JP2011168691A - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing polymer having high polymerization conversion of a monomer and a high molecular weight. <P>SOLUTION: The method for producing a polymer comprises polymerizing a monomer component containing a monomer (1) represented by general formula (1) (wherein R<SP>1</SP>denotes a hydrogen atom, a methyl group, or a trifluoromethyl group; R<SP>2</SP>denotes a single bond or a divalent hydrocarbon group; R<SP>3</SP>denotes a hydrogen atom or a monovalent organic group; and Rf<SP>1</SP>denotes an alkylene group in which at least one hydrogen atom is replaced with a fluorine atom) in a solvent component containing a solvent (S) represented by general formula (S) (wherein R<SP>4</SP>denotes a hydrogen atom or a monovalent organic group; R<SP>5</SP>and R<SP>6</SP>each independently denote a hydrogen atom, an alkyl group, or an acetyl group; and i denotes an integer of 0 or more). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a fluorine-containing polymer as a constituent of a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist, particularly a resist for ArF immersion exposure.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, a resist film is formed on a substrate with a resin composition containing a polymer having an acid-dissociable group, and the resist film has a short wavelength via a mask pattern. A fine resist pattern is formed by irradiating with radiation (excimer laser or the like) and exposing, and removing the exposed portion by alkali development. At this time, a “chemically amplified resist” is used in which a radiation-sensitive acid generator that generates an acid upon irradiation with radiation is contained in the resin composition, and the sensitivity is improved by the action of the acid.

  As a method for forming a finer resist pattern (for example, a line width of about 45 nm), the use of the “immersion exposure method (liquid immersion lithography)” is expanding. In this method, an immersion exposure liquid (for example, pure water, fluorine-based inert liquid, etc.) having a refractive index (n) larger than that of air or an inert gas in the exposure optical path space (between the lens and the resist film). Exposure is performed in a state where As a result, even when the numerical aperture (NA) of the lens is increased, there is an advantage that the depth of focus is hardly lowered and high resolution can be obtained.

  As a resin composition used in the above-described immersion exposure method, for example, for the purpose of preventing elution of an acid generator or the like from the resist coating to the immersion exposure solution and improving the drainage of the resist coating, etc. Various resin compositions containing a high fluorine-containing polymer have been proposed (for example, see Patent Documents 1 and 2).

  In the production of the above-mentioned fluorine-containing polymer, the polymerization conversion rate (yield) of the monomer is not high. Therefore, in order to obtain a fluorine-containing polymer with high yield, it has been proposed to polymerize in an isopropyl alcohol (hereinafter also simply referred to as “IPA”) solvent (see, for example, Patent Document 3).

International Publication No. 2007/116664 JP 2007-279663 A JP 2006-193687 A

  However, since IPA used in the polymerization method proposed in the above-mentioned Patent Document 3 has a low boiling point and flash point, when used on an industrial scale, it not only has a problem of polymerization efficiency, but also has sufficient safety. It is necessary to carry out the polymerization with consideration.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to provide a method for producing a fluorine-containing polymer having a high monomer conversion rate. is there.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have polymerized a monomer component containing a specific fluorine-containing monomer in a solvent component containing a specific solvent, thereby achieving the above-mentioned problem. The inventors have found that it is possible to achieve this, and have completed the present invention.

  That is, according to the present invention, the following polymer production method is provided.

  [1] Polymerization of a monomer component containing the monomer (1) represented by the following general formula (1) in a solvent component containing the solvent (S) represented by the following general formula (S) A process for producing a polymer comprising:

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ² is a single bond or a linear, branched, or cyclic group having 1 to 20 carbon atoms. A saturated or unsaturated divalent hydrocarbon group, R ³ represents a hydrogen atom or a monovalent organic group, Rf ¹ represents a methylene group in which at least one hydrogen atom is substituted with a fluorine atom, or at least A linear or branched alkylene group having 2 to 20 carbon atoms, in which one hydrogen atom is substituted with a fluorine atom. However, in the divalent hydrocarbon group represented by R ² , at least a part of the hydrogen atoms may be substituted with fluorine atoms.

In the general formula (S), R ⁴ represents a hydrogen atom or a monovalent organic group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, or an acetyl group, and i is 0 or more. Indicates an integer. In addition, when i is 1 or more, all R ⁴ are preferably the same atom or group.

  [2] The method for producing a polymer according to [1], wherein the solvent component contains 30% by mass or more of the solvent (S).

  [3] The method for producing a polymer according to [1] or [2], wherein the solvent component contains 60% by mass or more of the solvent (S).

  [4] The method for producing a polymer according to any one of [1] to [3], wherein the monomer component further contains a monomer (2) represented by the following general formula (2).

In the general formula (2), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and three R ⁸ are each independently a straight chain having 1 to 4 carbon atoms or A branched alkyl group, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or any two R ⁸ 's bonded to each other, 20 hydrocarbon rings or a ring derived therefrom, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent fat having 4 to 20 carbon atoms A cyclic hydrocarbon group or a group derived therefrom is shown.

  [5] The method for producing a polymer according to [4], wherein the monomer (2) is a monomer (2-1) represented by the following general formula (2-1).

In the general formula (2-1), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and R ¹⁰ is a linear or branched alkyl having 1 to 4 carbon atoms. Represents a group, and k represents an integer of 1 to 4.

  [6] The method according to any one of [1] to [5], wherein the monomer component further contains a monomer (3) having an alkali-soluble group (excluding the monomer (1)). A method for producing a polymer.

  [7] The monomer (3) is composed of a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following formula (3c). The method for producing a polymer according to the above [6], which is a monomer having at least one alkali-soluble group selected from the above.

In the general formula (3a), Rf ² represents a C 1-10 hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom. In the general formula (3b), Rf ³ represents at least one A methylene group or an alkylene group having 2 to 20 carbon atoms in which a hydrogen atom is substituted with a fluorine atom.

  [8] The method for producing a polymer according to [6] or [7], wherein the monomer (3) is a monomer (3-1) represented by the following general formula (3-1): .

In General Formula (3-1), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or a hydroxymethyl group, and R ¹² represents a divalent organic group.

  [9] The system according to any one of [1] to [8], wherein the monomer component further contains a monomer (4) having an alkali-reactive group (excluding the monomer (1)). A method for producing the polymer.

  [10] In the above [9], the monomer (4) is at least one selected from the group consisting of monomers represented by the following general formulas (4-1) to (4-7): The manufacturing method of the polymer of description.

In the general formulas (4-1) to (4-6), R ¹³ each independently represents a hydrogen atom or a methyl group. In the general formula (4-1), R ¹⁴ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, and l represents an integer of 1 to 3. In the general formulas (4-2) and (4-3), each A independently represents a single bond, an ether group, an ester group, a carbonyl group, a divalent chain hydrocarbon group having 1 to 30 carbon atoms, A divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a divalent group obtained by combining these, m is independently 0 or 1 is shown. In the above general formulas (4-3) and (4-5), B independently represents an oxygen atom or a methylene group. In the general formulas (4-4) and (4-5), R ¹⁵ each independently represents a hydrogen atom or a methoxy group. In the general formula (4-7), R ¹⁶ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and the plurality of R ¹⁷ are each independently a hydrogen atom or a chain having 1 to 5 carbon atoms. A hydrocarbon group is shown, n shows the integer of 2-4.

  [11] The polymer according to any one of [1] to [10], wherein the monomer (1) is a monomer (1-1) represented by the following general formula (1-1): Manufacturing method.

In the general formula (1-1), R ¹⁸ and R ²⁰ each independently represent a fluorine atom or a trifluoromethyl group, R ²¹ represents a hydrogen atom or a monovalent organic group, and R ¹⁹ each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a trifluoromethyl group, or a 2,2,2-trifluoroethyl group. 1-trifluoromethylethyl group or 3,3,3-trifluoropropyl group. However, two R ¹⁹ may be bonded to each other to form a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group.

  [12] The method for producing a polymer according to any one of [1] to [11], wherein the solvent (S) is a derivative of propylene glycol or a derivative of ethylene glycol.

  According to the method for producing a polymer of the present invention, a fluorine-containing polymer having a high polymerization conversion rate of a monomer can be produced.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

1. Production method of polymer:
The manufacturing method of the polymer of this invention is a method including superposing | polymerizing the monomer component containing a monomer (1) in the solvent component containing a solvent (S). The details will be described below.

1-1. Solvent component:
In the method for producing a polymer of the present invention, the solvent component is not particularly limited as long as it contains the solvent (S), and a conventionally known solvent (other solvent) can be mixed and used. In addition, the solvent component may contain the solvent (S) alone (100% by mass).

1-1-1. Solvent (S):
The solvent (S) is a solvent represented by the following general formula (S).

In the general formula (S), R ⁴ represents a hydrogen atom or a monovalent organic group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, or an acetyl group, and i is 0 or more. Indicates an integer. In addition, when i is 1 or more, all R ⁴ are preferably the same atom or group.

In the general formula (S), specific examples of the “monovalent organic group” represented by R ⁴ include methyl group, ethyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n- A butyl group, an i-butyl group, a t-butyl group, a phenyl group, a benzyl group, and the like can be given. Among these, a methyl group, an ethyl group, and the like are preferable from the viewpoint of operability due to the relatively low viscosity of the solvent.

In the general formula (S), specific examples of the “alkyl group” represented by R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group. Group, t-butyl group, n-hexyl group, 2-ethylhexyl group and the like. Among these, a methyl group, an ethyl group, a butyl group and the like are preferable from the viewpoint of operability due to the relatively low viscosity of the solvent.

  In the general formula (S), i is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

  Specific examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, Alkyl ethers of polyhydric alcohols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether; ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol ethyl ether Le acetate, and alkyl ether acetates of polyhydric alcohol such as propylene glycol monomethyl ether acetate.

  Among these solvents (S), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene from the viewpoints of good operability due to relatively low viscosity and easy availability. Glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate and the like are preferable.

  Among the preferable solvents (S) described above, a derivative of propylene glycol or a derivative of ethylene glycol is more preferable, and propylene glycol monomethyl ether (hereinafter also simply referred to as “PGME”), propylene glycol monomethyl ether acetate (hereinafter simply referred to as “PGME”). It is also described as “PGMEA”). By using a propylene glycol derivative or an ethylene glycol derivative as the solvent (S), a polymer having a higher monomer conversion and a higher molecular weight can be produced. This is because by using a propylene glycol derivative or an ethylene glycol derivative, chain transfer in which the radicals of the growing polymer chain move to components other than monomers such as solvents during the polymerization reaction is unlikely to occur. This is presumably because the radicals of the combined chain are less likely to be deactivated.

  Further, since PGME and PGMEA have a higher boiling point than IPA and methyl ethyl ketone (hereinafter also simply referred to as “MEK”), for example, polymerization at a higher temperature is possible without requiring equipment such as a pressure device. Even when a polymer is produced in large quantities, it can be produced efficiently. Moreover, since PGME and PGMEA have a flash point higher than IPA and MEK, they can be used more safely.

  The blending ratio of the solvent (S) in the solvent component is preferably 30% by mass or more, and particularly preferably 60% by mass or more. By setting the blending ratio of the solvent (S) to 30% by mass or more, it is speculated that radical deactivation of the growing polymer chain is more effectively suppressed during the polymerization reaction, and the conversion rate can be increased. .

1-1-2. Other solvents:
The other solvent other than the solvent (S) contained in the solvent component is not particularly limited as long as it is a solvent that does not inhibit the effect of containing the solvent (S) and does not inhibit the polymerization reaction. A polymerization solvent can be used. Specific examples of other solvents include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc. Cycloalkanes; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate, acetic acid n Saturated carboxylic acid esters such as butyl, i-butyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethanes and diethoxyethane Ethers such as methanol; methanol, Ethanol, 1-propanol, 2-propanol, it may be mentioned alcohols such as 4-methyl-2-pentanol. These other solvents can be used singly or in combination of two or more.

1-2. Monomer component:
In the method for producing a polymer of the present invention, the monomer component contains the monomer (1). In addition, it is preferable that this monomer component further contains the monomers (2)-(4) demonstrated below. The monomer component may further contain a monomer other than the monomers (1) to (4).

1-2-1. Monomer (1):
The monomer (1) is a compound represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ² is a single bond or a linear, branched, or cyclic group having 1 to 20 carbon atoms. A saturated or unsaturated divalent hydrocarbon group, R ³ represents a hydrogen atom or a monovalent organic group, Rf ¹ represents a methylene group in which at least one hydrogen atom is substituted with a fluorine atom, or at least A linear or branched alkylene group having 2 to 20 carbon atoms, in which one hydrogen atom is substituted with a fluorine atom. However, in the divalent hydrocarbon group represented by R ² , at least a part of the hydrogen atoms may be substituted with fluorine atoms.

In the general formula (1), specific examples of the “linear, branched, or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms” represented by R ² include methane, Linear or branched hydrocarbons such as ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane; cyclobutane, cyclopentane, cyclohexane , Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane And alicyclic hydrocarbons such as divalent groups obtained by removing two hydrogen atoms from aromatic hydrocarbons such as benzene and naphthalene.

In addition, the “straight, branched, or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms” represented by R ² described above is such that at least part of the hydrogen atoms are fluorine atoms. It may be replaced.

In the general formula (1), examples of the “monovalent organic group” represented by R ³ include a monovalent hydrocarbon group having 1 to 30 carbon atoms, an acid dissociable group, and an alkali dissociable group. be able to.

[Monovalent hydrocarbon group having 1 to 30 carbon atoms]
Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include, for example, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms and a monovalent cyclic hydrocarbon group having 3 to 30 carbon atoms. Etc.

[Acid-dissociable group]
As the acid dissociable group, for example, a group that substitutes a hydrogen atom of a polar functional group such as a hydroxyl group or a carboxyl group, and is a group that dissociates in the presence of an acid. Sex groups can be applied.

  Specific examples of the acid dissociable group include t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, (thiotetrahydropyranylsulfanyl) methyl group, (thiotetrahydrofuranylsulfanyl) methyl group, alkoxymethyl group, alkylsulfanyl. A methyl group etc. can be mentioned. In addition, as an alkoxy group in an alkoxymethyl group, a C1-C4 alkoxy group can be mentioned, for example. Moreover, as an alkyl group in an alkylsulfanylmethyl group, a C1-C4 alkyl group can be mentioned, for example.

  In addition to the acid dissociable group described above, examples of the acid dissociable group further include a group represented by the following general formula (1a-1).

In the general formula (1a-1), three R ^{22 s} are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic carbonization having 4 to 20 carbon atoms. A hydrogen group or a group derived therefrom, or any two R ²² 's bonded to each other to form a hydrocarbon ring having 4 to 20 carbon atoms or a ring derived therefrom, and the remaining one R ²² represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom.

Specific examples of the “linear or branched alkyl group having 1 to 4 carbon atoms” represented by R ²² in the general formula (1a-1) include a methyl group, an ethyl group, an n-propyl group, Examples include i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.

Specific examples of the “monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms” represented by R ²² in the general formula (1a-1) include norbornane, tricyclodecane, tetracyclododecane, and adamantane. And groups composed of alicyclic rings derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Among these, norbornane, tricyclodecane, tetracyclododecane, adamantane, a group composed of an alicyclic ring derived from cyclopentane or cyclohexane, and the like are preferable.

In the general formula (1a-1), as the “group derived from an alicyclic hydrocarbon group” represented by R ²² , for example, at least one hydrogen atom of the alicyclic hydrocarbon group described above, Examples include a group substituted with one or more of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms (hereinafter also referred to as “substituents”). Specific examples of the linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methyl group. A propyl group, a 1-methylpropyl group, a t-butyl group, etc. can be mentioned.

In the general formula (1a-1), specific examples of “a hydrocarbon ring having 4 to 20 carbon atoms formed by bonding any two R ^{22 s”} to each other include cyclobutane, cyclopentane, cyclohexane, Examples thereof include monocyclic hydrocarbon rings such as cyclooctane; polycyclic hydrocarbon rings such as norbornane, tricyclodecane and tetracyclododecane; bridged polycyclic hydrocarbon rings such as adamantane and the like. Among these, monocyclic hydrocarbon rings such as cyclopentane and cyclohexane are preferable.

In the general formula (1a-1), examples of the “ring derived from a hydrocarbon ring having 4 to 20 carbon atoms formed by bonding any two R ^{22 s} ” include the carbonization described above. Examples include a group in which at least one hydrogen atom of the hydrogen ring is substituted with one or more of the aforementioned substituents.

  Preferable examples of the acid dissociable group represented by the general formula (1a-1) include t-butyl group, 1- (1-ethyl-1-methyl) propyl group, 1- (1,1-dimethyl) Propyl group, 1-n- (1,1-dimethyl) butyl group, 1-n- (1,1-dimethyl) pentyl group, 1-n- (1,1-diethyl) propyl group, 1-n- ( 1,1-diethyl) butyl group, 1-n- (1,1-diethyl) pentyl group, 1- (1-methyl) cyclopentyl group, 1- (1-ethyl) cyclopentyl group, 1- (1-n- Propyl) cyclopentyl group, 1- (1-i-propyl) cyclopentyl group, 1- (1-methyl) cyclohexyl group, 1- (1-ethyl) cyclohexyl group, 1- (1-n-propyl) cyclohexyl group, 1 -(1-i-propyl) cyclohexyl group, 1- ( -Methyl-1- (2-norbornyl)) ethyl group, 1- (1-methyl-1- (2-tetracyclodecanyl)) ethyl group, 1- (1-methyl-1- (1-adamantyl)) Ethyl, 2- (2-methyl) norbornyl, 2- (2-ethyl) norbornyl, 2- (2-n-propyl) norbornyl, 2- (2-i-propyl) norbornyl, 2- ( 2-methyl) tetracyclodecanyl group, 2- (2-ethyl) tetracyclodecanyl group, 2- (2-n-propyl) tetracyclodecanyl group, 2- (2-i-propyl) tetracyclodecane Nyl group, 1- (1-methyl) adamantyl group, 1- (1-ethyl) adamantyl group, 1- (1-n-propyl) adamantyl group, 1- (1-i-propyl) adamantyl group, and these Fewer groups consisting of alicyclic rings Even of one hydrogen atom, it can be a group such as substituted with one or more substituents.

  As the acid dissociable group, among the above acid dissociable groups, a group represented by the general formula (1a-1), a t-butoxycarbonyl group, an alkoxymethyl group, and the like are preferable, and the general formula (1a-1) is preferable. ) Is particularly preferred. When the polymer contains such an acid dissociable group, the solubility of the polymer in the exposed portion in the developer can be improved.

[Alkali dissociable group]
The alkali-dissociable group is, for example, a group that substitutes a hydrogen atom of a polar functional group such as a hydroxyl group or a carboxyl group, and is a group that dissociates in the presence of an alkali. Sex groups can be applied.

  Examples of the alkali dissociable groups include alkali dissociable groups (1b-1) to (1b-3) represented by the following general formulas (1b-1) to (1b-3), respectively.

In the general formulas (1b-1) and (1b-2), R ²³ represents a halogen atom or an alkyl group, alkoxy group, acyl group, or acyloxy group having 1 to 10 carbon atoms. In the general formula (1b-1), p represents an integer of 0 to 5. In the general formula (1b-2), q represents an integer of 0 to 4. In the general formula (1b-3), two R ^{24 s} each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or two R ^24s are bonded to each other. A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.

In the general formulas (1b-1) and (1b-2), specific examples of the “halogen atom” represented by R ²³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, it can be assumed that the alkali dissociable group is easily dissociated in the presence of an alkali when R ²³ is a fluorine atom having excellent electron withdrawing property among these halogen atoms.

In the general formulas (1b-1) and (1b-2), specific examples of the “alkyl group having 1 to 10 carbon atoms” represented by R ²³ include a methyl group, an ethyl group, a 1-propyl group, 2- Propyl group, 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- ( 3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) Group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) Group, 3- (2-methylpentyl) group, 3- (3-methyl Pentyl) group and the like.

In the general formulas (1b-1) and (1b-2), specific examples of the “alkoxy group having 1 to 10 carbon atoms” represented by R ²³ include a methoxy group, an ethoxy group, an n-butoxy group, t- A butoxy group, a propoxy group, an isopropoxy group, etc. can be mentioned.

Specific examples of the “acyl group having 1 to 10 carbon atoms” represented by R ²³ in the general formulas (1b-1) and (1b-2) include an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group. be able to.

In the general formulas (1b-1) and (1b-2), specific examples of the “acyloxy group having 1 to 10 carbon atoms” represented by R ²³ include an acetoxy group, an ethylyloxy group, a butyryloxy group, and a t-butyryloxy group. , T-amylyloxy group, n-hexane carbonyloxy group, n-octane carbonyloxy group and the like.

Specific examples of the “alkyl group having 1 to 10 carbon atoms” represented by R ²⁴ in the general formula (1b-3) include R in the general formulas (1b-1) and (1b-2) described above. The same thing as the C1-C10 alkyl group shown by ²³ can be mentioned.

Specific examples of “a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by bonding two R ^{24 s} ” represented by two R ²⁴ in the general formula (1b-3) ” Examples include cyclopentyl group, cyclopentylmethyl group, 1- (1-cyclopentylethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group and the like.

  Specific examples of the alkali dissociable group (1b-3) include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, and a 2-pentyl group. 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group , 3- (2-methylpentyl) group and the like. Among these, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, and a 2-butyl group are preferable.

  By containing the repeating unit having such an alkali dissociable group, the polymer can improve the affinity for the developer during development.

  The above-mentioned “monovalent hydrocarbon group having 1 to 30 carbon atoms”, “acid-dissociable group”, and “alkali-dissociable group” are the types of radiation-sensitive acid generators contained in the resist, and development. Each can be appropriately selected depending on the type of the liquid, the conditions of the polymerization reaction, and the like.

In the general formula (1), represented by Rf ¹ "a methylene group in which at least one hydrogen atom is substituted with a fluorine atom, or a straight chain having 2 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom" Specific examples of “or a branched alkylene group” include groups represented by the following formulas (1c-1) to (1c-11).

  Among these, groups represented by the above formulas (1c-1) to (1c-4) or (1c-8) are preferable, and the above formulas (1c-3), (1c-4), or (1c- 8) is more preferable, and the group represented by the above formula (1c-4) is particularly preferable.

  The monomer (1) is preferably a monomer represented by the following general formula (1-1).

In the general formula (1-1), R ¹⁸ and R ²⁰ each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and R ²¹ represents a hydrogen atom or a monovalent organic group. Two R ^{19 s} independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a trifluoromethyl group, 2,2,2-trimethyl. A fluoroethyl group, a 1-trifluoromethylethyl group, or a 3,3,3-trifluoropropyl group is shown. However, two R ¹⁹ may be bonded to each other to form a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group.

In the general formula (1-1), R ²¹ has the same meaning as R ³ in the general formula (1).

  The monomer (1) is particularly preferably a monomer represented by the following formulas (1-1-1) to (1-1-6).

  For example, when the monomer (1) has an alkali dissociable group, it is represented by the compound represented by the following general formula (1A-1) and the following general formulas (1B-1) to (1B-3). It can be synthesized by reacting with any of the compounds.

In the general formula (1A-1), X ¹ represents a hydroxyl group or a halogen atom. In the general formula (1B-1), X ² represents a halogen atom and is preferably a chlorine atom. In the general formula (1B-2), X ³ represents a halogen atom, and is preferably a bromine atom. Incidentally, ^R 1, ^{R 2,} and Rf ¹ in the general formula (1A-1) is of the general formula ^(1), R 1, ^{R 2,} and the Rf ^1, the general formula (1B-1 ) and ^{(R 23} a 1B-2) in the said general formula (1b-1) and (1b-2) in ^{R 23,} p in the general formula (1B-1), the general formula ( P in 1b-1), q in the general formula (1B-2), q in the general formula (1b-2), and R ²⁴ in the general formula (1B-3) are R ^{24 in} formula (1b-3) has the same meaning as R ²⁴ .

  In addition to the synthesis method described above, the monomer (1) reacts a compound represented by the following general formula (1C-1) with a compound represented by the following general formula (1D-1) Can also be synthesized.

In the general formula (1C-1), X ⁴ represents a hydroxyl group or a halogen atom. Note that R ¹ in the general formula (1C-1) and R ² , R ³ , and Rf ¹ in the general formula (1D-1) are R ¹ , R in the general formula (1), respectively. ² , R ³ , and Rf ¹ .

  In the polymer, the content of the repeating units derived from the monomer (1) is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, based on 100 mol% in total of all repeating units. It is preferably 20 to 70 mol%, particularly preferably. When the content ratio of the repeating unit derived from the monomer (1) is 20 to 90 mol%, the water repellency of the resist film can be improved and water drainage can be improved.

1-2-2. Monomer (2):
The monomer (2) is a monomer represented by the following general formula (2).

In the general formula (2), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and three R ⁸ are each independently a straight chain having 1 to 4 carbon atoms or A branched alkyl group, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or any two R ⁸ 's bonded to each other, 20 hydrocarbon rings or a ring derived therefrom, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent fat having 4 to 20 carbon atoms A cyclic hydrocarbon group or a group derived therefrom is shown.

R ⁸ in the general formula (2) and R ²² in the general formula (1a-1) have the same meaning, and the group represented by [—C (R ⁸ ) ₃ ] represents the general formula (1a- The same explanation as the acid dissociable group represented by 1) can be made.

  The monomer (2) is preferably a monomer (2-1) represented by the following general formula (2-1).

In the general formula (2-1), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and R ¹⁰ is a linear or branched alkyl having 1 to 4 carbon atoms. Represents a group, and k represents an integer of 1 to 4.

Specific examples of the “linear or branched alkyl group having 1 to 4 carbon atoms” represented by R ¹⁰ in the general formula include “carbon represented by R ²² in the general formula (1a-1)”. Examples thereof are the same as those in the linear or branched alkyl group of formulas 1 to 4.

  In the polymer, the content of the repeating unit derived from the monomer (2) is usually 80 mol% or less and preferably 20 to 80 mol% with respect to 100 mol% in total of all repeating units, More preferably, it is -70 mol%.

1-2-3. Monomer (3):
As the monomer (3), any conventionally known monomer having an alkali-soluble group is used without particular limitation as long as it has an alkali-soluble group and is a monomer other than the monomer (1). be able to.

  The monomer (3) is selected from the group consisting of a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following formula (3c). A monomer having at least one alkali-soluble group is preferred.

In the general formula (3a), Rf ² represents a C 1-10 hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom. In the general formula (3b), Rf ³ represents at least one A methylene group or an alkylene group having 2 to 20 carbon atoms in which a hydrogen atom is substituted with a fluorine atom

In the general formula (3a), as a specific example of “a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom” represented by Rf ² , a trifluoromethyl group or the like is preferable.

In the general formula (3b), specific examples of the “methylene group or alkylene group having 2 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom” represented by Rf ³ include the following formula (3b-1 ) To (3b-8).

  The monomer (3) is preferably a monomer represented by the following general formula (3-1) from the viewpoint of ensuring water repellency of the resist film and compatibility with the developer. .

In General Formula (3-1), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or a hydroxymethyl group, and R ¹² represents a divalent organic group.

Specific examples of the “alkyl group having 1 to 4 carbon atoms” represented by R ¹¹ in the general formula (3-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and n-butyl. Group, i-butyl group, t-butyl group and the like.

In the general formula (3-1), examples of the “divalent organic group” represented by R ¹² include hydrocarbon groups having 1 to 20 carbon atoms. Specific examples thereof include linear or branched carbonization such as methane, ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane and decane. Hydrogen: cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3.3. ^1.1,7 ] alicyclic hydrocarbons such as decane; divalent groups obtained by removing two hydrogen atoms from aromatic hydrocarbons such as benzene and naphthalene. Note that these hydrocarbon groups may have an oxygen atom, a sulfur atom, an imino group, a carbonyl group, a carbonyloxy group, or an amide group.

  In the polymer, the content of the repeating unit derived from the monomer (3) is usually 50 mol% or less, preferably 5 to 30 mol%, based on the total 100 mol% of all repeating units. More preferably, it is -20 mol%. When the content ratio of the repeating unit derived from the monomer (3) is 50 mol% or less, the water repellency of the resist film can be improved and water drainage can be improved.

1-2-4. Monomer (4):
As the monomer (4), a monomer having an alkali-reactive group and any conventionally known monomer having an alkali-reactive group is not particularly limited as long as it is a monomer other than the monomer (1). Can be used.

  The monomer (4) is preferably at least one selected from the group consisting of monomers represented by the following general formulas (4-1) to (4-7).

In the general formulas (4-1) to (4-6), R ¹³ each independently represents a hydrogen atom or a methyl group. In the general formula (4-1), R ¹⁴ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, and l represents an integer of 1 to 3. In the general formulas (4-2) and (4-3), each A independently represents a single bond, an ether group, an ester group, a carbonyl group, a divalent chain hydrocarbon group having 1 to 30 carbon atoms, A divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a divalent group obtained by combining these, m is independently 0 or 1 is shown. In the above general formulas (4-3) and (4-5), B independently represents an oxygen atom or a methylene group. In the general formulas (4-4) and (4-5), R ¹⁵ each independently represents a hydrogen atom or a methoxy group. In the general formula (4-7), R ¹⁶ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and the plurality of R ¹⁷ are each independently a hydrogen atom or a chain having 1 to 5 carbon atoms. A hydrocarbon group is shown, n shows the integer of 2-4.

Specific examples of the “optionally substituted alkyl group having 1 to 4 carbon atoms” represented by R ¹⁴ in the general formula (4-1) include a methyl group, an ethyl group, an n-propyl group, i- A propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned. One or more hydrogen atoms in the alkyl group may be substituted. Specific examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a phenyl group, an acetoxy group, and an alkoxy group.

  Specific examples of the “divalent chain hydrocarbon group having 1 to 30 carbon atoms” represented by A in the general formulas (4-2) and (4-3) include a methylene group, an ethylene group, 2-propylene group, 1,3-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group A linear alkylene group such as a group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, a heptacamethylene group, an octadecamethylene group, a nonacamethylene group, an icosalen group; 1-methyl-1,3- Propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl 1,4-butylene group, methylidene group, ethylidene group, and a propylidene group, etc. branched alkylene group such as 2-propylidene group.

In the general formulas (4-2) and (4-3), specific examples of the “C3-C30 divalent alicyclic hydrocarbon group” represented by A include 1,3-cyclobutylene group 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclooctylene group, etc.
30 monocyclic cycloalkylene groups; polycyclic cycloalkylene groups such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc. Can do.

Specific examples of the “divalent aromatic hydrocarbon group having 6 to 30 carbon atoms” represented by A in the general formulas (4-2) and (4-3) include a phenylene group, a tolylene group, and a naphthylene group. And arylene groups such as a phenanthrylene group and an anthrylene group.

  In the polymer, the content of the repeating unit derived from the monomer (4) is usually 50 mol% or less, preferably 5 to 30 mol%, preferably 100 mol% of the total repeating units. More preferably, it is -20 mol%. When the content ratio of the repeating unit derived from the monomer (4) is 50 mol% or less, the water repellency of the resist film can be improved and water drainage can be improved.

1-3. polymerization:
In the method for producing a polymer of the present invention, a conventionally known polymerization method can be applied without particular limitation as long as it is a method by radical polymerization using the above-described solvent component and monomer component.

  The polymerization temperature is preferably 40 to 150 ° C, more preferably 50 to 120 ° C. In the present invention, since a solvent (S) having a relatively high boiling point is used, polymerization at a higher temperature can be performed. The time required for the polymerization is usually about 1 to 48 hours, and preferably 1 to 24 hours.

  Further, the polymerization initiator is not particularly limited as long as it is a radical polymerization initiator, and a conventionally known polymerization initiator can be used.

  Examples of radical polymerization initiators include hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. Specific examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane- 1-carbonitrile), azo compounds such as 4,4′-azobis (4-cyanovaleric acid); decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, bis (3,5,5-trimethylhexanoyl) per Examples thereof include organic peroxides such as oxide, succinic acid peroxide, and t-butylperoxy-2-ethylhexanoate. Among these, 2,2′-azobisisobutyronitrile (hereinafter, also simply referred to as “AIBN”), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyric acid Dimethyl and the like are preferable.

  The use ratio of the radical polymerization initiator is usually 0.5 to 30 mol% and preferably 1 to 20 mol% with respect to 100 mol% in total of all monomers.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. “%” In Examples and Comparative Examples is based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Mw and Mw / Mn]
The column “TSKguardcolumn superH-L, TSKgel SuperH4000, TSKgel SuperH2000 combination” was used for the GPC system (trade name “HLC8220”, manufactured by Tosoh Corporation), column temperature: 40 ° C., injection amount: 10 μl, measurement flow rate: 0.6 ml The mass average molecular weight of each polymer (hereinafter also referred to as “Mw”) and the number average molecular weight (hereinafter, “Mw”), based on monodisperse polystyrene, by gel permeation chromatography (GPC) under analysis conditions per minute. Also described as “Mn”). Furthermore, Mw / Mn was calculated from this measurement result. In addition, as a measurement sample, 0.05 g of the resin solution after polymerization was diluted to 5.00 g with tetrahydrofuran and filtered through a 0.45 μm filter.

[Conversion rate]
Using the nuclear magnetic resonance apparatus “ECP-500” manufactured by JEOL Ltd., the residual monomer concentration from the integral ratio of hydrogen on vinyl carbon of the monomer remaining in the polymerization solution obtained from ¹ H-NMR and the internal standard It was determined. From the concentration of the residual monomer obtained, the conversion rate of the polymer was calculated as a ratio (%) of the consumed monomer amount to the total monomer amount charged.

Example 1
11.21 g (25 mol%) of the monomer (M1) represented by the following formula (M1) as the monomer (1), and the monomer (2) represented by the following formula (M2) ( M2) 21.68 g (60 mol%), and monomer (3) represented by the following formula (M3) 7.11 g (15 mol%), propylene glycol as solvent (S) Dissolved in 40.0 g of monomethyl ether (PGME) (solvent component containing 100% by mass of solvent (S)), 1.32 g of azobisisobutyronitrile (AIBN) (5 mol% based on the total amount of monomers) ) Was added to prepare a monomer solution. On the other hand, 40.0 g of PGME was put into a 500 ml separable flask and purged with nitrogen for 30 minutes. After purging with nitrogen, the inside of the separable flask was heated to 80 ° C. with stirring, and the monomer solution was added dropwise over 3 hours using a dropping funnel. The point of time when the dropping was started was regarded as the polymerization start point, and the conversion rates at the respective points 6 hours and 8 hours after the polymerization start point were calculated. The conversion at 6 hours after the start of polymerization was 88.4%, and the conversion at 8 hours was 90.5%.

  After 8 hours from the start of polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling. The cooled polymerization solution was charged into 600 g of a mixed solution of 90% by mass of methanol / 10% by mass of water, and the precipitated white powder was separated by filtration. The white powder thus filtered was vacuum-dried at 50 ° C. for 12 hours to obtain a white powder polymer. Mw of the obtained polymer was 8158 and Mw / Mn was 2.04.

(Examples 2 to 5, Comparative Example 1)
A polymer was obtained in the same manner as in Example 1 except that the type of solvent and the amount of AIBN added were shown in Table 1 below.

In Table 1 above, the abbreviations of the solvents used are as follows:
PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate MEK: 2-butanone (methyl ethyl ketone)

  In addition, “PGME / MEK 60/40” in Example 4 means that a mixed solvent of PGME 60% by mass / MEK 40% by mass was used as a solvent, and “PGME / MEK 30/70” in Example 5 is This means that a mixed solvent of 30% by mass of PGME / 70% by mass of MEK was used as the solvent.

  From Table 1, it is clear that when the monomer component containing the monomer (1) is polymerized in the solvent component containing the solvent (S), the conversion rate of the monomer is increased.

  The polymer obtained by the method for producing a polymer of the present invention is useful as a component of a radiation sensitive resin composition used as a chemically amplified resist, particularly a resist for ArF immersion exposure.

Claims (12)

Polymerizing a monomer component containing the monomer (1) represented by the following general formula (1) in a solvent component containing the solvent (S) represented by the following general formula (S). A method for producing a polymer.

(In the above general formula (1), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R ² represents a single bond, or a linear, branched, or cyclic group having 1 to 20 carbon atoms. A saturated or unsaturated divalent hydrocarbon group, R ³ represents a hydrogen atom or a monovalent organic group, Rf ¹ represents a methylene group in which at least one hydrogen atom is substituted with a fluorine atom, or A linear or branched alkylene group having 2 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, provided that the divalent hydrocarbon group represented by R ² is at least a part thereof. May be substituted with fluorine atoms.)

(In the general formula (S), R ⁴ represents a hydrogen atom or a monovalent organic group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, or an acetyl group, and i is 0. (It is preferable that all of R ⁴ are the same atom or group when i is 1 or more.)   The manufacturing method of the polymer of Claim 1 in which the said solvent component contains the said solvent (S) 30 mass% or more.   The manufacturing method of the polymer of Claim 1 or 2 in which the said solvent component contains the said solvent (S) 60 mass% or more. The manufacturing method of the polymer as described in any one of Claims 1-3 in which the said monomer component further contains the monomer (2) represented by following General formula (2).

(In the above general formula (2), R ⁷ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and three R ⁸ are each independently a straight chain having 1 to 4 carbon atoms. Or a branched alkyl group, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or any two of R ⁸ are bonded to each other, and the number of carbon atoms is 4 Forming a hydrocarbon ring of ˜20 or a ring derived therefrom, and the remaining one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent having 4 to 20 carbon atoms An alicyclic hydrocarbon group or a group derived therefrom is shown.) The method for producing a polymer according to claim 4, wherein the monomer (2) is a monomer (2-1) represented by the following general formula (2-1).

(In the general formula (2-1), R ⁹ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and R ¹⁰ is a linear or branched group having 1 to 4 carbon atoms. Represents an alkyl group, and k represents an integer of 1 to 4.)   The polymer production according to any one of claims 1 to 5, wherein the monomer component further contains a monomer (3) having an alkali-soluble group (excluding the monomer (1)). Method. The monomer (3) is selected from the group consisting of a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following formula (3c). The method for producing a polymer according to claim 6, wherein the monomer has at least one alkali-soluble group.

(In the general formula (3a), Rf ² represents a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. In the general formula (3b), Rf ³ represents at least 1 A methylene group or an alkylene group having 2 to 20 carbon atoms in which two hydrogen atoms are substituted with fluorine atoms.) The method for producing a polymer according to claim 6 or 7, wherein the monomer (3) is a monomer (3-1) represented by the following general formula (3-1).

(In the general formula (3-1), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or a hydroxymethyl group, and R ¹² represents a divalent organic group. .)   The polymer according to any one of claims 1 to 8, wherein the monomer component further contains a monomer (4) having an alkali-reactive group (excluding the monomer (1)). Production method. The polymer according to claim 9, wherein the monomer (4) is at least one selected from the group consisting of monomers represented by the following general formulas (4-1) to (4-7). Manufacturing method.

(In the general formulas (4-1) to (4-6), each R ¹³ independently represents a hydrogen atom or a methyl group. In the general formula (4-1), R ¹⁴ represents a hydrogen atom. Or an optionally substituted alkyl group having 1 to 4 carbon atoms, and l represents an integer of 1 to 3. In the above general formulas (4-2) and (4-3), A is independently Single bond, ether group, ester group, carbonyl group, divalent chain hydrocarbon group having 1 to 30 carbon atoms, divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and 6 to 30 carbon atoms. In the general formulas (4-3) and (4-5) above, and each m independently represents 0 or 1. , B are each independently in an oxygen atom, or a methylene group. above general formula (4-4) and ^{(4-5), R 15,} it To be independently in a hydrogen atom, or a methoxy group. The above formula (4-7), R ¹⁶ is a hydrogen atom, a methyl group, or a trifluoromethyl group, a plurality of R ¹⁷ are each independently , A hydrogen atom, or a chain hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 to 4.) The method for producing a polymer according to any one of claims 1 to 10, wherein the monomer (1) is a monomer (1-1) represented by the following general formula (1-1).

(In the general formula (1-1), R ¹⁸ and R ²⁰ each independently represents a fluorine atom or a trifluoromethyl group, R ²¹ represents a hydrogen atom or a monovalent organic group, and 2 Each R ¹⁹ is independently hydrogen atom, methyl group, ethyl group, propyl group, butyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, trifluoromethyl group, 2,2,2-trifluoroethyl. Group, 1-trifluoromethylethyl group, or 3,3,3-trifluoropropyl group, provided that two R ¹⁹ are bonded to each other to form a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group. It may be formed.)   The method for producing a polymer according to any one of claims 1 to 11, wherein the solvent (S) is a derivative of propylene glycol or a derivative of ethylene glycol.