity and the better the solubility in an alkaline developer.
• Example 1-1 In a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, put 8.1 parts by mass of PGMEA and 32.5 parts by mass of ⁇ -butyrolactone in a nitrogen atmosphere, and raise the temperature of the hot water bath to 80 ° C while stirring. It was. Then, the following mixture 1 was dropped into the flask from a dropping funnel over 4 hours, and the temperature of 80 ° C. was further maintained for 3 hours to obtain a reaction solution.
• composition of Mixture 1 8.17 parts by mass (20 mol%) of monomer (m1), Monomer (m2) 10.20 parts by mass (30 mol%), 13.44 parts by mass (40 mol%) of monomer (m3), 4.12 parts by mass (10 mol%) of monomer (m4), Solvent: 8.9 parts by mass of PGMEA, 35.7 parts by mass of ⁇ -butyrolactone, and polymerization initiator: dimethyl-2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name)) 3. 91 parts by mass.
• the precipitate was separated by filtration, poured into the same amount of methanol as described above, and the precipitate was washed with stirring. Then, the precipitate after washing was filtered off to obtain a polymer wet powder.
• the polymer wet powder was dried under reduced pressure at 60 ° C. for about 36 hours to obtain a dry powdery polymer.
• the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polymer are shown in Table 1 (hereinafter, the same applies).
• the turbidity of the obtained polymer was measured by the above method.
• the results are shown in Table 1 (the same applies hereinafter).
• the copolymerization composition ratio shown in Table 1 is the charging ratio, but when the copolymerization composition ratio of the obtained polymer was measured by the above method, the constituent unit (m1) was 20.2 mol%, which was the constituent unit. (M2) was 30.1 mol%, the constituent unit (m3) was 39.7 mol%, and the constituent unit (m4) was 10.0 mol%, which were almost the same as the charging ratio.
• the pore size A resist composition was produced by filtering with a 0.1 ⁇ m polymer filter.
• Example 1-2 Comparative Example 1-1
• the charged composition of the monomer in Example 1-1 was changed as shown in Table 1.
• a polymer was produced and evaluated in the same manner as in Example 1-1. Further, using the obtained polymer, a resist composition was produced in the same manner as in Example 1-1.
• Example 1-1 The charged composition of the monomer in Example 1-1 was changed as shown in Table 1. A polymer was produced and evaluated in the same manner as in Example 1-1. Further, using the obtained polymer, a resist composition was produced in the same manner as in Example 1-1.
• Examples 3-1 and 4-1 and Comparative Example 3-1 The charged composition of the monomer in Example 1-1 was changed as shown in Table 1. A polymer was produced and evaluated in the same manner as in Example 1-1. Further, using the obtained polymer, a resist composition was produced in the same manner as in Example 1-1.
• the polymers of Examples 1-1, 1-2, 3-1 and 4-1 have high turbidity, so that they have high polarity and excellent solubility in an alkaline developer. ..
• A represents the quantitative value of the compound (1) by the calibration curve
• B represents the total of the quantitative values of the compound (1) and the compound (2) by the calibration curve.
• the content of the high molecular weight substance is the peak area in the measurement of gel permeation chromatography (hereinafter referred to as "GPC”.
• the weight average molecular weight (Mw) of the high molecular weight substance is determined by standard polystyrene from the elution time in the measurement of GPC (equipment: HLC-8320GPC of Toso Co., Ltd., column: Shodex LF-804 (3 pieces), eluent: tetrahydrofuran). Calculated using a calibration curve.
• the methanol produced by the reaction was removed by azeotrope with methyl methacrylate using Dean-Stark, and the mixture was stirred for 2.5 hours.
• the amount of the mixed solution of methanol and methyl methacrylate extracted during this period was 45.8 g.
• the response rate by GC analysis was 91%.
• 1.6 g of water and 6.9 g of Celite were added, and the mixture was stirred for 1 hour, and the obtained mixed solution was filtered under reduced pressure with a filter paper.
• GPC analysis and Mw measured molecular weight of Mw4.6 ⁇ 10 5 were detected 1.15 wt%.
• Step 2 30 mL of toluene was added to the obtained filtrate, 15 mL of water was added to wash the organic layer, and the aqueous layer was discharged using a separatory funnel. Then, 20 mL of water was added to wash the organic layer, and the aqueous layer was discharged using a separatory funnel. Next, 24 g of hexane was added and stirred to precipitate a gel-like high molecular weight substance. After adding magnesium sulfate and drying, the mixture was filtered under reduced pressure using a filter paper, and the filtrate was concentrated using an evaporator to obtain 22.1 g of crude 3-sulfolanyl methacrylate.
• the methanol produced by the reaction was removed by azeotrope with methyl methacrylate using Dean-Stark, and the mixture was stirred for 8 hours.
• the amount of the mixed solution of methanol and methyl methacrylate extracted during this period was 902 g.
• the reaction rate by GC analysis was 88%.
• 28 g of water and 121 g of Celite were added and stirred for 1 hour, and the obtained mixed solution was filtered under reduced pressure with a filter paper.
• GPC analysis and Mw measured molecular weight of Mw4.0 ⁇ 10 5 were detected 0.08 wt%.
• Step 2 900 mL of toluene was added to the obtained filtrate, 200 mL of water was added to wash the organic layer, and 242 g of the aqueous layer was separated. Next, 200 mL of water was added to wash the organic layer, and 204 g of the aqueous layer was separated. Next, 650 mL of hexane was added and stirred to precipitate a gel-like high molecular weight substance. After adding magnesium sulfate and drying, the mixture was filtered under reduced pressure using a filter paper, and the filtrate was concentrated using an evaporator to obtain 406 g of crude 3-sulfolanyl methacrylate.
• the methanol produced by the reaction was removed by azeotrope with methyl methacrylate using Dean-Stark, and the mixture was stirred for 6 hours.
• the amount of the mixed solution of methanol and methyl methacrylate extracted during this period was 1477 g.
• the response rate by GC analysis was 67%.
• the mixture was cooled to 70 ° C. or lower, 35 g (0.1 mol) of tetrabutoxytitanium was added, and the reaction solution was heated and refluxed at an internal temperature of 100 to 110 ° C. while blowing air at 20 mL / min.
• the methanol produced by the reaction was removed by azeotrope with methyl methacrylate using Dean-Stark, and the mixture was stirred for 7.5 hours.
• the amount of the mixed solution of methanol and methyl methacrylate extracted during this period was 2081 g.
• the response rate by GC analysis was 87%.
• the mixture was cooled to 70 ° C. or lower again, 3.5 g (0.01 mol) of tetrabutoxytitanium was added, and the reaction solution was heated and refluxed at an internal temperature of 100 to 110 ° C. while blowing air at 20 mL / min. After stirring for 3.5 hours, the reaction rate by GC analysis was 87%.
• the amount of the mixed solution of methanol and methyl methacrylate extracted during this period was 525 g. Then, after cooling to 70 ° C.
• Step 2 3000 g of toluene was added to the obtained filtrate, 812 g of water was added to wash the organic layer, and 965 g of the aqueous layer was separated. Next, 837 g of water was added to wash the organic layer, and 852 g of the aqueous layer was separated. Next, 2020 g of hexane was added and stirred to precipitate a gel-like high molecular weight substance. The high molecular weight substance was removed by pressure filtration with a filter paper, and the filtrate was concentrated using an evaporator to obtain 1641 g of crude 3-sulfolanyl methacrylate.
• the 3-sulfolanyl methacrylates obtained in Examples 5-1 to 5-3 were of high purity in which high molecular weight substances having a molecular weight of 5000 or more were not detected.
• the obtained 3-sulfolanyl methacrylate contained 0.11% by mass of a high molecular weight substance having a molecular weight of 5000 or more. From these results, it is possible to remove the high molecular weight substance by precipitating the high molecular weight substance with a poor solvent in the purification step, and to reduce the content of the high molecular weight substance having a molecular weight of 5000 or more to 0.1% by weight or less. Recognize.
• a polymer having good developer solubility, a resist composition containing the polymer, and a method for producing a substrate on which a pattern is formed using the resist composition can be obtained.
• a sulfonyl group-containing (meth) acrylic acid ester having a reduced high molecular weight can be obtained.
• the (meth) acrylic acid ester of the present embodiment has a reduced high molecular weight substance content and is useful for a wide range of applications such as plastics, paints, and adhesives. Further, it is suitable as a monomer constituting a polymer for resist, and is useful for improving lithography characteristics.

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