JP5652286B2 - Fluorine-containing compound and method for producing the fluorine-containing polymerizable monomer - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing compound and a method for producing the fluorine-containing polymerizable monomer. The fluorine-containing polymerizable monomer produced by the production method of the present invention is useful as a semiconductor resist material.

  Fluorine-containing compounds have functional characteristics such as water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index or low dielectric property. Used in a wide range of technical fields.

  For example, in the field of semiconductors, a fluorine-containing resist material is used as a resist material having excellent photosensitivity in the ultraviolet region when patterning using a photolithography method when forming a photomask. In response to the demand for the development of fluorine-containing resist materials, the sensitivity is improved.

  At present, lithography using an argon fluoride (hereinafter abbreviated as ArF) excimer laser that oscillates ultraviolet light with a wavelength of 193 nm has been put into practical use, and in the future, an extremely short wavelength of 13.5 nm will be used. Researches on fluorine-containing resist materials are being promoted with the aim of practical use of Extreme Ultra Violet (hereinafter abbreviated as EUV) lithography using ultraviolet light.

  In response to the increasingly sophisticated and diversifying demand for fluorine-containing resist materials, the fluorine-containing monomer used in fluorine-containing resist materials has excellent functions such as transparency, substrate adhesion, and etching resistance. It is desired. Today, various fluorine-containing monomers have been researched and developed for resist materials. Among them, fluorine-containing monomers having a ring structure such as a cyclohexane ring, a norbornene ring, and an adamantane ring are frequently used for resist applications.

  It has been reported that a fluorine-containing resist material obtained from a fluorine-containing monomer having a cyclohexane ring structure has high dry etching resistance during patterning in a semiconductor manufacturing process.

  In addition, a highly polar substituent such as a hydroxyl group greatly contributes to the adhesion of the resist film to the substrate, and the transparency of the resist film resin can be improved by introducing fluorine atoms. In addition, the fluorinated alcohol has a higher acidity than ordinary alcohol, and can impart solubility to an alkaline developer to the exposed portion of the resist film in photolithography. For example, Patent Document 1 discloses a method for producing 3,5-bis (2-hydroxyhexafluoroisopropyl) cyclohexyl trifluoromethyl acrylate and a resist polymer using the same.

  When a cyclohexane ring monomer having a polymerizable group, such as 3,5-bis (2-hydroxyhexafluoroisopropyl) cyclohexyl trifluoromethyl acrylate, is used as a resist material, the site where the highly polar group is introduced is more than the polymerizable group. It is desirable to introduce it selectively in the fourth position (para position) that is far away. Compared with the case where it is introduced at the 2-position (ortho-position) or the 3-position (meta-position), when a highly polar group is introduced at the para-position, the highly polar group protrudes outward due to the three-dimensional structure when polymerized. Therefore, the adhesion is improved when a resist film is formed. In addition, introduction into the para position increases the symmetry of the monomer structure, and heat resistance is expected by improving the glass transition point of the polymer. Furthermore, in the case of an acrylic polymerizable group, since the monomer molecule has an oxygen atom, it is possible to suppress intramolecular interaction with this oxygen atom by introducing a highly polar group at the para position. Thus, there is an effect of improving sensitivity to ultraviolet light.

As a method of introducing a polar group at the para-position, Non-Patent Document 1 uses BF ₃ as an acid catalyst, and the Friedel-Crafts reaction in which a hydroxylfluoroalkyl group is electrophilically substituted to an aromatic ring. A method of introducing a fluorine-containing ketone with selectivity is described.

JP 2004-83900 A

J. et al. Org. Chem. 1965, 30 (4), 1003-1005.

  As a method for synthesizing a polymerizable monomer in which a polar group is introduced into phenol, by replacing the hydrogen of the aromatic ring of the phenol with a fluorine-containing ketone by a Friedel-Crafts reaction, and bonding a hydroxyl fluoroalkyl group, a highly polar group is added to the phenol. It is possible to synthesize a phenol having a hydroxylfluoroalkyl group by introducing a fluorine-containing ketone. Subsequently, this is hydrogen-reduced, an aromatic ring is made into an alicyclic ring, and a polymerizable group is introduced into the alicyclic ring to obtain a fluorinated polymerizable monomer.

  In the obtained fluorine-containing polymerizable monomer, when a fluorine-containing ketone, which is a highly polar group, is introduced at the para position, the resist film has good adhesion to the substrate when formed into a resist film, high sensitivity to ultraviolet rays, and high sensitivity. Used as resist monomer to give material.

  However, when a fluorine-containing ketone is introduced into phenol, if an acid is used as a catalyst to perform a substitution reaction on the aromatic ring of the fluorine-containing ketone, the ortho- or para-position of the aromatic ring with respect to the hydroxyl group which is an electron-donating group. Thus, there was a problem that the mixture of isomers into which the fluorine-containing ketone was introduced was lacking, the selectivity of the introduction position was lacking, and the fluorine-containing compound into which the fluorine-containing ketone was introduced at the desired para-position could not be obtained.

For example, as a result of the inventors' further study on a method of introducing a fluorinated ketone into phenol by a Friedel-Crafts reaction using BF ₃ as an acid catalyst described in Non-Patent Document 1, the ortho-position and para-position of phenol The ratio of introduction of fluorine-containing ketone into 6 is 4, which is useful as a raw material for resist materials, etc., and fluorine-containing ketone is introduced at the para position of phenol, that is, a hydroxyl fluoroalkyl group is bonded to the para position of phenol. There was a problem that a fluorine-containing compound could not be obtained with high selectivity (see the comparative example in the present specification).

  In the present invention, a compound containing an OH group bonded to an aromatic ring such as phenol is reacted with a fluorinated ketone, and the fluorinated ketone is selectively introduced at the para position of the aromatic ring based on the OH group. An object of the present invention is to provide a production method for obtaining a fluorine-containing compound having a hydroxylfluoroalkyl group bonded to the position and obtaining a fluorine-containing polymerizable monomer useful as a resist material from the fluorine-containing compound.

  In order to solve the above problems, the inventor has intensively studied an acid catalyst in the Friedel-Crafts reaction, and by using hydrofluoric acid or fluorine-containing sulfonic acid, particularly fluorine-containing sulfonic acid as the acid catalyst, it has high selectivity. It has been found that a fluorine-containing ketone can be introduced at the para position of phenol. The reason why the para-position adduct as the target product was obtained with high selectivity is considered to be due to the high acidity of hydrofluoric acid or fluorine-containing sulfonic acid, which is an acid catalyst.

  That is, this invention is the manufacturing method of the fluorine-containing compound of the following [invention 1]-[invention 4], and its fluorine-containing polymerizable monomer.

[Invention 1]
General formula (1):

(In the formula (1), each R ¹ independently represents a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group, or an aryl group, A part may be substituted with a fluorine atom or an oxygen atom, X is an integer of 0 to 2, and Y is an integer of 0 to 8.)
A hydroxyaryl compound represented by:
General formula (2):

(In Formula (2), R ² and R ³ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, a branched or cyclic group having 3 to 20 carbon atoms, and a carbon atom. May be substituted with an oxygen atom, a part or all of a hydrogen atom may be substituted with a fluorine atom, or R ² and R ³ may be bonded to form a cyclic compound. Furthermore, it has at least one fluorine atom in either R ² or R ^3. )
A fluorine-containing ketone represented by the general formula (3), which is reacted in the presence of a fluorine-containing acid catalyst:

(In formula (3), R ^{1 to} R ³ , X and Y are the same as above.)
The manufacturing method of the fluorine-containing compound A represented by these.

[Invention 2]
The method of Invention 1, wherein the fluorinated acid catalyst is hydrofluoric acid or fluorinated sulfonic acid.

[Invention 3]
The method of Invention 2, wherein the fluorinated sulfonic acid is trifluoromethanesulfonic acid.

[Invention 4]
General formula (3) (obtained in Inventions 1 to 3):

(In Formula (3), each R ¹ is independently a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group, or an aryl group, A part thereof may be substituted with a fluorine atom or an oxygen atom, and R ² and R ³ are each independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or A cyclic alkyl group, part of the carbon atoms may be replaced by oxygen atoms, part or all of the hydrogen atoms may be replaced by fluorine atoms, and R ² and R ³ may be bonded to each other. Further, it may form a cyclic compound, and further has at least one fluorine atom in either R ² or R ^3. X represents an integer of 0 to 2, and Y represents an integer of 0 to 8. .)
The fluorine-containing compound A represented by general formula (4) is reduced by hydrogen in the presence of a ruthenium catalyst:

(In formula (4), R ^{1 to} R ³ , X and Y are the same as above.)
A step of synthesizing a fluorine-containing compound B represented by:
The synthesized fluorinated product B is represented by the general formula (5):

(In formula (5), R ⁴ is a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). A is F, Cl, or a general formula (6):

(In the formula (6), R ⁴ represents a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). Represents.)
Is reacted with an acrylic acid derivative compound represented by the general formula (7):

(In formula (7), R ^{1 to} R ⁴ , X and Y are the same as above.)
A step of synthesizing a fluorine-containing polymerizable monomer represented by:
The manufacturing method of the fluorine-containing polymerizable monomer containing this.

  According to the present invention, a compound having an OH group bonded to an aromatic ring, such as phenol or polyhydric phenol (polycyclic aromatic phenol), is reacted with a fluorine-containing ketone, and the compound in which the OH group is bonded to the aromatic ring is Provided are a fluorine-containing compound in which a fluorine-containing ketone is introduced with selectivity and a method for producing the fluorine-containing polymerizable monomer.

  Specifically, in the method of the present invention, an intensive study of an acid catalyst in the Friedel-Crafts reaction was conducted, and by using a fluorine-containing sulfonic acid, particularly trifluoromethanesulfonic acid, as an acid catalyst, phenol paraffin was obtained with high selectivity. It was possible to selectively introduce a fluorine-containing ketone at the position, that is, selectively bind a hydroxyl fluoroalkyl group to the para position of phenol.

  When the resist film is formed by the method of the present invention, a fluorine-containing ketone which is a highly polar group at the para position is used as a resist monomer which has good adhesion to the substrate, has high sensitivity to ultraviolet rays, and gives a sensitive resist material. The introduced fluorine-containing polymerizable monomer was obtained with good selectivity and good yield.

1. The manufacturing method of the fluorine-containing compound A This invention is general formula (1):

(In the formula (1), each R ¹ independently represents a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group, or an aryl group, A part thereof may be substituted with a fluorine atom or an oxygen atom. X is an integer of 0 to 2, Y is an integer of 0 to 8), and a general formula (2):

(In Formula (2), R ² and R ³ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, a branched or cyclic group having 3 to 20 carbon atoms, and a carbon atom. May be substituted with an oxygen atom, a part or all of a hydrogen atom may be substituted with a fluorine atom, or R ² and R ³ may be bonded to form a cyclic compound. Furthermore, a fluorine-containing ketone represented by the formula (3), wherein R ² or R ³ has at least one fluorine atom is reacted in the presence of a fluorine-containing acid catalyst. :

(In Formula (3), R < ¹ > -R < ³ >, X and Y are the same as the above.) It is a manufacturing method of the fluorine-containing compound A represented.

  That is, in the method for producing the fluorine-containing compound A of the present invention, the fluorine-containing ketone represented by the general formula (2) is reacted with the hydroxyaryl compound represented by the general formula (1), and the general formula (3) When a fluorine-containing compound A represented by the formula (1) is produced, a fluorine-containing ketone is introduced into the para-position of the aromatic ring with high selectivity by using a fluorine-based acid catalyst as the acid catalyst. The reaction to be bound proceeds. Examples of the fluorine-based acid catalyst include hydrofluoric acid, but fluorine-containing sulfonic acids are preferable, and trifluoromethanesulfonic acid is particularly preferable because of easy handling.

  If the reaction mechanism of the manufacturing method of the fluorine-containing compound A of this invention is guessed, it will be thought that the big electronegativity which a fluorine has in the reaction mechanism is concerned. It is considered that the acidity of the acid catalyst has been dramatically improved by the introduction of fluorine, and the para-adduct has been selectively obtained due to the strong acidity.

R ^{1 to} R ³ in the general formulas (1) to (3) are each independently a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, or an alkenyl group. Or it is an aryl group, Comprising: A fluorine atom and an oxygen atom may be included in the structure. Precisely, oxygen atoms in the structure may be replaced by fluorine atoms, that is, substituted, and carbon atoms may be replaced by oxygen atoms, that is, substituted. The structure of R ^{1 to} R ³ is not particularly limited within the above range, but the structure can be selected depending on the purpose of use.

Examples of the linear or branched or cyclic alkyl group having 1 to 25 carbon atoms that can be used for R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Examples include 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 or adamantyl group. , An alkenyl group includes a vinyl group, an allyl group, a butenyl group, a pentenyl group or an ethynyl group, and an aryl group includes a phenyl group, a benzyl group or a 4-methoxybenzyl group, and a hydrogen atom of the above functional group A part or all of may be substituted with a fluorine atom.

  Examples of those containing an oxygen atom include an alkoxycarbonyl group, an acetal group, and an acyl group. Specific examples are shown below.

  That is, 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.

  The acetal group includes methoxymethyl, methoxyethoxymethyl, ethoxyethyl, butoxyethyl, cyclohexyloxyethyl, benzyloxyethyl, phenethyloxyethyl, ethoxypropyl, benzyloxypropyl, phenethyloxy. Examples thereof include a propyl group, an ethoxybutyl group, an ethoxyisobutyl group or a chain ether thereof, a tetrahydrofuranyl group, a tetrahydropyranyl group or a cyclic ether thereof.

  As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group 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, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, thenoyl, nicotinoyl or isoni Chinoiru group, and the like.

  Furthermore, in the method of the present invention, those in which part or all of the hydrogen atoms of the alkoxycarbonyl group, acetal group or acyl group are substituted with fluorine atoms can be used.

In the method of the present invention, a fluorine-containing ketone having at least one fluorine atom is used for either R ² or R ³ .

  Examples of the fluorine-containing acid catalyst used for the reaction include fluorine-containing sulfonic acids represented by trifluoromethanesulfonic acid, fluorine-containing carboxylic acids represented by trifluoroacetic acid, and hydrofluoric acid. Among these, fluorine-containing sulfonic acids have a high effect of bonding a hydroxylfluoroalkyl group to the aromatic ring of the hydroxyaryl compound represented by the general formula (1) in the reaction, and among them, the effect of trifluoromethanesulfonic acid is high. It is suitably used in the method for producing the fluorine-containing compound A of the present invention.

  The use amount of these fluorine-containing sulfonic acids is not particularly limited, and a use amount of 0.01 mol or more and 0.5 mol or less is sufficient with respect to 1 mol of the hydroxyaryl compound represented by the general formula (1). Effects can be obtained. If it is less than 0.01 mol, the above-mentioned effects are not obtained, and it is not necessary to use more than 0.5 mol. From the viewpoint of preventing excessive use and suppressing reaction rate and side reaction, in the method for producing a fluorine-containing compound A of the present invention, 0.03 mol or more, 0, It is preferable to use it for 1 mol or less.

  In the method for producing the fluorine-containing compound A of the present invention, in the reaction of bonding a hydroxylfluoroalkyl group to the aromatic ring of the hydroxyaryl compound represented by the general formula (1), the reaction proceeds even without solvent, It is preferable to use an organic solvent in view of workability, ease of control of reaction conditions such as reaction temperature, and the like.

  The organic solvent used in the above reaction does not react with the hydroxyaryl compound represented by the general formula (1), the fluorinated ketone represented by the general formula (2), and the fluorinated sulfonic acid used as a catalyst, and is a precipitate. Any solvent can be used without particular limitation as long as it is a solvent that is stably dissolved without being generated, etc., but the solubility of these compounds and the reaction rate in the production method of the fluorine-containing compound A represented by the general formula (3) of the present invention From the viewpoint, hydrocarbons represented by benzene and toluene, and alkyl halides represented by chloroform and dichloroethane are preferably used.

  In the method for producing the fluorine-containing compound A of the present invention, these organic solvents may be used alone or in combination of two or more. In addition, the amount of these organic solvents used is not particularly limited, but from the viewpoint of kettle yield, solubility, and reaction rate, 0.1 liter or more with respect to 1 mol of the hydroxyaryl compound represented by the general formula (1), It is preferable to use so that it may become 5 liters or less. If it is less than 0.1 liter, there is a concern that it is not completely dissolved, and it is not necessary to make it more than 5 liter, and there is a concern that the reaction rate becomes slow. Particularly, it is preferably 0.1 liter or more and 3 liter or less.

  The reaction conditions in the production method of the fluorine-containing compound A of the present invention are adjusted while confirming the progress of the reaction by, for example, gas chromatography according to the raw material used, that is, the type of reaction reagent, the amount or concentration in the reaction, etc. This may be set as appropriate. However, with regard to the reaction temperature and reaction time, from the viewpoint of performing the reaction at a high reaction rate while suppressing side reactions, the reaction is carried out at 0 ° C. or more and 150 ° C. or less, for 0.5 hours or more and 24 hours or less. Further, in the method for producing a fluorine-containing compound A of the present invention, a fluorine-containing ketone is introduced at the para-position of the hydroxyaryl compound represented by the general formula (1), and the reaction is an exothermic reaction. In order to achieve this, it is preferable to perform stirring.

  In this way, by bonding the hydroxyl fluoroalkyl group to the aromatic ring of the hydroxyaryl compound represented by the general formula (1), it corresponds to the structure of the hydroxyaryl compound represented by the general formula (1) which is the raw material used. The fluorine-containing compound A represented by the general formula (3) can be obtained.

  Specifically, in the method for producing the fluorine-containing compound A of the present invention, phenol is used as the hydroxyaryl compound represented by the general formula (1), and hexafluoroacetone is used as the fluorine-containing ketone represented by the general formula (2). When trifluoromethanesulfonic acid is used for the reaction, 4- (2-hydroxyhexafluoroisopropyl) phenol, which is the fluorine-containing compound A represented by the general formula (3), is produced.

  Further, the recovery from the reaction solution of the fluorine compound A represented by the general formula (3) obtained by the method for producing the fluorine-containing compound A of the present invention is carried out by washing the reaction solution with a basic aqueous solution to remove the fluorine-containing acid. After the removal, it is washed with water or the like, and the solvent is distilled off from the organic layer under reduced pressure to separate the target fluorinated compound A.

  According to the method for producing a fluorinated compound A of the present invention, even if the product is separated by such a simple separation method, the purity of the fluorinated compound A as the target product is high, and it is particularly purified depending on the application. However, if it is desired to obtain a higher purity fluorine-containing compound A, purification can be carried out by column chromatography, distillation, recrystallization, etc. depending on the properties of the resulting fluorine-containing compound A. Preferably it is done.

If the typical example of the manufacturing method of the fluorine-containing compound A of this invention is shown, the phenol contained in the hydroxyaryl compound represented by General formula (1), and the fluorine-containing ketone represented by General formula (2) 4- (2-hydroxyhexafluoroisopropyl) phenol contained in the fluorine-containing compound A represented by the general formula (3) by reacting hexafluoroacetone contained in the fluorinated acid catalyst with trifluoromethanesulfonic acid as a fluorine-containing acid catalyst. Is a method using the following reaction.

  The method of the present invention can be applied not only to phenol but also to the introduction of a fluorinated ketone with good selectivity at the para position of a compound having an OH group bonded to the α position of α-naphthol or anthracene. In particular, it is also effective when introducing a fluorinated ketone into naphthol from the viewpoint of ease of reaction and handling during synthesis.

2. Method for Producing Fluorinated Polymerizable Monomer Next, the fluorinated polymerizable monomer represented by the general formula (7), which is useful as a resist material for semiconductors, the fluorinated compound A represented by the general formula (3) The method for producing the fluorine-containing polymerizable monomer of the present invention, which is led to the acrylic acid ester (monomer), will be described.

That is, the production method of the fluorine-containing polymerizable monomer of the present invention is obtained by the general formula (3) (obtained by the production method of the fluorine-containing compound A of Inventions 1 to 3):

(In Formula (3), each R ¹ is independently a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group, or an aryl group, A part thereof may be substituted with a fluorine atom or an oxygen atom, and R ² and R ³ are each independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or A cyclic alkyl group, part of the carbon atoms may be replaced by oxygen atoms, part or all of the hydrogen atoms may be replaced by fluorine atoms, and R ² and R ³ may be bonded to each other. Further, it may form a cyclic compound, and further has at least one fluorine atom in either R ² or R ^3. X represents an integer of 0 to 2, and Y represents an integer of 0 to 8. )) In the presence of a ruthenium catalyst. By performing reduction with hydrogen, general formula (4):

(In formula (4), R ^{1 to} R ³ , X and Y are the same as above.)
A step of synthesizing a fluorine-containing compound B represented by:
The synthesized fluorine-containing compound B is represented by the general formula (5):

(In formula (5), R ⁴ is a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). A is F, Cl, or a general formula (6):

(In the formula (6), R ⁴ represents a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). Represents.)
Is reacted with an acrylic acid derivative compound represented by the general formula (7):

(In formula (7), R ^{1 to} R ⁴ , X and Y are the same as above.)
A process for synthesizing a fluorine-containing polymerizable monomer represented by the formula:

If a typical example of a method for producing a fluorine-containing polymerizable monomer is shown, 4- (2-hydroxyhexafluoroisopropyl) phenol contained in the fluorine-containing compound A represented by the general formula (3) is reduced with hydrogen. A step of synthesizing 4- (2-hydroxyhexafluoroisopropyl) cyclohexanol contained in the fluorine-containing compound B represented by the general formula (4) by the reaction (hydrogenation reaction to an aromatic ring), and 4- ( 4- (2-hydroxyhexafluoroisopropyl) contained in the fluorine-containing polymerizable monomer represented by the general formula (7) by performing a methacryloyl esterification reaction on 2-hydroxyhexafluoroisopropyl) cyclohexanol It is the following method including a step of obtaining cyclohexyl methacrylate (esterification reaction).

  Hereinafter, the process of performing the “hydrogenation reaction to the aromatic ring” and the process of performing the “esterification reaction” will be described.

2.1 Hydrogenation reaction to the aromatic ring The fluorine-containing compound A represented by the general formula (3) is subjected to a hydrogen reduction reaction under a ruthenium catalyst, and hydrogen is added to the aromatic ring to form an alicyclic ring. The fluorine-containing compound B represented by (4) can be synthesized. When the fluorine-containing compound B is synthesized, the fluorine-containing compound A represented by the general formula (3) obtained by the method described in the inventions 1 to 3 can be suitably used as a raw material compound.

In this case, the ruthenium catalyst used is a ruthenium supported on a support selected from activated carbon, alumina, silica or clay, a ruthenium salt selected from RuCl ₃ , RuBr ₃ , or Ru (NO ₃ ) ₃ , A ruthenium complex selected from Ru (CO) ₅ , Ru (NO) ₅ , K ₄ [Ru (CN) ₆ ], or Ru (phen) ₃ Cl ₃ , or ruthenium oxide can be used. . In the chemical formula, phen is an abbreviation for phenanthroline.

  Among these ruthenium catalysts, in the step of synthesizing the fluorine-containing compound B, a solid-phase catalyst in which ruthenium is supported on a carrier exhibits high catalytic activity, is highly stable, and is easy to handle. It is preferable to use it.

The catalyst can be prepared by dissolving ruthenium in a solution, impregnating the solution with a support, and then reducing the catalyst with H ₂ gas while heating. In particular, a ruthenium carbon catalyst (hereinafter abbreviated as Ru / C), a ruthenium-alumina catalyst, and a ruthenium-silica catalyst are commercially available. For example, Ru / C is a 5 mass% Ru carbon powder manufactured by Yasuda Pharmaceutical Co., Ltd. (Water-containing product) A type, product number: AC4504 and the like are easily available and have high catalytic activity. In particular, when a water-containing product, for example, a product containing 50% by mass of water in the total weight of the catalyst is used, handling in the hydrogen reduction reaction is easy.

  Further, the ruthenium content in the solid content of the ruthenium catalyst is not particularly limited, but preferably 2% by mass or more and 10% by mass or less. For example, a 5% by mass catalyst is easily available and has high stability. Since it is easy to handle in the hydrogen reduction reaction, it is preferably used in the method of the present invention.

  In the step of synthesizing the fluorine-containing compound B, a hydrogen reduction reaction can also be performed in the presence of a plurality of these ruthenium catalysts. However, as long as there is no special effect when combined, it is more practical to use it alone.

  The amount of the ruthenium catalyst used in the hydrogen reduction reaction is usually 0.0002 mol or more and 0.04 mol or less in terms of Ru atom per mol of the fluorine-containing compound A represented by the general formula (3). When the amount is less than 0.0002 mol, the reaction rate decreases and it is not necessary to use more than 0.04 mol. Preferably, it is 0.0004 mol or more and 0.02 mol or less. Furthermore, it is preferably 0.001 mol or more and 0.01 mol or less.

  In the step of synthesizing the fluorine-containing compound B, hydrogen used for the reduction of the fluorine-containing compound A represented by the general formula (3) can be supplied to the reaction system at normal pressure (0.1 MPa) or more and 5 MPa or less. It is preferable to supply hydrogen under pressure because the reaction rate of the hydrogen reduction reaction is increased and the reaction operation is simple. Specifically, 0.2 MPa or more and 4 MPa or less are preferable. Furthermore, 0.5 MPa or more and 3 MPa or less are preferable. Although the hydrogen reduction reaction can be carried out even at a pressure lower than normal pressure, the reaction may be slow and complicated in terms of equipment, which is not practical.

  The ruthenium catalyst used in the hydrogen reduction reaction has high stability and can be used even in air. However, in order to maintain higher catalytic activity, the reaction is performed after replacing the inside of the reactive group with hydrogen gas and excluding air. Is particularly effective without oxygen inhibition of the reaction.

  In addition, when a solvent is used in the hydrogen reduction reaction, the hydrogen reduction reaction proceeds particularly smoothly. Therefore, it is preferable to use a solvent. There are no particular limitations on the type of solvent that can be used in the hydrogen reduction reaction, but aromatic compounds selected from the group consisting of benzene, toluene, xylene, and mesitylene, diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran. An ether solvent selected from the group consisting of: methanol, ethanol, propanol, 2-propanol, trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol Alcohol solvents are preferred, and these may be used alone or in combination with a plurality of solvents.

  The amount of the solvent used in the hydrogen reduction reaction is 0.005 g or more and 100 g or less with respect to 1 g of the fluorine-containing compound A represented by the general formula (3). If it is less than 0.005 g, it will not be used as a solvent, and it is not necessary to add more than 100 g. Preferably, they are 0.01 g or more and 20 g or less, More preferably, they are 0.1 g or more and 10 g or less.

  The reaction temperature for carrying out the hydrogen reduction reaction is usually 0 ° C. or higher and 150 ° C. or lower. If it is less than 0 ° C., the reaction rate is very slow and it is not a practical production method. Further, even when heated to a temperature exceeding 150 ° C., there is no significant change in the reaction rate, and heating is not necessary. Preferably, they are 30 degreeC or more and 120 degrees C or less, More preferably, they are 50 degreeC or more and 90 degrees C or less.

  The reactor that performs the hydrogen reduction reaction is a reaction in which tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, perfluoroalkoxy fluorine (hereinafter abbreviated as PFA) resin, glass or the like is lined on the inner surface of the reactor. A container, a glass container, or a stainless steel container may be used.

The time required for the hydrogen reduction reaction depends on the reaction temperature, the type of catalyst, or the amount of catalyst. It is preferable to observe the state of consumption of H ₂ as needed from the pressure in the reaction group, etc., and terminate the reaction when the consumption of H ₂ is virtually completed.

  In the step of synthesizing the fluorine-containing compound B, the fluorine-containing compound A represented by the general formula (3) is reduced with hydrogen in the presence of a ruthenium catalyst, whereby the fluorine-containing compound represented by the general formula (4). Compound B is obtained.

  Thereafter, the fluorine-containing polymerizable compound represented by the general formula (7) is obtained by reacting the fluorine-containing compound B represented by the general formula (4) with the acrylic acid derivative represented by the general formula (5). Can be obtained.

  In the method of the present invention, a reduction reaction with hydrogen is carried out in the presence of a ruthenium catalyst, that is, an aromatic site which is a target when hydrogenating an aromatic ring to obtain an alicyclic ring is not only phenol but also α-naphthol or Examples include compounds in which an OH group is bonded to the α-position of anthracene.

  However, the reaction of hydrogenation to form an alicyclic ring is easy for phenol, and 4- (2-hydroxyhexafluoroisopropyl) cyclohexyl methacrylate obtained by using the method of the present invention is an organic solvent for use as a resist solution. It can be suitably used as a photoresist material because of its good solubility and developer solubility after exposure in photolithography.

2.2 Esterification reaction The fluorine-containing compound B represented by the general formula (4) is reacted with the acrylic acid derivative represented by the general formula (5) to react with the fluorine-containing compound represented by the general formula (7). It is possible to obtain a polymerizable monomer by a general means of esterification.

  Below, the preferable operation method of the said esterification reaction, reaction conditions, etc. are described.

2.2.1 Esterification reaction when the acrylic acid derivative is an α-substituted acrylic acid halide When the acrylic acid derivative represented by the general formula (5) is an α-substituted acrylic acid halide, the esterification reaction is performed. Is preferably carried out in the presence of a base. In this case, the base includes at least one base selected from the group consisting of trimethylamine, triethylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. Are preferably used. Of these bases, pyridine and 2,6-dimethylpyridine are particularly preferably used in the esterification reaction.

  The amount of the base used in the esterification reaction is 0.2 mol or more and 2.0 mol or less with respect to 1 mol of the fluorine-containing compound B represented by the general formula (4). When the amount of the base is less than 0.2 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4), both the selectivity of the reaction and the yield of the target product are reduced. If it exceeds 0 mol, it will only increase the amount of base not involved in the reaction. Preferably, it is 0.5 mol or more and 1.5 mol or less, More preferably, it is 0.9 mol or more and 1.2 mol or less.

  The amount of the α-substituted acrylic acid halide as the acrylic acid derivative represented by the general formula (5) used in this reaction is 0 with respect to 1 mol of the fluorine-containing compound B represented by the general formula (4). It is not less than 2 mol and not more than 2.0 mol. When the amount of the α-substituted acrylate halide is less than 0.2 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4), the selectivity and yield of the target product in the esterification reaction Both decrease, and when it exceeds 2.0 mol, α-substituted acrylate halides that do not participate in the reaction increase. Preferably, it is 0.5 mol or more and 1.5 mol or less, More preferably, it is 0.9 mol or more and 1.2 mol or less.

  In the esterification reaction, hydrofluoric acid salt, hydrochloride salt, that is, the basic hydrohalide salt, is precipitated as a by-product, so use a solvent for the purpose of improving the operability of the esterification reaction. Is preferred. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds typified by benzene, toluene, xylene or mesitylene, ether solvents typified by diethyl ether, methyl-t-butyl ether, diisopropyl ether or tetrahydrofuran, It is preferable to use a halogen-based solvent typified by methylene chloride, chloroform or carbon tetrachloride. These may be used alone or in combination with a plurality of solvents.

  The amount of the solvent used for the esterification reaction is 0.5 g or more and 100 g or less with respect to 1 g of the fluorine-containing compound B represented by the general formula (4). When the amount of the solvent is less than 0.5 g with respect to 1 g of the fluorine-containing compound B represented by the general formula (4), the slurry concentration of the base hydrochloride precipitated during the reaction is too high, so that the operability is lowered. It is not necessary to use more than 100 g. Preferably, it is 1.0 g or more and 20 g or less, More preferably, it is 2.0 g or more and 10 g or less.

  The reaction temperature for carrying out the esterification reaction is −50 ° C. or higher and 200 ° C. or lower. If it is less than -50 degreeC, reaction rate will be very slow and it will not become a practical manufacturing method. Moreover, when it exceeds 200 degreeC, the ester compound represented by General formula (7) of the raw material (alpha) -substituted acrylic acid halide or a product superposes | polymerizes. Preferably, it is -20 degreeC or more and 150 degrees C or less, More preferably, it is 0 degreeC or more and 120 degrees C or less.

  In the esterification reaction, a polymerization inhibitor may be used for the purpose of preventing polymerization of the raw material α-substituted acrylate halide or the product ester compound.

  The polymerization inhibitor used is 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, phenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl At least one compound selected from 2-picrylhydrazyl or 1,1-diphenyl-2-picrylhydrazine, or commercially available products, trade names Nonflex F, Nonflex H, Nonflex DCD, Nonflex MBP Alternatively, Ozonon 35 (manufactured by Seiko Chemical Co., Ltd.), trade name Q-1300 or Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) can be mentioned and can be used in the method of the present invention.

  The amount of the polymerization inhibitor used in the present invention is 0.1 mol or less with respect to 1 mol of the fluorine-containing compound B represented by the general formula (4) of the raw material. If the amount of the polymerization inhibitor is less than 0.0001 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4), there is no effect, and even if it exceeds 0.1 mol, the ability to prevent polymerization There is no significant difference and it is not necessary to add more than 0.1 mole. Preferably, it is 0.0001 mol or more and 0.05 mol or less, More preferably, it is 0.0001 mol or more and 0.01 mol or less.

  The reactor for the esterification reaction should be a tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside the reactor, a glass or stainless steel reactor Is preferred.

2.2.2 Esterification reaction when the acrylic acid derivative represented by the general formula (5) is an α-substituted acrylic anhydride Next, the acrylic acid derivative represented by the general formula (5) is α- Esterification in the method for producing a fluorine-containing polymerizable monomer of the present invention when it is a substituted acrylic anhydride, that is, when A in the general formula (5) is a group represented by the general formula (6) The reaction will be described.

  The amount of the α-substituted acrylic anhydride used for the esterification reaction in the method for producing a fluorine-containing polymerizable monomer of the present invention is 1 mol of the fluorine-containing compound B represented by the general formula (4). Usually, it is 0.5 mol or more and 5.0 mol or less. When the amount of the α-substituted acrylic anhydride is less than 0.5 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4), the conversion rate and yield of the target product in the esterification reaction are reduced. Both rates are not sufficient, and if it exceeds 5.0 moles, only α-substituted acrylic anhydrides not involved in the reaction increase, which is not practical. Preferably, it is 0.7 mol or more and 3.0 mol or less, More preferably, it is 1.0 mol or more and 2.0 mol or less.

  In the method for producing a fluorine-containing polymerizable monomer of the present invention, an additive for promoting the esterification reaction can be added. As the additive used, at least one acid selected from methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid or trifluoromethanesulfonic acid, or Lewis acid is preferable. Used for.

  The amount of the additive used for the esterification reaction is 0.01 mol or more and 2.0 mol or less with respect to 1 mol of the fluorine-containing compound B represented by the general formula (4) of the substrate. If the amount of the additive is less than 0.01 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4) of the substrate, both the conversion rate of the esterification reaction and the yield of the target product are lowered. If the amount exceeds 2.0 mol, the amount of additive not involved in the reaction only increases, which is not practical. Preferably, it is 0.02 mol or more and 1.8 mol or less, More preferably, it is 0.05 mol or more and 1.5 mol or less.

  The reaction temperature for carrying out the esterification reaction is usually 80 ° C. or higher and 200 ° C. or lower when no additive is added. If it is less than 80 ° C., the reaction rate is extremely slow, and if it exceeds 200 ° C., the raw material α-substituted acrylic anhydride or the ester compound represented by the general formula (7) may be polymerized. Preferably, they are 100 degreeC or more and 180 degrees C or less, More preferably, they are 120 or more and 160 degrees C or less.

  On the other hand, when adding an additive, it is 0 degreeC or more and 80 degrees C or less. If it is less than 0 ° C., the reaction rate is too slow to be a practical production method. Moreover, when it exceeds 80 degreeC, a side reaction will advance easily and the selectivity of the target ester compound may fall, and it is unpreferable. Preferably, they are 10 degreeC or more and 70 degrees C or less, More preferably, they are 20 degreeC or more and 60 degrees C or less.

  In the esterification reaction in the method for producing a fluorine-containing polymerizable monomer of the present invention, the addition of an additive sufficiently reacts even at a low temperature, and the selectivity is improved. That is, in the method for producing a fluorine-containing polymerizable monomer of the present invention, an additive selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid or trifluoromethanesulfonic acid is reacted. It is particularly preferable to carry out the esterification reaction in the temperature range of 20 ° C. or higher and 60 ° C. or lower by coexisting in the system.

  The ester reaction proceeds even without solvent, but it is desirable to use a solvent in consideration of the uniformity of the reaction and the operability of the treatment after the reaction. In the esterification reaction, there is no particular limitation on the type of solvent that can be used, but it is represented by aromatic compounds represented by benzene, toluene, xylene or mesitylene, diethyl ether, methyl-t-butyl ether, diisopropyl ether or tetrahydrofuran. It is preferable to use a solvent selected from ether solvents, methylene chloride, chloroform, or halogen solvents represented by carbon tetrachloride. These may be used alone or in combination with a plurality of solvents. .

  The amount of the solvent used for the esterification reaction is usually 0.1 g or more and 100 g or less with respect to 1 g of the fluorine-containing compound B represented by the general formula (4). When the amount of the solvent is less than 0.1 g with respect to 1 g of the compound represented by the general formula (4), the use of a solvent such as uniformity of reaction and ease of operability of treatment after the reaction can be achieved. The benefits are not enough. There is no need to use more than 100 g. Preferably they are 0.5 g or more and 50 g or less, More preferably, they are 1.0 g or more and 20 or less.

  In the esterification reaction, a polymerization inhibitor may be allowed to exist for the purpose of preventing the polymerization of the α-substituted acrylic anhydride or the fluorine-containing ester compound which is the target product). Use an inhibitor.

  The polymerization inhibitor used is 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, phenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl At least one compound selected from 2-picrylhydrazyl or 1,1-diphenyl-2-picrylhydrazine, or commercially available products, trade names Nonflex F, Nonflex H, Nonflex DCD, Nonflex MBP Alternatively, Ozonon 35 (manufactured by Seiko Chemical Co., Ltd.), trade name Q-1300 or Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) can be mentioned and can be used in the method of the present invention.

  The amount of the polymerization inhibitor used in the present invention is 0.1 mol or less with respect to 1 mol of the fluorine-containing compound B represented by the general formula (4) of the raw material. If the amount of the polymerization inhibitor is less than 0.0001 mol relative to 1 mol of the fluorine-containing compound B represented by the general formula (4), there is no effect, and even if it exceeds 0.1 mol, the ability to prevent polymerization There is no significant difference and it is not necessary to add more than 0.1 mole. Preferably, it is 0.0001 mol or more and 0.05 mol or less, More preferably, it is 0.0001 mol or more and 0.01 mol or less.

  The reactor used for the esterification reaction is a reaction made of tetrafluoroethylene resin, chloro-trifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined on the inner surface of the reactor, glass, or stainless steel It is preferable to use a vessel.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited by these Examples.

Example 1
In Example 1, phenol and hexafluoroacetone were reacted using trifluoromethanesulfonic acid as a catalyst to obtain 4- (2-hydroxyhexafluoroisopropyl) phenol, which was subjected to hydrogen reduction reaction to give 4- (2-hydroxy Hexafluoroisopropyl) cyclohexanol, and finally methacryloyl esterification reaction using methacrylic anhydride to give 4- (2-hydroxyhexafluoroisopropyl) cyclohexyl methacrylate.

[Friedel Crafts reaction]
Phenol, 500 g, toluene, 500 g, hexafluoroacetone, 974 g, and trifluoromethanesulfonic acid, 40 g were charged into a 3.4 L stainless steel pressure vessel as outlined. While maintaining the internal temperature of the pressure vessel at 70 ° C., the mixture was stirred for 8 hours to perform a Friedel-Crafts reaction. After completion of the Friedel-Crafts reaction, 1000 g of diisopropyl ether was added, and the progress of the reaction was confirmed by gas chromatography. As a result, 4-(+ ( 2-Hydroxyhexafluoroisopropyl) phenol was obtained in a ratio of ortho adduct: para adduct = 1: 9. This was washed with sodium bicarbonate water and brine, and concentrated with an evaporator. The obtained solid was recrystallized in a mixed solvent of toluene, 1320 g and heptane, 1320 g to obtain 4-79- (4-hydroxyhexafluoroisopropyl) phenol, 979 g in a yield of 71% by mass.

¹ H-NMR (solvent: heavy acetone, reference material: TMS); δ (ppm) 6.96 (2H, dt, J = 9.2, 2.6 Hz), 7.48 (1H, bs), 7. 61 (2H, d, J = 9.2 Hz), 8.67 (1H, bs)
¹⁹ F-NMR (solvent: heavy acetone, reference material: C6F6); δ (ppm) 88.75 (6F, s)
[Hydrogen reduction reaction]
4- (2-Hydroxyhexafluoroisopropyl) phenol, 300 g, 5% ruthenium-carbon catalyst (water-containing product having a solid content of 50% by mass), diisopropyl ether, 750 g, in a 2 L stainless steel pressure vessel It was heated to 80 ° C. Hydrogen was injected into the container at a pressure of 2 MPa, and then stirred for 2 hours to perform a hydrogen reduction reaction. After the hydrogen reduction reaction, the catalyst is removed by filtering the reaction product, and then the filtrate after filtration is concentrated with an evaporator, and the resulting solid is recrystallized with a mixed solvent of toluene, 390 g, heptane, and 300 g. As a result, 299 g of 4- (2-hydroxyhexafluoroisopropyl) cyclohexanol was obtained in a yield of 97% by mass.

(Cis body):
¹ H-NMR (solvent: heavy acetone, reference material: TMS); δ (ppm) 1.18-2.18 (9H, m), 3.55 (1H, d, J = 2.4 Hz), 3. 99 (1H, d, J = 2.4 Hz), 6.43 (1H, s)
¹⁹ F-NMR (solvent: heavy acetone, reference material: C6F6); δ (ppm) 91.60 (6F, s)
(Trans body):
¹ H-NMR (solvent: heavy acetone, reference material: TMS); δ (ppm) 1.18-2.18 (9H, m), 3.52 (1H, m), 3.77 (1H, d, J = 4.4 Hz), 6.52 (1H, s)
¹⁹ F-NMR (solvent: heavy acetone, reference material: C6F6); δ (ppm) 91.47 (6F, s)
[Methacryloyl esterification reaction]
A 4-liter flask with a capacity of 2 L equipped with a stirrer, thermometer, reflux condenser, 300 g of 4- (2-hydroxyhexafluoroisopropyl) cyclohexanol, toluene, 600 g, methanesulfonic acid, 11 g, and methacrylic acid 182 g of anhydride was added and stirring was continued at 70 ° C. for 4 hours to carry out methacryloyl esterification reaction. After completion of the methacryloyl esterification reaction, 300 g of toluene was further added to the reaction product, followed by washing with sodium bicarbonate water and ion exchange water in this order. The washed organic phase was concentrated and recrystallized from 300 g of heptane to obtain 502 g of 4- (2-hydroxyhexafluoroisopropyl) cyclohexyl methacrylate in a yield of 92% by mass.

(Cis body):
¹ H-NMR (solvent: heavy acetone, reference material: TMS); δ (ppm) 1.45-2.20 (9H, m), 1.94 (3H, s), 5.06 (1H, d, J = 2.4 Hz), 5.63 (1H, s), 6.09 (1H, s), 6.57 (1H, s)
¹⁹ F-NMR (solvent: heavy acetone, reference material: C6F6); δ (ppm) 91.52 (6F, s)
(Trans body):
¹ H-NMR (solvent: heavy acetone, reference material: TMS); δ (ppm) 1.20-2.20 (9H, m), 1.90 (3H, s), 4.72 (1H, m) , 5.60 (1H, s), 6.04 (1H, s), 6.62 (1H, s)
¹⁹ F-NMR (solvent: heavy acetone, reference material: C6F6); δ (ppm) 91.43 (6F, s)
Comparative Example 1
Comparative Example 1 is an example in which the acid used in the Friedel-Crafts reaction of Example 1 was changed from trifluoromethanesulfonic acid to methanesulfonic acid having no fluorine.

[Friedel Crafts reaction]
Phenol, 20 g, toluene, 40 g, hexafluoroacetone, 37 g, and methanesulfonic acid, 2.0 g were charged into a stainless steel pressure vessel with a capacity of 300 mL. After the temperature in the pressure vessel was 120 ° C., the mixture was stirred for 18 hours to perform a Friedel-Crafts reaction. After completion of the Friedel-Crafts reaction, 40 g of diisopropyl ether was added, and when the progress of the Friedel-Crafts reaction was confirmed by gas chromatography, it was an adduct of hexafluoroacetone to the ortho position and an adduct of the para position to phenol. 4- (2-hydroxyhexafluoroisopropyl) phenol was obtained in the ratio of ortho adduct: para adduct = 6: 4. The reaction product was washed with aqueous sodium bicarbonate and then with brine, and concentrated with an evaporator. The obtained solid was recrystallized twice with a mixed solvent of toluene and heptane to obtain 13 g of 4- (2-hydroxyhexafluoroisopropyl) phenol in a yield of 23% by mass.

  Comparing Example 1 and Comparative Example 1, in Example 1, 4- (2-hydroxyhexafluoroisopropyl) phenol, which is an adduct of hexafluoroacetone to phenol, is ortho-adduct: para-adduct = 1: 9 and the selectivity of the target product para-adduct was good, and the para-adduct was obtained in good yield.

  On the other hand, the comparative example is 1 ortho adduct: para adduct = 6: 4, the ratio of the desired target product para adduct is small, and a large number of by-product ortho adducts are produced. The selectivity of the product was low and the yield of the desired product was low. Further, as an impurity, the time and effort of purification for removing the ortho adduct increased.

  In this way, when compared in the same reaction system, the Friedel-Crafts reaction is achieved by using trifluoromethanesulfonic acid, which is a sulfonic acid having fluorine, as compared with the case of using methanesulfonic acid having no fluorine. It was found that the selectivity at the time of addition of hexafluoroacetone to the para position of phenol was greatly improved.

  When the resist film is formed by the method of the present invention, a fluorine-containing ketone which is a highly polar group at the para position is used as a resist monomer which has good adhesion to the substrate, has high sensitivity to ultraviolet rays, and gives a sensitive resist material. The introduced fluorine-containing polymerizable monomer, 4- (2-hydroxyhexafluoroisopropyl) cyclohexyl methacrylate, was obtained with good selectivity and high yield. 4- (2-Hydroxyhexafluoroisopropyl) cyclohexyl methacrylate is suitably used as a photoresist material because of its good solubility in an organic solvent when used as a resist solution and good developer solubility after exposure in photolithography.

Claims (2)

General formula (1):

(In the formula (1), each R ¹ independently represents a hydrogen atom, a linear chain having 1 to 25 carbon atoms, a branched or cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group, or an aryl group, A part may be substituted with a fluorine atom or an oxygen atom, X is an integer of 0 to 2, and Y is an integer of 0 to 8.)
A hydroxyaryl compound represented by:
General formula (2):

(In Formula (2), R ² and R ³ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, a branched or cyclic group having 3 to 20 carbon atoms, and a carbon atom. May be substituted with an oxygen atom, a part or all of a hydrogen atom may be substituted with a fluorine atom, or R ² and R ³ may be bonded to form a cyclic compound. Furthermore, it has at least one fluorine atom in either R ² or R ^3. )
The fluorine-containing ketone represented by the general formula (3) is reacted in the presence of trifluoromethanesulfonic acid :

(In formula (3), R ^{1 to} R ³ , X and Y are the same as above.)
The manufacturing method of the fluorine-containing compound A represented by these. A step of producing a fluorine-containing compound A represented by the general formula (3) by the method according to claim 1 ;
Next , the fluorine-containing compound A is reduced with hydrogen in the presence of a ruthenium catalyst to thereby give a general formula (4):

(In formula (4), R ^{1 to} R ³ , X and Y are the same as above.)
A step of synthesizing a fluorine-containing compound B represented by:
Subsequently, the said fluorine-containing compound B is made into General formula (5):

(In formula (5), R ⁴ is a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). A is F, Cl or a general formula ( 6):

(In the formula (6), R ⁴ represents a hydrogen atom, C _m H _{2m + 1} , or C _n F _{2 n + 1} (m and n are each independently an integer of 1 to 4). Represents.)
Is reacted with an acrylic acid derivative compound represented by the general formula (7):

(In formula (7), R ^{1 to} R ⁴ , X and Y are the same as above.)
A step of synthesizing a fluorine-containing polymerizable monomer represented by:
The manufacturing method of the said fluorine-containing polymerizable monomer containing.