JP4770780B2 - Method for producing fluorine-containing polymerizable monomer - Google Patents

Description

The present invention relates to a method for producing a particular structure or hydroxy group or a protected or modified substituents containing fluorine-containing styrenic monomer or polymerization or copolymerized polymeric compound therewith, and further the polymer The present invention relates to an antireflection coating material or a resist material using a compound.

Fluorine-based compounds are in the field of advanced materials due to the characteristics of fluorine such as water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index, and low dielectric properties. It continues to be used or developed in a wide range of application fields. In particular, with regard to coating applications, active research is being conducted in fields such as antireflective coatings that apply low refractive index and transparency of visible light, and resist materials that apply transparency in the ultraviolet region (particularly in the vacuum ultraviolet wavelength region). Development is underway. The common polymer design in these application fields is to introduce as much fluorine as possible to achieve transparency at each wavelength used, while achieving adhesion to the substrate and high glass transition point (hardness). It is about to try.

However, various proposals have been made to improve the transparency at each wavelength by improving the fluorine content as a material design. However, the fluorine-containing monomer itself can be improved at the same time by improving hydrophilicity and adhesion and by improving the Tg. There are few examples of doing. Recently, in particular by fluorine-based norbornene compound of the fluorine-based styrene and hydroxy group containing a hydroxy group-containing is presented in the next generation F ₂ resist field of vacuum ultraviolet region, containing fluorine, and the polarity of the hydroxy groups The idea of coexisting has come to be seen. However, a sufficiently low refractive index required for an antireflection film is not yet obtained, and there are many factors to be improved. Therefore, the functions that these existing compounds can exhibit are not necessarily sufficient, and it has been desired to create a novel monomer or a raw material thereof that can give a more excellent polymer compound.

Therefore, the present invention has a high transparency and a low refractive index from a wide wavelength region, that is, from a vacuum ultraviolet ray to an optical communication wavelength region, by having a polar group in the same molecule while having a high fluorine content. In addition, a polymer compound using a method for producing a polymerizable monomer, which has both adhesion to a substrate, high film formability, and etching resistance, and further, an antireflection coating material and a resist using the polymer compound To provide materials.

As a result of intensive studies to solve the above-mentioned problems, the present inventors are a styrene-based monomer that is considered to be industrially easy to use, and has a high fluorine content and a specific hydroxy group. The fluorine-containing polymerizable monomer as a compound was synthesized, and the production method of the fluorine-containing polymerizable monomer of the present invention was completed.

That is, this invention provides the fluorine-containing polymerizable monomer which has a structure of General formula (2) .
(Wherein R ₃ and R ₄ are a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms, a fluorinated alkyl group, or an acid labile group (alkoxycarbonyl group or acetal group). Represents.)

Moreover, this invention is a manufacturing method of the fluorine-containing polymerizable monomer shown by General formula (2) which consists of the following three processes.
First step: benzene derivative represented by the general formula (4)

Of ethylbenzene by reacting with ethyl bromide in the presence of a Lewis acid or protonic acid catalyst to give an ethylbenzene derivative represented by the general formula (5)

Manufacturing process.
Second step: A step of producing a compound represented by the general formula (6) by reacting the ethylbenzene derivative of the general formula (5) obtained in the first step with bromine in the presence of a radical initiator to form a bromine.

Third step: A step of thermally decomposing the compound represented by the general formula (6) obtained in the second step to produce the compound represented by the general formula (2) .
(In the formulas (2) and (4) to (6), R ₃ and R ₄ are the same as the above formula (2) ).

Furthermore, the present invention is a polymer compound homopolymerized using the above polymerizable monomer, and further an antireflection material and a resist material using the polymer compound.

Hereinafter, embodiments of the present invention will be described in detail.

The specific styrenic monomer represented by the general formula (2) according to the present invention is a compound in which two fluorine-containing carbinol groups or hydroxyl groups thereof are protected with various functional groups in the molecule, In particular, when used as a resist material, it can be protected with a fluorine-containing functional group or an acid-labile functional group.

The monomer represented by the general formula (2) of the present invention has a structure in which hexafluoroacetone is bonded to the benzene ring of styrene. The bond composition ratio is not particularly limited, but is preferably a monomer having a structure in which hexafluoroacetone is bonded in order to improve low refractive index and high transparency, particularly transparency in the ultraviolet wavelength region.

Here, R ₃ and R ₄ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, a fluorinated alkyl group, a cyclic body having an aromatic ring, or an acid leaving group. And may contain an oxygen atom or a carbonyl bond). The structure is not particularly limited, but is based on the simplest and most transparent hydroxy group. Moreover, it can be modified with a substituent 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 alkyl group having 1 to 25 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, sec-butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, ethylhexyl group, norbornel group, and adamantyl group. Etc. can be exemplified. The fluorinated alkyl group is one in which a part or all of the alkyl group is substituted with a fluorine atom. In addition, those containing an oxygen atom include chain ether groups such as methoxymethyl (MOM) and methoxyethoxymethyl, cyclic ether groups such as tetrahydrofuranyl and tetrahydropyranyl, phenyl groups as aromatic cyclic rings, 4-methoxy As benzyl group and carbonyl group, acetyl group, propylcarbonyl group, pivaloyl group, hexylcarbonyl group, cyclohexylcarbonyl group, tert-butoxycarbonyl group (tert-BOC), benzoyl group, trifluoromethylcarbonyl group, Examples thereof include a fluoropropylcarbonyl group, a perfluoropivaloyl group, a perfluorohexylcarbonyl group, and a perfluorocyclohexylcarbonyl group.

Examples of the acid labile group include an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group (t-BOC) and a tert-amyloxycarbonyl group. Methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, and the like. As the acetal group, methoxymethyl group (MOM), ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxy Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, and the like. Examples include tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group. Can. 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 fluorine-containing polymerizable monomer having the structure of the general formula (2) of the present invention can be produced by a production method comprising the following three steps.
First step: benzene derivative represented by the general formula (4)

Of ethylbenzene by reacting with ethyl bromide in the presence of a Lewis acid or protonic acid catalyst to give an ethylbenzene derivative represented by the general formula (5)

Manufacturing process.
Second step: A step of producing a compound represented by the general formula (6) by reacting the ethylbenzene derivative of the general formula (3) obtained in the first step with bromine in the presence of a radical initiator to bromine.

Third step: A step of thermally decomposing the compound represented by the general formula (6) obtained in the second step to produce the compound represented by the general formula (2) .
(In formulas (2) and (4) to (6) , R ₃ and R ₄ are the same as above).

These three steps are represented in the scheme as follows (in each general formula in the scheme, R _{3 to} R ₄ in the formula are the same as those in the general formula (2) ).

Hereinafter, each step will be described in detail.
The first step is an ethylation step of the benzene derivative represented by the general formula (4), and is represented by the general formula (5) by reacting with an ethylating agent in the presence of a Lewis acid or a proton acid catalyst. This is a process for producing an ethylbenzene derivative.

As the ethylating agent, ethyl bromide, ethyl chloride, ethyl iodide, ethyl fluoride and the like can be used. However, when ethyl bromide is used, it is preferably employed because an appropriate reaction rate can be obtained. The amount of the ethylating agent used may be at least 1 mol per mol of the raw material benzene derivative (general formula (4)), and the reaction rate and the desired ethylated compound (general formula (5)). From the viewpoint of the yield, the amount is preferably 1.1 times to 20 times mole, more preferably 1.5 times to 10 times mole.

The acid catalyst used is aluminum chloride, aluminum bromide, gallium chloride, gallium bromide, ferric chloride (FeCl ₃ ), zinc chloride, antimony chloride, titanium tetrachloride, tin tetrachloride, boron trifluoride. Ti (OCH ₃ ) 4, Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OCH (CH ₃ ) ₂ ) ₄ , Zn (CH ₃ COO) ₂ .2H ₂ O, etc. A Lewis acid catalyst, a proton acid catalyst such as hydrogen fluoride, sulfuric acid, phosphoric acid, hydrogen chloride, or the like can be used. Among these, when a Lewis acid catalyst is used, the desired product can be obtained with a good yield, and therefore it is preferably employed. More preferably, aluminum chloride is used which allows the reaction to proceed quickly and is easily available.

As the amount of the acid catalyst, an amount of 0.1 mol% to 10 times mol can be used with respect to 1 mol of the benzene derivative (general formula (4)) as a raw material. Is too slow and the yield of the target ethylated product (general formula (5)) is very small, and it is not realistic. Can not. More preferably, 1 to 5 moles of acid catalyst is used with respect to the substrate to achieve an appropriate reaction rate and good yield.

Although reaction temperature is not specifically limited, Usually, reaction is possible in the range of room temperature to 100 degreeC. Since the reaction rate varies depending on the above-mentioned catalyst type, catalyst amount, reaction temperature, and the like, the reaction time is appropriately changed according to this. In practice, it is possible to carry out the reaction while sequentially analyzing the reaction solution during the reaction, and to react until the raw materials are consumed. A solvent for the reaction is not particularly required, but it is possible to add a solvent for the purpose of controlling the reaction temperature and taking advantage of handling due to a decrease in the viscosity of the reaction solution. The treatment after the reaction is not particularly limited, but it is possible to add the reaction solution to water or ice water and then extract the target product by extraction with an organic solvent or to extract the target product by flash distillation.

The second step is bromination of the ethylbenzene derivative (general formula (5)) produced in the first step, but bromine represented by general formula (6) is reacted with bromine in the presence of a radical initiator. This is a process for producing a chemical compound. Moreover, radical bromination reaction by light is also possible.

A radical initiator and bromine are added to an ethylbenzene derivative, stirred, and heated to decompose the radical initiator to generate radicals, and the α-position of the ethylated product is selectively brominated by radical chain reaction. . Although it does not specifically limit as a radical initiator, An azo initiator, a peroxide, etc. can be used. Among these, azobisisobutyronitrile (hereinafter referred to as AIBN) is preferable for controlling the reaction. Although the amount of the radical generator is not particularly limited, it is carried out in the range of 0.001 mol% to 50 mol% with respect to the substrate, and the range of 0.1 mol% to 10 mol% is appropriate from the viewpoint of the reaction rate. Are preferably employed.

The reaction temperature may be appropriately selected according to the decomposition temperature of the initiator to be used, but is usually in the range of 0 ° C to 50 ° C. The reaction time varies depending on the type of initiator used and the reaction temperature, but the reaction may be terminated when the raw materials are consumed, and the reaction time is usually 1 to 24 hours.

In the reaction of this step, the reaction can be carried out using a solvent. When a solvent is used, it is not particularly limited unless it reacts with a bromine radical, but methylene chloride, carbon tetrachloride, chloroform and the like can be used.

The radical bromination reaction by light can be basically similar to the method using a radical initiator. An ultraviolet lamp such as a high-pressure mercury lamp is preferably used as the light source, and bromination with bromine radicals generated by irradiating the reaction solution with ultraviolet rays directly or from outside the Pyrex (registered trademark) glass reactor is possible. The reaction temperature in this case is not particularly limited, but a range of 0 ° C. to 50 ° C. is preferably employed from the viewpoint of controllability of the reaction.

The third step is a step for producing a styrene derivative represented by the general formula (2) by debromination of the brominated compound (general formula (6)) obtained in the second step by thermal decomposition.

The reaction apparatus may be either a batch type or a flow type, and a flow type heating apparatus is preferably employed from the viewpoint of the yield of the product obtained and productivity. Since the debromination reaction by thermal decomposition occurs at 100 ° C. or higher, the reaction can be carried out by an apparatus capable of heating the brominated product to 100 ° C. and taking out the produced compound. In the case of the batch type, the same apparatus as the vacuum distillation apparatus can be used, and the brominated product (general formula (6)) is placed in a distillation apparatus whose system is 100 mmHg or less and heated to 100 ° C. or higher. The styrene derivative ( general formula (2) ) can be removed by distillation.

In the case of a flow-type heating device, brominated product (general formula (6)) is introduced little by little from one of the tubular reaction tubes heated to about 500 ° C., and styrene produced from the other reaction tube. It is also possible to obtain the derivative ( general formula (2) ) by introducing it into a cold trap and collecting it. In this case, by keeping the system at a reduced pressure of 100 mmHg or less, the brominated product can be easily introduced and the reaction rate can be increased. The flow reaction temperature is preferably 300 ° C. to 800 ° C., and more preferably a styrene derivative ( general formula (2) ) is obtained at a temperature of 400 ° C. to 600 ° C. with good yield. The method for introducing the brominated product into the flow reactor is not particularly limited, but if it is a vertical tubular furnace, a dripping method or a method of introducing it after once vaporizing in a vaporizing chamber is possible. In this case, the latter method can be adopted.

Next, the polymer compound according to the present invention will be described. The polymer compound of the present invention is a homopolymer of a polymerizable monomer represented by the general formulas (2) and (3) or a copolymer with another kind of copolymerizable monomer.

Next, a copolymer having a repeating unit represented by the general formula (7) of the present invention will be described.

(In the formula , at least one of R ₅ and R ₆ contains an acid labile group. The acid labile group is an acid leaving group and may contain oxygen, a carbonyl bond, or fluorine. Any integer, a: b represents a copolymerization ratio.) At least one of R ₅ and R ₆ is an acid labile group, and the acid labile group is an acid leaving group , Oxygen, carbonyl bond, and fluorine may be contained. Examples of the acid labile group include an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group (t-BOC) and a tert-amyloxycarbonyl group. Methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, and the like. As the acetal group, methoxymethyl group (MOM), ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxy Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, and the like. Examples include tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group. Can. 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, camphoroyl 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, a functional group 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 an acid-anxiety group is positive photosensitivity by the acid-anxiety group and dissolution in an alkaline aqueous solution after exposure to high-energy rays such as far-infrared rays, excimer lasers of 300 nm or less, and X-rays or electron beams. In order to further impart characteristics such as etching resistance and a high glass transition point, those having a fluorine group in the functional group further impart characteristics such as etching resistance and high glass transition point. It is possible to use properly.

Next, a copolymer having a repeating unit represented by the general formula (8) of the present invention will be described.

(In the formula , at least one of R ₇ and R ₈ contains a functional group other than an acid labile group. The functional group is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or fluorinated. And may include an aromatic ring, oxygen, a carbonyl bond, etc. a and b are arbitrary integers, and a: b represents a copolymerization ratio.)
At least one of R ₇ and R ₈ contains a functional group other than the above acid labile group, and the functional group is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or a fluorinated group. The alkyl group may contain an aromatic ring, oxygen, carbonyl bond, etc., and its structure is not particularly limited, but is preferably a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a sec-butyl group, a cyclo group. Examples thereof include a propyl group, a cyclopentyl group, a cyclohexyl group, an ethylhexyl group, a norbornel group, an adamantyl group and the like. The fluorinated alkyl group is a group in which a part or all of the alkyl group is substituted with a fluorine atom. For example, a trifluoromethyl group, a 2,2,2-trifluoromethylethyl group, 1,1, Examples include 1,3,3,3-hexafluoroisopropyl group.

The purpose of using a functional group other than an acid-anxiety group is to reduce hydrophilicity and improve solubility in an organic solvent. Those having fluorine in the functional group provide transparency, and those having a cyclic structure further impart characteristics such as etching resistance and a high glass transition point, and can be used for each application field of the present invention.

Next, if the monomer copolymerizable with the polymerizable monomer represented by the general formula (2) or the formula (3) of the present invention is specifically exemplified, at least an acrylic ester, a methacrylic ester, Copolymerization with one or more monomers selected from fluorine-containing acrylic ester, fluorine-containing methacrylate ester, styrene compound, fluorine-containing styrene compound, vinyl ether, fluorine-containing vinyl ether, and fluorine-containing olefin is preferable. .

The acrylic ester or methacrylic ester that can be used in the present invention can be used with no 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 amide, acrylonitrile, methacrylonitrile, alkoxysilane-containing vinyl silane, acrylic acid or methacrylic acid ester, t-butyl acrylate or methacrylate, 3-oxocyclohexyl acrylate or methacrylate, adamantyl acrylate or methacrylate, alkyladamantyl acrylate or methacrylate, Cyclohexyl acrylate or methacrylate , 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, maleic acid, fumaric acid, maleic anhydride and the like can be copolymerized as the above acrylate compounds containing α cyano group or similar compounds.

The fluorine-containing acrylic ester or fluorine-containing methacrylate used in the present invention is an acrylic ester or methacrylic ester having a fluorine atom group at the α-position or ester site of the acrylic, A cyano group may be introduced. 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. Furthermore, when α-trifluoromethylacrylic acid t-butyl ester (hereinafter referred to as TFMA-B) is used, the resulting polymer has an acid decomposability and can be applied to a resist material.

On the other hand, the monomer containing fluorine at the ester site is a perfluoroalkyl group as the ester site, a fluoroalkyl group that is a fluoroalkyl group, or a unit that coexists with a cyclic structure and fluorine at the ester site, Acrylic acid ester or methacrylic acid ester having a unit having a fluorinated benzene ring, a fluorinated cyclopentane ring, a fluorinated cyclohexane ring, a fluorinated cycloheptane ring or the like whose cyclic structure is substituted with, for example, fluorine or a trifluoromethyl group It is. 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- Examples include n-octyl methacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate, and the like.

Furthermore, as the styrene compound and fluorine-containing styrene compound that can be used in the present invention, a compound having one or more hexafluorocarbinol groups bonded thereto can be used in addition to styrene, fluorinated styrene, hydroxystyrene and the like. Further, styrene or hydroxystyrene substituted with hydrogen by a trifluoromethyl group, the above-mentioned styrene or fluorine-containing styrene compound in which a halogen, an alkyl group, or a fluorine-containing alkyl group is bonded to the α-position can be used.

In addition, vinyl ether, fluorine-containing vinyl ether, allyl ether, vinyl ester and the like are generally considered to have poor polymerization reactivity with the monomer of general formula (2) or formula (3) according to the present invention. It can be introduced by a copolymerization ratio, for example, an alkyl vinyl ether which may contain a hydroxy group such as a methyl group, an ethyl group, a hydroxyethyl group, a hydroxybutyl group, and a part or all of the hydrogen thereof May be substituted with fluorine. Further, cyclohexyl vinyl ether, cyclic vinyl ether having hydrogen or carbonyl bond in its cyclic structure, or a monomer in which part or all of hydrogen of the cyclic vinyl ether is substituted with fluorine can be used. Allyl ether, vinyl ester, and vinyl silane can be used without particular limitation as long as they are known compounds.

On the other hand, the other component of the copolymer is not particularly limited as long as it has copolymerization reactivity with the polymerizable monomer represented by the general formula (2) or (3). It can also be used. That is, olefins, fluorine-containing olefins, norbornene compounds, fluorine-containing norbornene compounds, and the like can also be used.

Examples of the olefin include ethylene and propylene, and examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and hexafluoroisobutene.

The norbornene compound and the fluorine-containing norbornene compound are norbornene monomers having a mononuclear structure or a plurality of nuclear structures, and these are copolymerized with the monomer of the general formula (2) or the formula (3) without any particular limitation. Is possible. In this case, allyl alcohol, fluorine-containing allyl alcohol, homoallyl alcohol, fluorine-containing homoallyl alcohol is acrylic acid, α-fluoroacrylic acid, methacrylic acid, all acrylic esters or methacrylic esters described in this specification, fluorine-containing A norbornene compound produced by the Diels Alder addition reaction of an unsaturated compound such as an acrylic ester or a methacrylic ester with cyclopentadiene or cyclohexadiene. 3- (5-bicyclo [2.2.1] hepten-2-yl ) -1,1,1-trifluoro-2- (trifluoromethyl) -2-propanol and the like.

The above copolymerizable compounds described here may be used alone or in combination of two or more.

According to the present invention, the copolymer composition ratio of the monomer of the general formula (2) or the formula (3) 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.

Next, a copolymer having a repeating unit represented by the general formula (9) of the present invention will be described.

( Wherein R ₃ or R ₄ is the same as in formula (2). R ₉ is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or a fluorinated alkyl group, It may contain a ring, oxygen, carbonyl bond, etc. a and b are arbitrary integers, and a: b represents a copolymerization ratio.) R ₉ is a straight chain, branched or A cyclic alkyl group or a fluorinated alkyl group which may contain an aromatic ring, oxygen, carbonyl bond, etc., and its structure is not particularly limited, but preferred R ₉ is exemplified by methyl group, ethyl group alkyl group such group, trifluoroethyl group or C _n F _{2n + 1} fluoroalkyl group having, hexafluoroisopropyl group, cyclopentyl, cyclohexyl, norbornel group, adamantyl group, butyl lactone group, further These hydroxy groups, those obtained by binding hexafluorocarbinol group is preferably employed. That is, specific examples of the vinyl ether of the copolymer component include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, octyl vinyl ether. And dodecyl vinyl ether. In addition, as perfluoroalkyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluoroisopropyl vinyl ether, perfluorobutyl vinyl ether, perfluoroisobutyl vinyl ether, perfluoro-sec-butyl vinyl ether, perfluoro- Examples thereof include t-butyl vinyl ether, perfluoropentyl vinyl ether, perfluorohexyl vinyl ether, perfluorooctyl vinyl ether, and perfluorododecyl vinyl ether. Also, vinyl ethers having a hydroxyl group may be used. Examples thereof include hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, Examples include diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and 1,4-cyclohexanedimethanol vinyl ether.

The purpose of using vinyl ether as a copolymerization component is to reduce aromatic rings and carbonyl bonds, and to obtain high transparency from vacuum ultraviolet rays to the visible range, and by using fluorine-containing vinyl ethers and vinyl ethers having hydroxyl groups. Another object of the present invention is to provide a novel fluorine-containing copolymer having further improved transparency, adhesion to a substrate, and high film-forming properties.

Next, a copolymer having a repeating unit represented by the general formula (10) of the present invention will be described.

(In the formula, R ₃ or R ₄ is the same as in the general formula (2). R ₁₀ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ₁₁ is a linear, branched or A cyclic alkyl group or a cyclic product having an aromatic ring and may contain a fluorine, oxygen, carbonyl bond, etc. R ₁₂ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms. Or a fluorinated alkyl group which may contain an aromatic ring, oxygen, a carbonyl bond, etc., or may be an acid labile group, a and b are arbitrary integers, and a: b is a copolymerization ratio. (N represents an integer of 1 to 3)
R ₁₀ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ₁₀ is preferably a trifluoromethyl group in order to increase the low refractive index and high transparency, particularly transparency in the ultraviolet wavelength region.

R ₁₁ represents an alkyl group that may be linear or branched, or an alkylene group that has a cyclic structure. For example, the structure can be used without limitation, such as a cyclic structure containing a linear or branched alkylene group such as methylene, ethylene, isopropylene, t-butylene, cyclobutene, cyclohexane, norbornene, adamantane group or the like.

R ₁₂ is a hydrogen atom, a hydrocarbon group which may contain a branch, a fluorine-containing alkyl group, a cyclic body having an aromatic or alicyclic ring, which may contain a bond such as oxygen or carbonyl, or an acid labile The group may be used. The structure is not particularly limited, but is based on the simplest and most transparent hydroxy group. In addition, depending on the purpose of use, methyl group, ethyl group, isopropyl group, n-propyl group, sec-butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, ethylhexyl group, norbornel group, adamantyl group, benzyl group An alkyl group having 1 to 25 carbon atoms which may have a ring, a fluorine-containing alkyl group partially or wholly substituted with a fluorine atom, and an oxygen atom as methoxymethyl (MOM) A chain ether group such as methoxyethoxymethyl, a cyclic ether group such as tetrahydrofuranyl and tetrahydropyranyl, a cyclic group having an aromatic ring, a phenyl group, a 4-methoxybenzyl group, and a carbonyl group, Propylcarbonyl group, pivaloyl group, hexylcarbonyl group, cyclohexyl Examples include carbonyl group, tert-butoxycarbonyl group (tert-BOC), benzoyl group, trifluoromethylcarbonyl group, perfluoropropylcarbonyl group, perfluoropivaloyl group, perfluorohexylcarbonyl group, perfluorocyclohexylcarbonyl group, etc. it can.

Examples of the acid labile group include an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group (t-BOC) and a tert-amyloxycarbonyl group. Methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, and the like. As the acetal group, methoxymethyl group (MOM), ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxy Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, and the like. Examples include tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group. Can. 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, camphoroyl 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. Further, 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 introducing an ester bonded with hexafluoroacetone as a copolymerization component is to improve transparency. The introduction of an acid labile group is positive photosensitivity, far infrared, excimer laser with a wavelength of 300 nm or less, X-ray, etc. This is to impart characteristics such as solubility in an alkaline aqueous solution after exposure to high energy rays or electron beams, and positive photosensitivity by a photoacid generator, and can be used for each application field of the present invention. .

Next, a copolymer having a repeating unit represented by the general formula (11) of the present invention will be described.

(In the formula, R ₃ or R ₄ is the same as that in the general formula (2) and R ₁₂ is the same as in the general formula (10). A and b are arbitrary integers, and a: b represents a copolymerization ratio.)
The purpose of introducing an ester having a norbornene skeleton is to impart characteristics such as a high glass transition point, cross-linking reactivity for solder heat resistance, and etching resistance.

The copolymer having the repeating unit represented by the general formula (12) of the present invention will be described.

(In the formula , R ₅ and R ₆ are the same as those in the general formula (7) and R ₉ is the same as in the general formula (9). R ₁₃ is a hydrogen atom, or a linear, branched or cyclic alkyl having 1 to 25 carbon atoms. Or a fluorinated alkyl group, which may contain an aromatic ring, oxygen, carbonyl bond, etc. a, b and c are arbitrary integers, and a: b: c represents a copolymerization ratio. )
R ₁₃ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or a fluorinated alkyl group, and may contain an aromatic ring, oxygen, carbonyl bond, etc. Although it does not restrict | limit in particular, It is necessary to be functional groups other than an acid labile group.

The purpose of introducing the fluorine-containing methacrylic acid ester is to obtain high transparency at wavelengths from vacuum ultraviolet rays to the visible range.

A copolymer having the repeating unit represented by the general formula (13) of the present invention will be described.

(Wherein, R _5, R ₆ are the general formula (7), .a R ₁₃ are the same .R ₁₄ is a general formula (12) represents a hydrogen atom or a methyl group,, c is an arbitrary integer, a: c represents a copolymerization ratio.)
The purpose of introducing the acrylic ester or methacrylic ester is to easily obtain the desired copolymer because the copolymer composition thereof is easy to prepare.

The copolymer having the repeating unit represented by the general formula (14) of the present invention will be described.

(In the formula , R ₅ and R ₆ are the same as those in the general formula (7) and R ₉ are the same as those in the general formula (9). A and b are arbitrary integers, and a: b represents a copolymerization ratio.) R ₉ is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or a fluorinated alkyl group, which may contain an aromatic ring, oxygen, carbonyl bond, etc., and its structure is not particularly limited. However, preferred examples of R ₉ include an alkyl group such as a methyl group, an ethyl group, a trifluoroethyl group, a fluoroalkyl group having C _n F _{2n + 1} , a hexafluoroisopropyl group, a cyclopentyl, a cyclohexyl, a norbornel group, An adamantyl group, a butyl lactone group, and those obtained by binding a hydroxy group or a hexafluorocarbinol group to these groups are preferably employed. That is, examples of the allyl ether of the copolymer component include methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, benzyl allyl ether, and cyclohexyl allyl ether. As the allyl ether having a hydroxyl group, for example, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, alkylene glycol monoallyl ether such as hydroxybutyl allyl ether, or allyl alcohol, And allyl ethers of polyhydric alcohols such as glyceryl monoallyl ether. Moreover, as an allyl ether having an epoxy group or an allyl ether having a β-ketoester group, allyl acetoacetate is exemplified. Examples of the fluorinated allyl ether include trifluoromethyl allyl ether, 2,2,2-trifluoroethyl allyl ether, 2,2,3,3-tetrafluoropropyl allyl ether, and the like. Further, homoallyl ether and fluorine-containing homoallyl ether can also be used as copolymerization components. For example, 3-butenyl methyl ether, 3-butenyl methyl ether, 3-butenyl propyl ether and 1,1-trifluoromethyl are exemplified. Examples include -3-butenyl methyl ether.

The purpose of using allyl ether as a copolymerization component is to reduce aromatic rings and carbonyl bonds, and to obtain high transparency at wavelengths from vacuum ultraviolet to the visible range, and also has fluorine-containing allyl ether and hydroxyl groups. By using allyl ether, an object is to provide a novel fluorine-containing copolymer having further improved transparency, adhesion to a substrate, high film-forming properties, and the like.

The polymer compound polymerization method according to the present invention is not particularly limited as long as it is a generally used method, but radical polymerization, ionic polymerization, etc. are preferable. Etc. can also be used. 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, Benzoyl peroxide is preferred.

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 isopropyl alcohol and ethylene glycol monomethyl ether. It is also possible to use various solvents such as water, ether, cyclic ether, chlorofluorocarbon, and aromatic. 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 ° C, particularly preferably 30 to 140 ° C.

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.

And as a number average molecular weight of the high molecular compound concerning this invention obtained, the range of 1,000-100,000 is preferable normally, Preferably the range of 3,000-50,000 is suitable.

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. Therefore, 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 dimethyl alcohol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and the like Derivatives, 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 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 adhesion to the substrate by polymerizing the monomer of the general formula (2) according to the present invention and the monomer of the alcohol side chain in which R ₃ is hydrogen. 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 according to the present invention is most preferably a positive resist composition containing, as a basic composition, a polymer compound whose solubility in an alkaline aqueous solution is changed by the action of an acid and an acid generator. In particular, it is suitable as a positive resist for F ₂ laser in the vacuum ultraviolet region typified by 248 nm KrF or 193 nm ArF excimer laser or 157 nm corresponding to the recent miniaturization of semiconductors. That is, the polymer compound whose solubility in an alkaline aqueous solution is changed by the action of an acid is such that R ₃ and R _{4 in} the general formula (2) are acid labile groups, but its structure is particularly limited. It is usable without. Examples of general acid labile groups include a tert-butyl group, a tert-butoxycarbonyl group, a methoxymethyl ether group and an ethoxymethyl ether group in at least part of R ₃ and R ₄ in the general formula (2) of the present invention. It is a functional group having a chain ether group, a lactone group structure having a cyclic structure, and the like, and an ester site thereof being cleaved by an acid. A polymer compound using such a monomer 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 irradiating the 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 optional 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.

"Example 1"
Production of Styrene Derivative (3,5-D-HFA-ST) represented by Formula (3) Three steps shown below for the styrene derivative represented by Formula (3) (hereinafter referred to as 3,5-D-HFA-ST) Was synthesized according to

First step: Ethylation reflux condenser tube of benzene derivative, dropping funnel, three-necked flask equipped with stirrer, 100 g of benzene derivative represented by formula (15) (hereinafter referred to as 1,3-Bis-HFAB) and anhydrous chloride 83 g of aluminum was added and heated in an oil bath at 50 ° C. In the dropping funnel, 133 g of ethyl bromide was added and dropped over 5 hours. After completion of the reaction, the reaction solution was poured into 500 ml of ice water. The black oily substance precipitated in the lower layer was taken out and washed with water. This was distilled under reduced pressure to obtain 30 g of an ethylbenzene derivative represented by the formula (16).
Boiling point: 80-84 ° C./2 mmHg,
NMR: ¹ H-NMR (TMS, CDCl ₃ ): 1.28 (t, 7.2 Hz, 3H), 2.75 (q, 7.2 Hz, 2H), 7.66 (s, 2H), 7. 92 (S, 1H)
Second Step: Bromination of Ethylbenzene Derivative Next, in a three-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, 25 g of ethylbenzene derivative (formula (16)) obtained in the first step, 10 g of bromine, AIBN0 0.1 g was added and heated in a 60 ° C. oil bath for 7 hours. After the reaction, the reaction solution was transferred to a separating funnel and washed with 5% aqueous sodium thiosulfate solution. This was distilled under reduced pressure to obtain 22 g of a brominated product (formula (17)).
Boiling point: 110-115 ° C / 2mmHg
¹ H-NMR (TMS, CDCl ₃ ): 2.07 (d, 6.8 Hz, 3H), 5.23 (q, 6.8 Hz, 1H), 7.92 (s, 2H), 8.00 ( S, 1H)
Third step: A quartz tube with an inner diameter of 20 mm filled with a broached pyrolytic ceramic Raschig ring was placed in a vertical electric tubular furnace. A dropping funnel was connected above the quartz tube and a trap cooled by a refrigerant mixed with dry ice and methanol was connected below. Furthermore, the trap outlet was connected to a vacuum pump. In the dropping funnel, 10 g of the brominated product (formula (17)) obtained in the second step was put, the pressure inside the apparatus was reduced to about 5 mmHg, and the quartz tube part was heated to about 500 ° C. The brominated product (formula (17)) is dropped from the dropping funnel at a rate of about 0.5 g / min, and the target styrene derivative (3,5-D-HFA-ST: formula (3)) produced by the thermal decomposition reaction is added. ) Was collected in a 7 g trap. ¹ H-NMR (TMS, CDCl ₃ ): 3.56 (s, 2H), 5.40 (d, 11.2 Hz, 1H), 5.85 (d, 17.6 Hz, 1H), 6.76 Hz ( dd, 17.6 Hz, 11.2 Hz, 1 H), 7.84 (s, 2 H), 7.96 (S, 1 H) GC-MS (EI method): m / e 436 (M ⁺ ), 367 (M ⁺ -CF _3).

“Examples 2 to 12” Using the 3,5-D-HFA-ST produced in Example 1 or a derivative thereof, homopolymerization or copolymerization was carried out to produce a polymer compound. The results are shown in Table 1.

"Example 2"
(Homopolymerization of 3,5-D-HFA-ST)
A 3-neck flask equipped with a reflux condenser and a stirrer was charged with 10 g of 3,5-D-HFA-ST, 0.2 g of AIBN as a polymerization initiator, and 40 g of n-butyl acetate 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 1 L of n-hexane 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.

"Example 3"
(Copolymerization of 3,5-D-HFA-ST and 3,5-D-HFA-ST-BOC)
Polymerization was carried out in the same manner as in Example 2 using 10 g of 3,5-D-HFA-ST and 8.0 g of 3,5-D-HFA-ST-BOC (see the following figure) as monomers. The results are shown in Table 1.

Example 4
(Copolymerization of 3,5-D-HFA-ST with 3,5-D-HFA-ST-TFET and MA-MAD)
Example 2 using 10 g of 3,5-D-HFA-ST as a monomer, 7.5 g of 3,5-D-HFA-TFET-ST (see below), and 6.5 g of MA-MAD (see below) Polymerization was carried out in the same manner as described above. The results are shown in Table 1.

"Example 5"
(Copolymerization of 3,5-D-HFA-ST and 4-HFA-ST)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST and 6.2 g of 4-HFA-ST (see the figure below) as monomers. The results are shown in Table 1.

"Example 6"
(Copolymerization of 3,5-D-HFA-ST and MA-HFIP)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST and 5.4 g of MA-HFIP (see the figure below) as monomers. The results are shown in Table 1.

"Example 7"
(Copolymerization of 3,5-D-HFA-ST and TFMA-B)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST and 5.0 g of TFMA-B (see the figure below) as monomers. The results are shown in Table 1.

"Example 8"
(Copolymerization of 3,5-D-HFA-ST and TFMA-MAD)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST as a monomer and 6.6 g of TFMA-MAD (see the figure below). The results are shown in Table 1.

"Example 9"
(Copolymerization of 3,5-D-HFA-ST-TFET and TFMA-B)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST-TFET and 9.0 g of TFMA-B as monomers. The results are shown in Table 1.

"Example 10"
(Copolymerization of 3,5-D-HFA-ST and TFMA-BTHB-NB-BOC) As a monomer, 10 g of 3,5-D-HFA-ST and TFMA-BTHB-NB-BOC (see the figure below) are used. Polymerization was carried out in the same manner as in Example 2 using 0 g. The results are shown in Table 1.

"Example 11"
(Copolymerization of 3,5-D-HFA-ST-BOC and TFMA-BTHB-NB)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST-BOC and 5.0 g of TFMA-BTHB-NB (see the figure below) as monomers. The results are shown in Table 1.

"Example 12"
(Copolymerization of 3,5-D-HFA-ST-BOC, TFMA-H-3,5-D-HFA-PH, H-HQ-VE)
As a monomer, 10 g of 3,5-D-HFA-ST-BOC, 8.5 g of TFMA-H-3,5-D-HFA-PH (see below), 3.0 g of H-HQ-VE (see below) The polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1.

"Example 13"
(Copolymerization of 3,5-D-HFA-ST-BOC, TFMA-B and TFE-VE)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST-BOC and 5.0 g of TFMA-B and TFE-VE (see the figure below) as monomers. The results are shown in Table 1.

"Example 14"
(Copolymerization of 3,5-D-HFA-ST, AB and HFIB)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST as a monomer, 6.0 g of AB (see the following figure), and 5.0 g of HFIB (see the following figure). The results are shown in Table 1.

"Example 15"
(Copolymerization of 3,5-D-HFA-ST-BOC, A-TFE, HFIB)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST-BOC, 9.0 g of A-TFE (see the following figure), and 5.0 g of HFIB as monomers. The results are shown in Table 1.

"Example 16"
(Copolymerization of 3,5-D-HFA-ST, A-CN and HFIB)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST as a monomer, 7.2 g of A-CN (see the following figure), and 4.8 g of HFIB. The results are shown in Table 1.

"Example 17"
(Copolymerization of 3,5-D-HFA-ST-MOM and A-OFCPE)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-D-HFA-ST-MOM (see the lower figure) and 10 g of A-OFCPE (see the lower figure) as monomers. The results are shown in Table 1.

"Example 18"
(Copolymerization of 3,5-HFA-ST-MOM, HB-AE, A-OFCPE)
Polymerization was carried out in the same manner as in Example 2, using 10 g of 3,5-HFA-ST-MOM, 5.0 g of HB-AE (see the figure below), and 10 g of A-OFCPE as monomers. The results are shown in Table 1.

"Example 19"
100 parts by weight (hereinafter referred to as “parts”) of the polymer compound obtained in Example 4 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.

"Example 20"
The polymer compounds of Examples 5 and 6 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 with a film thickness of 100 nanometers was measured at a wavelength of 157 nm, they were 71% and 69%, respectively, for Examples 5 and 6, and high transparency was exhibited at wavelengths in the vacuum ultraviolet region. did.

Next, after filtering the entire resist solution through a membrane filter having a pore diameter of 0.2 μm, each composition solution was spin-coated on a silicon wafer to obtain a resist film having a thickness of 250 nanometers. After pre-baking at 110 ° C., using a KrF excimer laser microscanner, exposure was performed at 248 nm, followed by post-exposure baking at 120 ° C. Thereafter, development was performed at 23 ° C. for 1 minute using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. As a result, a high-resolution pattern shape was obtained, and almost no development defects were observed.

Claims (2)

Fluorine-containing polymerizable monomer represented by the general formula (2) comprising the following three steps

Manufacturing method.
(Wherein R ₃ and R ₄ are a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms, a fluorinated alkyl group, an alkoxycarbonyl group or an acetal group)
First step: benzene derivative represented by the general formula (4)

Of ethylbenzene by reacting with ethyl bromide in the presence of a Lewis acid or protonic acid catalyst to give an ethylbenzene derivative represented by the general formula (5)

Manufacturing process.
Second step: A step of producing a compound represented by the general formula (6) by reacting the ethylbenzene derivative of the general formula (5) obtained in the first step with bromine in the presence of a radical initiator to form a bromine.

Third step: A step of thermally decomposing the compound represented by the general formula (6) obtained in the second step to produce the compound represented by the general formula (2).
(In the formulas (4) to (6) , the meanings of R ₃ and R ₄ are the same as those in the formula (2) . ) The production method according to claim 1, wherein the compound represented by the general formula (4) is 1,3-bis (hexafluoro-2-hydroxy-2-propyl) benzene.