JP4410508B2 - Fluorine-containing compounds and their polymer compounds - Google Patents

Description

  The present invention relates to a novel fluorine-containing compound containing a hydroxyl group or a substituent modified therewith, a polymer compound polymerized or copolymerized using the compound, and a resist material using the fluorine-containing compound and the polymer compound, or And an antireflection film material using the polymer compound.

  Fluorine compounds have features such as water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index, and low dielectric properties of fluorine atoms. It is used in a wide range of application fields, mainly in the cutting-edge field, and is mainly applied in the coating field that takes advantage of transparency at each wavelength. It is used as an anti-reflection film in the visible light region, as an optical device in the high wavelength region (optical communication wavelength band), as a resist material in the ultraviolet region, particularly in the vacuum ultraviolet region, and is still actively researched and developed. Yes. However, the functions that existing compounds can perform in response to increasingly sophisticated and diversified demands are not always sufficient, and the functions of transparency, substrate adhesion and etching resistance are excellent, and the reflection has all these functions. Creation of a dissolution inhibitor suitable as an anti-film material, a resist material, and a resist material is desired.

  Conventionally, in a wide wavelength range from the ultraviolet region to the near infrared region, it has high transparency and low refractive index, and also has anti-reflection that combines adhesion to the substrate, high film formability, etching resistance, and durability. No film material or resist material has been obtained.

  The present invention has been made in view of the above circumstances, and uses a novel fluorine-containing compound and a polymer compound using the same, and has high transparency in a wide wavelength region from the ultraviolet region to the near infrared region. An object of the present invention is to provide an antireflection film material or a resist material having a low refractive index and having adhesion to a substrate, high film-forming properties, etching resistance and durability, and a dissolution inhibitor suitable as a resist material. To do.

  As a result of intensive studies to achieve the above object, the present inventors have found that an alicyclic or aromatic fluorine-containing compound having a hydroxyl group or a functional group modified with the same in the same molecule and a polymer compound using the same Resist materials using these, and anti-reflective coating materials using these polymer compounds have high transparency and low refractive index in a wide wavelength range from the ultraviolet region to the near infrared region. In addition, it has been found that it has both adhesion to the substrate, high film-forming properties, etching resistance, and durability, and further finds that the fluorine-containing compound and the polymer compound are suitable as a dissolution inhibitor, thereby completing the present invention. It came to.

  In other words, the present invention includes the following fluorine-containing compounds 1 to 9, 10 polymer compounds, 11 antireflection film materials, and 12 and 13 resist materials described below.

1:
Fluorine-containing compound represented by the general formula (1) (wherein R ¹ represents a methyl group or a trifluoromethyl group, R ² and R ³ represent a hydrogen atom, a linear or branched chain having 1 to 25 carbon atoms) Or it is a group containing a cyclic hydrocarbon group or an aromatic hydrocarbon group, and a part thereof may contain a fluorine atom, an oxygen atom, or a carbonyl bond, l represents any integer of 0 to 2, m, n represents an arbitrary integer of 1 to 5 and satisfies m + n ≦ 6, and when R ^{1 to} R ³ are plural, R ^{1 to} R ³ may be the same or different.

2:
Fluorine-containing compound represented by the general formula (2) (wherein R ^{1 to} R ³ are the same as those in the general formula (1). L is 0 to 2, m, n is 1 to 9, and o is 1 to 8. represents any integer, when m + n ≦ o + 2 satisfy ^.R 1 to R ³ are a ^plurality, R 1 to R ³ may be the same or different.).

3:
Fluorine-containing compound represented by general formula (3) (wherein R ¹ and R ² are the same as in general formula (1). R ⁴ is a hydrogen atom, linear, branched or cyclic having 1 to 25 carbon atoms. A group containing a hydrocarbon group or an aromatic hydrocarbon group, and a part thereof may contain a fluorine atom, an oxygen atom, or a carbonyl bond, wherein l, m, n, and o are the same as those in the general formula (2). If R ^{1, R} 2, ^{R 4} is a ^plurality, R ^1, R 2, ^{R 4} may be the same or different.).

4:
A fluorine-containing compound represented by the general formula (4).

5:
A fluorine-containing compound represented by the general formula (5).

6:
At least one of R ² and R ³ is a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or a functional group in which some or all of the hydrogen atoms contained in these functional groups are substituted with fluorine atoms, or 3. The fluorine-containing compound according to 1 or 2 above, which is a substituent to be contained .

7:
1 or 2 above, wherein at least one of R ² and R ³ includes a substituent selected from a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a fluoroacryloyl group, a trifluoromethylacryloyl group, and a nonylfluorobutylacryloyl group. The fluorine-containing compound as described.

8:
^{4. The} fluorine-containing compound according to 3 above, wherein R ⁴ contains a substituent selected from a vinyl group, an allyl group, an epoxy group, an ethynyl group, or a group in which part or all of these functional groups are substituted with a fluorine atom.

9:
At least one of R ² and R ³ contains an acid labile group (the acid labile group is an acid leaving group, and may partially contain an oxygen atom, a carbonyl bond, or a fluorine atom). ~ 3 and the fluorine-containing compound according to any one of 6 to 8 above.

10:
The high molecular compound superposed | polymerized or copolymerized using the fluorine-containing compound in any one of said 1-3 and said 6-9.

11:
15. An antireflection film material for ultraviolet light or visible light using the polymer compound described in 10 above.

12:
A resist material containing the fluorine-containing compound according to 9 or the polymer compound according to 10 above.

13:
A resist material using the fluorine-containing compound according to 9 or the polymer compound according to 10 as a dissolution inhibitor.

The present invention will be described in detail below. In the compounds represented by the general formulas (1) to (3) of the present invention, R ¹ is a methyl group or a trifluoromethyl group, but it requires lower refractive index and higher transparency, particularly transparency in the ultraviolet wavelength region. When used for various applications, a trifluoromethyl group is preferably used.

R ^{2 to} R ⁴ according to the present invention are a hydrogen atom, a linear, branched or cyclic hydrocarbon group or an aromatic hydrocarbon group having 1 to 25 carbon atoms, and each has a fluorine atom, an oxygen atom, or a carbonyl bond. May be included. The structure of R ^{2 to} R ⁴ is not particularly limited, but the structure can be changed depending on the purpose of use. The purpose is to provide such characteristics as solubility in organic solvents and aqueous alkali solutions, high glass transition point, cross-linking reactivity for solder heat resistance, positive photosensitivity by photoacid generator and etching resistance. Therefore, it can be used for each application field of the present invention.

Examples of the linear, branched or cyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 25 carbon atoms that can be used for R ^{2 to} R ⁴ of the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, Cyclopropyl group, n-propyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, sec-pentyl group, neopentyl group, hexyl group, cyclohexyl group, ethylhexyl group, norbornyl group, adamantyl group Groups, vinyl groups, allyl groups, butenyl groups, pentenyl groups, ethynyl groups, phenyl groups, benzyl groups, 4-methoxybenzyl groups, etc., even if some or all of the above functional groups are substituted with fluorine atoms Good. Examples of those containing an oxygen atom include an alkoxycarbonyl group, an acetal group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, An i-propoxycarbonyl group etc. can be illustrated. As acetal group, methoxymethyl group, methoxyethoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group And cyclic ethers such as chain ether of ethoxybutyl group and ethoxyisobutyl group, tetrahydrofuranyl group and tetrahydropyranyl group. As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, Glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group Group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group And the like can be given. Furthermore, what substituted a part or all of the hydrogen atom of the said substituent by the fluorine atom can also be used.

  In addition, according to the present invention, the compounds represented by the general formulas (4) and (5) are suitably employed as the base material for the fluorine-containing compound or monomer of the present invention. According to the present invention, the compounds of the general formulas (4) and (5) are the most basic fluorine-containing compounds for deriving various fluorine-containing monomers represented by the general formulas (1) and (2). Useful as a compound.

Next, R ² and R ³ according to the present invention will be described. According to the present invention, R ² and R ³ are constituted by containing any of a hydrogen atom, an unsaturated bond, and an acid labile group. In the case of a fluorine-containing compound in which a plurality of R ² and R ³ are present, each R ² and R ³ may be the same or different. When R ² and R ³ are hydrogen atoms, they can be used in the form of raw material compounds for inducing various fluorine-containing compounds, or as they are added to coating materials together with other resins and crosslinking agents. In addition, when R ² and R ³ are unsaturated bonds, they can be used as polymerizable monomers for producing fluoropolymers or copolymers, and are also suitable as various raw material compounds including Diels-Alder reaction. It is. When R ² and R ³ are acid labile groups, when the application is a resist, they can be used as a dissolution inhibitor. Furthermore, a fluorine-containing compound in which a hydrogen atom, an unsaturated bond, an acid labile group and the like coexist in the molecule can also be used. Of R ² and R ^3, the fluorine-containing compound according to the above 6 to 8 containing an unsaturated bond according to the present invention will be described first. When one of R ² and R ³ is a polymerizable unsaturated bond, it is mainly used as a raw material for obtaining the polymer or copolymer according to the present invention, and a plurality of R ² and R ³ are unsaturated. In the case of bonding, it can be used mainly as a crosslinkable material.

The unsaturated bond that can be used for R ² and R ³ of the present invention is not particularly limited as long as it has polymerizability or reactivity, but may be a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or a functional group thereof . A substituent in which part or all of the hydrogen atoms contained in the group are substituted with fluorine atoms or a substituent containing them is suitably employed. Here, specific examples of the functional group in which a part or all of R ² and R ³ are substituted with a fluorine atom include a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, A trifluoroallyl group, a perfluoroallyl group, a fluoroacryloyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, etc. are mentioned. Those having a fluorine atom in the functional group are applied to further impart transparency and low refractive index.

Next, R ⁴ of the present invention will be described. R ^{4 that} can be used in the present invention is preferably a polymerizable functional group such as a vinyl group, an allyl group, an epoxy group, or an ethynyl group, but is not particularly limited thereto. Further, those in which part or all of these functional groups are substituted with fluorine atoms are also preferably employed. Here, specific examples of the functional group in which part or all of R ⁴ is substituted with a fluorine atom include a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group. Group, perfluoroallyl group, trifluoroepoxy group and the like.

  The purpose of using the functional group is to improve the polymerizability of the fluorine-containing compound. Those having a fluorine atom in the functional group further impart transparency and low refractive index, and can be selectively used for each application field of the present invention.

Next, the acid labile group that can be used for R ² and R ³ of the present invention will be described. The acid labile group according to the present invention is applied to a part or all of R ² and R ³ , and can also be used in combination with the aforementioned unsaturated bond group. The acid labile groups of R ² and R ³ are so-called acid leaving groups, and some of them may contain an oxygen atom, a carbonyl bond, or a fluorine atom.

The acid labile group that can be used in the present invention can be used without particular limitation as long as it is a group that undergoes elimination due to effects such as a photoacid generator or hydrolysis. Examples thereof include a alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group. As an acetal group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, An ethoxyisobutyl group etc. are mentioned. R ² and R
^{When 3} is a hydrogen atom, an acetal group obtained by adding vinyl ether to the hydroxyl group can also be used. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, and t-butyl. Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, Glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group Group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group And the like can be given. Furthermore, those in which some or all of the hydrogen atoms of these acid labile groups are substituted with fluorine atoms can also be used.

  The purpose of using the acid labile group is that the positive photosensitivity due to the acid-anxiety group and the exposure to an alkaline aqueous solution after exposure to high-energy rays such as far ultraviolet rays, excimer lasers, X-rays, or electron beams with a wavelength of 300 nm or less. It is to develop solubility, and those having a fluorine atom in the functional group are transparent, and those containing a cyclic structure are to further impart characteristics such as etching resistance and high glass transition point. It is possible to use properly for each field.

  Next, the polymer compound according to the present invention will be described. The polymer compound of the present invention is a polymer material obtained by homopolymerizing or copolymerizing a fluorine-containing compound having a polymerizable unsaturated bond in the molecule among the general formulas (1) to (3).

  If the monomer copolymerizable with the polymerizable fluorine-containing compound of the present invention is specifically exemplified, at least acrylic ester, methacrylic ester, fluorine-containing acrylic ester, fluorine-containing methacrylate, styrene compound Copolymerization with one or more monomers selected from fluorine-containing styrene compounds, vinyl ethers, fluorine-containing vinyl ethers, allyl ethers, fluorine-containing allyl ethers, olefins, fluorine-containing olefins, norbornene compounds, and fluorine-containing norbornene compounds. Is preferred.

The acrylic ester or methacrylic ester that can be used in the present invention can be used without particular limitation on the ester side chain, but examples of known compounds include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, n-propyl acrylate or methacrylate. , Isopropyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, lauryl acrylate or methacrylate, 2-hydroxyethyl acrylate or Methacrylate, 2-hydroxypropyl acrylate or meta Acrylic acid or methacrylic acid alkyl ester such as relate, ethylene glycol, propylene glycol, acrylate or methacrylate containing tetramethylene glycol group, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide, etc. Unsaturated amides, acrylonitrile, methacrylonitrile, alkoxysilane-containing vinyl silanes or acrylic acid or methacrylic acid esters, tert-butyl acrylate or methacrylate, 3-oxocyclohexyl acrylate or methacrylate, adamantyl acrylate or methacrylate, alkyladamantyl acrylate or methacrylate, Cyclohexyl acrylate or methacrylate Rate, tricyclodecanyl acrylate or methacrylate, acrylate or methacrylate having a ring structure such as lactone ring or norbornene ring, acrylic acid, methacrylic acid, and the like. Furthermore, it is also possible to copolymerize the above acrylate compounds containing a cyano group at the α-position, and maleic acid, fumaric acid, maleic anhydride and the like as similar compounds.

  In addition, as the fluorine-containing acrylic ester and fluorine-containing methacrylate used in the present invention, a fluorine atom or a monomer having a fluorine atom contained in the α-position of the acrylic, or a fluorine atom contained in the ester site A fluorine-containing compound which is an acrylic ester or methacrylic ester composed of a substituent and contains fluorine at both the α-position and the ester portion is also suitable. Furthermore, a cyano group may be introduced at the α-position. For example, as a monomer having a fluorine-containing alkyl group introduced at the α-position, a trifluoromethyl group, trifluoroethyl group, nonafluoro-n- A monomer having a butyl group or the like is preferably employed, and the ester moiety in that case does not necessarily contain fluorine. When α-trifluoromethylacrylic acid alkyl ester is used as a copolymerization component, the yield of the polymer is relatively high, and the solubility of the resulting polymer in an organic solvent is good, which is preferably employed.

On the other hand, the monomer containing fluorine at the ester site includes a perfluoroalkyl group as the ester site, a fluoroalkyl group as a fluoroalkyl group, and a unit having a cyclic structure and a fluorine atom at the ester site. , Units having a fluorinated benzene ring, a fluorinated cyclopentane ring, a fluorinated cyclohexane ring, a fluorinated cycloheptane ring, etc., whose cyclic structure is substituted with, for example, a fluorine atom, a trifluoromethyl group, a hexafluorocarbinol group, etc. Acrylic acid ester or methacrylic acid ester having An ester of acrylic acid or methacrylic acid in which the ester moiety is a fluorine-containing t-butyl ester group can also be used. As these fluorine-containing functional groups, a monomer used in combination with the α-position fluorine-containing alkyl group can be used. Among such units, particularly representative ones are exemplified in the form of monomers, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1 , 1,3,3,3-hexafluoroisopropyl acrylate, heptafluoroisopropyl acrylate, 1,1-dihydroheptafluoro-n-butyl acrylate, 1,1,5-trihydrooctafluoro-n-pentyl acrylate, 1, 1,2,2-tetrahydrotridecafluoro-n-octyl acrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3 , 3-Tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluo Isopropyl methacrylate, heptafluoroisopropyl methacrylate, 1,1-dihydroheptafluoro-n-butyl methacrylate, 1,1,5-trihydrooctafluoro-n-pentyl methacrylate, 1,1,2,2-tetrahydrotridecafluoro- n-octyl methacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate, 6- [3,3,3-trifluoro-2-hydroxy -2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptyl-2-yl acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] Bisik [2.2.1] Heptyl-2-yl 2- (trifluoromethyl) acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2. 2.1] Heptyl-2-yl methacrylate, 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl acrylate, 1,4-bis (1,1,1, 1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl methacrylate, 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl 2-trifluoro And methyl acrylate.

  Furthermore, styrene compounds and fluorine-containing styrene compounds that can be used in the present invention include styrene, fluorinated styrene, hydroxystyrene, etc., and one or more functional groups modified with a hexafluorocarbinol group or its hydroxyl group. Can be used. That is, styrene or hydroxystyrene substituted with hydrogen by a fluorine atom or a trifluoromethyl group, the above styrene having a halogen, an alkyl group or a fluorine-containing alkyl group bonded to the α-position, or a styrene containing a perfluorovinyl group can be preferably used. is there.

  Further, as vinyl ether, fluorine-containing vinyl ether, allyl ether, fluorine-containing allyl ether, alkyl vinyl ether which may contain hydroxy group such as methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, hydroxybutyl group or the like Alkyl allyl ether, cyclohexyl group, cyclic vinyl having hydrogen or carbonyl bond in its cyclic structure, allyl ether, fluorine-containing vinyl ether in which part or all of hydrogen of the above functional group is substituted with fluorine atom, fluorine-containing Allyl ether can also be used. In addition, if it is a compound containing vinyl ester, vinyl silane, an olefin, a fluorine-containing olefin, a norbornene compound, a fluorine-containing norbornene compound, and another polymerizable unsaturated bond, it can be used without a restriction | limiting in particular.

  Examples of olefins include ethylene, propylene, isobutene, cyclopentene, and cyclohexene. Examples of fluorine-containing olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and hexafluoroisobutene. It can be illustrated.

  The norbornene compound and the fluorine-containing norbornene compound are norbornene monomers having a single nucleus or a plurality of nucleus structures. In this case, fluorine-containing olefin, allyl alcohol, fluorine-containing allyl alcohol, homoallyl alcohol, and fluorine-containing homoallyl alcohol are acrylic acid, α-fluoroacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid, described in the present specification. All acrylates, methacrylates, fluorine-containing acrylic esters or fluorine-containing methacrylates, 2- (benzoyloxy) pentafluoropropane, 2- (methoxyethoxymethyloxy) pentafluoropropene, 2- (tetrahydroxy Di of unsaturated compounds such as pyranyloxy) pentafluoropropene, 2- (benzoyloxy) trifluoroethylene, 2- (methoxymethyloxy) trifluoroethylene with cyclopentadiene and cyclohexadiene A norbornene compound produced by the els-Alder addition reaction, which is 3- (5-bicyclo [2.2.1] hepten-2-yl) -1,1,1-trifluoro-2- (trifluoromethyl) -2 -Propanol and the like can be exemplified. The above copolymerizable compounds may be used alone or in combination of two or more.

  The copolymer composition ratio of the fluorine-containing compound of the present invention is not particularly limited, and is preferably selected between 10 and 100%. More preferably, it is 30 to 100%. If it is less than 30%, sufficient transparency and film formability are not exhibited depending on the wavelength range of the application field.

  The polymerization method of the polymer compound according to the present invention is not particularly limited as long as it is a generally used method, but radical polymerization, ionic polymerization and the like are preferable, and in some cases, coordination anion polymerization, living anion polymerization and the like are performed. It is also possible to use it. Here, a more general radical polymerization method will be described. That is, in the presence of a radical polymerization initiator or a radical initiator, it can be carried out by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization in either batch, semi-continuous or continuous operation. Just do it.

  The radical polymerization initiator is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds. Particularly, azobisisobutyronitrile, t-butylperoxypivalate, Di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, Hydrogen peroxide, ammonium persulfate and the like are preferable.

  The reaction vessel used for the polymerization reaction is not particularly limited. In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those which do not inhibit radical polymerization are preferable, and typical ones are ester-based solvents such as ethyl acetate and n-butyl acetate, ketone-based solvents such as acetone and methyl isobutyl ketone, and hydrocarbons such as toluene and cyclohexane. And alcohol solvents such as methanol, isopropyl alcohol, and ethylene glycol monomethyl ether. It is also possible to use various solvents such as water, ethers, cyclic ethers, chlorofluorocarbons, and aromatics. These solvents can be used alone or in admixture of two or more. Moreover, you may use together molecular weight regulators, such as a mercaptan. The reaction temperature of the copolymerization reaction is appropriately changed depending on the radical polymerization initiator or the radical polymerization initiation source, and is usually preferably 20 to 200 degrees, particularly preferably 30 to 140 degrees.

  As a method for removing the organic solvent or water as a medium from the solution or dispersion of the polymer compound according to the present invention thus obtained, any of the known methods can be used. There are methods such as filtration or heating distillation under reduced pressure. The number average molecular weight of the obtained polymer compound of the present invention is usually in the range of 1,000 to 100,000, preferably 3,000 to 50,000.

  Next, application fields according to the present invention will be described. The present invention is based on coating applications, and is usually used for application by dissolving the polymer compound of the present invention in an organic solvent to form a film. Accordingly, the organic solvent to be used is not particularly limited as long as the polymer compound is soluble, but ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, Polyhydric alcohols such as diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; , Cyclic ethers such as dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, pyrubi Esters such as methyl acid, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, aromatic solvents such as xylene and toluene, fluorinated solvents such as chlorofluorocarbons, alternative chlorofluorocarbons, perfluoro compounds, hexafluoroisopropyl alcohol, For the purpose of improving the coating property, a terpene-based petroleum naphtha solvent or a paraffinic solvent, which is a high-boiling weak solvent, can be used. These may be used alone or in combination of two or more.

The antireflection film according to the present invention is obtained by coating the polymer compound according to the present invention on the surface of glass, plastic, liquid crystal panel, plasma display panel, electroluminescence panel, etc. with a very thin film, and having a single layer or other refractive index. It can also be used in combination with a thin film having In order to improve the antireflection performance, the refractive index of the polymer compound in ultraviolet light or visible light needs to be 1.42 or less, preferably 1.4 or less. Usually, the higher the fluorine content, the lower the refractive index. On the other hand, when the fluorine content is increased, there is a drawback that the adhesion to the substrate is lowered. In that case, it is possible to improve the adhesiveness to the substrate by polymerizing a fluorine-containing compound in which a part of R ² and R ³ is an adhesive group such as hydrogen or a lactone ring. The thickness of the antireflection film according to the present invention varies depending on the refractive index of the object to be coated, but is generally in the range of 500 to 2000 angstroms.

The resist material according to the present invention contains both a dissolution inhibitor whose solubility in an alkaline aqueous solution is changed by the action of an acid and a polymer compound, or a dissolution inhibitor incorporated into a polymer compound. These are particularly suitable as positive resist materials, and are 248 nm KrF or 193 nm ArF excimer lasers corresponding to the recent miniaturization of semiconductors, F ₂ laser positive resists in the vacuum ultraviolet region typified by 157 nm, electron beam resists, It is also suitable as an X-ray resist. That is, the dissolution inhibitor whose solubility in an alkaline aqueous solution is changed by the action of an acid is such that at least one of R ² and R ³ becomes an acid labile group, but its structure can be used without any particular limitation. It is. A general acid labile group is the acid labile group described above, which is a functional group that is cleaved by an acid. A polymer compound using such a dissolution inhibitor is insoluble or hardly soluble in an alkaline aqueous solution before being irradiated with active energy rays, and is generated by the acid generated from the acid generator by irradiation with active energy rays. It is hydrolyzed and becomes soluble in alkaline aqueous solution.

  There is no restriction | limiting in particular about the photo-acid generator used for this invention composition, Arbitrary things can be selected and used from what is used as an acid generator of a chemically amplified resist. Examples of such acid generators include bissulfonyldiazomethanes, nitrobenzyl derivatives, onium salts, halogen-containing triazine compounds, cyano group-containing oxime sulfonate compounds, and other oxime sulfonate compounds. These acid generators may be used alone or in combination of two or more, and the content thereof is usually 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer compound. Is selected within the range. If this amount is less than 0.5 parts by weight, the image forming property is insufficient, and if it exceeds 20 parts by weight, a uniform solution is hardly formed, and the storage stability tends to be lowered.

  As a method of using the resist of the present invention, a resist pattern forming method of a conventional photoresist technique is used, but in order to suitably perform it, first, a resist composition solution is spinner or the like on a support such as a silicon wafer. And drying to form a photosensitive layer, which is irradiated with an excimer laser beam through a desired mask pattern by an exposure apparatus or the like and heated. Next, this is developed using a developer, for example, an alkaline aqueous solution such as a 0.1 to 10% by weight tetramethylammonium hydroxide aqueous solution. With this forming method, a pattern faithful to the mask pattern can be obtained.

  The fields of application of the present invention further include optionally miscible additives, such as additional resins, quenchers, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, antifoaming agents, phases. Various additives such as a solubilizer, an adhesion agent, and an antioxidant can be contained.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

  The compound represented by the general formula (4) was synthesized by the following method.

Nitration Concentrated sulfuric acid (1.83 L) and a compound represented by the general formula (6) (1 kg) were placed in a three-necked flask equipped with a mechanical stirrer and a thermometer. Concentrated nitric acid (0.74 L) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 18 hours. The reaction solution is poured into ice, divided into two layers, the aqueous layer is extracted twice with methylene chloride, the combined organic layer is washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate is evaporated. Concentrated with. The obtained residue was distilled under reduced pressure to obtain a compound represented by the general formula (7) (1.05 kg, 95%).
¹ H-NMR (TMS, CDCl ₃ ): 4.13 (2H, br), 8.45 (1H
, S), 8.78 (2H, s)
Amination A compound (340 g) represented by the general formula (7), palladium-carbon (3.4 g), and methanol (1.36 L) were placed in a pressure vessel made of SUS. Hydrogen was introduced while maintaining the internal temperature at 65 ° C. and the hydrogen pressure at 5 kgf / cm 2, and the mixture was stirred for 3 hours. After completion of the reaction, the reaction mixture was filtered under reduced pressure, and the filtrate was concentrated with an evaporator. The obtained solid was washed with methylene chloride, filtered, and dried under vacuum to obtain a compound represented by the general formula (8) (281 g, 88%).
¹ H-NMR (TMS, CDCl ₃ ): 4.57 (2H, br), 5.91 (2H, s), 7.12 (1H, s), 7.29 (2H, s)
Phenolization A compound (20 g) represented by the general formula (8) and 20% aqueous sulfuric acid (300 mL) were placed in a three-necked flask equipped with a dropping funnel, a mechanical stirrer, and a thermometer, and cooled to 0 ° C. An aqueous solution (19 mL) of sodium sulfite (3.6 g) was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour. The reaction solution was added dropwise to 20% sulfuric acid water (90 mL) at 110 ° C. The black oily substance precipitated in the lower layer was taken out, washed with water, and distilled under reduced pressure to obtain the compound represented by the general formula (4) (8.5 g, 42%).
¹ H-NMR (TMS, CDCl ₃ ): 3.73 (3H, br), 7.34 (2H, s), 7.66 (1H, s)
GC-MS (EI method): m / e 426 (M ^<+> ).

  Synthesis of a compound represented by the general formula (5).

  A suspension of the compound represented by the general formula (4) (50 g) and the rhodium-carbon catalyst (0.5 g) in THF (200 mL) was placed in a SUS pressure vessel and heated to 130 ° C. Hydrogen was introduced while maintaining the hydrogen pressure at 80 kgf / cm 2 and stirred for 4 hours. After the reaction, the catalyst was removed by filtration, the filtrate was concentrated with an evaporator, and the residue was distilled under reduced pressure to obtain the compound represented by the general formula (5) (41 g, 85%). Disappearance was confirmed.

  Synthesis of a compound represented by the general formula (9).

  In a three-necked flask equipped with a stirrer, thermometer, Dean-Stark water separator, and reflux condenser, a toluene (50 mL) solution of the compound (15 g) represented by the general formula (4) and acrylic acid (3.8 g) Concentrated sulfuric acid (0.05 mL) was added and refluxed for 5 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain the compound represented by the general formula (9) (8.8 g, 52%), and the absorption of ester carbonyl was confirmed by IR spectrum.

  Synthesis of compound represented by general formula (10)

  A compound (15 g) represented by the general formula (4), triethylamine (8.9 g) and a solution of methylene chloride (50 mL) are placed in a three-necked flask equipped with a dropping funnel, a stirrer, and a thermometer. Acrylic acid chloride (8.0 g) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 3 hours. After completion, the reaction solution was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain the compound represented by the general formula (10) (12.0 g, 64%), and the absorption of ester carbonyl was confirmed by IR spectrum.

  Synthesis of compound represented by general formula (11)

  In a three-necked flask equipped with a stirrer, thermometer, Dean-Stark water separator and reflux condenser, toluene (50 mL) of the compound represented by the general formula (4) (15 g) and trifluoromethylacrylic acid (7.4 g) ) Solution and concentrated sulfuric acid (0.05 mL) were added and refluxed for 9 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain a compound represented by the general formula (11) (11 g, 58%), and the absorption of ester carbonyl was confirmed by IR spectrum.

  Synthesis of compound represented by general formula (12)

  A dimethylformamide (80 mL) solution of the compound (20 g) represented by the general formula (4) was added to a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled with ice. Next, sodium hydride (3.4 g) was added, and the mixture was stirred until hydrogen was no longer generated. Allyl bromide (8.5 g) in dimethylformamide (20 mL) was added dropwise, and the mixture was stirred at room temperature. After completion of the reaction, water was added and extracted with diethyl ether. The organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound represented by the general formula (12) (15.6 g, 72%), and absorption of double bonds was confirmed by IR spectrum. did.

  Synthesis of compound represented by general formula (13)

  In a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, the compound represented by the general formula (4) (10 g), ethyl vinyl ether (2.5 g), paratoluenesulfonic acid monohydrate (0.4 g) And toluene (60 mL) were added, and the mixture was stirred at room temperature for 7 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain the compound represented by the general formula (13) (5.6 g, 48%), and the disappearance of hydroxyl absorption was confirmed by IR spectrum.

  Synthesis of compound represented by general formula (14)

In a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, a compound (10 g) represented by the general formula (4), nonafluorobutyl vinyl ether (9.2 g), paratoluenesulfonic acid monohydrate (0. 4 g) and toluene (60 mL) were added, and the mixture was stirred at room temperature for 19 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain the compound (5.7 g, 35%) represented by the general formula (14), and the disappearance of hydroxyl absorption was confirmed by IR spectrum.

  Synthesis of compound represented by general formula (15)

  A compound (18 g) represented by the general formula (13), triethylamine (12.8 g) and methylene chloride (45 mL) are added to a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and the mixture is cooled with ice. A solution of trifluoromethylacrylic acid chloride (8.6 g) in methylene chloride (20 mL) is added dropwise, and the mixture is stirred at room temperature for 7 hours. After completion of the reaction, the reaction solution was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound (9.6 g, 43%) represented by the general formula (15). Absorption was confirmed.

  Synthesis of compound represented by general formula (16)

A dimethylformamide (50 mL) solution of the compound (17 g) represented by the general formula (13) was added to a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled with ice. Next, sodium hydride (2.0 g) was added, and the mixture was stirred until hydrogen was not generated. Then, dimethylformamide (20 mL) of allyl bromide (6.2 g) was added dropwise, and the mixture was stirred at room temperature. After completion of the reaction, water was added and extracted with diethyl ether. The organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound represented by the general formula (16) (12.3 g, 67%), and absorption of double bonds was confirmed by IR spectrum. did.
[ Reference Example 11]

  Synthesis of compound represented by general formula (17)

In a three-necked flask equipped with a stirrer, thermometer, Dean-Stark water separator, and reflux condenser, toluene (100 mL) of the compound represented by the general formula (5) (30 g) and trifluoromethylacrylic acid (15.9 g) ) Solution and concentrated sulfuric acid (0.1 mL) were added and refluxed for 9 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain the compound represented by the general formula (17) (27.6 g, 73%), and the absorption of ester carbonyl was confirmed by IR spectrum.
[ Reference Example 12]

  Synthesis of compound represented by general formula (18)

A dimethylformamide (50 mL) solution of the compound (10 g) represented by the general formula (5) was added to a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled with ice. Next, sodium hydride (1.8 g) was added, and the mixture was stirred until hydrogen was not generated. Then, dimethylformamide (10 mL) of allyl bromide (4.3 g) was added dropwise, and the mixture was stirred at room temperature. After completion of the reaction, water was added and extracted with diethyl ether. The organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound (6.4 g, 63%) represented by the general formula (18), and the absorption of double bonds was confirmed by IR spectrum. did.
[ Reference Example 13]

  Synthesis of compound represented by general formula (19)

In a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, the compound represented by the general formula (5) (13 g), ethyl vinyl ether (3.3 g), p-toluenesulfonic acid monohydrate (0.5 g) And toluene (70 mL) were added, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water and saturated brine, and concentrated with an evaporator. The residue was distilled under reduced pressure to obtain a compound (8.3 g, 55%) represented by the general formula (19), and the disappearance of hydroxyl absorption was confirmed by IR spectrum.
[ Reference Example 14]

  Synthesis of compound represented by general formula (20)

A compound (9 g) represented by the general formula (19), triethylamine (6.5 g) and methylene chloride (20 mL) are added to a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled with ice.
A solution of trifluoromethylacrylic acid chloride (4.4 g) in methylene chloride (20 mL) is added dropwise, followed by stirring at room temperature for 19 hours. After completion, the reaction solution was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound represented by the general formula (20) (7.6 g, 68%). Absorption was confirmed.
[ Reference Example 15]

  Synthesis of compound represented by general formula (21)

A compound (15 g) represented by the general formula (17), potassium carbonate (13.1 g), and acetone (100 mL) were added to a three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel. Next, chloromethyl methyl ether (5.4 g) was added and refluxed. After completion of the reaction, water was added and extracted with diethyl ether. The organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound (7.5 g, 43%) represented by the general formula (21), and the disappearance of hydroxyl group absorption was confirmed by IR spectrum. did. MOM represents CH ₃ OCH ₂ —.
[ Reference Example 16]

  Synthesis of the compound represented by the general formula (23)

A compound (20 g) represented by the general formula (5), triethylamine (16.4 g) and methylene chloride (85 mL) are placed in a three-necked flask equipped with a triflating stirrer, a thermometer, and a dropping funnel, and cooled to -30 ° C. It was. Next, trifluoromethanesulfonic anhydride (19.6 g) was added dropwise and stirred for 5 hours. After completion of the reaction, the organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound (14.9 g, 57%) represented by the general formula (22). Absorption was confirmed.

Vinylation A three-necked flask equipped with a stirrer, a thermometer and a dropping funnel was charged with the compound represented by the general formula (22) (10 g), copper iodide (0.3 g) and THF (30 mL), and the temperature was kept at -30 ° C. Chilled. Next, a THF (30 mL) solution of vinylmagnesium bromide (5.4 g) was added dropwise and stirred for 18 hours. After completion of the reaction, the organic layer was washed with water and saturated brine, and distilled under reduced pressure to obtain the compound (5.7 g, 70%) represented by the general formula (23). Absorption was confirmed.

  Polymerization of the compound represented by the general formula (11)

Into a three-necked flask equipped with a reflux condenser and a stirrer, the compound represented by the general formula (11) (10 g) was added, AIBN (0.2 g) was added as a polymerization initiator, and n-butyl acetate (40 g) was used as a polymerization solvent. ) The flask was heated in an oil bath at 60 ° C. and reacted for 20 hours. After the reaction, the reaction solution was added to n-hexane (1 L) and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 18 hours. The composition of the obtained polymer was determined from ¹ H-NMR and ¹⁹ F-NMR, and the molecular weight (Mw, Mn, Mw / Mn) was determined from GPC analysis (standard polystyrene). The results are shown in Table 1.

  Copolymerization of compound represented by general formula (11) and compound represented by general formula (24)

  Polymerization was carried out in the same manner as in Example 17, using the compound (10 g) represented by the general formula (11) and the compound (8.0 g) represented by the general formula (24). The results are shown in Table 1. tBOC represents t-butyloxycarbonyl.

  Copolymerization of compound represented by general formula (15) and compound represented by general formula (25)

  Polymerization was carried out in the same manner as in Example 17, using the compound represented by the general formula (15) (10 g) and the compound represented by the general formula (25) (7.5 g). The results are shown in Table 1.

  Copolymerization of compound represented by general formula (12) and compound represented by general formula (26)

  Polymerization was carried out in the same manner as in Example 17, using the compound (10 g) represented by the general formula (12) and the compound (10 g) represented by the general formula (26). The results are shown in Table 1.

  Copolymerization of compound represented by general formula (17) and compound represented by general formula (27)

  Polymerization was carried out in the same manner as in Example 17, using the compound (8.2 g) represented by the general formula (17) and the compound (10 g) represented by the general formula (27). The results are shown in Table 1.

  Copolymerization of compound represented by general formula (20) and compound represented by general formula (25)

Polymerization was carried out in the same manner as in Example 17, using the compound represented by the general formula (20) (9.3 g) and the compound represented by the general formula (25) (10 g). The results are shown in Table 1.
[ Reference Example 23]

  Copolymerization of compound represented by general formula (18) and compound represented by general formula (28)

Polymerization was carried out in the same manner as in Example 17, using the compound represented by the general formula (18) (10 g) and the compound represented by the general formula (28) (12 g). The results are shown in Table 1.
[ Reference Example 24]

  Copolymerization of compound represented by general formula (21) and compound represented by general formula (29)

Polymerization was carried out in the same manner as in Example 17, using the compound represented by the general formula (21) (15 g) and the compound represented by the general formula (29) (7.7 g). The results are shown in Table 1.
[ Reference Example 25]

  Copolymerization of compound represented by general formula (20), compound represented by general formula (30), compound represented by general formula (31)

The same as Example 17 using the compound (10 g) represented by the general formula (20), the compound (5.4 g) represented by the general formula (30), and the compound (6.8 g) represented by the general formula (31) Polymerization was carried out by the method. The results are shown in Table 1.
[ Reference Example 26]

  Copolymerization of compound represented by general formula (23) and compound represented by general formula (28)

  Polymerization was carried out in the same manner as in Example 17, using the compound (10 g) represented by the general formula (23) and the compound (10 g) represented by the general formula (28). The results are shown in Table 1.

  100 parts by weight (hereinafter referred to as “parts”) of the polymer compound obtained in Example 17 was dissolved in methyl isobutyl ketone and adjusted to a solid content concentration of about 30%. These were spread on a glass plate to produce a 50 micron film. After 1 hour of natural drying, forced drying was performed for 30 minutes with a hot air dryer at 100 ° C. to promote the crosslinking reaction. When these refractive indexes were measured with the Abbe refractometer, it was 1.376. Next, the above 30% solution was further diluted to a concentration of about 2%, and then a thin film was formed on a glass substrate by spin coating and dried at 100 ° C. for 3 minutes. The film thickness was 1030 angstroms. When the reflectance of the obtained glass plate was measured, antireflection performance at a high level of 0.9% with respect to the wavelength range of 650 nm was observed.

The polymer compounds of Examples or Reference Examples 17 to 26 were dissolved in propylene glycol methyl acetate and adjusted to a solid content of 14%. Furthermore, Midori Chemical's triphenylsulfonium triflate (TPS105) was dissolved in 2 parts by weight as an acid generator with respect to 100 parts by weight of the polymer compound to prepare two types of resist solutions. When these were spin-coated and the light transmittance of a film thickness of 100 nanometers was measured at a wavelength of 157 nm, they were 71%, 69%, 68%, 61%, 72%, 65, respectively, with respect to Examples or Reference Examples 17 to 26. %, 68%, 74%, 63%, 71%, and high transparency was exhibited at wavelengths in the vacuum ultraviolet region.

Next, the resist solutions of Examples 18 and 21, and Reference Examples 23, 24, and 26 were filtered through a membrane filter having a pore size of 0.2 μm, and then each composition solution was spin-coated on a silicon wafer to form a resist film having a thickness of 250 nanometers. Got. After pre-baking at 110 ° C., exposure with 248 nm ultraviolet light was performed through a photomask, and then post-exposure baking was performed at 120 ° C. Thereafter, development was performed at 23 ° C. for 1 minute using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and a pattern shape free from development defects was obtained.

Claims (12)

Fluorine-containing compound represented by general formula (1) (wherein the substituent is coordinated at the 1-position, 3-position or 5-position, R ¹ represents a methyl group or a trifluoromethyl group, R ² , R ³ Is a group containing a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group, and a part thereof may contain a fluorine atom, an oxygen atom or a carbonyl bond. L represents 0 , m represents 1 and n represents 2. When R ^{1 to} R ³ are plural, R ^{1 to} R ³ may be the same or different.
The fluorine-containing compound according to claim 1, wherein R ¹ is a trifluoromethyl group. At least one of R ² and R ³ is a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or a functional group in which some or all of the hydrogen atoms contained in these functional groups are substituted with fluorine atoms, or The fluorine-containing compound according to claim 1, which is a substituent to be contained. ^{2. At} least one of R ² and R ³ includes a substituent selected from a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a fluoroacryloyl group, a trifluoromethylacryloyl group, and a nonylfluorobutylacryloyl group. 2. The fluorine-containing compound according to 2. At least one of R ² and R ³ contains an acid labile group (the acid labile group is an acid leaving group, and may partially contain an oxygen atom, a carbonyl bond, or a fluorine atom). The fluorine-containing compound according to 1 or 2. At least one of R ² and R ³ contains an acid labile group (the acid labile group is an acid leaving group, and may partially contain an oxygen atom, a carbonyl bond, or a fluorine atom). 5. The fluorine-containing compound according to 3 or 4. 5. A polymer compound obtained by polymerizing or copolymerizing the fluorine-containing compound according to claim 3 or 4 by radical polymerization or ionic polymerization. A polymer compound obtained by polymerizing or copolymerizing the fluorine-containing compound according to claim 6 by radical polymerization or ionic polymerization. An antireflection film material for ultraviolet light or visible light using the polymer compound according to claim 7 or 8. A resist material containing the fluorine-containing compound according to claim 5 or the polymer compound according to claim 8. A resist material using the fluorine-containing compound according to claim 5 or the polymer compound according to claim 8 as a dissolution inhibitor. A fluorine-containing compound represented by the general formula (4).