JP5618291B2 - NOVEL FLUORINE-CONTAINING COMPOUND, METHOD FOR PRODUCING POLYMER OF FLUORINE-CONTAINING COMPOUND, OPTICAL ELEMENT, FUNCTIONAL THIN FILM, AND RESIST FILM CONTAINING POLYMER OF FLUORINE-CONTAINING COMPOUND - Google Patents

Description

  The present invention relates to a novel fluorine-containing compound that is highly transparent and soluble in a general-purpose solvent, a method for producing a polymer of the fluorine-containing compound, an optical element comprising the polymer of the fluorine-containing compound, a functional thin film, and a resist film. .

  Polytetrafluoroethylene (PTFE), which is a typical example of a fluorine-based polymer, is known as a resin having high heat resistance and excellent chemical resistance, but is opaque because it is crystalline, and is used as an optical or transparent functional film. It cannot be applied. Polymers having a fluorine-containing cyclic structure in the main chain, for example, polymers obtained by cyclopolymerizing perfluorobutenyl vinyl ether monomers (Cytop (registered trademark)) and Teflon (registered trademark) AF are amorphous transparent polymers. Yes, it is used as an optical material such as a plastic optical fiber, an optical waveguide, or a low reflection film, but its use is limited because of its low glass transition temperature and an expensive material. Moreover, although the polymer having these fluorine-containing cyclic structures is solvent-soluble, the solvent that can be used is a special fluorine-based solvent, and when forming a functional thin film on an inorganic or organic substrate or substrate, Costs tend to be high in terms of materials and manufacturing.

  Patent Document 1 includes a glass transition temperature between 60 and 150 ° C. to produce an amorphous, transparent coating or molded product having good dissolution characteristics in a number of organic solvents. A polymer having a fluorine cyclic structure and a fluorine-containing monomer (2-allyl-perfluoroalkyl-trifluorovinyl ether) for obtaining the polymer are disclosed. However, the fluorine-containing monomer disclosed in Patent Document 1 has a special fluorine-containing compound as a raw material for synthesis, and additionally includes a plurality of synthesis routes. The cost of the fluorine monomer increases.

  On the other hand, since octafluorocyclopentene (OFCP) is produced industrially in large quantities for use as an etching gas and can be easily obtained, it is advantageous in terms of cost if used as a monomer for polymerization, but OFCP is poor in polymerizability. Therefore, as disclosed in Patent Documents 2 and 3, copolymers with other monomers are mainly studied. However, the copolymers disclosed in Patent Documents 2 and 3 have a low glass transition temperature and are limited in application range in terms of heat resistance.

  Therefore, in order to solve these problems, the present inventors have previously described OFCP and homoallyl alcohol or a derivative thereof as a fluorine-containing polymer that is highly transparent, can be dissolved in a general-purpose solvent, and is less expensive than conventional ones. A fluorine-containing polymer produced by radical polymerization of 1,6-diene type ether obtained by reacting benzene was proposed (see Patent Document 4). The fluorine-containing polymer disclosed in Patent Document 4 has a cyclic structure in the main chain and has a glass transition temperature of 175 ° C. or higher, and thus produces a highly heat-resistant and transparent coating or molded product. Therefore, application as a fluorine-containing polymer is expected.

JP-A-6-72939 JP 2001-122928 A JP 2001-272504 A Japanese Patent No. 4399608

  The fluoropolymer described in Patent Document 4 has a high glass transition temperature. However, when a transparent coating or molded product is produced as described in Patent Document 1, a low stress is required. In some cases, a fluorine-containing polymer having a glass transition temperature of less than 175 ° C. may be required in order to make it flexible or impart flexibility. The fluoropolymer described in Patent Document 4 has a cyclic main chain, and thus has a high glass transition temperature. On the other hand, a significant structural change is required to lower the glass transition temperature. Although it is possible to adjust properties such as glass transition temperature by copolymerization with other monomers, it is generally necessary to copolymerize with expensive fluorine-containing monomers in polymers where the fluorine content is desired to be increased. is there.

  As described above, the conventional fluoropolymer cannot sufficiently cope with the production of a transparent coating or a molded product requiring various characteristics. In order to meet this requirement, a novel functional fluoropolymer that can be synthesized at a low cost and has different thermal characteristics and mechanical properties from conventional fluoropolymers, and a functional fluoropolymer for obtaining the same. A fluorine-containing monomer (fluorine-containing compound) is essential. In particular, a fluorine-containing compound that has a high content of fluorine contained in the fluorine-containing polymer and can constitute a polymer having various thermal characteristics and mechanical characteristics is demanded.

  Accordingly, an object of the present invention is to provide a novel fluorine-containing compound having a high fluorine content and a radical polymerization of the fluorine-containing compound, which can be synthesized from a low-cost raw material in order to solve the above-described problems. Another object of the present invention is to provide a novel method for producing a polymer that is highly transparent and can be dissolved in a general-purpose solvent, and an optical element, a functional thin film, and a resist film comprising the polymer of the fluorine-containing compound.

  As a result of intensive studies on the chemical structure and synthesis method of octafluorocyclopentene (OFCP), which is easily available as a synthesis raw material, the present inventor has obtained a new fluorine-containing compound as a result of cost reduction of the fluorine-containing compound. The present invention has been found out that it can be obtained.

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素、炭素数１〜４のアルキル基又はアリール基を示す）
（２）本発明は、前記の式（１）に記載の含フッ素化合物において、Ｒ^１及びＲ^２がそれぞれ独立に水素、メチル基又はフェニル基であり、Ｒ^３及びＲ^４が水素である含フッ素化合物を提供する。
（３）本発明は、前記の式（１）に記載の含フッ素化合物のクライゼン転位反応によって得られる下記式（２）で表される構造を有する含フッ素化合物を提供する。

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素、炭素数１〜４のアルキル基又はアリール基を示す）
（４）本発明は、前記（３）に記載の含フッ素化合物において、Ｒ^１及びＲ^２がそれぞれ独立に水素、メチル基又はフェニル基であり、Ｒ^３及びＲ^４が水素である含フッ素化合物を提供する。
（５）本発明は、請求項１〜４の何れかに記載の含フッ素化合物を、単独でラジカル重合又は他のラジカル重合可能なモノマーとラジカル共重合して得られる前記含フッ素化合物の重合体の製造方法を提供する。
（６）本発明は、前記（５）に記載の方法によって製造される含フッ素化合物の重合体からなる光学素子を提供する。
（７）本発明は、前記（６）に記載の光学素子が保護膜、低反射膜又は撥水性膜であることを特徴とする含フッ素化合物の重合体からなる光学素子を提供する。
（８）本発明は、前記（６）に記載の光学素子がレンズ、プリズム、導光板、光導波路又は光ファイバーであることを特徴とする含フッ素化合物の重合体からなる光学素子を提供する。
（９）本発明は、前記（５）に記載の方法によって製造される含フッ素化合物の重合体からなり、摺動性又は低汚染性の塗料又は薄膜として使用される機能性薄膜を提供する。
（１０）本発明は、前記（５）に記載の方法によって製造される含フッ素化合物の重合体からなるリソグラフィ用のレジスト膜を提供する。 That is, the configuration of the present invention is as follows.
(1) The present invention provides a fluorine-containing compound having a structure represented by the following formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group)
(2) The present invention provides the fluorine-containing compound represented by the above formula (1), wherein R ¹ and R ² are each independently hydrogen, a methyl group or a phenyl group, and R ³ and R ⁴ are hydrogen. A fluorine compound is provided.
(3) The present invention provides a fluorine-containing compound having a structure represented by the following formula (2) obtained by the Claisen rearrangement reaction of the fluorine-containing compound described in the above formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group)
(4) The present invention is the fluorine-containing compound according to (3), wherein R ¹ and R ² are each independently hydrogen, a methyl group or a phenyl group, and R ³ and R ⁴ are hydrogen. I will provide a.
(5) The present invention is a polymer of the above-mentioned fluorine-containing compound obtained by radically copolymerizing the fluorine-containing compound according to any one of claims 1 to 4 with a monomer capable of radical polymerization or other radical polymerization alone. A manufacturing method is provided.
(6) The present invention provides an optical element comprising a polymer of a fluorine-containing compound produced by the method described in (5) above.
(7) The present invention provides an optical element comprising a polymer of a fluorine-containing compound, wherein the optical element according to (6) is a protective film, a low reflection film or a water repellent film.
(8) The present invention provides an optical element comprising a polymer of a fluorine-containing compound, wherein the optical element according to (6) is a lens, a prism, a light guide plate, an optical waveguide, or an optical fiber.
(9) The present invention provides a functional thin film comprising a polymer of a fluorine-containing compound produced by the method described in (5) above, and used as a sliding or low-contamination paint or thin film.
(10) The present invention provides a resist film for lithography comprising a polymer of a fluorine-containing compound produced by the method described in (5) above.

  The novel fluorine-containing compound according to the present invention can be synthesized by using an easily available fluorine-containing compound, so that the fluorine-containing polymer produced by the polymerization is highly transparent and can be used as a general-purpose solvent. Since it is melted and has excellent moldability, it is easy to produce a coating or molded product.

The polymer of the fluorine-containing compound according to the present invention is not only soluble in a general-purpose solvent and has excellent moldability, but also has a high fluorine content, and appropriately selects substituents R ¹ , R ² , R ³ and R ^4. By doing so, an optical element having a desired low refractive index property can be provided at low cost. In addition, the coating thin film or functional thin film comprising the polymer of the fluorine-containing compound according to the present invention can exhibit excellent properties in wear resistance, stain resistance or water repellency. In addition, since a resist film for lithography made of a polymer of the fluorine-containing compound has a high fluorine content, it has high sensitivity and can form a high-resolution pattern.

This is a synthesis route of a fluorine-containing compound obtained in the present invention. This is a synthetic route by Claisen rearrangement reaction of another fluorine-containing compound obtained in the present invention. 2 is a GC-MS spectrum of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone synthesized in Example 5. FIG. 2 is a ¹ H-NMR spectrum of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone synthesized in Example 5. 2- (2-Butenyl) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone and / or 1- (2-butenyl) -1-allyloxy- synthesized in Example 6 It is a GC-MS spectrum of 3,3,4,4,5,5-hexafluorocyclopentanone. In Example 11, 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone and / or 2-allyl-2-allyloxy-3,3,4,4,5 , 5-hexafluorocyclopentanone and their fluorine-containing compounds are obtained by homoradical polymerization of polymers obtained by infrared absorption.

と、下記のアリルアルコール又はその誘導体

（ここでＲ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素、炭素数１〜４のアルキル基又はアリール基を示す）
を反応させることによって得られる。 The fluorine-containing compound having a structure represented by the above formula (1) is octafluorocyclopentene having a structure represented by the following formula (3):

And the following allyl alcohol or derivatives thereof

(Here, R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group)
Is obtained by reacting.

FIG. 1 shows a synthesis route of a fluorine-containing compound having a structure represented by the above formula (1). In FIG. 1, when one kind of allyl alcohol or a derivative thereof (in the above formulas (4) and (5), R ¹ = R ² and R ³ = R ⁴ ) is used, 1 mol of octafluorocyclopentene is used. The fluorine-containing compound shown in 2a of FIG. 1 is synthesized by reacting 2 mol or more of allyl alcohol or a derivative thereof (synthesis route 1 of FIG. 1). In addition, when two types of homoallyl alcohol having different substituents or derivatives thereof (in the above formulas (4) and (5), R ¹ ≠ R ² and / or R ³ ≠ R ⁴ ) are used, An allyl alcohol having a group R ¹ and R ³ or a derivative thereof is reacted with approximately the same equivalent as octafluorocyclopentene, and then the substituents R ¹ and R ³ with respect to 1 mol of the compound shown as 1b in FIG. The fluorine-containing compound shown in 2b of FIG. 1 is synthesized by reacting 1 mol or more of allyl alcohol having different substituents R ² and R ⁴ or a derivative thereof (synthesis route 2 of FIG. 1). In the present invention, as allyl alcohol or a derivative thereof, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, methyl group, ethyl group, propyl group, n-butyl group or phenyl group, benzyl group or tolyl. Although those substituted with an aryl group such as a group are used, R ¹ and R ² are independently hydrogen, considering that the raw materials are easily available, the material cost is low, and there is not much polymerization inhibition. It is preferable to use a compound which is a methyl group or a phenyl group, and R ³ and R ⁴ are hydrogen.

  The reaction is usually carried out under atmospheric pressure, and is preferably carried out in the presence of KOH in a non-solvent. The reaction time is usually 1 to 24 hours in the synthesis route 1 shown in FIG. Further, in the synthesis route 2 shown in FIG. 1, the reaction time in the former stage is usually 1 to 24 hours, and the reaction time in the latter stage is usually 1 to 100 hours. The reaction temperature is set between −50 ° C. and 50 ° C., preferably in the range of −20 ° C. to 40 ° C. In the present invention, one synthesis reaction can be performed in two or more stages using different reaction temperatures and reaction times. In that case, the reaction temperature and reaction time can be changed within the above ranges in each stage.

  In the present invention, the fluorine-containing compound having the structure represented by the above formula (2) is synthesized by a Claisen rearrangement reaction of the compound 2a or 2b shown in FIG. FIG. 2 shows this reaction. FIG. 2A shows the Claisen rearrangement reaction of the compound 2a shown in FIG. 1, and FIG. 2B shows the Claisen rearrangement reaction of the compound 2b shown in FIG. The Claisen rearrangement reaction can be easily performed at a temperature in the range of 100 ° C to 250 ° C.

  The fluorine-containing compound having the structural formula represented by the above formula (1) has a double bond remaining in the cyclopentene ring, and this double bond is unlikely to participate in radical polymerization. If this double bond remains in the polymer, light absorption occurs in the ultraviolet region, which may cause a decrease in the transparency of the polymer. On the other hand, since the fluorine-containing compound having the structure represented by the above formula (2) loses the double bond of the cyclopentene ring by the Claisen rearrangement reaction, a polymer having excellent transparency can be obtained by radical polymerization.

  The fluorine compound having a structure represented by the above formula (1) or formula (2) is transparent and a polymer soluble in a general-purpose solvent is obtained through a radical polymerization reaction. The polymerization can be carried out in bulk, solution, suspension or emulsion. In the present invention, in order to prevent water, a surfactant or a dispersant from being mixed into the polymer, a polymerization reaction using a block or a solution is preferred.

  In the present invention, the polymerization medium used for solution polymerization is not particularly limited as long as it does not significantly inhibit the polymerization. For example, alcohols such as t-butyl alcohol, isopropanol, ethanol, and methanol, n-hexane, and n-peptane. Saturated hydrocarbons such as toluene, xylene, etc., fluorines such as trichlorotrifluoroethane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, etc. Are used alone or in admixture.

  The polymerization temperature is in the range of 50 to 150 ° C. When the polymerization reaction is completely performed, post-polymerization can be additionally performed at a temperature higher than the initial polymerization temperature. The temperature during post-polymerization is set in the range of 80 to 200 ° C. The polymerization time is usually 1 to 48 hours. When the polymerization temperature is set low, although the molecular weight of the polymer can be increased, it is necessary to lengthen the polymerization time.

  As the polymerization initiator, a general radical initiator can be used, for example, a peroxide such as benzoyl lauroyl peroxide or t-butylcumyl peroxide, an azo compound such as azobisisobutylnitrile, a water-soluble peroxide. Or persulfate is used.

  In the present invention, the homopolymer of the fluorine-containing compound represented by the above formula (2) has a glass transition temperature of 80 to 140 ° C. However, in the present invention, the glass transition temperature can be set and adjusted to be lower than 80 ° C. or higher than 140 ° C. by a copolymer with another polymerizable monomer.

  Moreover, a polymer can be obtained also about the fluorine-containing compound represented by said Formula (1), The glass transition temperature of the homopolymer is 60-150 degreeC. Similarly to the homopolymer of the fluorine-containing compound represented by the above formula (2), the glass transition temperature can be freely adjusted by a copolymer with another polymerizable monomer.

  Since the fluorine-containing compound having the structure represented by the above formula (1) or formula (2) has two double bonds in one molecule, it may form a crosslinked structure in the polymerization reaction. Although a polymer having a crosslinked structure is generally difficult to dissolve in a general-purpose solvent, the polymer according to the present invention has high solubility in a general-purpose solvent because the crosslinking density is not high. In addition, as described later, a cyclization reaction may occur during the polymerization reaction, and the main chain structure of the polymer becomes a linear structure in which the ring structure is linked by an ethylene group, and exhibits excellent solubility in general-purpose solvents. . However, the polymer by the fluorine-containing compound of the present invention is not limited to a polymer that is soluble in a general-purpose solvent. For example, it is possible to make a polymer having a high degree of crosslinking by examining the polymerization conditions or the type of polymerizable monomer used in copolymerization. As a result, a polymer that does not dissolve in not only a general-purpose solvent but also a fluorinated solvent can be formed, and can be applied as a coating or molded product having heat resistance and / or solvent resistance.

  The fluorine-containing compound having the structure represented by the above formula (1) becomes a polymer having a cyclopentene ring even after polymerization, and a double bond may remain in the polymer. When it is desired to maintain the transparency of the polymer even after long-term use, a hydrogenation catalyst is used to eliminate the double bond in the polymer, or a hydrogenation reaction is performed, and a phenol compound or amine is used to suppress coloring. You may mix | blend antioxidants, such as a compound. In addition, the polymer obtained by polymerizing the fluorine-containing compound having the structure represented by the above formula (1) may have a high crosslinking density because the cyclization reaction is difficult to occur during the polymerization reaction. . Therefore, a polymer composition for obtaining a heat-resistant and / or solvent-resistant transparent coating or molded product can be obtained by adding a water addition reaction or an antioxidant after polymerization. On the other hand, a polymer made of a fluorine-containing compound having a structure represented by the above formula (2) does not contain a double bond in the molecule, and therefore becomes a polymer having excellent transparency even in long-term use.

  The polymerizable monomer used for copolymerization with the fluorine-containing compound of the present invention is a compound having a polymerizable double bond and is not particularly limited. However, olefins, vinyl ethers, allyl ethers, vinyl carboxylates, Examples thereof include allyl carboxylate, methacrylic acid ester, acrylic acid ester and the like. In the present invention, methacrylic acid ester or acrylic acid ester generally used in bulk or solution polymerization under normal pressure is suitable, for example, methyla (meth) acrylate, ethyla (meth) acrylate, propyla (meth). Examples include acrylate, hydroxyethyla (meth) acrylate, benzyla (meth) acrylate, phenyla (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate and the like. In addition to these, a (meth) acrylate having a long chain alkyl group such as lauryl (meth) acrylate and octyl (meth) acrylate, trifluoroethyl (meth) acrylate and 2,3,3,3-pentafluoropropyl Short chain fluoroalkyl (meth) acrylates such as (meth) acrylate or long chain fluoroalkyl (meth) acrylates such as 1,1,2,2-tetrahydroperfluorooctyl (meth) acrylate can be used.

  Next, an optical element, a functional thin film and a resist film made of a polymer of a fluorine-containing compound according to the present invention, and methods for producing them will be described.

  A polymer of a fluorine-containing compound or a copolymer thereof according to the present invention is excellent in transparency and has a high content of fluorine element having low refractive index property, low contamination property and water repellency, so that it can be used for lenses, prisms, conductive films. It can be used as a protective film for optical elements such as an optical plate, an optical disk, a mirror, a low reflection film or a water repellent film. When the optical element is an inorganic substance such as glass, ceramic or metal, the polymer of the fluorine-containing compound according to the present invention is a general-purpose product such as tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, butyl acetate, etc. After coating and coating using a solution dissolved in a solvent at a predetermined concentration, a protective film or a low reflection film is formed by a heat drying method. In the case where the optical element is a plastic, primer treatment is performed in advance so that the plastic optical element is not easily dissolved in the general-purpose solvent, and then the polymer of the fluorine-containing compound according to the present invention or a copolymer thereof is used. A method of applying and coating with a solution having a polymer is employed. When the plastic optical element is a crosslinkable resin, a solution containing a polymer of a fluorine-containing compound or a copolymer thereof according to the present invention may be directly coated on the plastic optical.

  In the present invention, the fluorine-containing compound according to the present invention can be used to form a coat film by plasma polymerization on an optical element substrate by a vacuum deposition method, a sputtering method, or the like. Further, after the composition comprising the fluorine-containing compound or other monomer copolymerizable with the fluorine-containing compound according to the present invention is dissolved in a solvent such as alcohol together with a thermal polymerization initiator or a photopolymerization initiator, It is also possible to form a coat film by applying it on the surface and evaporating and drying the solvent, followed by heat polymerization or photopolymerization such as ultraviolet rays.

  The polymer of a fluorine-containing compound or a copolymer thereof according to the present invention can be used as a material for lenses, prisms, optical fibers or optical waveguides used as plastic optical elements. The plastic lens or prism can be produced by injection molding or injection compression molding using a lens-shaped or prism-shaped mold, as in the case of acrylic resin or polycarbonate resin. The plastic optical fiber is composed of two types of polymers, a core and a clad. The polymer of the fluorine-containing compound of the present invention or a copolymer thereof is used as a material for the core and / or the clad according to the refractive index. be able to. The production of plastic optical fiber is obtained by supplying the core material and the clad material to the compound spinning machine, respectively, melt-spinning the core and the clad at a high temperature, and forming into a fiber having a predetermined core diameter and clad diameter. . The optical waveguide is formed, for example, by coating a polymer of a fluorine-containing compound according to the present invention or a copolymer thereof as a positive resist material on a substrate and forming a core pattern by radiation such as X-rays or electron beams. It is obtained by coating a low refractive index material such as silicone resin or perfluoro resin around the periphery.

  In the present invention, when a plastic optical element is formed, a method by plasma polymerization of a fluorine-containing compound according to the present invention can be employed as in the case of a protective film or a low reflection film. Moreover, after forming the external shape of a plastic optical element using the composition which mixed the polymerization initiator by heat or light with the fluorine-containing compound by this invention, it superposes | polymerizes by heat or light, and produces an optical element. Also good. For example, a clad of a plastic optical fiber can be formed by applying a fluorine compound according to the present invention together with a photopolymerization initiator in a low refractive index monomer around a core and then photopolymerizing. it can.

  Since the fluorine-containing compound polymer or copolymer thereof according to the present invention has a large content of elemental fluorine having an effect of reducing the friction coefficient during sliding, it has low wear and / or low contamination functionality. The coating material or the material for the thin film can be used. The functional paint or thin film can be produced by the same method as in the case of the protective film or the low reflection film.

  An acrylic polymer such as polymethylmethacrylate is a decomposable polymer by radiation such as X-rays or electron beams, but has a drawback of low sensitivity when used as a resist material. It is known that a fluorine-containing polymer having a large X-ray or electron beam absorption coefficient can be used as a positive resist having high sensitivity and high resolution. The polymer of the fluorine-containing compound of the present invention or a copolymer thereof may be used as a resist material by applying a solution dissolved in a general-purpose solvent on a substrate such as silicon or glass and then evaporating and drying the solvent. it can. The resist film thickness is set to a desired value by adjusting the type of solvent used and the non-volatile content of the resist solution and optimizing the coating method such as the spin coat method and the doctor blade method.

  EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[Example 1]
<Synthesis of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene>
Under an argon atmosphere, a mixture of 2.46 g (44.0 mmol) of KOH and 4.24 g (20.0 mmol) of octafluorocyclopentene (OFCP) was cooled to 0 ° C., and 2.7 ml (40.0 mmol) of allyl alcohol was slowly added dropwise. did. The mixture was stirred at 0 ° C. for 1 hour and then returned to room temperature and stirred for 4 hours. The obtained reaction mixture was washed with purified water, dried over an anhydrous sodium sulfate column, and the resulting oily residue was distilled under reduced pressure (0.1 kPa / bath temperature 90 to 100 ° C.) through a reaction tube. The yield of the synthesized product is 4.94 g (17.2 mmol), and the yield is 86%. As a result of analysis by various spectra, this synthesized product shows the following detection peaks, and thus 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene (FIG. 1). It was confirmed that the structure is a fluorine-containing compound in which R ¹ , R ² , R ³ and R ⁴ are all hydrogen.

¹⁹ F-NMR (nuclear magnetic resonance absorption spectrum) δ [ppm]
-55.03 (2F, s), -35.23 (4F, s)
¹ H-NMR δ [ppm] 4.72 (4H, m), 5, 41 (4H, m),
5.97 (2H, m).
IR (infrared absorption spectrum) [cm ⁻¹ ] 1685 (C═C)
MS (mass spectrum) [m / e] 288

[Example 2]
<Synthesis of 1,2-bis (2-butenyloxy) -3,3,4,4,5,5-hexafluorocyclopentene>
Under an argon atmosphere, a mixture of 1.43 g (24.0 mmol) of KOH and 4.24 g (20.0 mmol) of OFCP was cooled to 0 ° C., and crotyl alcohol 2 having a structure of (CH ₃ ) CH═CH—CH ₂ —OH. .88 g (40.0 mmol) was slowly added dropwise. The mixture was stirred at 0 ° C. for 1 hour as it was, then raised to room temperature and stirred for 22 hours. The obtained reaction mixture was washed with purified water, dried over an anhydrous sodium sulfate column, and the resulting oily residue was distilled under reduced pressure (0.1 kPa / bath temperature 110 to 120 ° C.) through a reaction tube. The yield was 66.0%. As a result of analysis by ¹⁹ F-NMR, ¹ H-NMR, IR and MS, this synthesized product was analyzed by 1,2-bis (2-butenyloxy) -3,3,4,4,5,5-hexafluorocyclopentene ( It was confirmed that the structure shown by 2a in FIG. 1 was a fluorine-containing compound in which R ¹ and R ² are methyl groups, and R ³ and R ⁴ are hydrogen.

[Example 3]
<Synthesis of 1,2-bis (3-phenyl-2-propenyloxy) -3,3,4,4,5,5-hexafluorocyclopentene>
In an argon atmosphere, a mixture of 1.43 g (24.0 mmol) of KOH and 4.24 g (20.0 mmol) of OFCP was cooled to 0 ° C., and cinnamyl having the structure of (C ₆ H ₅ ) CH═CH—CH ₂ —OH. 5.36 g (40.0 mmol) of alcohol was slowly added dropwise. The mixture was stirred as it was at 0 ° C. for 1 hour, then raised to room temperature and stirred for 14 hours. The obtained reaction mixture was washed with purified water, dried over an anhydrous sodium sulfate column, and the resulting oily residue was distilled under reduced pressure (0.1 kPa / bath temperature 120 ° C.) through a reaction tube. This synthesized product was analyzed by ¹⁹ F-NMR, ¹ H-NMR, IR and MS, and as a result, 1,2-bis (3-phenyl-2-propenyloxy) -3,3,4,4,5,5 -It was confirmed to be hexafluorocyclopentene (a fluorine-containing compound having a structure shown by 2a in Fig. 1, wherein R ¹ and R ² are phenyl groups, and R ³ and R ⁴ are hydrogen).

[Example 4]
<Synthesis of 1- (2-butenyloxy) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentene>
In order to synthesize 1- (2-butenyloxy) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentene, first, 1- (2-butenyloxy) -2,3,3,4 , 4,5,5-Peptafluorocyclopentene was synthesized. Under an argon atmosphere, a mixture of 1.43 g (24.0 mmol) of KOH and 4.24 g (20.0 mmol) of OFCP was cooled to 0 ° C., and 1.44 g (20.0 mmol) of crotyl alcohol was slowly added dropwise. The mixture was stirred at 0 ° C. for 1 hour as it was, then raised to room temperature and stirred for 22 hours. The obtained reaction mixture was washed with purified water, dried over an anhydrous sodium sulfate column, and the resulting oily residue was distilled under reduced pressure (0.1 kPa / bath temperature 65-80 ° C.) through a reaction tube. Yield 3.5 g (13.3 mmol). Yield 66%. As a result of analysis by ¹⁹ F-NMR, ¹ H-NMR, IR and MS, this synthesized product was analyzed by 1- (2-butenyloxy) -2,3,3,4,4,5,5-peptafluorocyclopentene ( It was confirmed that the structure shown by 1b in FIG. 1 was a fluorine-containing compound in which R ¹ is a methyl group and R ³ is hydrogen.

1.70 g (6.00 mmol) of 1- (2-butenyloxy) -2,3,3,4,4,5,5-peptafluorocyclopentene synthesized in this way and 0.43 g (7.20 mmol) of KOH The mixture was cooled to 0 ° C. under an argon atmosphere, and 0.35 g (6.00 mmol) of allyl alcohol was slowly added dropwise. The mixture was stirred as it was at 0 ° C. for 1 hour, then raised to room temperature and stirred for 66 hours. The obtained oily residue was washed with purified water, dried over an anhydrous sodium sulfate column, and then the oily residue obtained was subjected to reduced pressure treatment (0.1 kPa / bath temperature 100 to 110 ° C.) using a reaction tube. The yield of this synthesized product was 1.50 g (5.00 mmol), and the yield was 83%. As a result of analysis by ¹⁹ F-NMR, ¹ H-NMR, IR and MS, 1- (2-butenyloxy) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentene It was confirmed that it is a structure shown by 2b in FIG. 1 and R ¹ is a methyl group and R ² , R ³ and R ⁴ are hydrogen.

[Example 5]
<Synthesis of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone>
Under an argon atmosphere, 4.94 g (17.2 mmol) of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene obtained in Example 1 was added at a bath temperature of 170 to 180 ° C. For 4 hours, and then vacuum distillation (0.1 kPa / bath temperature 90 to 150 ° C.) was performed. The yield of the synthesized product was 4.49 g (15.6 mmol), and the yield was 91%. The GC-MS spectrum and ¹ H-NMR spectrum of this synthesized product are shown in FIGS. 3 and 4, respectively. As a result of analysis by various spectra, the following detection peaks are shown, so that 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentanone (in 3a of FIG. 2) It was confirmed that the structure is a fluorine-containing compound in which R ¹ , R ² , R ^3, and R ⁴ are all hydrogen.

¹⁹ F-NMR δ [ppm] −62.04 (1F, d),
-61.01 (1F, d), -57.50 (1F, d),
-56.32 (1F, d), -51.27 (1F, t),
-46.36 (1F, s)
¹ H-NMR δ [ppm] 2.73 (2H, m), 4.01 (2H, m),
5.23 (1H, m), 5.27 (1H, m),
5.31 (1H, m), 5.75 (1H, m),
5.81 (1H, m), 5.87 (1H, m)
IR [cm ⁻¹ ] 1788 (C═O), 1645 (C═C), 1168 (C—O)
MS [m / e] 288

[Example 6]
<2- (2-butenyl) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone and / or 1- (2-butenyl) -1-allyloxy-3,3,4 Of 4,4,5,5-hexafluorocyclopentanone>
Under an argon atmosphere, 1.50 g (4.96 mmol) of 1- (2-butenyloxy) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentene obtained in Example 4 was added at a bath temperature of 170. After refluxing at ~ 180 ° C for 4 hours, vacuum distillation (0.1 kPa / bath temperature 130-140 ° C) was performed. The yield of the synthesized product was 0.87 g (2.28 mmol), and the yield was 58%. The GC-MS spectrum of this synthesized product is shown in FIG. From the GC-MS spectrum shown in FIG. 5, 2- (2-butenyl) -2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone (having the structure shown by 3b in FIG. 2). The substituent R ¹ is a methyl group, and R ² , R ³ and R ⁴ are hydrogen) and / or 1- (2-butenyl) -1-allyloxy- ³ , ^{3, 4, 4,} 5 5- (a structure represented by 3c of FIG. 2, the substituents R ¹ is a methyl group, R ^2, a fluorine-containing compound R ³ and R ⁴ are hydrogen) hexafluoropropane cyclopentanone generation of confirmed It was.

[Examples 7 to 11]
<Homofluoropolymerization and solution polymerization of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone>
In solution polymerization, toluene was used as a polymerization medium. 1.44 g of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentanone obtained in Example 5 was added to a glass polymerization tube in a predetermined amount of a polymerization initiator ( After dissolving in 1 ml of toluene together with benzoyl peroxide (BOP) or azoisobutylnitrile (AIBN)), (1) degassing under cooling at -78 ° C. and (2) room temperature dissolution was repeated three times, sealed, The polymerization was carried out at a temperature of for a predetermined time. Thereafter, the polymer containing toluene was dissolved in ethyl acetate, dropped into hexane and reprecipitated, and then the solvent was distilled off under reduced pressure.

  In the single bulk polymerization, a predetermined amount of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene obtained in Example 5 and a polymerization initiator are placed in a glass polymerization tube. BPO or AIBN was uniformly mixed and added, (1) Degassing under cooling at −78 ° C. and (2) room temperature dissolution were repeated three times, sealed, and then heated and polymerized at a predetermined temperature for a predetermined time. Thereafter, the obtained polymer was dissolved in ethyl acetate, dropped into hexane and reprecipitated, and then the solvent was distilled off under reduced pressure.

  As a result of carrying out the polymerization by changing the charge amount of the initiator and the polymerization conditions (temperature and time), the number average molecular weight (Mn), the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn) of the obtained polymer and Table 1 shows the glass transition temperature (Tg). The molecular weight of the polymer was determined by gel permeation chromatography (GPC) using tetrahydrofuran as the fluid medium. The Tg of the polymer was measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min, and the temperature at the midpoint of the inflection point in the endothermic curve was taken as Tg.

In order to examine the degree of polymerization of the polymer obtained in Example 11, IR measurement was performed on the fluorine-containing compound (monomer) before polymerization and the polymer after polymerization. Infrared absorption (IR) spectra before and after polymerization are shown in FIG. Absorption of the C═C bond (1654 cm ⁻¹ ) observed in the fluorine-containing compound (monomer) has almost completely disappeared in the polymer after polymerization, and the double bonds of both the allyloxy group and the allyl group are not polymerized. Confirmed to be involved. Since the polymer obtained in Example 11 is soluble in a general-purpose solvent such as ethyl acetate, the crosslinking density is not increased or a cyclic structure represented by the following formula (6) is formed. it is conceivable that.

  As shown in Table 1, in the polymer obtained by polymerizing the fluorine-containing compound having the structure represented by the above formula (2) of the present invention, the glass transition temperature is improved by optimizing the polymerization conditions. A polymer having a temperature higher than 108 ° C. of Cytop (registered trademark), which is a transparent fluorine-containing polymer, can be obtained. In addition, the polymers shown in Table 1 were measured by UV-vis spectrum measurement using a film thickness of 0.5 mm. As a result, when BPO was used as a polymerization initiator, 280 nm or more, and when AIBN was used, It was found that the light transmittance was 90% or more in the ultraviolet and visible regions of 245 nm or more, and it was confirmed that the film had excellent transparency.

[Examples 12 to 14]
<Bulk polymerization of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone and other polymerizable monomer>
Monomer capable of copolymerization with 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene (fluorinated compound 3a) obtained in Example 5 in a glass polymerization tube As methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (FEMA) or 1- (3-butenyloxy) -2,3,3,4,4,5-heptafluorocyclopentene (fluorinated compound A) Are mixed in a blending amount of 50/50 (mol%), and a predetermined amount of AIBN or BPO is added to make the monomer composition uniform. The dissolution was repeated three times, sealed, and then polymerized by heating at a predetermined temperature for a predetermined time. 1- (3-Butenyloxy) -2,3,3,4,4,5-heptafluorocyclopentene (fluorine-containing compound A) was synthesized by the same method as described in the aforementioned Japanese Patent No. 4399608. Monomer. Thereafter, the obtained polymer was dissolved in ethyl acetate, dropped into hexane and reprecipitated, and then the solvent was distilled off under reduced pressure. Table 2 shows the glass transition temperature (Tg) of the polymer obtained as a result of polymerization by changing the charge of the initiator and the polymerization conditions (temperature and time).

[Examples 15 to 19]
<Single bulk polymerization and solution polymerization of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene>
Instead of 2-allyl-2-allyloxy-3,3,4,4,5,5-hexafluorocyclopentanone as a fluorine-containing compound, a fluorine-containing compound having a structure represented by the above formula (1) Using 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene, single bulk polymerization and solution polymerization were performed in the same manner as in Examples 7-11. Table 3 shows the glass transition temperature (Tg) of the obtained polymer.

  As shown in Table 3, the single bulk and solution polymerization of 1,2-bis (allyloxy) -3,3,4,4,5,5-hexafluorocyclopentene has a slightly higher Tg than the polymer shown in Table 1. It was found that there is a tendency to have. Moreover, as a result of performing the UV-vis spectrum measurement using the film thickness of 0.5 mm, the polymer shown in Table 3 has excellent transparency similar to the polymers obtained in Examples 7 to 11. It could be confirmed.

[Example 20]
<Preparation of protective film and low reflection film>
The polymers obtained in Examples 11, 13, and 14 were dissolved using tetrahydrofuran (THF) as a solvent so as to have a nonvolatile content of 10% by mass to obtain a uniform transparent solution. After applying this solution on the glass substrate, THF was volatilized by performing a heat-drying process under the conditions of 60 ° C. for 30 minutes and 100 ° C. for 20 minutes to produce a 10 μm uniform protective film on the glass substrate. As a comparative example, a solution in which polymethyl methacrylate (PMMA) was dissolved in 10% by weight of THF was applied on a glass substrate, and heat-dried under the same conditions as described above. A protective film was produced.

  The test sample thus obtained was stained with soot, and then wiped off with a cloth, and the amount of soot remaining on the sample surface was compared to evaluate the contamination resistance of the film surface. As a result, the protective film produced from the polymers obtained in Examples 11, 13, and 14 showed almost no stain, whereas the sample using PMMA as the protective film was stained black.

  In addition, the reflectance of each glass substrate sample on which a protective film was formed was evaluated before evaluating the stain resistance by soot. As a result, it was confirmed that the reflectance of the glass substrate using the polymer obtained in Examples 11, 13 and 14 as the protective film can be significantly reduced as compared with the glass substrate using PMMA as the protective film.

[Example 21]
<Production of plastic optical fiber>
Polymethylmethacrylate (PMMA; with a refractive index of 1.492) produced by continuous bulk polymerization was used as a core material, and the polymers obtained in Examples 11 to 13 were used as clad materials, respectively, and supplied to the composite spinning machine, The core and the clad were melt-spun at the core and the clad at 235 ° C. to produce a plastic optical fiber having a fiber system of 1000 μm (core diameter: 98 μm, clad thickness: 5.0 μm). When light was incident on the plastic optical fiber thus spun to a length of 5 m using a light emitting element (LED) from one end of the optical fiber, light emission was observed from the other end. Since the polymers obtained in Optical Examples 11 to 13 were highly transparent and had a refractive index of less than 1.45, it was confirmed that they could be applied as a clad material for plastic optical fibers.

  Further, composite spinning was performed using the polymer obtained in Example 12 as a core material and a vinylidene fluoride / tetrafluoroethylene (80 mol% / 20 mol%) copolymer (refractive index of 1.403) as a cladding material. The core and the clad were melt melt-spun at a core and a clad at 240 ° C. to produce a plastic optical fiber having a fiber type of 1000 μm (core diameter: 98 μm, clad thickness: 5.0 μm). When the plastic optical fiber spun to 5 m obtained in this way was made to enter light using an LED from one end of the optical fiber, emission of light was observed from the other end. The polymer obtained in Example 12 was confirmed to be highly transparent and applicable as a core material for plastic optical fibers.

[Example 22]
<Production of wear-resistant paint or thin film>
Using mild steel as a base metal, the mild steel was ultrasonically washed in trichlorethylene, then dried at 300 ° C. for 20 minutes, surface roughened with sandpaper, and washed with water. Next, after the polymer obtained in Example 13 was dissolved in methyl ethyl ketone at a nonvolatile content concentration of 10% by mass, it was coated on the mild steel and dried under conditions of 70 ° C. for 30 minutes and 120 ° C. for 1 hour. Thus, a sliding material having a coating film with a film thickness of 30 μm was produced. As a comparative example, after applying polytetrafluoroethylene (PTFE) dispersion paint on mild steel subjected to the same surface treatment as described above, pre-drying at 90 ° C. for 30 minutes and performing a baking treatment at 380 ° C. for 45 minutes Then, a sliding material having a coating film made of PTFE having a film thickness of 30 μm was produced by cooling.

Place the mild steel having a coating film made of the polymer or PTFE obtained in Example 13 on the lower side, and use a wear characteristic evaluation device of a system in which a mild steel cylinder not coated with the coating is in contact with the rotating steel, The amount of wear after rotating for 15 minutes under a constant pressure of 1.4 kgf / cm ² and a sliding speed of 41 cm / second was measured. As a result, the coating film made of the polymer obtained in Example 13 and the coating film made of PTFE had very little wear, and no change was observed in the surface appearance of the mild steel having the coating film. Although the polymer obtained in Example 13 has a slightly larger amount of wear than the coating film made of PTFE, it has been confirmed that it has almost no influence on the properties as a sliding material and can be used as a wearable coating film. .

[Example 23]
<Preparation of positive resist>
A solution obtained by dissolving the polymer obtained in Example 11 in tetrahydrofuran (THF) at a nonvolatile content concentration of 5% by mass was spin-coated on a silicon substrate, and then heat-dried under conditions of 60 ° C. for 30 minutes and 100 ° C. for 30 minutes. As a result, THF was volatilized to form a uniform resist film of 5 μm on the silicon substrate. As a comparative example, a solution in which polymethyl methacrylate (PMMA) was dissolved in 5% by weight of THF was spin-coated on a silicon substrate, and heat-dried under the same conditions as described above, and 5 μm on the silicon substrate. A resist film was prepared. Next, using a mask having five straight lines patterned with a width of 5 μm and a line spacing of 10 μm, patterning was performed by irradiating both resist films with an electron beam. Since the pattern is formed by polymer decomposition of the portion irradiated with the electron beam, the silicon substrate was washed with alcohol and water after the electron beam irradiation to remove the decomposition product. Comparing the energy of the minimum electron beam capable of forming a rectangular pattern having a width of 5 μm and a spacing of 5 μm for both resist films, the polymer resist film obtained in Example 11 is used more than the PMMA resist film. It was confirmed that the electron beam energy can be reduced and the sensitivity is increased by about one digit.

  As described above, the novel fluorine-containing compound according to the present invention and the polymer obtained by polymerizing the fluorine-containing compound can freely set the glass transition (Tg), and are transparent and soluble in general-purpose solvents. Functional polymer having a functional group and a polymerizable monomer capable of forming the functional polymer, and can be applied to a wide range of applications such as an optical element and a functional paint, thin film or resist film having wear resistance, low contamination, or water repellency. Therefore, the usefulness is extremely high.

Claims (10)

A fluorine-containing compound having a structure represented by the following formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group) The fluorine-containing compound according to claim 1, wherein R ¹ and R ² are each independently hydrogen, a methyl group or a phenyl group, and R ³ and R ⁴ are hydrogen. The fluorine-containing compound which has a structure represented by following formula (2) obtained by the Claisen rearrangement reaction of the fluorine-containing compound of Claim 1.

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an aryl group) The fluorine-containing compound according to claim 3, wherein R ¹ and R ² are each independently hydrogen, a methyl group or a phenyl group, and R ³ and R ⁴ are hydrogen.   The manufacturing method of the polymer of the said fluorine-containing compound obtained by radical-copolymerizing the fluorine-containing compound in any one of Claims 1-4 independently with the radical polymerization or another radically polymerizable monomer.   An optical element comprising a polymer of a fluorine-containing compound produced by the method according to claim 5.   An optical element comprising a polymer of a fluorine-containing compound, wherein the optical element according to claim 6 is a protective film, a low reflection film, or a water repellent film.   An optical element comprising a polymer of a fluorine-containing compound, wherein the optical element according to claim 6 is a lens, a prism, a light guide plate, an optical waveguide, or an optical fiber.   A functional thin film comprising a polymer of a fluorine-containing compound produced by the method according to claim 5 and used as a wear-resistant or low-contamination paint or thin film.   A resist film for lithography comprising a polymer of a fluorine-containing compound produced by the method according to claim 5.

Images