CN100384799C - Fluorine-containing compound, fluorine-containing polymer and method for producing the same - Google Patents

Abstract

A fluorine compound which has functional groups in a high concentration, can hence have sufficient properties attributable to the functional groups, and is highly transparent in a wide wavelength region. It is a fluorinated diene represented by the following formula (1): CF2=CFCH2CH(C(R<1>)(R<2>)(OH))CH2CH=CH2 (1) wherein R<1> and R<2> each independently represents fluorine or C5 or lower fluoroalkyl.

Description

Fluorine-containing compound, fluorine-containing polymer and method for producing the same

technical field

The present invention relates to novel fluorochemicals, fluoropolymers and methods for their manufacture.

Background technique

As a fluoropolymer having a functional group, there are known fluoropolymers containing a functional group used in fluorine-based ion exchange membranes or curable fluororesin coatings, etc., but they are all polymers whose basic skeleton is linear, Obtained by copolymerization of fluoroolefins represented by tetrafluoroethylene and monomers with functional groups.

In addition, polymers containing functional groups and having a fluorine-containing alicyclic structure in the main chain are also known. As a method for introducing functional groups into polymers having a fluorine-containing alicyclic structure in the main chain, it is known The method of polymerizing the terminal group of the polymer obtained; the method of treating the polymer at high temperature to oxidize and decompose the side chain or terminal of the polymer to form a functional group; copolymerize the monomer with a functional group, and introduce it by adding hydrolysis and other treatments as needed method (for example, refer to patent documents 1, 2, 3, 4).

As a method of introducing a functional group into a polymer having a fluorine-containing alicyclic structure in the main chain, there are the above-mentioned methods, but in the method of introducing a functional group by treating the terminal group of the polymer, the concentration of the functional group is low and sufficient functional groups cannot be obtained. Disadvantages of features. Also, in the introduction method of copolymerizing a monomer having a functional group, if the concentration of the functional group is high, there are problems such as a decrease in mechanical properties due to a decrease in the glass transition temperature (Tg).

[Patent Document 1] Japanese Patent Laid-Open No. 4-189880

[Patent Document 2] Japanese Patent Laid-Open No. 4-226177

[Patent Document 3] Japanese Patent Laid-Open No. 6-220232

[Patent Document 4] International Publication No. 02/064648 Pamphlet

disclosure of invention

The problem to be solved by the invention

The problem to be solved by the present invention is to provide a fluorine-containing compound, a fluorine-containing polymer and a production method thereof, which have a high concentration of functional groups, can obtain sufficient functional group characteristics, and have high transparency in a wide wavelength range. In addition, as a chemically amplified resist, it is possible to form, in particular, transparency to far ultraviolet rays such as KrF and ArF excimer lasers or vacuum ultraviolet rays such as _F2 excimer lasers, excellent dry etching properties and sensitivity, A resist composition for a resist pattern excellent in resolution, dissolution rate, flatness, and the like. In addition, there is also provided a resist film protection film for protecting a resist film from a liquid immersion solvent in a liquid immersion lithography (lithography) process.

Solution to the problem

The present invention is the following inventions for solving the above-mentioned problems.

The present invention provides a fluorine-containing diene represented by the following formula (1).

CF ₂ =CFCH ₂ CH(C(R ¹ )(R ² )(OH))CH ₂ CH=CH ₂ (1) In the formula, R ¹ and R ² independently represent a fluorine atom or the number of carbon atoms is less than or equal to 5 of fluoroalkyl.

The present invention provides a fluorine-containing polymer (A) having a monomer unit obtained by cyclopolymerization of a fluorine-containing diene represented by the above formula (1) and a production method thereof.

In addition, the present invention provides a resist protection film composition characterized by containing a fluoropolymer (A) and a solvent for dissolving or dispersing the fluoropolymer (A).

Effect of the present invention

According to the present invention, a fluorinated polymer having an aliphatic ring structure in the main chain and a hydroxyl group in the side chain can be produced. The fluorine-containing polymer obtained by the invention has high chemical stability and heat resistance. Moreover, since the hydroxyl group is introduced into the side chain, the characteristics of the hydroxyl group can be fully exerted without causing a decrease in Tg, which is difficult to achieve with conventional fluorine-containing polymers. In particular, since the ring side chain has a hydroxyl group with high acidity, the solubility to an alkaline aqueous solution is improved. And it has high transparency in a wide range of wavelengths.

The best way to practice the invention

According to the present invention, a fluorine-containing diene (hereinafter referred to as fluorine-containing diene (1)) represented by the following general formula (1) and a fluorine-containing diene (1) containing monomer units obtained by cyclopolymerization can be provided. Fluoropolymer (A) and its production method.

CF ₂ =CFCH ₂ CH(C(R ¹ )(R ² )(OH))CH ₂ CH=CH ₂ (1) In the formula (1), R ¹ and R ² independently represent the number of fluorine atoms or carbon atoms Fluoroalkyl groups of 5 or less. In particular, R ¹ and/or R ² are preferably trifluoromethyl, more preferably trifluoromethyl at the same time.

The fluorine-containing diene of the present invention can be synthesized by a known method. For example, starting from CH ₂ =CHC(R ¹ )(R ² )OH, in the presence of a free radical initiator, CF ₂ ClCFClI is added to the double bond to form CF ₂ ClCFClCH ₂ CHIC(R ¹ )(R ² )OH, react it with CH ₂ =CHCH ₂ MgCl to form CF ₂ ClCFClCH ₂ CH(C(R ¹ )(R ² )OH)CH ₂ CH=CH ₂ , then dechlorinate to have to. Various fluorine-containing dienes (1) as follows can be obtained by changing R ¹ and R ² .

Specific examples of the fluorine-containing diene (1) of the present invention include the following, but are not limited thereto.

The fluorine-containing diene (1) is cyclized and polymerized under relatively mild conditions to obtain a cyclized polymer having a hydroxyl group in the ring side chain.

The following monomer units (a) to (c) are produced by cyclopolymerization of the fluorine-containing diene (1). According to the results of spectral analysis, etc., it is considered that the fluorine-containing polymer (A) has one or more monomers selected from the group consisting of monomer units (a), monomer units (b) and monomer units (c). An aggregate of unit structures.

The fluorine-containing polymer (A) preferably has monomer units obtained by cyclopolymerization of fluorine-containing dienes (1) (hereinafter referred to as monomer units (1)), and has hydroxyl groups of monomer units (1) that are A blocked monomer unit (hereinafter, referred to as a blocked monomer unit (1)). The ratio of the blocked monomer unit (1) to the total of the monomer unit (1) and the blocked monomer unit (1) is preferably 50 mol% or less, particularly preferably 15 to 40 mol% . Capping is the replacement of hydrogen atoms of hydroxyl groups with blocking groups. Specific examples of the blocked hydroxyl group include -OCH ₃ , -OCF ₃ , -O(tC ₄ H ₉ ), -OCH ₂ OCH ₃ , -OCH ₂ OC ₂ H ₅ , -OCH ₂ OCH ₂ OCH ₃ , -OCH ₂ OCH ₂ CF ₃ , -OCOO(tC ₄ H ₉ ), -OCH(CH ₃ )OC ₂ H ₅ , 2-tetrahydropyranyloxy, and groups shown below.

The fluorine-containing polymer (A) containing the monomer unit (1) and the blocked monomer unit (1) can be obtained by blocking the hydroxyl group of the fluorine-containing diene (1). It can be obtained by copolymerization with fluorine-containing diene (1). Alternatively, it can be obtained by capping a part of hydroxyl groups of the monomer unit (1) in the fluoropolymer (A) having the monomer unit (1).

In addition to the monomer unit (1), the fluorine-containing polymer (A) may contain monomer units derived from other radically polymerizable monomers (except for the end-capping unit body unit (1)). The ratio of the monomer unit derived from the other radically polymerizable monomer to the total monomer units is preferably at most 50 mol%, particularly preferably at most 15 mol%.

Examples of other radically polymerizable monomers include α-olefins such as ethylene, propylene, and isobutylene; fluorine-containing olefins such as tetrafluoroethylene and hexafluoropropylene; perfluoro(2,2-dimethyl -1,3-Dioxol) and other fluorine-containing cyclic monomers; perfluoro(butenyl vinyl ether) and other cyclopolymerizable dienes; 1,1,2,3,3-pentafluoro -4-trifluoromethyl-4-hydroxy-1,6-heptadiene, 1,1,2-trifluoro-4-[3,3,3-trifluoro-2-hydroxy-2-trifluoromethyl Cyclopolymerizable hydrofluorinated dienes such as propyl]-1,6-heptadiene; acrylates such as methyl acrylate and ethyl methacrylate; vinyl acetate, vinyl benzoate, gold steel Vinyl esters such as vinyl alkanoate; vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether; cyclic olefins such as cyclohexene, norbornene, norbornadiene; maleic anhydride, chlorinated vinyl etc.

The fluorine-containing polymer (A) of the present invention can be obtained by polymerizing the fluorine-containing diene (1) alone or with other copolymerizable monomers under a polymerization initiator. The polymerization initiation source is not limited as long as the radical polymerization reaction can proceed smoothly, for example, a radical generating agent, light, ionizing radiation, and the like. A radical generator is particularly preferred, and examples of the radical generator include peroxides, azo compounds, and persulfates. Among the free radical generators, peroxides are preferred. As specific peroxides, the following compounds may, for example, be mentioned.

C ₆ H ₅ -C(O)O-OC(O)-C ₆ H ₅

C ₆ F ₅ -C(O)O-OC(O)-C ₆ F ₅

C ₃ F ₇ -C(O)O-OC(O)-C ₃ F ₇

(CH ₃ ) ₃ CC(O)O-OC(O)-C(CH ₃ ) ₃

(CH ₃ ) ₂ CH-C(O)O-OC(O)-CH(CH ₃ ) ₂

(CH ₃ ) ₃ CC ₆ H ₁₀ -C(O)O-OC(O)-C ₆ H ₁₀ -C(CH ₃ ) ₃

(CH ₃ ) ₃ COC(O)O-OC(O)-OC(CH ₃ ) ₃

(CH ₃ ) ₂ CH-OC(O)O-OC(O)-O-CH(CH ₃ ) ₂

(CH ₃ ) ₃ CC ₆ H ₁₀ -OC(O)O-OC(O)-OC ₆ H ₁₀ -C(CH ₃ ) ₃

In the formula, -C ₆ H ₅ represents a phenyl group, -C ₆ F ₅ represents a heptafluorophenyl group, and -C ₆ H ₁₀ - represents a cyclohexylene group.

The method of polymerization is not particularly limited, for example, bulk polymerization of directly polymerized monomers; fluorinated hydrocarbons, chlorinated hydrocarbons, chlorofluorocarbons, Solution polymerization in alcohols, hydrocarbons, and other organic solutions; suspension polymerization in aqueous media with or without an appropriate organic solvent; emulsion polymerization by adding an emulsifier to aqueous media, etc.

The temperature and pressure for the polymerization are not particularly limited, and appropriate conditions are preferably selected in consideration of various factors such as the boiling point of the monomer, the heating source, and removal of the heat of polymerization. For example, a suitable temperature can be selected between 0°C and 200°C, and a practically suitable temperature can be set between room temperature and 100°C. In addition, the polymerization pressure may be under reduced pressure or under increased pressure, and suitable polymerization may be carried out at about normal pressure to about 100 atmospheres, or even about normal pressure to about 10 atmospheres.

The molecular weight of the fluorine-containing polymer (A) of the present invention is not particularly limited as long as it can be uniformly dissolved in the organic solvent (C) described later and can be uniformly coated on the substrate, and is usually converted to polystyrene The number average molecular weight of the compound is preferably 1,000 to 100,000, more preferably 2,000 to 30,000. By setting the number average molecular weight to 1,000 or more, it is possible to reduce the possibility of occurrence of defects such as defects in the obtained resist pattern, reduction in residual film rate after development, and reduction in shape stability during heat treatment of the pattern. In addition, when the number average molecular weight is 100,000 or less, the coatability of the resist composition described later can be maintained well, and good developability can be maintained.

The fluorine-containing polymer (A) of the present invention can be used as a base polymer for photoresists. That is, a composition (C) containing a fluorine-containing polymer (A), an acid-generating compound (B) that generates an acid when irradiated with light, and an organic solvent can be used as a resist composition. Hereinafter, taking a preferred form of the fluoropolymer (A), that is, a fluoropolymer (A) having a monomer unit (1) and a blocked monomer unit (1) as an example, the fluoropolymer will be described in detail. (A) A resist composition (hereinafter referred to as a resist composition (D)) as a base polymer.

As described above, the acid-generating compound (B) that generates an acid upon exposure to light generates an acid upon exposure. By the action of this acid, part or all of the blocking groups of the blocking monomer units (1) in the fluoropolymer (A) are cleaved (deblocking). As a result, the exposed portion is easily soluble in an alkaline developing solution, and a positive resist pattern can be formed with an alkaline developing solution. As the acid-generating compound (B) that generates acid upon exposure to light, acid-generating compounds used in general chemically amplified resists can be used, such as onium salts, halogen-containing compounds, diazoketone compounds, Sulfone compounds, sulfonic acid compounds, etc. Examples of these acid-generating compounds (B) include the following.

The onium salt may, for example, be an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt or a pyridinium salt. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, Bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium dodecylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate , triphenylsulfonium king salt, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, 1-(naphthylacetylmethyl)sulfonium trifluoromethanesulfonate, cyclo Hexylmethyl(2-oxocyclohexyl)sulfonium triflate, Dicyclohexyl(2-oxocyclohexyl)sulfonium triflate, Dimethyl(4-hydroxynaphthyl)sulfonium toluene Sulfonate, dimethyl(4-hydroxynaphthyl)sulfonium dodecylbenzenesulfonate, dimethyl(4-hydroxynaphthyl)sulfonium naphthalenesulfonate, triphenylsulfonium camphorsulfonate, ( 4-hydroxyphenyl)benzylmethylsulfonium tosylate, etc.

The halogen-containing compound may, for example, be a hydrocarbon containing a halogenated alkyl group or a heterocyclic compound containing a halogenated alkyl group. As specific examples, phenyl-bis(trichloromethyl)-s-triazine, methoxyphenyl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl) Methyl)-s-triazine, etc. (trichloromethyl)-s-triazine derivatives; 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, etc.

基苯甲酰甲基砜、二(苯磺酰基)甲烷等。作为磺酸化合物，可例举如烷基磺酸酯、烷基磺酰亚胺、卤代烷基磺酸酯、芳基磺酸酯、亚氨基磺酸酯等。作为具体例，可例举如苯偶姻甲苯磺酸盐、1，8-萘二羧酸酰亚胺三氟甲磺酸盐等。产酸化合物(B)可单独使用也可混合2种或2种以上使用。Examples of the sulfone compound include β-ketosulfone, β-sulfonyl sulfone, and α-diazo compounds of these compounds. Specific examples include, for example, 4-triphenacylsulfone,

phenylphenacylsulfone, bis(benzenesulfonyl)methane, etc. The sulfonic acid compound may, for example, be alkylsulfonate, alkylsulfonimide, halogenated alkylsulfonate, arylsulfonate or iminosulfonate. Specific examples include benzoin tosylate, 1,8-naphthalene dicarboxylic acid imide trifluoromethanesulfonate, and the like. The acid generating compound (B) may be used alone or in combination of two or more.

The above-mentioned organic solvent (C) is not particularly limited as long as it is a solvent capable of dissolving both components of the fluoropolymer (A) and the acid generating compound (B). Examples include alcohols such as methanol and ethanol; ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; acetates such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; propylene glycol monomethyl ether , propylene glycol monoethyl ether and other glycol monoalkyl ethers; propylene glycol monomethyl ether acetate, carbitol acetate and other glycol monoalkyl ether esters, etc.

Generally, relative to 100 parts by mass of the fluoropolymer (A), the ratio of each component in the resist composition (D) is preferably 0.1 to 20 parts by mass of the acid generating compound (B) and 50 to 50 parts by mass of the organic solvent (C). 2000 parts by mass. More preferably, the acid generating compound (B) is 0.1-10 mass parts and the organic solvent (C) is 100-1000 mass parts with respect to 100 mass parts of fluoropolymers (A).

Sufficient sensitivity and developability can be obtained by making the amount of the acid-generating compound (B) 0.1 parts by mass or more, and by making it 10 parts by mass or less, the transparency to radiation can be sufficiently secured, and a more accurate image can be obtained. resist pattern.

Also according to the purpose, an acid-cracking additive for improving pattern contrast, a surfactant for improving coatability, and a nitrogen-containing alkali for adjusting an acid-generating pattern may be appropriately incorporated into the resist composition (D). Compounds, adhesion aids for improving the adhesion to substrates, storage stabilizers for improving the storage stability of the composition, and the like. In addition, the resist composition of the present invention is preferably filtered through a filter of 0.1 to 2 μm after mixing the components uniformly.

A resist film can be formed by coating a dry resist composition (D) on a substrate such as a silicon wafer. As the coating method, spin coating, flow coating, roll coating and the like can be used. The formed resist film is irradiated with light through a patterned mask, and then developed to form a pattern.

Examples of irradiation light include ultraviolet rays such as g-line with a wavelength of 436nm and i-line with a wavelength of 365nm; KrF excimer laser with a wavelength of 248nm, ArF excimer laser with a wavelength of 193nm, and _F Far ultraviolet or vacuum ultraviolet rays such as molecular lasers. The resist composition (D) is a resist useful for using ultraviolet rays with a wavelength of 250 nm or less, especially ultraviolet rays with a wavelength of 200 nm or less (ArF excimer laser or _F2 excimer laser) as a light source combination.

Various alkaline aqueous solutions can be used as the developing treatment solution. The base may, for example, be sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylamine hydroxide, triethylamine or the like.

Since the fluoropolymer (A) of the present invention is insoluble in water and soluble in a developing solution, it can be used as a base polymer for resist protection films. A resist protective film is formed by mixing the solvent (E) for dissolving or dispersing the fluoropolymer (A) and the fluoropolymer (A), coating and drying on the resist film. The coating method can be spin coating, flow coating, roll coating and the like. The formed resist protective film is irradiated with light through a patterned mask, and then developed to remove the resist protective film to form a pattern of the resist film.

The solvent (E) is not particularly limited as long as it can dissolve or disperse the fluoropolymer (A). A soluble solvent is preferred. Also, since it is applied on a resist film, it is preferably a solvent that has little influence on the resist material. Examples of the solvent (E) include alcohols such as methanol and ethanol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; acetates such as ethyl acetate and butyl acetate; aromatic compounds such as toluene and xylene; Hydrocarbons; glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate and carbitol acetate; fluorine-based solvents, etc. A mixture of the above-mentioned solvents may also be used, and in the case of a water-soluble organic solvent, a mixture with water may also be used.

Usually, 50-2000 mass parts of solvent (E) is suitable with respect to 100 mass parts of fluoropolymers (A). Preferably, the solvent (E) is 100-1000 mass parts with respect to 100 mass parts of fluoropolymers (A). It is preferable to filter through a 0.1-2 μm filter membrane after uniformly mixing the fluoropolymer (A) and the solvent (E).

Other components other than the fluoropolymer (A) and the solvent (E) may also be contained. The resist protective film is preferably used in a liquid immersion lithography process for improving resolution. Best for use in liquid immersion lithography processes using water.

Examples of irradiation light include ultraviolet rays such as g-line with a wavelength of 436nm and i-line with a wavelength of 365nm; KrF excimer laser with a wavelength of 248nm, ArF excimer laser with a wavelength of 193nm, and _F Far ultraviolet or vacuum ultraviolet rays such as molecular lasers. The fluorine-containing polymer (A) of the present invention is useful in applications where ultraviolet rays with a wavelength of 250 nm or less, especially ultraviolet rays with a wavelength of 200 nm or less (ArF excimer laser or _F2 excimer laser) are used as light sources The base polymer used for the resist protection film.

Example

Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited thereto.

The abbreviations used in the following examples are as follows.

THF: tetrahydrofuran; BPO: benzoyl peroxide; PFBPO: perfluorobenzoyl peroxide; PFB: perfluorobutyryl peroxide; PSt; polystyrene; R225: dichloropentafluoropropane (solvent).

(Example 1)

[Synthesis of CF ₂ =CFCH ₂ CH(C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂ ]

500 g of CF ₂ ClCFClI, 344 g of CH ₂ =CHC(CF ₃ ) ₂ OH, and 32.6 g of BPO were added to a 1 L (liter) glass reactor, and heated at 95° C. for 71 hours. The reaction crude liquid was distilled under reduced pressure to obtain 544 g of CF ₂ ClCFClCH ₂ CHI(C(CF ₃ ) ₂ OH) (55-58°C/0.2kPa).

Add 344 g of CF ₂ ClCFClCH ₂ CHI (C(CF ₃ ) ₂ OH) synthesized above and 1.7 L of dehydrated THF into a 5 L glass reactor, and cool to -70°C. 1.8 L of a 2M-THF solution of CH ₂ =CHCH ₂ MgCl was added dropwise thereto over 4 hours.

After raising the temperature to 0° C. and stirring for 16 hours, 1.6 L of saturated aqueous ammonium chloride solution was added, and the temperature was raised to room temperature. The reaction solution was separated, and the organic layer was concentrated with an evaporator, followed by distillation under reduced pressure to obtain 287 g of CF ₂ ClCFClCH ₂ CH(C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂ (62-66°C/0.2kPa) . 97 g of zinc and 300 g of water were added to a 1 L glass reactor, and heated to 90°C. 287 g of CF ₂ ClCFClCH ₂ CH(C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂ synthesized above was added dropwise thereto, and stirred for 24 hours. 70 mL of hydrochloric acid was added dropwise to the reaction solution and stirred for 2 hours, then the liquid was separated by filtration, and vacuum distillation was carried out to obtain 115 g of CF ₂ =CFCH ₂ CH(C(CF ₃ ) ₂ OH)CH ₂ CH=CH ₂ (53-54 °C/1kPa).

NMR spectrum

¹ H-NMR (399.8MHz, solvent: CDCl ₃ , reference: tetramethylsilane) δ (ppm): 2.53 (m, 5H), 3.49 (m, 1H), 5.15 (m, 2H), 5.79 (m, 2H).

¹⁹ F-NMR (376.2MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -73.6 (m, 6F), -104.1 (m, 1F), -123.1 (m, 1F), -175.4 ( m, 1F).

(Example 2)

5 g of the monomer obtained in Example 1 was charged into a glass pressure-resistant reactor with an inner volume of 30 mL. Next, 0.13 g of PFBPO was added as a polymerization initiator. After freezing and degassing in the system, the tube was sealed, and the polymerization was carried out in a constant temperature vibration tank (70° C.) for 19 hours. After the polymerization, the reaction solution was diluted with R225 and dropped into hexane to reprecipitate the polymer, and then vacuum-dried at 115° C. for 18 hours. As a result, 3.32 g of an amorphous polymer (hereinafter referred to as polymer 1A) having a fluorine-containing ring structure in the main chain was obtained. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was: number average molecular weight (Mn) 26300, weight average molecular weight (Mw) 56300, Mw/Mn=2.14. This is a polymer having a Tg of 124° C. as measured by differential scanning calorimetry (DSC) and a white powder at room temperature. The resulting polymer is soluble in acetone, THF, ethyl acetate, methanol, R225; insoluble in hexane.

It was confirmed by ¹⁹ F-NMR and ¹ H-NMR that it was a cyclized polymer having the following monomer units (d), (e) and (f).

(Example 3)

4 g of the monomer obtained in Example 1 and 2.2 g of ethyl acetate were charged into a glass pressure-resistant reactor having an inner volume of 30 mL. Next, 6.23 g of a 3 wt% R225 solution of PFB as a polymerization initiator was added. After freezing and degassing in the system, the tube was sealed and polymerized in a constant temperature vibration tank (20° C.) for 41 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 90° C. for 21 hours. As a result, 1.33 g of an amorphous polymer (hereinafter referred to as polymer 2A) having a fluorine-containing ring structure in the main chain was obtained. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was: number average molecular weight (Mn) 15600, weight average molecular weight (Mw) 25100, Mw/Mn=1.61. This is a polymer having a Tg of 118° C. as measured by differential scanning calorimetry (DSC) and a white powder at room temperature. The resulting polymer was soluble in acetone, THF, methanol; insoluble in R225.

(Example 4)

10 g of the monomer obtained in Example 1 was charged into a glass-made pressure reactor having an inner volume of 50 mL. Next, 40.6 g of a 3 wt % R225 solution of PFB as a polymerization initiator was added. After freezing and degassing in the system, the tube was sealed, and polymerization was carried out in a constant temperature vibration tank (20°C) for 18.5 hours. After the polymerization, the reaction solution was diluted with R225 and dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 120° C. for 15 hours. As a result, 8.5 g of an amorphous polymer (hereinafter referred to as polymer 3A) having a fluorine-containing ring structure in the main chain was obtained. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was: number average molecular weight (Mn) 15500, weight average molecular weight (Mw) 26000, Mw/Mn=1.69. This is a polymer having a Tg of 117° C. as measured by differential scanning calorimetry (DSC) and a white powder at room temperature. The resulting polymer was soluble in acetone, THF, methanol; insoluble in R225.

(Example 5)

2 g of the monomer obtained in Example 1 and 1.6 g of dioxane were charged into a glass pressure-resistant reactor having an inner volume of 30 mL. Next, 9.14 g of a 3 wt% R225 solution of PFB as a polymerization initiator was added. After freezing and degassing in the system, the tube was sealed, and the polymerization was carried out in a constant temperature vibration tank (20° C.) for 18 hours. After the polymerization, the reaction solution was diluted with R225 and dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 100° C. for 16 hours. As a result, 1.65 g of an amorphous polymer (hereinafter referred to as polymer 4A) having a fluorine-containing ring structure in the main chain was obtained. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was: number average molecular weight (Mn) 8800, weight average molecular weight (Mw) 13400, Mw/Mn=1.53. This is a polymer having a Tg of 115° C. as measured by differential scanning calorimetry (DSC) and a white powder at room temperature. The obtained polymer is soluble in acetone, THF, methanol; soluble in R225.

(Example 6)

4 g of the polymer obtained in Example 4, 2.7 g of a 6.6 wt % methanol solution of sodium hydroxide, and 80 g of methanol were added to a 200 ml glass reactor, and stirred at room temperature for 20 hours. After concentrating the reaction solution with an evaporator, it was dissolved in 120 g of dehydrated THF. Next, 0.38 g of chloromethyl methyl ether was added, followed by stirring at room temperature for 90 hours. The reaction solution was filtered through celite, and concentrated with an evaporator. The concentrate was dissolved in R225, washed with water, and separated. The R225 layer was dropped into hexane, and the polymer was reprecipitated, followed by vacuum drying at 110° C. for 16 hours. As a result, 3.3 g of an amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as polymer 5A) was obtained. According to ¹⁹ F-NMR and ¹ H-NMR analysis, the methoxymethylation rate of the polymer was 32 mol%. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was 15800 in number average molecular weight (Mn), 25900 in weight average molecular weight (Mw), and Mw/Mn=1.64. This is a polymer having a Tg of 111° C. as measured by differential scanning calorimetry (DSC) and a white powder at room temperature. The resulting polymer was soluble in acetone, THF, methanol and R225.

(Examples 7-11) Measurement of Transparency in Vacuum Ultraviolet Range 157nm

1 g of polymers 1A to 5A synthesized in Examples 2 to 6 were dissolved in 10 g of propylene glycol monomethyl ether acetate, and filtered through a PTFE filter with a pore size of 0.2 μm. The above-mentioned adjusted solution was coated on a CaF substrate at room temperature using a spin coater at 1000 rotations. After coating, it baked at 100 degreeC for 15 minutes, and produced the coating film with a film thickness of 0.15 micrometers. The transmission spectra of these samples were measured at 157 nm. The light transmittance (%) at 157 nm is shown in Table 1. In addition, the measuring device used was the following device.

KV-201AD Extreme Ultraviolet Spectroscopy System (Spectrometer)

Wavelength range 120~300nm

Resolution can be 1~4nm

【Table 1】

Polymer 157nm light transmittance (%) Example 7 1A 90 Example 8 2A 93 Example 9 3A 93 Example 10 4A 95 Example 11 5A 90

(Examples 12-13) Measurement of Solubility to Alkaline Developer

1 g each of the polymers 3A and 5A synthesized in Examples 4 and 6 were dissolved in 10 g of propylene glycol monomethyl ether acetate, filtered through a filter made of PTFE with a pore size of 0.2 μm, and coated on a silicon substrate. A 2.38% tetramethylammonium hydroxide aqueous solution was dropped on the silicon substrate coated with the polymer, and the solubility was evaluated. The results are shown in Table 2.

【Table 2】

Polymer Solubility to Alkaline Developer Example 12 3A dissolve Example 13 5A insoluble

(Example 14)

2 g of the monomer obtained in Example 1 and 2.67 g of ethyl acetate were charged into a glass pressure-resistant reactor having an inner volume of 30 mL. Next, 0.076 g of IPP (isopropyl peroxydicarbonate) was added as a polymerization initiator. After freezing and degassing in the system, the tube was sealed, and the polymerization was carried out in a constant temperature vibration tank (40° C.) for 19 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, and vacuum drying was performed at 100° C. for 21 hours. As a result, 1.37 g of an amorphous polymer (hereinafter referred to as polymer 6A) having a fluorine-containing ring structure in the main chain was obtained. The PSt-equivalent molecular weight measured by GPC using THF as a solvent was: number average molecular weight (Mn) 5700, weight average molecular weight (Mw) 10500, Mw/Mn=1.84. It is a white powdery polymer at room temperature. The obtained polymer was soluble in acetone, THF, methanol and R225.

(Example 15, 16)

Dissolve 1 g each of the polymers 3A and 6A synthesized in Examples 4 and 14 in 9 g of PGMEA (propylene glycol monomethyl ether acetate), and filter through a filter made of PTFE with a pore size of 0.2 μm to obtain a resist film. with composition.

The above composition for resist protective film was spin-coated on a silicon substrate, and heat-treated at 100° C. for 90 seconds after coating to form a resist protective film with a film thickness of 0.21 μm. Table 3 shows the light transmittance and water contact angle of the resist protective film thus obtained.

【table 3】

Polymer 193nm transmittance (%) Contact angle (degrees) Example 15 3A 99.3 74 Example 16 6A 98.5 74

(Example 17, 18) to the mensuration of alkali developing solution solubility

1 g of polymers 3A and 6A synthesized in Examples 4 and 14 were dissolved in 9 g of PGMEA (propylene glycol monomethyl ether acetate), filtered through a PTFE filter with a pore size of 0.2 μm, and coated on a silicon substrate. The silicon substrate coated with the polymer was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution and ultrapure water for 30 seconds, and the solubility was evaluated. The results are shown in Table 4.

【Table 4】

Polymer Solubility to Alkaline Developer Solubility in ultrapure water Example 17 3A dissolve insoluble Example 18 6A dissolve insoluble

Possibility of industrial use

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

Claims (5)

1. the fluorine-containing diene shown in the following formula (1)

CF ₂＝CFCH ₂CH(C(R ¹)(R ²)(OH))CH ₂CH＝CH ₂ (1)

In the formula, R ¹And R ²Represent independently that respectively fluorine atom or carbonatoms are smaller or equal to 5 fluoroalkyl.

2. fluorine-containing diene as claimed in claim 1, its feature also is, R ¹And R ²Be trifluoromethyl.

3. fluoropolymer (A) is characterized in that, have by claim 1 or 2 described fluorine-containing diene cyclopolymerizations and monomeric unit.

4. the manufacture method of fluoropolymer (A) is characterized in that, cyclopolymerization claim 1 or 2 described fluorine-containing diene.

5. the protective membrane composition of etchant resist is characterized in that, contains the solvent of described fluoropolymer of claim 3 (A) and dissolving or dispersion fluoropolymer (A).