CN1832973A - Fluorine-containing copolymer, method for producing the same, and anti-corrosion composition containing the same - Google Patents

Abstract

Provided is a fluoropolymer having functional groups and having high transparency in a wide wavelength region, and a resist composition comprising the fluoropolymer. A fluorinated copolymer having units derived from a monomer unit formed by cyclopolymerization of a fluorinated diene represented by the following formula (1) : CF2 = CFCH2CH(CH2C(CF3)2(OR1))CH2CH=CH2 (1) wherein R1 is a hydrogen atom, an alkyl group having at most 20 carbon atoms, which may have an etheric oxygen atom, an alkoxycarbonyl group having at most 6 carbon atoms, or CH2R2 (wherein R2 is an alkoxycarbonyl group having at most 6 carbon atoms), and units derived from a monomer unit formed by cyclopolymerization of another monomer or units derived from a monomer unit formed by polymerization of an acrylic monomer, and a resist composition having such a fluorinated copolymer as a base polymer.

Description

Fluorine-containing copolymer, method for producing the same, and anti-corrosion composition containing the same

technical field

The present invention relates to a novel fluorine-containing copolymer, a method for producing the same, and a resist composition.

Background technique

Fluoropolymers Having Functional Groups Functional group-containing fluoropolymers used for fluorine-based ion exchange membranes, curable fluororesin coatings, and the like are known. Among these polymers, the basic skeleton is a straight-chain polymer obtained by copolymerizing fluoroolefin represented by tetrafluoroethylene and a monomer having a functional group.

In addition, polymers containing functional groups and having a fluorine-containing alicyclic structure in the main chain are also known. The method of introducing a functional group into a polymer having a fluorine-containing alicyclic structure in the main chain is known as a method of utilizing the terminal group of the polymer obtained by polymerization, or by subjecting the polymer to high temperature treatment to oxidatively decompose the side chain or terminal of the polymer to form A method of introducing a functional group, a method of introducing a monomer having a functional group by copolymerization and, if necessary, performing treatment such as hydrolysis (see, for example, Patent Documents 1, 2, 3, and 4).

The methods for introducing functional groups into polymers having a fluorine-containing alicyclic structure in the main chain include the above-mentioned methods, but in the method of introducing functional groups by treating the terminal groups of the polymer, the concentration of functional groups is low and sufficient functional group characteristics cannot be obtained. shortcoming. In addition, in the method of introducing a monomer having a functional group by copolymerization, if the concentration of the functional group is increased, the glass transition temperature (Tg) is lowered to cause problems such as lowering of mechanical properties.

Patent Document 1: Japanese Patent Laid-Open No. H4-189880

Patent Document 2: Japanese Patent Laid-Open No. 4-226177

Patent Document 3: Japanese Patent Laid-Open No. 6-220232

Patent Document 4: International Publication No. 02/064648 Pamphlet

disclosure of invention

Problems to be solved by the present invention

The present invention provides a fluorine-containing copolymer having high functional group concentration, sufficient functional group characteristics, and high transparency over a wide wavelength range, and a method for producing the same. In addition, the present invention provides a chemically amplified resist that has good transparency and dry etching properties for extreme ultraviolet rays such as KrF and ArF excimer lasers and vacuum ultraviolet rays such as _F2 excimer lasers, and can obtain sensitivity and resolution. , dissolution rate, flatness, heat resistance and other good resist pattern resist composition.

Solution to the problem

The present invention has been made to solve the above-mentioned problems, and has the following main contents.

(1) Fluorinated copolymer (A1), which has two types of units derived from fluorinated dienes represented by the following formula (1) through cyclopolymerization and monomer units produced by cyclopolymerization of fluorine-containing dienes having functional groups represented by the following formula (2) (excluding fluorine-containing dienes represented by formula (1)).

CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1)

In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² (R ² is a carbon number less than or equal to 15 alkoxycarbonyl), R ¹ alkyl, alkoxycarbonyl and R ² part or all of the hydrogen atoms may be replaced by fluorine atoms.

CF ₂ =CR ³ -Q-CR ⁴ =CH ₂ (2)

In the formula, R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, a fluoroalkyl group or a cyclic aliphatic hydrocarbon group with 3 or less carbon atoms, and Q represents a functional group or An alkylene group, an oxyalkylene group, a fluoroalkylene group, or a fluorinated oxyalkylene group (Okisifluoroalkylen group) as a side chain group containing a functional group.

(2) Fluorinated copolymer (A2), said fluorinated copolymer (A2) has two kinds of units, said units are respectively derived from the fluorinated diene represented by the following formula (1) by cyclopolymerization. and a monomer unit produced by polymerizing an acrylic monomer represented by the following formula (3).

CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1)

In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² (R ² is a carbon number less than or equal to 15 alkoxycarbonyl), R ¹ alkyl, alkoxycarbonyl and R ² part or all of the hydrogen atoms may be replaced by fluorine atoms.

CH ₂ =CR ⁵ COOR ⁶ (3)

In the formula, ^R5 represents a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, or a fluoroalkyl group with 3 or less carbon atoms. R ⁶ represents an alkyl group with 20 carbon atoms or less, and a part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, alkyl groups or fluoroalkyl groups.

(3) The method for producing the fluorine-containing copolymer (A1) or the fluorine-containing copolymer (A2), wherein the fluorine-containing diene represented by the formula (1) is combined with the fluorine-containing diene represented by the formula (2) ) or the acrylic monomer represented by the formula (3) is radically copolymerized.

(4) A resist composition, characterized in that the resist composition contains the fluorine-containing copolymer (A1) or the fluorine-containing copolymer (A2), and an acid-generating compound (B) that generates an acid upon exposure to light. and an organic solvent (C).

The effect of the invention

According to the present invention, a fluorinated copolymer having an alicyclic structure in the main chain and a functional group in the side chain can be produced. The fluorine-containing copolymer obtained in the present invention has high chemical stability and heat resistance. Furthermore, since a functional group is introduced into the side chain of the ring, sufficient functional group characteristics can be obtained without lowering the Tg, which was difficult to achieve with conventional fluorine-containing polymers. In addition, the copolymer also has high transparency in a broad wavelength region. The resist composition of the present invention can be used as a chemically amplified resist, and in particular can be easily formed with good transparency and dry etching properties for far ultraviolet rays such as KrF and ArF excimer lasers and vacuum ultraviolet rays such as _F2 excimer lasers. Moreover, it has good resist pattern in terms of sensitivity, resolution, flatness, and heat resistance.

The best way to practice the invention

According to the present invention, a fluorine-containing copolymer (A1) or a fluorine-containing copolymer (A2) can be obtained, and the two types of units possessed by the fluorine-containing copolymer (A1) are respectively derived from The fluorine-containing diene represented by (hereinafter referred to as fluorine-containing diene (1).) The monomer unit generated and the fluorine-containing diene containing functional groups represented by the following formula (2) through cyclopolymerization (which does not include the formula (1) The fluorine-containing diene represented. Hereinafter referred to as the fluorine-containing diene (2).) The monomer unit generated by the fluorine-containing copolymer (A2) has two kinds of units derived from the cyclopolymerization A monomer unit produced by fluorine-containing diene (1) and a monomer unit produced by polymerizing an acrylic monomer represented by the following formula (3) (hereinafter referred to as acrylic monomer (3).).

CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1)

In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² (R ² is a carbon number less than or equal to 15 alkoxycarbonyl), R ¹ alkyl, alkoxycarbonyl and R ² part or all of the hydrogen atoms may be replaced by fluorine atoms.

The alkyl group having 20 or less carbon atoms which may have an etheric oxygen atom may, for example, be an alkyl group which may be substituted with an aryl group or a cycloalkyl group, a cycloalkyl group, an alkoxymethyl group, a cyclic ether group, and the like. The cycloalkyl group here can not only exemplify monocyclic cycloalkyl groups such as cyclohexyl, but also exemplify multicyclic cycloalkyl groups such as bridged ring cycloalkyl groups such as adamantyl groups, and bicyclic cycloalkyl groups such as bicyclohexyl groups. wait. In addition, the alkyl part of the alkoxy group in the above-mentioned alkoxymethyl group or the like may be a cycloalkyl group as described above. In addition, the above-mentioned alkyl group may have an etheric oxygen atom (among them, alkoxymethyl group is one type) between carbon atoms. In addition, a substituent such as an alkyl group or an alkoxy group may exist in the above-mentioned aryl group and cycloalkyl group.

Specific examples of an alkyl group having 20 or less carbon atoms that may have an etheric oxygen atom include methyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, -CH( CH ₃ )OC ₂ H ₅ , -CH ₂ OCH ₂ (tert-C ₄ H ₉ ), -CH ₂ OCH ₂ CF ₃ , -CH ₂ OCF ₂ CF ₃ , -CH ₂ OCF ₂ CF ₂ H, 2-tetra Hydropyranyl and alkoxymethyl as follows, but not limited to these compounds.

In addition, the following giant groups having 20 or more carbon atoms can also be introduced.

The alkoxycarbonyl can be exemplified by tert-butoxycarbonyl (-COO(tC ₄ H ₉ )), -COO(2-AdM, etc., CH ₂ R ² can be exemplified by CH ₂ COO (tert-C ₄ H ₉ ) , CH ₂ COO (2-AdM), etc. Wherein 2-AdM is 2-methyladamantyl-2-base. Because it is easy to obtain, R ¹ is preferably a hydrogen atom, methoxymethyl, tert-butyl, tert-butoxycarbonyl, 2-cyclohexylcyclohexyloxymethyl, menthyloxymethyl or cyclohexyloxymethyl.

CF ₂ =CR ³ -Q-CR ⁴ =CH ₂ (2)

In the formula, R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, a fluoroalkyl group or a cyclic aliphatic hydrocarbon group with 3 or less carbon atoms, and Q represents a functional group or An alkylene group, an oxyalkylene group, a fluoroalkylene group, or a fluorooxyalkylene group having a side chain group of a functional group. Particularly preferably, R ³ is a fluorine atom and R ⁴ is a hydrogen atom.

Q is a side chain organic group having a functional group or containing a functional group. The functional group in the present invention represents a group that imparts a desired function. Examples include an ion exchange group, an adhesive group, a crosslinking group, and a developing group. Group etc. The functional group can be exemplified by OR ⁷ (R ⁷ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ⁸ , R ⁸ is a carbon Alkoxycarbonyl group with 15 or less atoms), COOR ⁹ (R ⁹ is a hydrogen atom or an alkyl group with 5 or less carbon atoms), sulfonic acid group, amino group, epoxy group, trialkoxysilyl group, cyano group wait. Specific examples of R ⁷ include the same groups as those described above for R ¹ . The functional group is preferably OR ⁷ or COOR ⁹ , and in this case, the functional group substitution rate (relative to the sum of OR ¹ and OR ⁷ or COOR ⁹ in (Formula 1), these R ¹ , R ⁷ and R ⁹ are not the ratio of hydrogen atoms) are preferably 0 to 95 mol%, more preferably 5 to 75 mol%, particularly preferably 10 to 60%.

The functional group-containing side chain organic group may, for example, be a monovalent organic group such as a functional group-containing alkyl group, a functional group-containing fluoroalkyl group, a functional group-containing alkoxy group, or a functional group-containing fluoroalkoxy group. The number of carbon atoms in the portion of the functional group-containing side chain organic group other than the functional group is preferably 8 or less, particularly preferably 6 or less.

Specific examples of the fluorine-containing diene (2) in the present invention include the following compounds, but are not limited thereto.

The acrylic monomer (3) in the present invention is a compound represented by the following formula (3).

CH ₂ =CR ⁵ COOR ⁶ (3)

In the formula, ^R5 represents a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, or a fluoroalkyl group with 3 or less carbon atoms. Because it is particularly easy to obtain, it is preferably a hydrogen atom, a fluorine atom, a methane group or trifluoromethyl group. R ⁶ represents an alkyl group with 20 carbon atoms or less, and a part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, alkyl groups or fluoroalkyl groups. The alkyl group having 20 or less carbon atoms may, for example, be an alkyl group which may be substituted with an aryl group or a cycloalkyl group, a cycloalkyl group, an alkoxymethyl group, a cyclic ether group, a cyclic ester group, and the like. The cycloalkyl group here can not only exemplify monocyclic cycloalkyl groups such as cyclohexyl, but also exemplify multicyclic cycloalkyl groups such as bridged ring cycloalkyl groups such as adamantyl groups, and bicyclic cycloalkyl groups such as bicyclohexyl groups. wait. In addition, the alkyl part of the alkoxy group in the above-mentioned alkoxymethyl group or the like may be a cycloalkyl group as described above. In addition, the above-mentioned alkyl group may have an etheric oxygen atom (among them, alkoxymethyl group is one type) between carbon atoms. In addition, substituents such as an alkyl group, a hydroxyl group, and an alkoxy group may exist in the above-mentioned aryl group and cycloalkyl group.

When R ⁶ does not have the aforementioned cyclic structure, it is particularly preferably an alkyl group having 6 or less carbon atoms or a fluoroalkyl group having 6 or less carbon atoms. As the acrylic monomer (3), it is particularly preferable that ^R5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and that ^R6 is an alkyl group having 6 or less carbon atoms or an alkyl group having 6 or less carbon atoms. Fluoroalkyl.

Specific examples of the acrylic monomer (3) include the following acrylates.

CH ₂ =CH—CO ₂ CH(CF ₃ )(CH ₃ ),

CH ₂ =CH—CO ₂ CH(CF ₃ ) ₂ ,

CH ₂ =CH-CO ₂ C(CF ₃ )(CH ₃ ) ₂ ,

CH ₂ =CH—CO ₂ C(CF ₃ ) ₂ (CH ₃ ),

CH ₂ =CH—CO ₂ C(CF ₃ ) ₃ ,

CH ₂ =CF-CO ₂ CH(CH ₃ ) ₂ ,

CH ₂ =CF-CO ₂ CH(CF ₃ )(CH ₃ ),

CH ₂ =CF-CO ₂ CH(CF ₃ ) ₂ ,

CH ₂ =CF-CO ₂ C(CH ₃ ) ₃ ,

CH ₂ =CF-CO ₂ C(CF ₃ )(CH ₃ ) ₂ ,

CH ₂ =CF-CO ₂ C(CF ₃ ) ₂ (CH ₃ ),

CH ₂ =CF-CO ₂ C(CF ₃ ) ₃ ,

CH ₂ =C(CH ₃ )—CO ₂ CH(CF ₃ )(CH ₃ ),

CH ₂ =C(CH ₃ )—CO ₂ CH(CF ₃ ) ₂ ,

CH ₂ =C(CH ₃ )—CO ₂ C(CF ₃ )(CH ₃ ) ₂ ,

CH ₂ =C(CH ₃ )—CO ₂ C(CF ₃ ) ₂ (CH ₃ ),

CH ₂ =C(CH ₃ )—CO ₂ C(CF ₃ ) ₃ ,

CH ₂ =C(CF ₃ )—CO ₂ CH(CH ₃ ) ₂ ,

CH ₂ =C(CF ₃ )—CO ₂ CH(CF ₃ )(CH ₃ ),

CH ₂ =C(CF ₃ )—CO ₂ CH(CF ₃ ) ₂ ,

CH ₂ =C(CF ₃ )—CO ₂ C(CH ₃ ) ₃ ,

CH ₂ =C(CF ₃ )—CO ₂ C(CF ₃ )(CH ₃ ) ₂ ,

CH ₂ =C(CF ₃ )—CO ₂ C(CF ₃ ) ₂ (CH ₃ ),

CH ₂ =C(CF ₃ )-CO ₂ C(CF ₃ ) ₃ ,

CH ₂ =CF-CO ₂ CH ₃ ,

CH ₂ =C(CF ₃ )—CO ₂ CH ₃ ,

CH ₂ =C(CH ₃ )—CO ₂ CH ₂ CH(CH ₃ )CH ₂ CH ₂ CH ₂ CH ₃ ,

_CH2 =C( _CH3 ) _-CO2CH2 (CH( _CH3 )) _{3H .}

Since the acrylic monomer (3) is obtained by combining CH ₂ =CHR ⁵ COOH and R ⁶ OH by esterification, acrylic monomer (3) of various structures can be easily synthesized.

In the fluorine-containing copolymer (A2), the functional group substitution ratio (the ratio of these R ¹ and R ⁶ not to hydrogen atoms relative to the sum of OR ¹ in (Formula 1) and COOR ⁶ in (Formula 3)) is preferably 0 to 95 mol%, more preferably 5 to 75 mol%, particularly preferably 10 to 60%.

Hereinafter, the unit derived from the monomer unit produced by cyclopolymerizing a fluorine-containing diene (1) in this invention is called a monomer unit (1). The same applies to the fluorine-containing diene (2) and the acrylic monomer (3).

In the fluorinated copolymer (A1) of the present invention, the ratio of monomer unit (1)/monomer unit (2) is preferably from 10 to 90 mol %/90 to 10 mol %. Monomer unit (1)/monomer unit (2) is particularly preferably 50 to 90 mol %/50 to 10 mol %. Similarly, in the fluorinated copolymer (A2) of the present invention, the ratio of monomer unit (1)/monomer unit (3) is preferably from 10 to 90 mol %/90 to 10 mol %. Monomer unit (1)/monomer unit (3) is particularly preferably 50 to 90 mol %/50 to 10 mol %.

The fluorine-containing copolymer (A1) contains monomer unit (1) and monomer unit (2) as essential components, and may contain other radically polymerizable monomers (hereinafter referred to as other monomer.) of the monomer unit. The proportion of other monomer units is preferably equal to or less than 50 mol%, particularly preferably equal to or less than 15 mol%. The same applies to the fluorinated copolymer (A2). Of course, the monomer unit (1), the monomer unit (2) and the monomer unit (3) may be contained at the same time.

Other monomers include α-olefins such as ethylene, propylene, and isobutylene, fluorine-containing olefins such as tetrafluoroethylene and hexafluoropropylene, fluorine-containing vinyl ethers such as perfluoropropyl vinyl ether, and perfluoro(2, 2-Dimethyl-1,3-dioxol) and other fluorine-containing cyclic monomers, perfluoro(butenyl vinyl ether) and other cyclopolymerizable perfluorodienes and hydrofluorodienes, Alkyl (meth)acrylates such as methyl acrylate and ethyl methacrylate, vinyl esters such as vinyl acetate, vinyl benzoate, vinyl adamantate, etc., ethyl vinyl ether, cyclohexyl vinyl ether Such as vinyl ethers, cyclohexene, norbornene, norbornadiene and other cyclic olefins, maleic anhydride, vinyl chloride, etc.

The fluorine-containing copolymer (A1) or fluorine-containing copolymer (A2) of the present invention can be prepared by combining fluorine-containing diene (1) with fluorine-containing diene (2) or acrylic monomer (3) and other The monomers are obtained by copolymerization in the presence of a polymerization initiator. The polymerization initiation source is not particularly limited as long as the polymerization reaction proceeds in a radical manner, and examples thereof include radical initiators, light, and ionizing radiation. Particularly preferred are radical generators, and examples thereof include peroxides, azo compounds, and persulfates. Specific examples of radical initiators include azobisisobutyronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, di-tert-butyl peroxydicarbonate, and tert-butyl peroxypivalate. Esters, perfluorobutyryl peroxide, perfluorobenzoyl peroxide, etc.

The method of polymerization is not particularly limited, and examples include so-called bulk polymerization in which monomers are directly used for polymerization, and in fluorinated hydrocarbons, chlorinated hydrocarbons, chlorofluorocarbons, alcohols, hydrocarbons, and other organic solvents that can dissolve monomers. Solution polymerization carried out, suspension polymerization carried out in the presence or absence of a suitable organic solvent in an aqueous medium, emulsion polymerization carried out by adding an emulsifier in an aqueous medium, and the like.

The temperature and pressure at which the polymerization is carried out are not particularly limited, and are preferably set appropriately in consideration of various factors such as the boiling point of the monomer, the heat source used, and the removal of polymerization heat. For example, suitable temperature setting can be performed within the range of 0°C to 200°C, and practically suitable temperature setting can be performed at room temperature to 100°C. In addition, the polymerization pressure may be under reduced pressure or under increased pressure. In practice, ideal polymerization can be carried out at about normal pressure to 100 atm, more preferably about normal pressure to 10 atm.

The molecular weight of the fluorinated copolymer (A1) or the fluorinated copolymer (A2) of the present invention is not particularly limited as long as it can be uniformly dissolved in the organic solvent (C) described below and uniformly coated on the substrate. The suitable number average molecular weight converted into polystyrene is 1000-100,000, preferably 2000-50,000. By making the number-average molecular weight greater than or equal to 1000, when used as a resist composition, better resist patterns can be obtained, the residual film rate after development is sufficient, and the shape stability of patterns during heat treatment is also better. Moreover, by making the number average molecular weight 100,000 or less, the coatability of the resist composition is improved, and sufficient developability can be maintained.

The fluorinated copolymer (A1) of the present invention may have two or more monomer units (1) in which R ¹ is different. Likewise, it may have two or more different monomer units (2). The same applies to the fluorinated copolymer (A2).

For the fluorine-containing copolymer (A1) of the present invention, when it is a fluorine-containing copolymer having R ¹ as a monomer unit (1) of a hydrogen atom, or when the functional group in the monomer unit (2) is a hydroxyl group, it can also be obtained by William The hydrogen atom of the monomer unit (1) or the hydrogen atom of the hydroxyl group in the monomer unit (2) is converted into an organic group by a known method such as a synthetic method. The same applies to the hydrogen atoms of the monomer units (1) of the fluorinated copolymer (A2). Conversely, in the fluorinated copolymers (A1) and (A2), when R ¹ is a group other than a hydrogen atom, R ¹ can be converted into a hydrogen atom by hydrolysis or the like.

In the case of converting the hydroxyl hydrogen atom of the monomer unit (1) in the fluorine-containing copolymers (A1) and (A2) into an organic group, as the converted organic group, ^R1 is preferably one of hydrogen atoms outside the aforementioned R ¹ . When the functional group in the monomer unit (2) is a hydroxyl group, the organic group after converting the hydroxyl group into an organic group is preferably the above-mentioned OR ⁷ (wherein R ⁷ is not a hydrogen atom) or the like. Same as above, the OR ¹ of the monomer unit (1), the side chain functional group of the monomer unit (2), and the COOR ⁶ of the monomer unit (3) in the fluorine-containing copolymers (A1) and (A2) are respectively Can be converted to other groups after forming the copolymer. Other groups are preferably within the range of the aforementioned respective groups. The "unit derived from a monomer unit" in the present invention refers to a monomer unit itself, and a unit obtained by chemical conversion of a monomer unit through functional group conversion or the like after polymerization.

Through the polymerization of the fluorine-containing diene (1) in the present invention, it is possible to generate the following monomer units (a) to (c), and according to the results of spectroscopic analysis, etc., the cyclopolymerization of the fluorine-containing diene (1) can be A polymer having one or more monomer units selected from monomer units (a), monomer units (b) and monomer units (c) is obtained. The main chain of the polymer refers to a carbon chain composed of carbon atoms constituting a polymerizable unsaturated bond (in the case of the fluorinated diene (1), four carbon atoms constituting a polymerizable unsaturated double bond).

In addition, through the cyclopolymerization of the fluorine-containing diene (2) in the present invention, it is possible to generate the following monomer units (d) to (f), and according to the results of spectroscopic analysis, etc., the Cyclization polymerization can obtain a polymer having one or more monomer units selected from monomer units (d), monomer units (e) and monomer units (f). The main chain of the polymer refers to a carbon chain composed of carbon atoms constituting a polymerizable unsaturated bond (in the case of the fluorinated diene (2), four carbon atoms constituting a polymerizable unsaturated double bond).

The present invention also provides a fluorine-containing copolymer (A1) or a fluorine-containing copolymer (A2) (hereinafter also collectively referred to as a fluorine-containing copolymer (A1) or a fluorine-containing copolymer (A2) as a fluorine-containing copolymer), which generates acid when exposed to light. A resist composition of an acid-generating compound (B) and an organic solvent (C).

The acid-generating compound (B) in the present invention that generates an acid upon exposure to light generates an acid by light exposure. Due to this acid, the blocked acidic groups present in the fluorine-containing copolymer are decomposed (deblocked). As a result, the exposed portion of the resist film becomes easily soluble in the alkaline developing solution, and a positive resist pattern is formed by the alkaline developing solution. Such an acid-generating compound (B) that generates an acid upon exposure to light can be an acid-generating compound used in general chemically amplified resist materials, and examples thereof include onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds, Sulfonic acid compounds, etc. Examples of these acid-generating compounds (B) include the following compounds.

The above-mentioned onium salts may, for example, be iodonium salts, sulfonium salts, phosphonium salts, diazonium salts or pyridinium salts. Specific examples of preferred onium salts include diphenyliodide trifluoromethanesulfonate, diphenyliodine pyrenesulfonate, diphenyliodide dodecylbenzenesulfonate, bis(4-tert-butyl trifluoromethanesulfonate) phenyl)iodide, bis(4-tert-butylphenyl)iodide dodecylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonanoate, triphenylsulfonium perfluorooctylsulfonate, hexa Triphenylsulfonium fluoroantimonate, 1-(naphthylacetylmethyl)sulfonium trifluoromethanesulfonate (1-(naphtyl acetomechl) triolanium triflet), cyclohexylmethyl trifluoromethanesulfonate ( 2-Oxycyclohexyl)sulfonium, Dicyclohexyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, Dimethyl(4-hydroxynaphthyl)sulfonium toluenesulfonate, Dimethyl dodecylbenzenesulfonate (4-hydroxynaphthyl)sulfonium, dimethyl(4-hydroxynaphthyl)sulfonium naphthalenesulfonate, triphenylsulfonium camphensulfonate, (4-hydroxyphenyl)benzylmethylsulfonium toluenesulfonate, etc.

The aforementioned halogen-containing compound may, for example, be a halogen-alkyl-containing hydrocarbon or a halogen-alkyl-containing heterocyclic compound. Specific examples include phenyl-bis(trichloromethyl)-s-triazine, methoxyphenyl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl) -s-triazine, etc. (trichloromethyl)-s-triazine derivatives, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, etc.

The aforementioned sulfone compound may, for example, be β-ketosulfone, β-sulfonylsulfone, or α-diazo compound of these compounds. Specific examples include 4-triphenacylsulfone, mesitylphenacylsulfone, bis(benzenesulfo)methane, and the like. The sulfonic acid compound may, for example, be alkylsulfonate, alkylsulfonimide, haloalkylsulfonate, arylsulfonate or iminosulfonate. Specific examples include benzoin tosylate, 1,8-naphthalimide triflate, and the like. In the present invention, the acid generating compound (B) may be used alone or in combination of two or more.

The organic solvent (C) in the present invention is not particularly limited as long as it dissolves the two components of the fluorinated copolymer and the acid generating compound (B). Examples include alcohols such as methanol and ethanol, ketones such as acetone, methyl isobutyl ketone, and cyclohexanone, acetates such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, propylene glycol monomethyl ether, and propylene glycol Glycol monoalkyl ethers such as monoethyl ether, glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate, etc.

The ratio of each component in the resist composition of the present invention is usually 0.1-20 parts by mass of the acid generating compound (B) and 50-2000 parts by mass of the organic solvent (C) relative to 100 parts by mass of the fluorine-containing copolymer. Preferably, the amount of the acid generating compound (B) is 0.1 to 10 parts by mass, and the amount of the organic solvent (C) is 100 to 1000 parts by mass relative to 100 parts by mass of the fluorinated copolymer.

Sufficient sensitivity and developability can be imparted by making the amount of the acid-generating compound (B) equal to or greater than 0.1 parts by mass, and by making it equal to or less than 10 parts by mass, sufficient transparency to radiation can be ensured to obtain more accurate resist pattern.

In the resist composition of the present invention, acid-decomposable additives for improving pattern contrast, surfactants for improving coatability, nitrogen-containing basic compounds for adjusting acid-generating patterns, Adhesion aids for improving the adhesion with substrates, storage stabilizers for improving the storage stability of the composition, and the like. In addition, the resist composition of the present invention is preferably used after mixing the components uniformly and filtering through a filter of 0.1 to 2 μm.

A resist film is formed by applying and drying the resist composition of the present invention on a substrate such as a silicon wafer. As the coating method, spin coating, flow coating, roll coating and the like can be used. Light is applied to the formed resist film through a pattern-drawn mask, and then it is developed to form a pattern.

Examples of light to be irradiated include ultraviolet light such as g-line with a wavelength of 436nm and i-line with a wavelength of 365nm, extreme ultraviolet rays such as KrF excimer laser with a wavelength of 248nm, ArF excimer laser with a wavelength of 193nm, and _F2 excimer laser with a wavelength of 157nm, and vacuum ultraviolet rays. . The resist composition of the present invention is a resist composition suitable for applications using ultraviolet rays with a wavelength of 250 nm or less, particularly ultraviolet rays with a wavelength of 200 nm or less (ArF excimer laser and F ₂ excimer laser) as a light source. In addition, the resist composition can also be used for exposure using the so-called liquid immersion technique, which utilizes the large refractive index of water, other organic compounds containing fluorine atoms, etc. to enhance resolution.

Aqueous solutions of various alkalis can be used as the developing treatment solution. The base may, for example, be sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, triethylamine or the like.

Example

Hereinafter, examples of the present invention will be described in detail, but the present invention is not limited to these examples.

Abbreviations used in the following examples are as follows.

THF: Tetrahydrofuran. AIBN: Azobisisobutyronitrile. BPO: Benzoyl Peroxide. PSt: polystyrene, R225: dichloropentafluoropropane (solvent). IPP: Diisopropyl peroxydicarbonate. PFB: Perfluoroperoxybutyryl. PFBPO: Perfluorobenzoyl peroxide.

(Synthesis Example 1) Synthesis of CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂

Add 118g of CF ₂ ClCFClI and 1.1g of AIBN into a 200mL glass reactor and heat to 75°C. Thereto, 75.8 g of CH ₂ =CHCH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ was added dropwise over 1 hour, and stirred at 75° C. for 7 hours after the dropwise addition was completed. Next, it was distilled under reduced pressure to obtain 144 g of CF ₂ ClCFClCH ₂ CHI (CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ ) (80-85° C./0.16 kPa).

144g of CF ₂ ClCFClCH ₂ CHI (CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ ) synthesized above and 550 ml of dehydrated THF were added into a 2L glass reactor and cooled to -75°C. Thereto, 220 ml of a 2M-THF solution of CH ₂ =CHCH ₂ MgCl was added dropwise over 2 hours.

After stirring at -75°C for 3 hours, 400 ml of saturated aqueous ammonium chloride solution was added, and the temperature was raised to room temperature. The reaction solution was separated, the organic layer was concentrated with an evaporator, and then distilled under reduced pressure to obtain 66.3 g of _{CF 2} ClCFClCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ )CH ₂ CH=CH ₂ (54-56°C /0.08kPa, hereinafter referred to as monomer 2 precursor).

Add 66.3g of CF ₂ ClCFClCH ₂ CH (CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ ) CH ₂ CH=CH ₂ and 200 ml of methanol synthesized above into a 500 ml glass reactor, add a catalytic amount of concentrated hydrochloric acid, Heat at 60°C for 19 hours. The reaction solution was cooled to room temperature, 30ml of water was added and separated. The organic layer was then washed with 150 ml of water to obtain 63 g of a crude solution. Next, 30 g of zinc, 78 g of dioxane and 22 g of water were added into a 200 mL glass reactor and heated to 85°C. 63 g of the crude solution above was added dropwise thereto, followed by stirring for 24 hours. The reaction solution was filtered, dilute hydrochloric acid was added and the layers were separated. Wash the organic layer with saturated brine, and distill under reduced pressure to obtain 23.6 g of CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂ (54-56°C/0.5kPa, hereinafter referred to as monomer 1 ).

NMR spectrum of monomer 1

¹ H-NMR (399.8MHz, solvent: CDCl ₃ , reference: tetramethylsilane) δ (ppm): 1.92 (m, 2H), 2.33 (m, 5H), 3.74 (br, 1H), 5.12 (m, 2H), 5.75 (m, 1H).

¹⁹ F-NMR (376.2MHz, solvent: CDCl ₃ , reference: CFCl3) δ (ppm): -77.3 (m, 3F), -77.8 (m, 3F), -92.9 (m, 1F), -104.2 (dd , J=32.24, 85.97Hz, 1F), -123.5(dd, J=85.97, 113.9Hz, 1F), -171.9(m, 1F).

(Example 1)

6.00 g of Monomer 1, 0.35 g of tert-butyl methacrylate, and 6.36 g of ethyl acetate were charged into a glass pressure-resistant reactor with an inner volume of 30 mL. Next, add 0.190g PFBPO as polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 125° C. for 10 hours. As a result, 3.56 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 1A) was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 10600, the weight average molecular weight (Mw) was 20600, and Mw/Mn=1.94 among the PSt-equivalent molecular weights measured by GPC. When measured by differential scanning calorimetry (DSC), Tg was not observed in the range of 40 to 180°C, and it was a white powdery polymer at room temperature.

The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurements was repeating unit consisting of monomer 1/repeating unit consisting of tert-butyl methacrylate=75/25 mol%. The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in R225, perfluoro(2-butyltetrahydrofuran), and perfluoro-n-octane.

(Example 2)

3.00g monomer 1 and 1.23g 1,1,2,3,3-pentafluoro-4-hydroxy-4-trifluoromethyl-1,6-pentadiene, 1.36g 1,1,2,3 , 3-pentafluoro-4-methoxymethoxy-4-trifluoromethyl-1,6-pentadiene, 0.19g of dioxane and 8.18g of ethyl acetate were added to a glass resistant in the pressure reactor. Next, 0.210 g of PFBPO was added as a polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 125° C. for 10 hours. As a result, 5.09 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 2A) was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 12300, the weight average molecular weight (Mw) was 29100, and Mw/Mn=2.37 among the PSt-equivalent molecular weights measured by GPC.

As measured by differential scanning calorimetry (DSC), the Tg was 114° C., and it was a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurement is, repeating unit composed of monomer 1/repeating unit composed of 1,1,1,3,3,4,5,5-octafluoro-2 -Recurring unit composed of propenyl-4-penten-2-ol/from 1,1,2,3,3-pentafluoro-4-methoxymethoxy-4-trifluoromethyl-1,6 -Recurring unit constituted by pentadiene=56/22/22 mol%.

The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in R225, perfluoro(2-butyltetrahydrofuran), and perfluoro-n-octane.

(Example 3)

Add 4.48g of monomer 1, 0.6g of 1,1,2-trifluoro-4-tert-butoxycarbonyl-1,6-pentadiene and 7.63g of ethyl acetate into a glass-made pressure-resistant reaction chamber with an inner volume of 30ml device. Next, add 0.191g PFBPO as polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 100° C. for 17 hours. As a result, 4.01 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 3A) was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 10,700, the weight average molecular weight (Mw) was 20,500, and Mw/Mn=1.91 among the PSt-equivalent molecular weights measured by GPC.

Measured by differential scanning calorimetry (DSC), the Tg is 100°C, and it is a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurement is: repeating unit consisting of monomer 1/1,1,2-trifluoro-4-tert-butoxycarbonyl-1,6 -Recurring unit composed of pentadiene=81/19 mol%.

The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

(Example 4)

2.50 g of Monomer 1, 0.147 g of tert-butyl-2-trifluoromethacrylate, and 4.17 g of ethyl acetate were charged into a glass pressure-resistant reactor with an inner volume of 30 CC. Next, 6.62 g of an R225 solution of PFB (containing 3% by weight of PFB) was added as a polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (20°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 90° C. for 23 hours. As a result, 2.37 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 4A) was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 17,400, the weight average molecular weight (Mw) was 50,600, and Mw/Mn=2.91 among the PSt-equivalent molecular weights measured by GPC. As measured by differential scanning calorimetry (DSC), the Tg is 105° C., and it is a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurements was repeating unit consisting of monomer 1/repeating unit consisting of tert-butyl methacrylate=91/9 mol%. The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in R225, perfluoro(2-butyltetrahydrofuran), and perfluoro-n-octane.

(Example 5)

5.00 g of Monomer 1, 0.362 g of 3-hydroxy-1-adamantyl methacrylate, and 8.45 g of ethyl acetate were charged into a glass pressure-resistant reactor with an inner volume of 30 CC. Next, 0.211 g of PFBPO was added as a polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 90° C. for 20 hours. As a result, 2.67 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 5A) was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 11,700, the weight average molecular weight (Mw) was 22,500, and Mw/Mn=1.92 among the PSt-equivalent molecular weights measured by GPC. Measured by differential scanning calorimetry (DSC), the Tg is 130° C., and it is a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurements is: repeating unit consisting of monomer 1/repeating unit consisting of 3-hydroxy-1-adamantyl methacrylate = 63/ 37 mol%. The obtained polymer is soluble in acetone, THF, ethyl acetate, and 2-perfluorohexyl ethanol, but insoluble in R225, perfluoro(2-butyltetrahydrofuran), and perfluoro-n-octane.

(Example 6)

102.1 g of monomer 2 precursor, 26 g of zinc and 100.0 g of N-methylpyrrolidone were added to a 300 ml flask and heated at 75° C. for 40 hours. After adding 300 g of water to the reaction liquid and stirring, zinc was removed by filtration under reduced pressure. The filtrate was liquid-separated to obtain 41.2 g of an organic layer. The organic layer was simply distilled under reduced pressure to simply remove low boiling point components and high boiling point components to obtain 31.0 g of CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₃ )CH ₂ CH =CH ₂ (hereinafter referred to as monomer 2).

Add 0.93 g of monomer 2, 2.33 g of 1,1,2,3,3-pentafluoro-4-hydroxy-4-trifluoromethyl-1,6-pentadiene and 4.44 g of ethyl acetate to the inner volume 30ml glass pressure reactor. Next, 0.111 g of PFBPO was added as a polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 120° C. for 24 hours. As a result, 2.81 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 15,200, the weight average molecular weight (Mw) was 38,000, and Mw/Mn=2.50 among the PSt-equivalent molecular weights measured by GPC. As measured by differential scanning calorimetry (DSC), the Tg was 113° C., and it was a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurement is, repeating unit composed of monomer 2/1,1,2,3,3-pentafluoro-4-methoxymethoxy Repeating unit composed of 4-trifluoromethyl-1,6-pentadiene = 26/74 mol%.

The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

(Example 7)

4.50 g of monomer 1, 1.36 g of 1,1,2,3,3-pentafluoro-4-methoxymethoxy-4-trifluoromethyl-1,6-pentadiene and 8.79 g of ethyl acetate The ester was added to a glass pressure-resistant reactor with an inner volume of 30 mL. Next, 0.220 g of PFBPO was added as a polymerization initiator. After freezing and degassing the system, seal the tube and polymerize in a constant temperature vibration tank (70°C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum-dried at 100° C. for 10 hours to obtain a white polymer.

This obtained polymer was dissolved in 50 ml of methanol, and 2 ml of a separately prepared methanol solution containing 0.12 g of sodium hydroxide was added dropwise, followed by stirring overnight at room temperature under a nitrogen atmosphere. Next, methanol was removed with an evaporator, 50 ml of THF was added, and 0.4 g of CF ₃ CH ₂ OCH ₂ Cl was added dropwise under a nitrogen atmosphere. As it was, it was stirred under a nitrogen atmosphere for 2 days, and the solution became cloudy and white due to generation of sodium chloride. The reaction solution was filtered through celite, and concentrated with an evaporator. The concentrate was dissolved in R225, washed with water, and separated. The R225 layer was dropped into hexane to reprecipitate the polymer, and then vacuum-dried at 100° C. for 20 hours. As a result, 5.55 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained. Using THF as a solvent, the number average molecular weight (Mn) was 12,500, the weight average molecular weight (Mw) was 29,400, and Mw/Mn=2.35 among the PSt-equivalent molecular weights measured by GPC. As measured by differential scanning calorimetry (DSC), the Tg is 105° C., and it is a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurement is: repeating unit composed of monomer 1/repeating unit composed of CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OCH ₂ OCH ₂ CF ₃ ) Repeating unit consisting of CH ₂ CH=CH ₂ / 1,1,2,3,3-pentafluoro-4-methoxymethoxy-4-trifluoromethyl-1,6-pentadiene Constituent repeating units = 68/10/22 mol%.

The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

(Embodiment 8)

In Example 7, except that 0.4 g of CF ₃ CH ₂ OCH ₂ Cl was replaced with 0.44 g of chloromethyl cyclohexyl ether, the same operation as in Example 7 was carried out to obtain 5.50 g of CF 3 CH 2 OCH 2 Cl having a fluorine-containing ring structure in the main chain. non-crystalline polymer. Using THF as a solvent, the number average molecular weight (Mn) was 12300, the weight average molecular weight (Mw) was 30600, and Mw/Mn=2.49 among the PSt-equivalent molecular weights measured by GPC. As measured by differential scanning calorimetry (DSC), the Tg was 103° C., and it was a white powdery polymer at room temperature. The polymer composition calculated by ¹⁹ F-NMR and ¹ H-NMR measurement is: repeating unit composed of monomer 1/repeating unit composed of CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ OCH ₂ OC ₆ H ₁₁ ) Repeating unit consisting of CH ₂ CH=CH ₂ /1,1,2,3,3-pentafluoro-4-methoxymethoxy-4-trifluoromethyl-1,6-pentadiene Constituent repeating units = 69/9/22 mol%.

The obtained polymer is soluble in acetone, THF, ethyl acetate, methanol, and 2-perfluorohexyl ethanol, but insoluble in perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

(Embodiments 9-13)

Polymer 1A, 2A, 3A, 4A or 5A and 0.05g trimethylsulfonium trifluoromethanesulfonate synthesized in 1g of Examples 1 to 5 were dissolved in 10g of propylene glycol monomethyl ether acetate, and a pore size of 0.2 μm was used. Filtration was carried out with a filter made of PTFE to obtain a resist composition.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist composition was spin-coated, and heat-treated at 80° C. for 2 minutes after coating to form a resist film with a film thickness of 0.3 μm. In a nitrogen-substituting exposure test apparatus, the substrate on which the resist film was formed was placed, and a mask patterned with chrome was attached to a quartz plate. After irradiating KrF excimer laser light through this mask, it exposed at 100 degreeC for 2 minutes, and baked. Image development was performed at 23 degreeC for 1 minute using tetramethylammonium hydroxide aqueous solution (2.38 mass %), and it wash|cleaned with pure water for 1 minute subsequently. The light transmittance and development test results of the resist film are shown in Table 1.

[Table 1] polymer 157nm light transmittance (%) Line and space width (1/1) (μm) Example 9 1A 53 0.16 Example 10 2A 48 0.16 Example 11 3A 50 0.16 Example 12 4A 47 0.16 Example 13 5A twenty one 0.17

Possibility of industrial use

The fluorine-containing copolymer of the present invention can be used, for example, in ion exchange resins, ion exchange membranes, fuel cells, various battery materials, optical fibers, electronic parts, transparent film materials, Agricultural films, adhesives, fiber materials, weather-resistant coatings, etc.

Claims (6)

1. Fluorine-containing copolymer (A1), it is characterized in that, described fluorine-containing copolymer (A1) has two kinds of units, and described unit is respectively derived from the fluorine-containing two represented by following formula (1) by cyclopolymerization ene and monomer units produced by cyclopolymerization of fluorine-containing dienes containing functional groups represented by the following formula (2), wherein the fluorine-containing dienes represented by formula (2) do not include A fluorine-containing diene represented by formula (1); CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1) In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² , and R ² is a carbon number less than or equal to The alkoxycarbonyl group of 15, the alkyl group, alkoxycarbonyl group of ^R1 and part or all of the hydrogen atoms of ^R2 may be replaced by fluorine atoms; CF ₂ =CR ³ -Q-CR ⁴ =CH ₂ (2) In the formula, R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, a fluoroalkyl group or a cyclic aliphatic hydrocarbon group with 3 or less carbon atoms, and Q represents a functional group or An alkylene group, an oxyalkylene group, a fluoroalkylene group or a fluorooxyalkylene group of a functional group-containing side chain group. 2. Fluorine-containing copolymer (A2), it is characterized in that, described fluorine-containing copolymer (A2) has two kinds of units, and described unit is respectively derived from the fluorine-containing two represented by the following formula (1) by cyclopolymerization A monomer unit produced by olefin and a monomer unit produced by polymerizing an acrylic monomer represented by the following formula (3); CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1) In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² , and R ² is a carbon number less than or equal to The alkoxycarbonyl group of 15, the alkyl group, alkoxycarbonyl group of ^R1 and part or all of the hydrogen atoms of ^R2 may be replaced by fluorine atoms; CH ₂ =CR ⁵ COOR ⁶ (3) In the formula, R ⁵ represents a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, or a fluoroalkyl group with 3 or less carbon atoms, R ⁶ represents an alkyl group with 20 or less carbon atoms, and the alkyl group Some hydrogen atoms may be substituted with fluorine atoms, alkyl groups or fluoroalkyl groups. 3. The manufacture method of fluorine-containing copolymer (A1), it is characterized in that, make the fluorine-containing diene represented by following formula (1) and the fluorine-containing diene that contains functional group represented by following formula (2) carry out free reaction Based copolymerization, wherein, the fluorine-containing diene represented by formula (2) does not include the fluorine-containing diene represented by formula (1); CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1) In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² , and R ² is a carbon number less than or equal to The alkoxycarbonyl group of 15, the alkyl group, alkoxycarbonyl group of ^R1 and part or all of the hydrogen atoms of ^R2 may be replaced by fluorine atoms; CF ₂ =CR ³ -Q-CR ⁴ =CH ₂ (2) In the formula, R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, a fluoroalkyl group or a cyclic aliphatic hydrocarbon group with 3 or less carbon atoms, and Q represents a functional group or An alkylene group, an oxyalkylene group, a fluoroalkylene group or a fluorooxyalkylene group of a functional group-containing side chain group. 4. A method for producing a fluorine-containing copolymer (A2) having a ring structure in the main chain, characterized in that the fluorine-containing diene represented by the following formula (1) and the acrylic monomer represented by the following formula (3) are body for free radical copolymerization; CF ₂ =CFCH ₂ CH(CH ₂ C(CF ₃ ) ₂ (OR ¹ ))CH ₂ CH=CH ₂ (1) In the formula, R ¹ is a hydrogen atom, an alkyl group with 20 or less carbon atoms that may have an etheric oxygen atom, an alkoxycarbonyl group with 15 or less carbon atoms, or CH ₂ R ² , and R ² is a carbon number less than or equal to The alkoxycarbonyl group of 15, the alkyl group, alkoxycarbonyl group of ^R1 and part or all of the hydrogen atoms of ^R2 may be replaced by fluorine atoms; CH ₂ =CR ⁵ COOR ⁶ (3) In the formula, ^R5 represents a hydrogen atom, a fluorine atom, an alkyl group with 3 or less carbon atoms, or a fluoroalkyl group with 3 or less carbon atoms; ^R6 represents an alkyl group with 20 or less carbon atoms; Some hydrogen atoms may be substituted with fluorine atoms, alkyl groups or fluoroalkyl groups. 5. A resist composition, characterized in that it contains the fluorine-containing copolymer (A1) according to claim 1, an acid-generating compound (B) that generates an acid upon exposure to light, and an organic solvent (C) 6. A resist composition characterized by comprising the fluorine-containing copolymer (A2) according to claim 2, an acid-generating compound (B) that generates an acid upon exposure to light, and an organic solvent (C).