JP2007177046A - Optical part using fluorine-containing cyclic olefin polymer - Google Patents
Optical part using fluorine-containing cyclic olefin polymer Download PDFInfo
- Publication number
- JP2007177046A JP2007177046A JP2005375776A JP2005375776A JP2007177046A JP 2007177046 A JP2007177046 A JP 2007177046A JP 2005375776 A JP2005375776 A JP 2005375776A JP 2005375776 A JP2005375776 A JP 2005375776A JP 2007177046 A JP2007177046 A JP 2007177046A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- cyclic olefin
- polymer
- containing cyclic
- olefin polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 180
- 239000011737 fluorine Substances 0.000 title claims abstract description 156
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 88
- 230000003287 optical effect Effects 0.000 title claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract 7
- 239000000463 material Substances 0.000 claims abstract description 46
- 125000001153 fluoro group Chemical group F* 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 149
- 229920000642 polymer Polymers 0.000 description 84
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 76
- 239000000243 solution Substances 0.000 description 70
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 66
- 238000005984 hydrogenation reaction Methods 0.000 description 59
- 239000010408 film Substances 0.000 description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- -1 hexafluoroisopropyl group Chemical group 0.000 description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 38
- 150000001336 alkenes Chemical group 0.000 description 31
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 22
- 239000000178 monomer Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 20
- 239000010409 thin film Substances 0.000 description 20
- 239000012528 membrane Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 18
- 238000002834 transmittance Methods 0.000 description 18
- 239000004417 polycarbonate Substances 0.000 description 17
- 229920000515 polycarbonate Polymers 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 14
- 238000004528 spin coating Methods 0.000 description 14
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 13
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- 230000004075 alteration Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 13
- 229910052723 transition metal Inorganic materials 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 7
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- 238000011156 evaluation Methods 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 3
- RNVJDIGFTGLKCE-UHFFFAOYSA-N 2,3,3-trifluoro-2-(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)(F)C2(F)F RNVJDIGFTGLKCE-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229960004624 perflexane Drugs 0.000 description 3
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000306 polymethylpentene Polymers 0.000 description 3
- 239000011116 polymethylpentene Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- ICGUZQMJLPIVHP-UHFFFAOYSA-N 2,3-difluoro-2-(1,1,2,2,2-pentafluoroethyl)-3-(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)C(F)(F)F)(F)C2(F)C(F)(F)F ICGUZQMJLPIVHP-UHFFFAOYSA-N 0.000 description 2
- PBNBTJLQHASCPE-UHFFFAOYSA-N 5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C(F)(F)F)CC1C=C2 PBNBTJLQHASCPE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、Ｄ線波長光に対する屈折率が１．４８以下であり、かつ、少なくとも一般式（１）で表される繰り返し構造単位を有するフッ素含有環状オレフィンポリマーを含む光学部品材料に関し、詳しくは、該光学部品材料を成形して得られる反射防止膜および光学レンズに関する。
The present invention relates to an optical component material including a fluorine-containing cyclic olefin polymer having a refractive index of 1.48 or less with respect to D-line wavelength light and having at least a repeating structural unit represented by the general formula (1). The present invention relates to an antireflection film and an optical lens obtained by molding the optical component material.
近年のマルチメディア技術の発達に伴って、撮影記録映像の高画質化や受像映像の高精細化が要求されている。受像映像の高精細化では、受像機器のディスプレイ表面での反射を小さくして、光の映り込みによる見づらさを低減する必要がある。また、撮影時の高画質化のためには、使用するカメラやビデオカメラの光学系内で発生する収差を補正する必要がある。 With the development of multimedia technology in recent years, there has been a demand for higher image quality of captured and recorded images and higher definition of received images. In order to increase the definition of the received image, it is necessary to reduce the reflection on the display surface of the image receiving device to reduce the difficulty in viewing due to the reflection of light. In addition, in order to improve the image quality at the time of shooting, it is necessary to correct aberrations occurring in the optical system of the camera or video camera used.
一般に、ディスプレイ表面での反射を抑制するために、表面には反射防止処理が施されている。非特許文献１によると、反射抑制には、表面に凹凸をつけて反射光を散乱させて防眩効果を利用する方法と、反射波の光の干渉効果を利用する方法がある。後者の効果を利用する反射防止膜は、高屈折率の透明基材と低屈折率の薄膜から構成されている。そして、反射防止効果を向上させるためには、より屈折率の低い材料を薄膜に使用することが有効であることが記載されている。
また、非特許文献２によると、撮像機器の光学系内で発生する収差には、球面収差、コマ収差、非点収差、歪曲収差、像面収差といった単色収差と色収差がある。特に、色収差が大きくなると色にじみが大きくなり、カラー画像としての画質が極端に低下する。この色収差補正は、高屈折率レンズとアッベ数の大きいレンズを組み合わせた、組み合わせレンズによって改善できることが記載されている。
Generally, in order to suppress reflection on the display surface, the surface is subjected to antireflection treatment. According to Non-Patent Document 1, there are two methods for suppressing reflection: a method of using unevenness on the surface and scattering the reflected light to use the antiglare effect, and a method of using the interference effect of reflected wave light. The antireflection film utilizing the latter effect is composed of a transparent substrate having a high refractive index and a thin film having a low refractive index. In order to improve the antireflection effect, it is described that it is effective to use a material having a lower refractive index for the thin film.
According to Non-Patent Document 2, the aberrations generated in the optical system of the imaging device include monochromatic aberrations such as spherical aberration, coma aberration, astigmatism, distortion aberration, and field aberration, and chromatic aberration. In particular, when the chromatic aberration increases, the color blur increases, and the image quality as a color image extremely decreases. It is described that this chromatic aberration correction can be improved by a combination lens in which a high refractive index lens and a lens having a large Abbe number are combined.
色収差補正のための高屈折率レンズ材料としてポリカーボネート、アッベ数の大きいレンズ材料としてフッ化カルシウムが知られている。しかしながら、フッ化カルシウムはポリカーボネートと異なって無機化合物の結晶であるために、レンズとして使用するには単結晶から削りだし研磨を行う必要がある。さらに、軟らかく傷が付きやすいこと、劈開しやすいことから、製造コストが高価であるとともに、大量生産に適さない問題があった。 Polycarbonate is known as a high refractive index lens material for correcting chromatic aberration, and calcium fluoride is known as a lens material having a large Abbe number. However, since calcium fluoride is a crystal of an inorganic compound unlike polycarbonate, it needs to be cut from a single crystal and polished for use as a lens. Furthermore, since it is soft and easily scratched and is easy to cleave, there are problems that it is expensive to manufacture and is not suitable for mass production.
従って、これらの問題を解決するための無色透明な低屈折率の材料やアッベ数の大きい有機材料が望まれていた。
無色透明な低屈折率材料として、非特許文献３には、以下の一般式（２）であらわされる繰り返し構造単位を含む、Ｄ線波長光に対する屈折率が１．２９〜１．３１のパーフルオロポリマーが開示されている。
Therefore, a colorless and transparent low refractive index material and an organic material having a large Abbe number for solving these problems have been desired.
As a colorless and transparent low-refractive index material, Non-Patent Document 3 includes perfluorocarbons having a refractive index of 1.29 to 1.31 with respect to D-line wavelength light, including a repeating structural unit represented by the following general formula (2). A polymer is disclosed.
また上記のパーフルオロポリマーは、熱安定性が悪いために、高温で加熱成形すると、ポリマーが分解して腐食性のフッ素ガスを発生させる。このフッ素ガスによって、ステンレス製の成形用金型は腐食されるため、金型には耐腐食性を有する高価な材料を使用する必要がある。
In addition, since the above-mentioned perfluoropolymer has poor thermal stability, when it is thermoformed at a high temperature, the polymer is decomposed to generate corrosive fluorine gas. Since this fluorine gas corrodes the molding die made of stainless steel, it is necessary to use an expensive material having corrosion resistance for the die.
この他の溶融成形可能な低屈折率でアッベ数の大きい材料として、例えば、屈折率１．４６、アッベ数６１のポリ（４−メチル−１−ペンテン）がある。しかしながら、ポリ（４−メチル−１−ペンテン）は結晶性ポリマーであるために、成形により結晶化した部分の収縮率が大きく、また成形品中に非晶部分と結晶部分が存在することによって乱反射が生じて透明性を低下させるため、反射防止膜や光学レンズに必要な精密成形やレンズ用途には不向きである。
従って、フッ素原子を含まない溶媒にも可溶であり、屈折率が低く、透明性が高く、および表面極性が高い、即ち水接触角が小さい、反射防止膜用の材料、また、屈折率が低く、高いアッベ数を有し、透明性が高く、表面極性が高く、および熱可塑性であるとともに、熱安定性が良好である、光学レンズ用の材料の開発が望まれている。
As another material having a low refractive index and a large Abbe number that can be melt-molded, for example, poly (4-methyl-1-pentene) having a refractive index of 1.46 and an Abbe number of 61 is available. However, since poly (4-methyl-1-pentene) is a crystalline polymer, the shrinkage ratio of the part crystallized by molding is large, and the amorphous part and the crystalline part exist in the molded product, so that irregular reflection occurs. Therefore, it is not suitable for precision molding and lens applications required for antireflection films and optical lenses.
Therefore, it is also soluble in a solvent not containing fluorine atoms, has a low refractive index, high transparency, and high surface polarity, that is, a low water contact angle, a material for an antireflection film, and a refractive index. Development of materials for optical lenses that have low, high Abbe numbers, high transparency, high surface polarity, thermoplasticity, and good thermal stability is desired.
特許文献２には、１５７ｎｍの紫外線に対する吸収係数が３．０μｍ−１以下の高い透明性を示す部分的にフッ素原子を含有するフッ素含有環状オレフィンポリマーがあげられており、その透明性を活かしたペリクル膜への適用が開示されている。しかしながら、Ｄ線波長光に対する屈折率、アッベ数、表面極性、溶媒への溶解性についての特性や、それらの特性を利用した用途については開示されていない。
本発明は、Ｄ線波長光に対する屈折率が１．４８以下であり、かつ、少なくとも一般式（１）で表される繰り返し構造単位を有するフッ素含有環状オレフィンポリマーを含む光学部品材料、並びに、該光学部品材料を成形して得られる反射防止膜および光学レンズを提供することである。
The present invention provides an optical component material comprising a fluorine-containing cyclic olefin polymer having a refractive index with respect to D-line wavelength light of 1.48 or less and having at least a repeating structural unit represented by the general formula (1), and An object is to provide an antireflection film and an optical lens obtained by molding an optical component material.
本発明者らは、上記課題を解決すべく鋭意検討した結果、従来のパーフルオロポリマーと異なって、特定の構造を有するフッ素含有環状オレフィンポリマーが、屈折率が低く、フッ素を含まない溶媒にも可溶であり、表面極性が高いことから、反射防止膜用の材料に好適に使用できること、および、熱可塑性であるとともに、熱安定性が高く、表面極性が高く、透明性に優れ、高いアッベ数を有することから光学レンズ用の材料として好適に使用できることを見いだし、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a fluorine-containing cyclic olefin polymer having a specific structure, unlike a conventional perfluoropolymer, has a low refractive index and is free of fluorine. Since it is soluble and has a high surface polarity, it can be suitably used as a material for an antireflection film, and it is thermoplastic, has high thermal stability, high surface polarity, excellent transparency, and high Abbe Therefore, the present invention has been completed by finding that it can be suitably used as a material for optical lenses.
すなわち本発明は、
［１］Ｄ線波長光に対する屈折率が１．４８以下であり、かつ、少なくとも一般式（１）で表される繰り返し構造単位を有するフッ素含有環状オレフィンポリマーを含む光学部品材料の提供。
That is, the present invention
[1] Providing an optical component material including a fluorine-containing cyclic olefin polymer having a refractive index of 1.48 or less with respect to D-line wavelength light and having at least a repeating structural unit represented by the general formula (1)
［２］一般式（１）で表わされる繰り返し構造単位中のフッ素原子の含有率が２０〜７５質量％である、前記［１］に記載の光学部品材料の提供。
［３］フッ素含有環状オレフィンポリマーの水接触角が１０５°以下である、前記［１］または［２］に記載の光学部品材料の提供。
［４］フッ素含有環状オレフィンポリマーのアッベ数が６０以上である、前記[１]〜[３]に記載の光学部品材料の提供。
［５］前記［１］〜［４］に記載の光学部品材料を成形して得られる反射防止膜の提供。
［６］前記［１］〜［４］に記載の光学部品材料を成形して得られる光学レンズを提供することである。
[2] The provision of the optical component material according to [1], wherein the content of fluorine atoms in the repeating structural unit represented by the general formula (1) is 20 to 75% by mass.
[3] The optical component material according to [1] or [2], wherein the fluorine-containing cyclic olefin polymer has a water contact angle of 105 ° or less.
[4] The optical component material according to [1] to [3], wherein the Abbe number of the fluorine-containing cyclic olefin polymer is 60 or more.
[5] An antireflection film obtained by molding the optical component material according to [1] to [4].
[6] An optical lens obtained by molding the optical component material according to any one of [1] to [4].
本発明の、Ｄ線波長光に対する屈折率が１．４８以下であり、かつ、少なくとも一般式（１）で表される繰り返し構造単位を有するフッ素含有環状オレフィンポリマーは、フッ素原子を含まない有機溶媒に可溶であり、表面極性が高く、即ち水接触角が小さいことから、反射防止膜として好適に使用することができる。 The fluorine-containing cyclic olefin polymer of the present invention having a refractive index with respect to D-line wavelength light of 1.48 or less and having at least a repeating structural unit represented by the general formula (1) is an organic solvent containing no fluorine atom. Since it is soluble in water and has a high surface polarity, that is, a small water contact angle, it can be suitably used as an antireflection film.
また、熱可塑性であるとともに、優れた熱安定性を有することから射出成形を行なうことができ、光学レンズ等を生産効率良く得ることができる。
また、表面極性が高いことから、薄膜やレンズの表面硬度を強化するための表面コート層との密着性が良好であり、更に透明性に優れ、アッベ数が６０以上と大きいことから、色収差補正に際して高屈折率のレンズと組み合わせて好適に用いることができ、工業的に極めて価値がある。
Moreover, since it is thermoplastic and has excellent thermal stability, injection molding can be performed, and an optical lens or the like can be obtained with high production efficiency.
In addition, since the surface polarity is high, the adhesion with the surface coat layer for enhancing the surface hardness of the thin film and the lens is good, the transparency is excellent, and the Abbe number is as large as 60 or more, so chromatic aberration correction. In this case, it can be suitably used in combination with a lens having a high refractive index, and is extremely valuable industrially.
以下に、本発明におけるフッ素含有環状オレフィンポリマーからなる光学部品材料について詳述する。 Below, the optical component material which consists of a fluorine-containing cyclic olefin polymer in this invention is explained in full detail.
［フッ素含有環状オレフィンポリマー］
本発明におけるフッ素含有環状オレフィンポリマーは、少なくとも一般式（１）で表される繰り返し構造単位を有することを特徴としている。
[Fluorine-containing cyclic olefin polymer]
The fluorine-containing cyclic olefin polymer in the present invention is characterized by having at least a repeating structural unit represented by the general formula (1).
さらに詳しくは、式（１）中Ｒ1〜Ｒ4としては、例えば、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、トリフルオロエチル基、ペンタフルオロエチル基、ヘキサフルオロイソプロピル基、ヘプタフルオロイソプロピル基、ヘプタフルオロプロピル基、ヘキサフルオロ−２−メチルイソプロピル基、ノナフルオロブチル基、パーフルオロシクロペンチル基等のフッ素を含有する炭素原子数１〜１０のアルキル；トリフルオロメトキシ基、トリフルオロエトキシ基、ペンタフルオロプロポキシ基、ペンタフルオロブトキシ基、ヘキサフルオロ−２−メチルイソプロポキシ基、ヘプタフルオロブトキシ基、パーフルオロシクロペントキシ基等のフッ素を含有する炭素原子数１〜１０のアルコキシ；メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、２−メチルイソプロポキシメチル基、ブトキシメチル基等の炭素原子数２〜１０のエーテル基含有アルキルから選ばれる。また、ｎは、０または１の整数である。
More specifically, R 1 to R 4 in the formula (1) are, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a hexafluoroisopropyl group, or a heptafluoroisopropyl. Group, a heptafluoropropyl group, a hexafluoro-2-methylisopropyl group, a nonafluorobutyl group, a perfluorocyclopentyl group and other fluorine-containing alkyls having 1 to 10 carbon atoms; a trifluoromethoxy group, a trifluoroethoxy group, C1-C10 alkoxy containing fluorine such as pentafluoropropoxy group, pentafluorobutoxy group, hexafluoro-2-methylisopropoxy group, heptafluorobutoxy group, perfluorocyclopentoxy group; methoxymethyl group, Etoki Methyl group, propoxymethyl group, butoxymethyl group, selected from 2-methyl-iso-propoxymethyl group, an ether group-containing alkyl having 2 to 10 carbon atoms such as butoxymethyl groups. N is an integer of 0 or 1.
本発明においてフッ素含有環状オレフィンポリマーは、一般式（１）で表される繰り返し構造単位のみでもよく、一般式（１）のＲ1〜Ｒ4、Ｘおよびｎの少なくとも１つが互いに異なる二種類以上の構造単位からなるものであってもよい。さらに本発明の効果を損なわない範囲であれば一般式（１）で表される繰り返し構造単位以外の繰り返し構造単位を含んでいてもよいが、一般式（１）以外の繰り返し構造単位の含有量は、５０質量％以下であることが好ましい。 In the present invention, the fluorine-containing cyclic olefin polymer may be only the repeating structural unit represented by the general formula (1), and at least one of R 1 to R 4 , X and n in the general formula (1) is different from each other. It may consist of the following structural units. Furthermore, as long as the effect of the present invention is not impaired, a repeating structural unit other than the repeating structural unit represented by the general formula (1) may be included, but the content of the repeating structural unit other than the general formula (1). Is preferably 50% by mass or less.
本発明において、一般式（１）で表わされる構造単位中のフッ素原子の含有率は、以下の数式（１）により求めることができる。
フッ素原子の含有率（質量％）＝（ Ｆｎ × １９ ） × １００ ／ Ｆｗ （１）
ここで、数式（１）中、Ｆｎは一般式（１）で表わされる構造単位中のフッ素原子の数、Ｆｗは一般式（１）で表わされる構造単位の式量を表わす。
数式（１）で表されるフッ素原子の含有率は、２０〜７５質量％、好ましくは２０〜７０質量％である。
また、構造単位の同定と該構造単位中のフッ素含有率の測定は、ＮＭＲと元素分析を用いることによって測定することもできる。
In this invention, the content rate of the fluorine atom in the structural unit represented by General formula (1) can be calculated | required by the following Numerical formula (1).
Content of fluorine atom (% by mass) = (Fn × 19) × 100 / Fw (1)
In formula (1), Fn represents the number of fluorine atoms in the structural unit represented by general formula (1), and Fw represents the formula weight of the structural unit represented by general formula (1).
The content rate of the fluorine atom represented by Numerical formula (1) is 20-75 mass%, Preferably it is 20-70 mass%.
The identification of the structural unit and the measurement of the fluorine content in the structural unit can also be performed by using NMR and elemental analysis.
従来フッ素原子を含むポリマーは、そのポリマー中のフッ素原子の割合が多くなると屈折率は低くなるが、同時に表面極性は小さく、即ち水との接触角は大きくなる。
これに対して、一般式（１）で表わされる特定の構造を有するとともに、上記のフッ素含有率が特定の範囲にある、本発明のフッ素含有環状オレフィンポリマーは、フッ素原子による電子吸引効果によって紫外領域での光吸収が小さくなり、Ｄ線波長光に対する屈折率が１．４８以下と低いとともに、水接触角が１０５°以下の極めて優れた特性を有するポリマーである。
Conventional polymers containing fluorine atoms have a lower refractive index when the proportion of fluorine atoms in the polymer increases, but at the same time the surface polarity is small, that is, the contact angle with water is large.
On the other hand, the fluorine-containing cyclic olefin polymer of the present invention having a specific structure represented by the general formula (1) and having the above-described fluorine content in a specific range is ultraviolet light due to an electron withdrawing effect by fluorine atoms. Light absorption in the region is small, the refractive index with respect to D-line wavelength light is as low as 1.48 or less, and the polymer has extremely excellent characteristics with a water contact angle of 105 ° or less.
本発明においてフッ素含有環状オレフィンポリマーは、ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量（Ｍｗ）は、５００〜１，０００，０００、好ましくは５，０００〜３００，０００の範囲にある。この重量平均分子量（Ｍｗ）が５００以上であると、ポリマーとしての物性が発現することから好ましい。また、１，０００，０００以下であると、薄膜形成や射出成形時の流動性が損なわれることがなく好ましい。また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比である分子量分布（Ｍｗ／Ｍｎ）は、１．０〜５．０の範囲にあるが、例えば均一な厚みの薄膜形成や良好な射出成形性を得るためには、分子量分布は広い方が好ましく、１．４〜５．０、さらに１．５〜３．０であることが好ましい。
また、本発明におけるフッ素含有環状オレフィンポリマーは低屈折率であり、アッベ数が高い（以降、アッベ数が高いことを、高アッベ数と記載する）光学的特徴を有する。
なお、アッベ数とは、以下の数式（２）により表される数値で、可視光領域における屈折率変化の程度を示している。
In the present invention, the fluorine-containing cyclic olefin polymer has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 500 to 1,000,000, preferably 5,000 to 300,000. It is in the range. It is preferable that the weight average molecular weight (Mw) is 500 or more because physical properties as a polymer are expressed. Moreover, when it is 1,000,000 or less, the fluidity at the time of thin film formation or injection molding is not impaired, which is preferable. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is in the range of 1.0 to 5.0. In order to obtain good injection moldability, the molecular weight distribution is preferably wide, and is preferably 1.4 to 5.0, more preferably 1.5 to 3.0.
Moreover, the fluorine-containing cyclic olefin polymer in the present invention has a low refractive index and a high Abbe number (hereinafter, a high Abbe number is referred to as a high Abbe number).
The Abbe number is a numerical value represented by the following mathematical formula (2) and indicates the degree of change in the refractive index in the visible light region.
アッベ数（νｄ）＝（ｎｄ−１）／（ｎｆ−ｎｃ） （２）
ここで、数式（２）中、ｎｄはＤ線屈折率（波長５８９ｎｍ）、ｎｆはＦ線屈折率（波長４８６ｎｍ）、ｎｃはＣ線屈折率（波長６５６ｎｍ）を表わす。
従って、高アッベ数の物質は、可視光領域において屈折率変化が小さく直進性の高い性質であることを表している。
Abbe number (νd) = (nd−1) / (nf−nc) (2)
In formula (2), nd represents the D-line refractive index (wavelength 589 nm), nc represents the F-line refractive index (wavelength 486 nm), and nc represents the C-line refractive index (wavelength 656 nm).
Therefore, a substance having a high Abbe number has a property that the refractive index change is small in the visible light region and the straightness is high.
本発明のフッ素含有環状オレフィンポリマーのアッベ数は６０以上、好ましくは６０〜１２０であり、さらに６０〜１００であることが好ましい。
本発明におけるフッ素含有環状オレフィンポリマーは低屈折率で、高アッベ数であることから、例えば、ディスプレイや反射防止膜等の情報表示分野の光学フィルム；カメラ、ビデオカメラ、プロジェクションテレビ、レーザープリンター、マイクロレンズアレイ等の撮像および投影用光学レンズ；光ファイバー、光ファイバー用コネクター、光導波路等の情報伝送部品などの光学部品材料に好適に用いることができる。
The Abbe number of the fluorine-containing cyclic olefin polymer of the present invention is 60 or more, preferably 60 to 120, and more preferably 60 to 100.
Since the fluorine-containing cyclic olefin polymer in the present invention has a low refractive index and a high Abbe number, for example, an optical film for information display fields such as a display and an antireflection film; a camera, a video camera, a projection television, a laser printer, a micro Optical lenses for imaging and projection such as lens arrays; optical component materials such as optical transmission materials such as optical fibers, optical fiber connectors, and optical waveguides.
本発明におけるフッ素含有環状オレフィンポリマーは、一般式（１）で表わされる特定の構造を有することにより、Ｄ線に対する極めて低い屈折率を得ることができ、Ｄ線波長光に対する屈折率は、１．４８以下、好ましくは１．３０〜１．４８であり、この屈折率範囲において、光は優れた直進性を示す。なお、屈折率の下限値は空気の１であり、水は１．３３である。
また、本発明のフッ素含有環状オレフィンポリマーは、可視光領域の光線透過率が８０％以上、好ましくは８５〜１００％であることが好ましい。
The fluorine-containing cyclic olefin polymer in the present invention has a specific structure represented by the general formula (1), so that an extremely low refractive index with respect to D-line can be obtained. It is 48 or less, preferably 1.30 to 1.48. In this refractive index range, light exhibits excellent straightness. The lower limit of the refractive index is 1 for air and 1.33 for water.
The fluorine-containing cyclic olefin polymer of the present invention has a light transmittance in the visible light region of 80% or more, preferably 85 to 100%.
また、本発明におけるフッ素含有環状オレフィンポリマーの水接触角は１０５°以下、好ましくは５０〜１０５°、さらに８０〜１００°であることが好ましい。また、一般式（１）中のＸを酸素とすることによって、Ｘが炭素原子の場合よりも水接触角をさらに小さくすることができる。
また、本発明のフッ素含有環状オレフィンポリマーは、３００℃で５分間加熱したときの質量減少量が０．１％未満、好ましくは０．０７％未満であり、熱可塑性で且つ熱安定性に優れることから溶融成形することができる。
Further, the water contact angle of the fluorine-containing cyclic olefin polymer in the present invention is 105 ° or less, preferably 50 to 105 °, more preferably 80 to 100 °. In addition, when X in the general formula (1) is oxygen, the water contact angle can be further reduced as compared with the case where X is a carbon atom.
Further, the fluorine-containing cyclic olefin polymer of the present invention has a mass reduction amount of less than 0.1%, preferably less than 0.07% when heated at 300 ° C. for 5 minutes, and is thermoplastic and excellent in thermal stability. Therefore, it can be melt-molded.
［フッ素含有環状オレフィンポリマーの製造］
本発明においてフッ素含有環状オレフィンポリマーは、一般式（４）で表わされるフッ素含有環状オレフィン単量体を、開環重合触媒によって開環重合し、得られる重合体の主鎖のオレフィン部を水素添加処理することによって合成することができる。
[Production of fluorine-containing cyclic olefin polymer]
In the present invention, the fluorine-containing cyclic olefin polymer is obtained by subjecting the fluorine-containing cyclic olefin monomer represented by the general formula (4) to ring-opening polymerization using a ring-opening polymerization catalyst, and hydrogenating the olefin part of the main chain of the resulting polymer. It can be synthesized by processing.
さらに詳しくは、式（４）中Ｒ1〜Ｒ4としては、例えば、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、トリフルオロエチル基、ペンタフルオロエチル基、ヘキサフルオロイソプロピル基、ヘプタフルオロイソプロピル基、ヘプタフルオロプロピル基、ヘキサフルオロ−２−メチルイソプロピル基、ノナフルオロブチル基、パーフルオロシクロペンチル基等のフッ素を含有する炭素原子数１〜１０のアルキル；トリフルオロメトキシ基、トリフルオロエトキシ基、ペンタフルオロプロポキシ基、ペンタフルオロブトキシ基、ヘキサフルオロ−２−メチルイソプロポキシ基、ヘプタフルオロブトキシ基、パーフルオロシクロペントキシ基等のフッ素を含有する炭素原子数１〜１０のアルコキシ；メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、２−メチルイソプロポキシメチル基、ブトキシメチル基等の炭素原子数２〜１０のエーテル基含有アルキルから選ばれる。また、ｎは、０または１の整数である。 More specifically, R 1 to R 4 in the formula (4) are, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, hexafluoroisopropyl group, heptafluoroisopropyl. Group, a heptafluoropropyl group, a hexafluoro-2-methylisopropyl group, a nonafluorobutyl group, a perfluorocyclopentyl group and other fluorine-containing alkyls having 1 to 10 carbon atoms; a trifluoromethoxy group, a trifluoroethoxy group, C1-C10 alkoxy containing fluorine such as pentafluoropropoxy group, pentafluorobutoxy group, hexafluoro-2-methylisopropoxy group, heptafluorobutoxy group, perfluorocyclopentoxy group; methoxymethyl group, Etoki Methyl group, propoxymethyl group, butoxymethyl group, selected from 2-methyl-iso-propoxymethyl group, an ether group-containing alkyl having 2 to 10 carbon atoms such as butoxymethyl groups. N is an integer of 0 or 1.
一般式（４）で表わされるフッ素含有環状オレフィン単量体は、例えばＷＯ２００２／０８８２１６号公報に記載されている合成方法によって得ることができる。 The fluorine-containing cyclic olefin monomer represented by the general formula (4) can be obtained by, for example, a synthesis method described in WO2002 / 088216.
また、本発明においてフッ素含有環状オレフィンポリマーの製造に用いる単量体としては、一般式（４）で表されるフッ素含有環状オレフィン単量体のみでもよく、一般式（４）のＲ1〜Ｒ4、Ｘおよびｎの少なくとも１つが互いに異なる二種類以上の単量体を組み合わせて用いてもよい。さらに本発明の効果を損なわない範囲であれば一般式（４）で表されるフッ素含有環状オレフィン単量体以外の単量体を含んでいてもよい。 Further, R 1 as the monomer used to produce fluorine-containing cycloolefin polymer in the present invention, the general formula (4) represented by the fluorine-containing cycloolefin monomers alone may be in the general formula (4) to R 4 , or two or more monomers different from each other in at least one of X and n may be used in combination. Furthermore, a monomer other than the fluorine-containing cyclic olefin monomer represented by the general formula (4) may be included as long as the effect of the present invention is not impaired.
フッ素含有環状オレフィン単量体の開環重合において使用する重合触媒としては、例えば開環メタセシス重合触媒を挙げることができる。開環メタセシス重合触媒としては、開環メタセシス重合を行うことができる触媒であれば限定はされないが、例えば、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＢｕｔ）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ２ＣＦ３）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣ（ＣＦ３）３）２、Ｗ（Ｎ−２，６−（ＭＥ）２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣ（ＣＦ３）３）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＢｕｔ）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ２ＣＦ３）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２、またはＷ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＢｕｔ）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＢｕｔ）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＢｕｔ）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ２（ＣＦ３））２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣＭｅ２（ＣＦ３））２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣＭｅ２（ＣＦ３））２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ（ＣＦ３）２）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣＭｅ（ＣＦ３）２）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣＭｅ（ＣＦ３）２）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ２（ＣＦ３））２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ（ＣＦ３）２）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＰｈ）２（ＰＲ３）、またはＷ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＢｕｔ）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＢｕｔ）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＢｕｔ）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ２（ＣＦ３））２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣＭｅ２（ＣＦ３））２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣＭｅ２（ＣＦ３））２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ（ＣＦ３）２）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣＭｅ（ＣＦ３）２）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣＭｅ（ＣＦ３）２）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣ（ＣＦ３）３）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅ２）（ＯＣ（ＣＦ３）３）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＨＣＰｈ２）（ＯＣ（ＣＦ３）３）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ２（ＣＦ３））２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣＭｅ（ＣＦ３）２）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＣ（ＣＦ３）３）２（Ｐｙ）、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＨＣＭｅＰｈ）（ＯＰｈ）２（Ｐｙ）等のタングステン系アルキリデン触媒。 Examples of the polymerization catalyst used in the ring-opening polymerization of the fluorine-containing cyclic olefin monomer include a ring-opening metathesis polymerization catalyst. The ring-opening metathesis polymerization catalyst, but are not limited to as long as the catalyst can be performed ring-opening metathesis polymerization, for example, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N- 2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OC (CF 3) 3) 2, W (N-2,6- (ME) 2 C 6 H 3 ) (CHBu t) (OC (CF 3) 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 C 3) 2, W (N- 2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2 C 6 H 3 ) (CHCMe 2 Ph) (OC (CF 3 ) 3 ) 2 , W (N-2,6-Me 2 C 6 H 3 ) (CHCMe 2 Ph) (OC (CF 3 ) 3 ) 2 , or W (N -2,6-Me 2 C 6 H 3 ) (CHCHCMePh) (OBu t) 2 (PR 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCMe 2) (OBu t) 2 ( PR 3), W (N- 2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OBu t) 2 (PR 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCMePh ) (OCMe 2 (CF 3) ) 2 (PR 3), W (N-2,6-M 2 C 6 H 3) (CHCHCMe 2) (OCMe 2 (CF 3)) 2 (PR 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe 2 (CF 3) ) 2 (PR 3 ), W (N-2,6-Me 2 C 6 H 3 ) (CHCHCMePh) (OCMe (CF 3 ) 2 ) 2 (PR 3 ), W (N-2,6-Me 2 C 6 H 3) (CHCHCMe 2) (OCMe (CF 3) 2) 2 (PR 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe (CF 3) 2) 2 (PR 3 ), W (N-2,6-Me 2 C 6 H 3 ) (CHCHCMePh) (OC (CF 3 ) 3 ) 2 (PR 3 ), W (N-2,6-Me 2 C 6 H 3) (CHCHCMe 2) (OC (CF 3) 3) 2 PR 3), W (N- 2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OC (CF 3) 3) 2 (PR 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (PR 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe (CF 3) 2) 2 (PR 3), W (N-2,6 -Pr i 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (PR 3), W (N-2,6-Pr i 2 C 6 H 3 ) (CHCHCMePh) (OPh) 2 (PR 3 ), or W (N-2,6-Me 2 C 6 H 3 ) (CHCHCMePh) (OBu t ) 2 (Py), W (N-2,6- Me 2 C 6 H 3) ( CHCHCMe 2) (OBu t) (Py), W (N- 2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OBu t) 2 (Py), W (N-2,6-Me 2 C 6 H 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (Py), W (N-2,6-Me 2 C 6 H 3) (CHCHCMe 2) (OCMe 2 (CF 3)) 2 (Py), W (N-2 , 6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe 2 (CF 3)) 2 (Py), W (N-2,6-Me 2 C 6 H 3) (CHCHCMePh) (OCMe (CF 3 2 ) 2 (Py), W (N-2,6-Me 2 C 6 H 3 ) (CHCHCMe 2 ) (OCMe (CF 3 ) 2 ) 2 (Py), W (N-2,6-Me 2) C 6 H 3) (CHCHCPh 2 ) (OCMe (CF 3) 2 2 (Py), W (N -2,6-Me 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (Py), W (N-2,6-Me 2 C 6 H 3 ) (CHCHCMe 2 ) (OC (CF 3 ) 3 ) 2 (Py), W (N-2,6-Me 2 C 6 H 3 ) (CHCHCPh 2 ) (OC (CF 3 ) 3 ) 2 (Py), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (Py), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh ) (OCMe (CF 3) 2 ) 2 (Py), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (Py), W (N- 2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OPh) 2 Tungsten alkylidene catalysts such as (Py).
また、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＢｕｔ）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ２ＣＦ３）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣ（ＣＦ３）３）２、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣ（ＣＦ３）３）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ３）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ２（ＣＦ３））２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＢｕｔ）２（ＰＲ３）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ２ＣＦ３）２（ＰＲ３）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２（ＰＲ３）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２（ＰＲ３）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＢｕｔ）２（Ｐｙ）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ２ＣＦ３）２（Ｐｙ）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２（Ｐｙ）、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２（Ｐｙ）、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２（Ｐｙ）（但し、式中のＰｒｉはｉｓｏ−プロピル基を示し、Ｒはメチル基、エチル基等のアルキル基またはメトキシ基、エトキシ基等のアルコキシ基を示し、Ｂｕｔはｔｅｒｔ−ブチル基を示し、Ｍｅはメチル基を示し、Ｐｈはフェニル基を示し、Ｐｙはピリジン基を示す。）等のモリブデン系アルキリデン触媒や、Ｒｕ（ＣＨＣＨＣＰｈ２）（ＰＰｈ３）２Ｃｌ２（但し、式中のＰｈはフェニル基を示す。）等のルテニウム系アルキリデン触媒をあげることができる。 Further, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, Mo ( N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3 ) (CHBu t ) (OC (CF 3 ) 3 ) 2 , Mo (N-2,6-Me 2 C 6 H 3 ) (CHBu t ) (OC (CF 3 ) 3 ) 2 , Mo (N-2) , 6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 (CF 3) ) 2, Mo (N-2,6 -Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2, Mo (N-2,6-Me 2 C 6 H 3) (CHCMe 2 Ph ) (OC (CF 3) 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) ( CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2 (PR 3), Mo (N-2,6 -Me 2 C 6 H 3) (CHCMe 2 Ph) (OC ( CF 3) 3) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2 (Py), Mo (N-2,6-Pr i 2 C 6 H 3) ( CHCMe 2 Ph) (OCMe 2 CF 3) 2 (Py), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (Py), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2 (Py), Mo (N-2,6-Me 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2 (Py) ( where, Pr i in the formula represents an iso- propyl group, R represents an alkyl group such as methyl group and ethyl group or represents methoxy group, an alkoxy group such as ethoxy group, Bu t is tert- A butyl group, Me represents a methyl group, Ph represents a phenyl group, and Py represents a pyridine group. And a ruthenium alkylidene catalyst such as Ru (CHCHCPh 2 ) (PPh 3 ) 2 Cl 2 (wherein Ph represents a phenyl group).
また、上記開環メタセシス重合触媒の他に、有機遷移金属錯体、遷移金属ハロゲン化物または遷移金属酸化物と、助触媒としてのルイス酸との組み合せからなる開環メタセシス重合触媒を用いることもでき、例えば、Ｗ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ｔｈｆ）（ＯＢｕｔ）２Ｃｌ２、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ｔｈｆ）（ＯＢｕｔ）２Ｃｌ２、（但し、式中のＰｒｉはｉｓｏ−プロピル基を示し、Ｂｕｔはｔｅｒｔ−ブチル基を示し、ｔｈｆはテトラヒドロフランを示す。）等のタングステン、モリブデン等の遷移金属ハロゲン錯体；ＭｏＣｌ６、ＷＣｌ６、ＲｅＣｌ５、ＴｉＣｌ４、ＲｕＣｌ３、ＩｒＣｌ３等の遷移金属ハロゲン化物；トリメチルアルミニウム等の有機アルミニウム化合物、テトラメチル錫等の有機錫化合物等の助触媒があげられる。
さらにまた、これらの開環メタセシス重合触媒は、単独または、二種以上を組合わせて用いてもよい。
In addition to the above ring-opening metathesis polymerization catalyst, a ring-opening metathesis polymerization catalyst comprising a combination of an organic transition metal complex, a transition metal halide or a transition metal oxide, and a Lewis acid as a cocatalyst can be used. For example, W (N-2,6-Pr i 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, Mo (N-2,6-Pr i 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, (where, Pr i in the formula represents an iso- propyl group, Bu t represents a tert- butyl group, thf denotes tetrahydrofuran.) tungsten or the like, a transition metal halide complexes such as molybdenum ; MoCl 6, WCl 6, ReCl 5, TiCl 4, RuCl 3, transition metal halides such as IrCl 3; organoaluminum compound of trimethyl aluminum Cocatalyst organotin compounds such as tetramethyl tin and the like.
Furthermore, these ring-opening metathesis polymerization catalysts may be used alone or in combination of two or more.
フッ素含有環状オレフィン単量体の開環メタセシス重合において、フッ素含有環状オレフィン単量体と開環メタセシス重合触媒とのモル比は、タングステン、モリブデン、またはルテニウム等の遷移金属アルキリデン触媒の場合は、遷移金属アルキリデン錯体１モルに対して、該単量体が１０モル以上であり、好ましくは３０モル以上である。また、有機遷移金属ハロゲン錯体または遷移金属ハロゲン化物または酸化物と有機金属化合物からなる開環メタセシス触媒の場合、有機遷移金属ハロゲン錯体または遷移金属ハロゲン化物または酸化物１モルに対して、該単量体が１０モル以上、好ましくは３０モル以上であり、助触媒としての有機金属化合物は、有機遷移金属ハロゲン錯体または遷移金属ハロゲン化物または酸化物１モルに対して０．１〜１００モル、好ましくは１〜５０モルとなる範囲である。 In the ring-opening metathesis polymerization of a fluorine-containing cyclic olefin monomer, the molar ratio between the fluorine-containing cyclic olefin monomer and the ring-opening metathesis polymerization catalyst is a transition metal alkylidene catalyst such as tungsten, molybdenum, or ruthenium. The monomer is 10 mol or more, preferably 30 mol or more, per 1 mol of the metal alkylidene complex. Further, in the case of a ring-opening metathesis catalyst comprising an organic transition metal halogen complex or transition metal halide or oxide and an organic metal compound, the amount of the monomer is 1 mol per mole of the organic transition metal halogen complex or transition metal halide or oxide. The body is 10 mol or more, preferably 30 mol or more, and the organometallic compound as a co-catalyst is 0.1 to 100 mol, preferably 1 to 100 mol, preferably 1 mol of the organic transition metal halide complex or transition metal halide or oxide. It is the range which becomes 1-50 mol.
また、フッ素含有環状オレフィン単量体の開環メタセシス重合は、無溶媒でも溶媒を使用しても良いが、特に使用する溶媒としては、テトラヒドロフラン、ジエチルエーテル、ジブチルエーテル、ジメトキシエタンまたはジオキサン等のエーテル類、酢酸エチル、酢酸プロピルまたは酢酸ブチル等のエステル類、ベンゼン、トルエン、キシレンまたはエチルベンゼン等の芳香族炭化水素、ペンタン、ヘキサンまたはヘプタン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサンまたはデカリン等の脂肪族環状炭化水素、またはメチレンジクロライド、ジクロロエタン、ジクロロエチレン、テトラクロロエタン、クロロベンゼンまたはトリクロロベンゼン等のハロゲン化炭化水素、フルオロベンゼン、ジフルオロベンゼン、ヘキサフルオロベンゼン、トリフルオロメチルベンゼン、メタキシレンヘキサフルオリド等のフッ素含有芳香族炭化水素、パーフルオロヘキサン等のフッ素含有脂肪族炭化水素、パーフルオロシクロデカリン等のフッ素含有脂肪族環状炭化水素、パーフルオロ−２−ブチルテトラヒドロフラン等のフッ素含有エーテル類が挙げられ、これらの２種類以上を組合わせて使用しても良い。 In addition, the ring-opening metathesis polymerization of the fluorine-containing cyclic olefin monomer may be a solvent-free or a solvent, and particularly a solvent used is an ether such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane or dioxane. , Esters such as ethyl acetate, propyl acetate or butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane or heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethyl Aliphatic cyclic hydrocarbons such as cyclohexane or decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene or trichlorobenzene, fluoro Fluorine-containing aromatic hydrocarbons such as benzene, difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, metaxylene hexafluoride, fluorine-containing aliphatic hydrocarbons such as perfluorohexane, and fluorine-containing aliphatics such as perfluorocyclodecalin. Fluorine-containing ethers such as cyclic hydrocarbons and perfluoro-2-butyltetrahydrofuran may be mentioned, and two or more of these may be used in combination.
本発明において、触媒効率を高めるため、および分子量分布を制御するために、連鎖移動剤としてオレフィンを使用することができる。オレフィンとしては、例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、オクテン等のオレフィンまたはこれらのフッ素含有オレフィンがあげられ、さらに、ビニルトリメチルシラン、アリルトリメチルシラン、アリルトリエチルシラン、アリルトリイソプロピルシラン等のケイ素含有オレフィンまたはこれらのフッ素およびケイ素含有オレフィンがあげられ、また、ジエンとしては、１、４−ペンタジエン、１、５−ヘキサジエン、１、６−ヘプタジエン等の非共役系ジエンまたはこれらのフッ素含有非共役系ジエンがあげられる。さらに、これらオレフィン、フッ素含有オレフィン、ジエンまたはフッ素含有ジエンはそれぞれ単独または２種類以上を併用しても良い。 In the present invention, an olefin can be used as a chain transfer agent in order to increase the catalyst efficiency and to control the molecular weight distribution. Examples of the olefin include olefins such as ethylene, propylene, butene, pentene, hexene, and octene or fluorine-containing olefins thereof, and further, vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane, and the like. Examples of the diene include silicon-containing olefins and fluorine and silicon-containing olefins. Examples of the diene include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, and the like. Examples thereof include conjugated dienes. Furthermore, these olefins, fluorine-containing olefins, dienes or fluorine-containing dienes may be used alone or in combination of two or more.
上記のオレフィン、フッ素含有オレフィン、ジエンまたはフッ素含有ジエンの使用量は、オレフィンまたはジエンがフッ素含有環状オレフィン単量体１モルに対して０．００１〜１０００モル、好ましくは０．０１〜１００モルの範囲である。また、オレフィンまたはジエンが遷移金属アルキリデン錯体のアルキリデンまたは遷移金属ハロゲン化物の１モルに対して０．１〜１０００モル、好ましくは１〜５００モルの範囲である。 The olefin, fluorine-containing olefin, diene or fluorine-containing diene is used in an amount of 0.001 to 1000 mol, preferably 0.01 to 100 mol, relative to 1 mol of the fluorine-containing cyclic olefin monomer. It is a range. Further, the olefin or diene is in the range of 0.1 to 1000 mol, preferably 1 to 500 mol, relative to 1 mol of the alkylidene or transition metal halide of the transition metal alkylidene complex.
フッ素含有環状オレフィン単量体の開環メタセシス重合では、該単量体の反応性および重合溶媒ヘの溶解性によっても異なるが、溶媒に対するフッ素含有環状オレフィン単量体の濃度は５〜１００質量％、好ましくは１０〜６０質量％の範囲が好ましく、通常−３０〜１５０℃の反応温度で１０分〜１２０時間反応させ、ブチルアルデヒド等のアルデヒド類、アセトン等のケトン類、メタノール等のアルコール類等の失活剤で反応を停止し、重合体の溶液を得ることができる。 In the ring-opening metathesis polymerization of the fluorine-containing cyclic olefin monomer, the concentration of the fluorine-containing cyclic olefin monomer with respect to the solvent is 5 to 100% by mass, although it varies depending on the reactivity of the monomer and the solubility in the polymerization solvent. The range of 10 to 60% by mass is preferable, and the reaction is usually performed at a reaction temperature of −30 to 150 ° C. for 10 minutes to 120 hours, aldehydes such as butyraldehyde, ketones such as acetone, alcohols such as methanol, and the like. The reaction can be stopped with a quencher to obtain a polymer solution.
フッ素含有環状オレフィンポリマーは、フッ素含有環状オレフィン単量体を開環メタセシス重合して得られたポリマーの主鎖のオレフィン部を、例えば触媒により水素添加反応することによって得ることができる。そして、その水素添加触媒は使用する溶媒の水素添加反応を起こさずに、該ポリマーの主鎖のオレフィン部を水素添加できる触媒であれば、均一系金属錯体触媒でも不均一系の金属担持触媒であってもかまわない。均一系金属錯体触媒として、例えば、クロロトリス（トリフェニルホスフィン）ロジウム、ジクロロトリス（トリフェニルホスフィン）オスミウム、ジクロロヒドリドビス（トリフェニルホスフィン）イリジウム、ジクロロトリス（トリフェニルホスフィン）ルテニウム、ジクロロテトラキス（トリフェニルホスフィン）ルテニウム、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム、ジクロロトリス（トリメチルホスフィン）ルテニウム等があげられ、不均一系金属担持触媒として、例えば、活性炭担時パラジウム、アルミナ担持パラジウム、活性炭担持ロジウム、アルミナ担持ロジウム等があげられる。これら水添触媒は、単独または二種類以上を組合わせて使用することができる。 The fluorine-containing cyclic olefin polymer can be obtained by hydrogenating the olefin part of the main chain of a polymer obtained by ring-opening metathesis polymerization of a fluorine-containing cyclic olefin monomer, for example, with a catalyst. The hydrogenation catalyst is a homogeneous metal complex catalyst or a heterogeneous metal supported catalyst as long as it can hydrogenate the olefin part of the main chain of the polymer without causing a hydrogenation reaction of the solvent used. It does not matter. Examples of homogeneous metal complex catalysts include chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) osmium, dichlorohydridobis (triphenylphosphine) iridium, dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenyl) Phosphine) ruthenium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, dichlorotris (trimethylphosphine) ruthenium, and the like. Examples of heterogeneous metal-supported catalysts include palladium on activated carbon, palladium on alumina, rhodium on activated carbon, Examples thereof include rhodium supported on alumina. These hydrogenation catalysts can be used alone or in combination of two or more.
上記の主鎖のオレフィン部の水素添加処理をするに際して、公知の不均一系または均一系水素添加触媒を使用する場合、水素添加触媒の使用量は、水素添加触媒中の金属成分が、水素添加処理前のポリマー１００質量部に対して５×１０−４質量部〜１００質量部であり、好ましくは１×１０−２質量部〜３０質量部である。 When using a known heterogeneous or homogeneous hydrogenation catalyst for the hydrogenation treatment of the olefin part of the main chain, the amount of the hydrogenation catalyst used is that the metal component in the hydrogenation catalyst is hydrogenated. It is 5 * 10 <-4> mass part-100 mass parts with respect to 100 mass parts of polymers before a process, Preferably it is 1 * 10 <-2> mass part-30 mass parts.
水素添加処理の際に用いられる溶媒としては、水素添加処理前のフッ素含有環状オレフィンポリマーを溶解することができるとともに、溶媒自体が水素添加されないものであればどのようなものでもよく、例えば、テトラヒドロフラン、ジエチルエーテル、ジブチルエーテル、ジメトキシエタンなどのエーテル類、酢酸エチル、酢酸プロピルまたは酢酸ブチル等のエステル類、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、デカリンなどの脂肪族環状炭化水素、メチレンジクロリド、ジクロロエタン、ジクロロエチレン、テトラクロロエタン、クロルベンゼン、トリクロルベンゼンなどのハロゲン化炭化水素、フルオロベンゼン、ジフルオロベンゼン、ヘキサフルオロベンゼン、トリフルオロメチルベンゼン、メタキシレンヘキサフルオリド等のフッ素含有芳香族炭化水素、パーフルオロヘキサン等のフッ素含有脂肪族炭化水素、パーフルオロシクロデカリン等のフッ素含有脂肪族環状炭化水素、パーフルオロ−２−ブチルテトラヒドロフラン等のフッ素含有エーテル類等があげられ、これらは２種以上を組合わせて使用してもよい。 The solvent used in the hydrogenation treatment may be any solvent as long as it can dissolve the fluorine-containing cyclic olefin polymer before the hydrogenation treatment and the solvent itself is not hydrogenated. For example, tetrahydrofuran , Ethers such as diethyl ether, dibutyl ether and dimethoxyethane, esters such as ethyl acetate, propyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatics such as pentane, hexane and heptane Hydrocarbon, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin and other aliphatic cyclic hydrocarbons, methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, trichloro Halogenated hydrocarbons such as benzene, fluorine-containing aromatic hydrocarbons such as fluorobenzene, difluorobenzene, hexafluorobenzene, trifluoromethylbenzene and metaxylene hexafluoride, fluorine-containing aliphatic hydrocarbons such as perfluorohexane, Examples thereof include fluorine-containing aliphatic cyclic hydrocarbons such as fluorocyclodecalin, fluorine-containing ethers such as perfluoro-2-butyltetrahydrofuran, and these may be used in combination of two or more.
上記の主鎖のオレフィン部の水素添加反応は、使用する水素添加触媒の種類にもよるが、水素圧力が通常、常圧〜３０ＭＰａ、好ましくは０．５〜２０ＭＰａ、特に好ましくは２〜１５ＭＰａの範囲で行われ、その反応温度は、通常０〜３００℃の温度であり、好ましくは室温〜２５０℃、特に好ましくは５０〜２００℃の温度範囲である。水素添加反応の実施様式は、触媒を溶媒中に分散または溶解して行う方法、触媒をカラムなどの容器に充填し、固定相としてポリマー溶液を流通させて行う方法などが例示できる。また、これらの方法以外の様式であってもよい。 Although the hydrogenation reaction of the olefin part of the main chain depends on the type of hydrogenation catalyst used, the hydrogen pressure is usually from normal pressure to 30 MPa, preferably from 0.5 to 20 MPa, particularly preferably from 2 to 15 MPa. The reaction temperature is usually from 0 to 300 ° C., preferably from room temperature to 250 ° C., particularly preferably from 50 to 200 ° C. Examples of the mode of carrying out the hydrogenation reaction include a method in which the catalyst is dispersed or dissolved in a solvent, and a method in which the catalyst is packed in a container such as a column and the polymer solution is circulated as a stationary phase. In addition, a mode other than these methods may be used.
さらに、主鎖のオレフィン部の水素添加処理は、水素添加処理前のフッ素含有環状オレフィンポリマーを、重合溶媒から貧溶媒中に析出させポリマーを単離した後に、再度溶媒に溶解して水素添加処理を行なう方法、または、主鎖のオレフィン部が水素添加処理前のフッ素含有環状オレフィンポリマーを重合溶媒から単離することなく、上記の均一系錯体触媒または、または不均一系金属単持触媒によって、該ポリマー溶液をそのまま用いて水素添加反応を行う方法など、特に制限無く採用することができる。
またフッ素含有環状オレフィンポリマーのオレフィン部の水素添加率に特に制限はないが、８０％以上、好ましくは９０〜１００％であることが好ましい。水素添加率が８０％未満であれば、オレフィン部に起因する光の吸収によって、屈折率が高くなったり、耐熱性または耐候性を悪化させることがある。
また、水素添加反応を行なうに際して、該ポリマー中に重合に使用したモノマーが残存していてもよく、該モノマーが同時に水素添加されてもよい。
Furthermore, the hydrogenation treatment of the main chain olefin part is carried out by precipitating the fluorine-containing cyclic olefin polymer before the hydrogenation treatment in a poor solvent from the polymerization solvent, isolating the polymer, and then dissolving it again in the solvent to perform the hydrogenation treatment. Without isolating the fluorine-containing cyclic olefin polymer in which the olefin portion of the main chain is before the hydrogenation treatment from the polymerization solvent, by the above homogeneous complex catalyst or the heterogeneous metal single-supported catalyst, A method of performing a hydrogenation reaction using the polymer solution as it is can be employed without particular limitation.
Moreover, there is no restriction | limiting in particular in the hydrogenation rate of the olefin part of a fluorine-containing cyclic olefin polymer, However, It is 80% or more, Preferably it is 90-100%. When the hydrogenation rate is less than 80%, the refractive index may be increased or the heat resistance or weather resistance may be deteriorated due to light absorption caused by the olefin part.
Moreover, when performing hydrogenation reaction, the monomer used for superposition | polymerization may remain in this polymer, and this monomer may be hydrogenated simultaneously.
本発明の水素添加されたフッ素含有環状オレフィンポリマーを含む溶液から、フッ素含有環状オレフィンポリマーを回収する方法としては特に制限はなく、例えば、撹拌下の貧溶媒中に反応溶液を排出しフッ素含有環状オレフィンポリマーを凝固させる濾過法、遠心分離法、デカンテーション法等により回収する方法、反応溶液中にスチームを吹き込んでフッ素含有環状オレフィンポリマーを析出させるスチームストリッピング法、反応溶液から溶媒を加熱等により直接除去する方法等があげられる。 The method for recovering the fluorine-containing cyclic olefin polymer from the solution containing the hydrogenated fluorine-containing cyclic olefin polymer of the present invention is not particularly limited. For example, the reaction solution is discharged into a poor solvent under stirring and the fluorine-containing cyclic olefin polymer is discharged. Filtration method for coagulating olefin polymer, centrifugal separation method, recovery method by decantation method, steam stripping method for blowing fluorine into the reaction solution to precipitate fluorine-containing cyclic olefin polymer, heating solvent from reaction solution, etc. For example, a direct removal method may be used.
［反射防止膜］
本発明の反射防止膜について具体的に説明する。
反射防止膜とは、該膜の表面での光の反射を抑制する機能を有する膜であり、光の反射抑制には、膜の表面に凹凸をつけて反射光を散乱させて防眩効果を利用する方法と、反射波の光の干渉効果を利用する方法がある。後者の効果を利用する反射防止膜は、高屈折率の透明基材と低屈折率の薄膜から構成されている。
本発明における反射防止膜は、一般式（１）で表わされるフッ素含有環状オレフィンポリマーからなる低屈折率の薄膜が、透明基材の片面、両面、中間のいずれに設けられていてもよく、また、本発明における反射防止膜は、透明基材上に設けられた低屈折率の塗布膜の他に、透明基材上に設けられた低屈折率の自立フィルムを含む。
本発明における透明基材としては、無機材料でも有機材料であっても特に制限はない。無機材料としては、例えば、ガラス、石英、スパッタリングや蒸着によって形成された酸化チタン、酸化ニオブ、酸化錫をドープした酸化インジウム等が例示される。また、有機材料としては、例えば、ポリカーボネート樹脂、アクリル樹脂、ポリエチレンテレフタレート樹脂、ノルボルネン樹脂、塩化ビニル樹脂、スチレン樹脂、ジエチレングリコールジアリルカーボネート樹脂等が例示される。
[Antireflection film]
The antireflection film of the present invention will be specifically described.
The antireflection film is a film having a function of suppressing the reflection of light on the surface of the film, and for suppressing the reflection of light, the surface of the film is made uneven to scatter the reflected light and to have an antiglare effect. There are a method of using and a method of using the interference effect of reflected light. The antireflection film utilizing the latter effect is composed of a transparent substrate having a high refractive index and a thin film having a low refractive index.
In the antireflection film of the present invention, a low refractive index thin film made of a fluorine-containing cyclic olefin polymer represented by the general formula (1) may be provided on one side, both sides, or the middle of a transparent substrate. The antireflection film in the present invention includes a low refractive index self-supporting film provided on the transparent substrate, in addition to the low refractive index coating film provided on the transparent substrate.
The transparent substrate in the present invention is not particularly limited, whether it is an inorganic material or an organic material. Examples of the inorganic material include glass, quartz, titanium oxide formed by sputtering or vapor deposition, niobium oxide, indium oxide doped with tin oxide, and the like. Examples of the organic material include polycarbonate resin, acrylic resin, polyethylene terephthalate resin, norbornene resin, vinyl chloride resin, styrene resin, and diethylene glycol diallyl carbonate resin.
本発明の反射防止膜は、一般式（１）で表わされるフッ素含有環状オレフィンポリマーを溶媒に溶解した溶液を調製した後に、均一に塗布、乾燥することによって透明基材に設ける方法、押出成形等の溶融成形方法によって透明基材に設ける方法によって得ることもできる。また本発明の効果を損なわない範囲でフッ素含有環状オレフィンポリマーを他の樹脂と混合して使用しても、貼り合わせても、ラミネートされても良い。 The antireflection film of the present invention is prepared by preparing a solution in which the fluorine-containing cyclic olefin polymer represented by the general formula (1) is dissolved in a solvent, and then uniformly applying and drying the solution, extrusion molding, etc. It can also obtain by the method of providing in a transparent base material by the melt-molding method of this. In addition, the fluorine-containing cyclic olefin polymer may be used by mixing with other resins, bonded, or laminated as long as the effects of the present invention are not impaired.
本発明のフッ素含有環状オレフィンポリマーは、可視光領域の光線透過率が８０％以上、であることが好ましい。該光線透過率が８０％以上においては、反射防止膜としてＣＲＴや液晶ディスプレイ表面に設定しても、映像がぼけて見えることがなく好ましい。
本発明におけるフッ素含有環状オレフィンポリマーは、フッ素含有置換基を一般式（１）に示す特定の位置に持つ特定の構造を有することから、フッ素を含まない有機溶媒にも良好に溶ける。一方、非特許文献３や特許文献１のパーフルオロポリマーでは、分子全体がフッ素で覆われた構造であるために、有機溶媒をはじく撥油性が強く、フッ素含有有機溶媒のみだけが該ポリマーを溶解できる。
The fluorine-containing cyclic olefin polymer of the present invention preferably has a light transmittance in the visible light region of 80% or more. When the light transmittance is 80% or more, even if the antireflection film is set on the surface of a CRT or a liquid crystal display, the image is not blurred and is preferable.
Since the fluorine-containing cyclic olefin polymer in the present invention has a specific structure having a fluorine-containing substituent at a specific position shown in the general formula (1), the fluorine-containing cyclic olefin polymer is well soluble in an organic solvent not containing fluorine. On the other hand, the perfluoropolymers of Non-Patent Document 3 and Patent Document 1 have a structure in which the entire molecule is covered with fluorine, so that the oil repellency is strong to repel organic solvents, and only the fluorine-containing organic solvent dissolves the polymer. it can.
本発明のフッ素含有環状オレフィンポリマー溶液を調製する際の溶媒としては、フッ素含有有機溶媒の他にもフッ素を含まない有機溶媒を使用することができる。より安価な溶媒を使用するためには、フッ素を含まない有機溶媒であることが好ましい。
フッ素含有有機溶媒としては、特に制限はないが、例えば、メタキシレンヘキサフロライド、ベンゾトリフロライド、フルオロベンゼン、ジフルオロベンゼン、ヘキサフルオロベンゼン、トリフルオロメチルベンゼン、メタキシレンヘキサフルオリド等のフッ素含有芳香族炭化水素；パーフルオロヘキサン、パーフルオロオクタン等のフッ素含有脂肪族炭化水素；パーフルオロシクロデカリン等のフッ素含有脂肪族環状炭化水素；パーフルオロ−２−ブチルテトラヒドロフラン等のフッ素含有エーテル類等をあげることができる。また、フッ素を含まない有機溶媒としては、特に制限はないが、例えば、テトラヒドロフラン（ＴＨＦ）、１，２−ジメトキシエタン等のエーテル類；酢酸エチル等のエステル類；メチルイソブチルケトン、シクロヘキサノン等のケトン類等をあげることができる。
As a solvent for preparing the fluorine-containing cyclic olefin polymer solution of the present invention, an organic solvent containing no fluorine can be used in addition to the fluorine-containing organic solvent. In order to use a cheaper solvent, an organic solvent containing no fluorine is preferable.
The fluorine-containing organic solvent is not particularly limited. For example, fluorine-containing organic solvents such as metaxylene hexafluoride, benzotrifluoride, fluorobenzene, difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, metaxylene hexafluoride, etc. Aromatic hydrocarbons; fluorine-containing aliphatic hydrocarbons such as perfluorohexane and perfluorooctane; fluorine-containing aliphatic cyclic hydrocarbons such as perfluorocyclodecalin; fluorine-containing ethers such as perfluoro-2-butyltetrahydrofuran, etc. I can give you. In addition, the organic solvent not containing fluorine is not particularly limited. For example, ethers such as tetrahydrofuran (THF) and 1,2-dimethoxyethane; esters such as ethyl acetate; ketones such as methyl isobutyl ketone and cyclohexanone Can be listed.
本発明において、本発明のフッ素含有環状オレフィンポリマー溶液を透明基材上に均一に塗布する方法としては特に制限はなく、例えば、スピンコート、ディップコート、ダイコート、スプレーコート、バーコート、ロールコート、カーテンフローコートなどの方法があげられる。
本発明の反射防止膜の反射率は、空気と低屈折率薄膜との境界で反射した入射光の一部と、低屈折率の薄膜と透明基材の境界面で反射した入射光の干渉光によって決定される。そのために、低屈折率薄膜の膜厚は、光が干渉作用をおこす程度に薄いものが好ましい。
本発明の反射防止膜の膜厚は、使用するフッ素含有環状オレフィンポリマーの屈折率や測定波長にも依存するが、０．０５〜１０μｍであり、０．０５〜３μｍであることが好ましい。この範囲であると、優れた反射防止効果が得られる。膜厚が薄すぎれば、例えば、入射光との干渉作用による反射率の低減が不十分になることがある。また、膜厚が厚すぎれば、例えば、薄膜が乾燥した際にソリが発生して透明基材から剥離することがある。
In the present invention, the method for uniformly applying the fluorine-containing cyclic olefin polymer solution of the present invention on a transparent substrate is not particularly limited, and examples thereof include spin coating, dip coating, die coating, spray coating, bar coating, roll coating, Examples include curtain flow coating.
The reflectance of the antireflection film of the present invention is such that the incident light reflected at the boundary between the air and the low refractive index thin film, and the interference light of the incident light reflected at the boundary surface between the low refractive index thin film and the transparent substrate Determined by. Therefore, the film thickness of the low refractive index thin film is preferably thin enough to cause interference of light.
Although the film thickness of the antireflection film of the present invention depends on the refractive index and measurement wavelength of the fluorine-containing cyclic olefin polymer to be used, it is 0.05 to 10 μm, preferably 0.05 to 3 μm. Within this range, an excellent antireflection effect can be obtained. If the film thickness is too thin, for example, the reflectance may not be sufficiently reduced due to interference with incident light. If the film thickness is too thick, for example, when the thin film is dried, warping may occur and the film may be peeled off from the transparent substrate.
また本発明のフッ素含有環状オレフィンポリマーの水接触角は１０５°以下であることが好ましい。水接触角が１０５°以下であれば、反射防止膜等の成形品表面と該成形品表面に施した表面コート材料との密着性が高く、コート材料を剥離しにくくできる。 The water contact angle of the fluorine-containing cyclic olefin polymer of the present invention is preferably 105 ° or less. When the water contact angle is 105 ° or less, the adhesion between the surface of the molded product such as an antireflection film and the surface coating material applied to the surface of the molded product is high, and the coating material can be hardly peeled off.
本発明の反射防止膜では、耐擦傷性を向上させるためのハードコート層を設けることも好ましい態様である。ハードコート層は、例えば、透明基材と本発明のフッ素含有環状オレフィンポリマーからなる低屈折率の薄膜の間に設けることができる。そして、ハードコート層材料としては、特に制限されないが、例えば、シランカップリング剤、アクリル系樹脂等があげられる。
また、本発明における反射防止膜は、屈折率の異なる多層の膜を積層することによって、さらに低い反射率を得ることもできる。例えば、透明基材と低屈折率の薄膜との中間、あるいはハードコート層と低屈折率の薄膜との中間に、さらに高い屈折率の薄膜を設けることによって反射率の低い反射防止膜を得ることができる。
In the antireflection film of the present invention, it is also a preferable aspect to provide a hard coat layer for improving the scratch resistance. A hard-coat layer can be provided between the transparent base material and the low refractive index thin film which consists of a fluorine-containing cyclic olefin polymer of this invention, for example. The hard coat layer material is not particularly limited, and examples thereof include silane coupling agents and acrylic resins.
Further, the antireflection film in the present invention can obtain a lower reflectance by laminating a plurality of films having different refractive indexes. For example, an antireflection film having a low reflectivity can be obtained by providing a thin film having a higher refractive index in the middle of a transparent substrate and a thin film having a low refractive index, or between a hard coat layer and a thin film having a low refractive index. Can do.
［光学レンズ］
本発明の光学レンズについて具体的に説明する。
光学レンズは、例えば、カメラ、ビデオカメラ等に使用する撮像レンズ；プロジェクションテレビ等に使用する投影用レンズ；レーザープリンターに使用するｆθレンズやマイクロレンズアレイ等に使用されるレンズである。
[Optical lens]
The optical lens of the present invention will be specifically described.
The optical lens is, for example, an imaging lens used for a camera, a video camera, or the like; a projection lens used for a projection television or the like; an fθ lens used for a laser printer, a lens used for a microlens array, or the like.
本発明の光学レンズは、一般式（１）で表わされるフッ素含有環状オレフィンポリマーを成形することによって得ることができる。
本発明におけるフッ素含有環状オレフィンポリマーは、３００℃で５分間加熱したときの質量減少量が０．１％未満であり、熱可塑性で且つ熱安定性に優れることから溶融成形することができる。加熱時の質量減少が小さいポリマーは、例えば、成型金型腐食の原因となるフッ化水素などの腐食性の高いフッ素含有ガスの発生量が少なくなるため、金型に耐腐食性を有する高価な材質を使用する必要がない。
The optical lens of the present invention can be obtained by molding a fluorine-containing cyclic olefin polymer represented by the general formula (1).
The fluorine-containing cyclic olefin polymer in the present invention has a mass reduction amount of less than 0.1% when heated at 300 ° C. for 5 minutes, is thermoplastic and has excellent thermal stability, and can be melt-molded. Polymers with small mass loss upon heating, for example, reduce the amount of highly corrosive fluorine-containing gases such as hydrogen fluoride that cause corrosion of molding molds, so that the mold has an expensive corrosion resistance. There is no need to use material.
本発明におけるフッ素含有環状オレフィンポリマーから光学レンズを成形する方法は特に限定されず、例えば、射出成形、プレス成形、圧縮成形、射出圧縮成形、押出成形などがあげられる。また、本発明の光学レンズを溶融成形する場合の成型温度は、３３０℃以下であることが好ましい。３３０℃以下であれば、５分間加熱したときの質量減少量は０．１％未満となり、質量減少に伴うフッ化水素などの腐食性の高いフッ素含有ガスの発生量が少ない。さらに、成形する際には、透明性の低下やアッベ数に影響を与えない範囲で、紫外線吸収剤、酸化防止剤、難燃剤、帯電防止剤、着色剤等の添加剤を添加することもできる。 The method for molding an optical lens from the fluorine-containing cyclic olefin polymer in the present invention is not particularly limited, and examples thereof include injection molding, press molding, compression molding, injection compression molding, and extrusion molding. Moreover, it is preferable that the shaping | molding temperature in the case of melt-molding the optical lens of this invention is 330 degrees C or less. If it is 330 degrees C or less, the mass reduction | decrease amount when it heats for 5 minutes will be less than 0.1%, and there are few generation | occurrence | production amounts of highly corrosive fluorine-containing gas, such as hydrogen fluoride accompanying mass reduction. Furthermore, when molding, additives such as ultraviolet absorbers, antioxidants, flame retardants, antistatic agents, and coloring agents can be added within a range that does not affect the decrease in transparency and Abbe number. .
本発明のフッ素含有環状オレフィンポリマーを成形して得られる光学レンズのアッベ数は、６０以上、好ましくは６０〜１２０、さらに好ましくは６０〜１００である。アッベ数が６０以上であれば、例えば、高屈折レンズと組み合わせて使用した場合に、必要とする色収差の補正効果を得ることができる。
さらに、本発明における光学レンズは、光の乱反射によって生じる透明性の低下を示す一つの指標であるヘイズ値が２％以下であることが好ましく、１％以下であることがより好ましい。なお、ヘイズの下限値は０．５％程度である。
The Abbe number of the optical lens obtained by molding the fluorine-containing cyclic olefin polymer of the present invention is 60 or more, preferably 60 to 120, and more preferably 60 to 100. When the Abbe number is 60 or more, for example, when used in combination with a high refractive lens, a necessary chromatic aberration correction effect can be obtained.
Furthermore, the optical lens in the present invention preferably has a haze value of 2% or less, more preferably 1% or less, which is one index showing a decrease in transparency caused by irregular reflection of light. The lower limit of haze is about 0.5%.
また、本発明のフッ素含有環状オレフィンポリマーの反射防止膜、光学レンズ以外の用途としては、透明シート材料、透明フィルム材料、透明防湿膜材料、透明保護膜材料等をあげることができる。
In addition to the antireflection film and the optical lens of the fluorine-containing cyclic olefin polymer of the present invention, a transparent sheet material, a transparent film material, a transparent moisture-proof film material, a transparent protective film material, and the like can be given.
以下、実施例において、本発明を説明するが、本発明はこれらの例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these examples.
実施例において得られたポリマーの各物性値は、以下の方法により測定を行った。
なお、Ｄ線屈折率、全光線透過率、ヘイズ、水接触角測定には、厚さ１ｍｍの熱プレス成形試料を使用した。アッベ数の測定には、酸化防止剤のＩＲＧＡＮＯＸ１０１０を添加し、厚さ３ｍｍに射出成形した試料を使用した。
The physical property values of the polymers obtained in the examples were measured by the following methods.
In addition, the hot press molding sample of thickness 1mm was used for D-line refractive index, total light transmittance, haze, and water contact angle measurement. For the Abbe number measurement, an anti-oxidant IRGANOX 1010 was added and a sample injection-molded to a thickness of 3 mm was used.
［フッ素含有率］
構造単位中のフッ素原子の含有率は、以下の数式（１）により算出した。
フッ素原子の含有率（質量％）＝（ Ｆｎ × １９ ） × １００ ／ Ｆｗ （１）
ここで、数式（１）中、Ｆｎは一般式（１）で表わされる構造単位中のフッ素原子の数、Ｆｗは一般式（１）で表わされる構造単位の式量を表わす。
[Fluorine content]
The fluorine atom content in the structural unit was calculated by the following mathematical formula (1).
Content of fluorine atom (% by mass) = (Fn × 19) × 100 / Fw (1)
In formula (1), Fn represents the number of fluorine atoms in the structural unit represented by general formula (1), and Fw represents the formula weight of the structural unit represented by general formula (1).
［重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）］
ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）を使用して、テトラヒドロフラン（ＴＨＦ）に溶解したポリマーの重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を以下の条件で、ポリスチレンスタンダードによって分子量を較正して測定した。
検出器：日本分光製８３０−ＲＩおよび８７５−ＵＶ
カラム：Ｓｈｏｄｅｘ ｋ−８０６Ｍ，８０４，８０３，８０２．５
流量１．０ｍｌ／分
[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer dissolved in tetrahydrofuran (THF) were calibrated with polystyrene standards under the following conditions. It was measured.
Detector: JASCO 830-RI and 875-UV
Column: Shodex k-806M, 804, 803, 802.5
Flow rate 1.0ml / min
［フッ素含有環状オレフィンポリマーの水素添加率］
水素添加反応を行った開環メタセシス重合体の粉末を重水素化クロロホルム、または重水素化テトラヒドロフラン、またはヘキサフルオロベンゼンと重水素化クロロホルムの混合溶媒に溶解し、２７０ＭＨｚ−１Ｈ−ＮＭＲスペクトルを用いてδ＝４．５〜７．０ｐｐｍの主鎖の二重結合炭素に結合する水素に由来する吸収スペクトルの積分値より水素添加率を算出した。
[Hydrogenation rate of fluorine-containing cyclic olefin polymer]
The hydrogenated ring-opening metathesis polymer powder was dissolved in deuterated chloroform, deuterated tetrahydrofuran, or a mixed solvent of hexafluorobenzene and deuterated chloroform, and 270 MHz-1H-NMR spectrum was used. The hydrogenation rate was calculated from the integrated value of the absorption spectrum derived from hydrogen bonded to the double bond carbon of the main chain at δ = 4.5 to 7.0 ppm.
［熱安定性］
島津製作所製ＤＴＧ−６０Ａを用い、測定試料を空気雰囲下で温度３００℃まで昇温した後に、そのままの温度にて２０分間加熱を継続して質量減少量の測定を行った。
[Thermal stability]
Using a DTG-60A manufactured by Shimadzu Corporation, the measurement sample was heated to a temperature of 300 ° C. in an air atmosphere, and then heated at the same temperature for 20 minutes to measure the mass loss.
［屈折率およびアッベ数］
Ｄ線屈折率および、アッベ数は、アタゴ社製多波長アッベ屈折計を用いて測定を行なった。屈折率の測定は、表面が鏡面状のステンレス板を用いて熱プレス成形して得られた厚さ１ｍｍの試験片、またアッベ数の測定は、熱安定剤としてＩＲＧＡＮＡＸ１０１０を添加した試料を射出成形して得られた、厚さ３ｍｍの試験片を用いて測定を行なった。
[Refractive index and Abbe number]
The D-line refractive index and Abbe number were measured using a multi-wavelength Abbe refractometer manufactured by Atago. The refractive index is measured by hot press molding using a stainless steel plate having a mirror surface, and the Abbe number is measured by injection molding a sample to which IRGANAX 1010 is added as a thermal stabilizer. Measurement was performed using a 3 mm-thick test piece.
［全光線透過率およびヘイズ］
日本電色工業製ヘイズメーターＮＤＨ２０００を用いて、表面が鏡面状のステンレス板を用いて熱プレス成形して得られた厚さ１ｍｍの試験片の可視領域の全光線透過率とヘイズを評価した。
[Total light transmittance and haze]
Using a Nippon Denshoku haze meter NDH2000, the total light transmittance and haze in the visible region of a test piece having a thickness of 1 mm obtained by hot press molding using a stainless steel plate having a mirror surface was evaluated.
［水接触角］
協和界面科学製自動接触角計ＣＡ−Ｖ型を用いて、表面が鏡面状のステンレス板を用いて熱プレス成形して得られた厚さ１ｍｍの試験片を使用し、純水を滴下する液滴法によって測定し、解析ソフトＦＡＭＡＳを使用することによって評価を行った。
[Water contact angle]
A liquid in which pure water is dropped using a test piece with a thickness of 1 mm obtained by hot press molding using a stainless steel plate with a mirror-like surface using an automatic contact angle meter CA-V manufactured by Kyowa Interface Science. It was measured by the drop method and evaluated by using analysis software FAMAS.
［反射率］
日立製Ｕ−４１００分光光度計を用いて測定して、厚さ２ｍｍの樹脂板上に塗布した反射防止膜の平均反射率を３８０〜７８０ｎｍの波長領域において測定し、波長４５０〜６５０ｎｍの平均反射率を算出して反射率とした。
[Reflectance]
Measured using a Hitachi U-4100 spectrophotometer, the average reflectance of the antireflection film coated on a resin plate having a thickness of 2 mm was measured in the wavelength region of 380 to 780 nm, and the average reflection at a wavelength of 450 to 650 nm. The rate was calculated as the reflectance.
［実施例１］
５−（トリフルオロメチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのＴＨＦ溶液に、Ｍｏ（Ｎ−２，６−（ＭＥ）２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣ（ＣＦ３）３）２のＴＨＦ溶液を添加し、６０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。得られたポリマーの水素添加率は１００％、フッ素含有率は３５質量％、重量平均分子量（Ｍｗ）は４３０００、分子量分布（Ｍｗ／Ｍｎ）は、１．５４であった。
次いで、得られた水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリカーボネート上に厚さ９０ｎｍの反射防止膜を作成した。
Ｄ線光波長における屈折率は１．４５、光線透過率は９４．０％、水接触角は９５°であった。また、ポリカーボネート上に形成した反射防止膜の反射率は０．５％であった。
[Example 1]
To a THF solution of 5- (trifluoromethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene, Mo (N-2,6- (ME) 2 C 6 H 3 ) (CHBu A solution of t ) (OC (CF 3 ) 3 ) 2 in THF was added, and ring-opening metathesis polymerization was performed at 60 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain a THF solution of a fluorine-containing cyclic olefin polymer. The obtained polymer had a hydrogenation rate of 100%, a fluorine content of 35% by mass, a weight average molecular weight (Mw) of 43,000, and a molecular weight distribution (Mw / Mn) of 1.54.
Subsequently, the obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and an antireflection film having a thickness of 90 nm was formed on the polycarbonate by spin coating.
The refractive index at the D-line light wavelength was 1.45, the light transmittance was 94.0%, and the water contact angle was 95 °. Moreover, the reflectance of the antireflection film formed on the polycarbonate was 0.5%.
［実施例２］
５，５，６−トリフルオロ−６−（トリフルオロメチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンの酢酸エチル溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２の酢酸エチル溶液を添加し、７０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーの酢酸エチル溶液を得た。得られたポリマーの水素添加率は１００％、フッ素含有率は５２質量％、重量平均分子量（Ｍｗ）は３８０００、分子量分布（Ｍｗ／Ｍｎ）は、１．７０であった。
次いで、得られた水素添加後のポリマーの酢酸エチル溶液を０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリエチレンテレフタレート上に厚さ１２０ｎｍの反射防止膜を作成した。
Ｄ線光波長における屈折率は１．４１、光線透過率は９４．３％、水接触角は９４°であった。また、ポリエチレンテレフタレートに形成した反射防止膜の反射率は０．４％であった。
[Example 2]
To an ethyl acetate solution of 5,5,6-trifluoro-6- (trifluoromethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene, Mo (N-2,6-Pr An ethyl acetate solution of i 2 C 6 H 3 ) (CHCMe 2 Ph) (OCMe (CF 3 ) 2 ) 2 was added, and ring-opening metathesis polymerization was performed at 70 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain an ethyl acetate solution of a fluorine-containing cyclic olefin polymer. The resulting polymer had a hydrogenation rate of 100%, a fluorine content of 52% by mass, a weight average molecular weight (Mw) of 38000, and a molecular weight distribution (Mw / Mn) of 1.70.
Next, the obtained ethyl acetate solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 120 nm was formed on polyethylene terephthalate by spin coating.
The refractive index at the D-ray light wavelength was 1.41, the light transmittance was 94.3%, and the water contact angle was 94 °. The reflectance of the antireflection film formed on polyethylene terephthalate was 0.4%.
［実施例３］
実施例２の水素添加後のポリマーの酢酸エチル溶液を用いて、スピンコートによってポリカーボネート上に厚さ２１０ｎｍの反射防止膜を作成した。ポリカーボネートに形成した反射防止膜の反射率は０．５％であった。
[Example 3]
An antireflective film having a thickness of 210 nm was formed on the polycarbonate by spin coating using the ethyl acetate solution of the polymer after hydrogenation in Example 2. The reflectance of the antireflection film formed on the polycarbonate was 0.5%.
［実施例４］
５，６−ジフルオロ−５−（トリフルオロメチル）−６−（ペンタフルオロエチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのＴＨＦ溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２のＴＨＦ溶液を添加し、６０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。
[Example 4]
To a THF solution of 5,6-difluoro-5- (trifluoromethyl) -6- (pentafluoroethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene was added Mo (N-2 , 6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2 in THF was added and subjected to ring-opening metathesis polymerization at 60 ° C.. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain a THF solution of a fluorine-containing cyclic olefin polymer.
次いで、得られた水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。得られたポリマーの水素添加率は１００％、フッ素含有率は６０質量％、重量平均分子量（Ｍｗ）は４５０００、分子量分布（Ｍｗ／Ｍｎ）は、１．７９であった。
次いで、粉体状のフッ素含有環状オレフィンポリマーをメチルエチルケトンに溶解させ、０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリカーボネート上に厚さ１１０ｎｍの反射防止膜を作成した。
Ｄ線光波長における屈折率は１．３９、光線透過率は９５．４％、水接触角は９５°であった。また、ポリカーボネートに形成した反射防止薄膜の反射率は０．４％であった。
Next, the obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then precipitated by adding to methanol, followed by filtration to obtain a powdery fluorine-containing cyclic olefin polymer. The obtained polymer had a hydrogenation rate of 100%, a fluorine content of 60% by mass, a weight average molecular weight (Mw) of 45000, and a molecular weight distribution (Mw / Mn) of 1.79.
Next, the powdery fluorine-containing cyclic olefin polymer was dissolved in methyl ethyl ketone, filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 110 nm was formed on the polycarbonate by spin coating.
The refractive index at the D-line light wavelength was 1.39, the light transmittance was 95.4%, and the water contact angle was 95 °. Moreover, the reflectance of the antireflection thin film formed on the polycarbonate was 0.4%.
［実施例５］
実施例４の水素添加後のポリマーのメチルエチルケトン溶液を用いて、スピンコートによってポリエチレンテレフタレート上に１９０ｎｍの反射防止膜を作成した。ポリエチレンテレフタレートに形成した反射防止膜の反射率は０．５％であった。
[Example 5]
A 190 nm antireflection film was formed on polyethylene terephthalate by spin coating using the methyl ethyl ketone solution of the polymer after hydrogenation in Example 4. The reflectance of the antireflection film formed on polyethylene terephthalate was 0.5%.
［実施例６］
５，６−ジフルオロ−５，６−（トリフルオロメチル）−７−オキサ−ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンの酢酸エチル溶液に、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２の酢酸エチル溶液を添加し、７０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーの酢酸エチル溶液を得た。得られたポリマーの水素添加率は９９．８％、フッ素含有率は５６質量％、重量平均分子量（Ｍｗ）は７００００、分子量分布（Ｍｗ／Ｍｎ）は、１．７５であった。
次いで、得られた水素添加後のポリマーの酢酸エチル溶液を０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリカーボネート上に厚さ１０５ｎｍの反射防止膜を作成した。
Ｄ線光波長における屈折率は１．３８、光線透過率は９５．５％、水接触角は８５°であった。また、ポリカーボネートに形成した反射防止膜の反射率は０．４％であった。
[Example 6]
To an ethyl acetate solution of 5,6-difluoro-5,6- (trifluoromethyl) -7-oxa-bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene was added Mo (N-2 , 6-Me 2 C 6 H 3 ) (CHCMe 2 Ph) (OC (CF 3 ) 3 ) 2 in ethyl acetate was added, and ring-opening metathesis polymerization was performed at 70 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain an ethyl acetate solution of a fluorine-containing cyclic olefin polymer. The obtained polymer had a hydrogenation rate of 99.8%, a fluorine content of 56% by mass, a weight average molecular weight (Mw) of 70000, and a molecular weight distribution (Mw / Mn) of 1.75.
Subsequently, the obtained ethyl acetate solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 105 nm was formed on the polycarbonate by spin coating.
The refractive index at the D-line light wavelength was 1.38, the light transmittance was 95.5%, and the water contact angle was 85 °. Further, the reflectance of the antireflection film formed on the polycarbonate was 0.4%.
［実施例７］
実施例６の水素添加後のポリマーの酢酸エチル溶液を用いて、スピンコートによってポリカーボネート上に厚さ１８０ｎｍの反射防止膜を作成した。ポリカーボネートに形成した反射防止膜の反射率は０．５％であった。
[Example 7]
An antireflective film having a thickness of 180 nm was formed on polycarbonate by spin coating using the ethyl acetate solution of the polymer after hydrogenation in Example 6. The reflectance of the antireflection film formed on the polycarbonate was 0.5%.
［実施例８］
等モル数の５，５，６−トリフルオロ−６−（トリフルオロメチル）ビシクロ［２．２．１］ヘプト−２−エンと５，６−ジフルオロ−５，６−（トリフルオロメチル）−７−オキサ−ビシクロ［２．２．１］ヘプト−２−エンに、さらに１，５−ヘキサジエンを加えた酢酸エチル溶液に、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣ（ＣＦ３）３）２の酢酸エチル溶液を添加し、７０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーの酢酸エチル溶液を得た。得られたポリマーの水素添加率は９９．３％、フッ素含有率は５４質量％、重量平均分子量（Ｍｗ）は１１７０００、分子量分布（Ｍｗ／Ｍｎ）は、１．５２であった。
[Example 8]
Equimolar numbers of 5,5,6-trifluoro-6- (trifluoromethyl) bicyclo [2.2.1] hept-2-ene and 5,6-difluoro-5,6- (trifluoromethyl)- To an ethyl acetate solution obtained by adding 1,5-hexadiene to 7-oxa-bicyclo [2.2.1] hept-2-ene, Mo (N-2,6-Me 2 C 6 H 3 ) (CHCMe) 2 Ph) (OC (CF 3 ) 3 ) 2 in ethyl acetate was added, and ring-opening metathesis polymerization was performed at 70 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain an ethyl acetate solution of a fluorine-containing cyclic olefin polymer. The hydrogenation rate of the obtained polymer was 99.3%, the fluorine content was 54% by mass, the weight average molecular weight (Mw) was 117,000, and the molecular weight distribution (Mw / Mn) was 1.52.
次いで、得られた水素添加処理後のポリマーの酢酸エチル溶液を０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリエチレンテレフタレート上に厚さ１１５ｎｍの反射防止膜を作成した。
Ｄ線光波長における屈折率は１．３９、光線透過率は９５．３％、水接触角は９２°であった。また、ポリエチレンテレフタレートに形成した反射防止薄膜の反射率は０．４％であった。
Subsequently, the obtained ethyl acetate solution of the polymer after the hydrogenation treatment was filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 115 nm was formed on polyethylene terephthalate by spin coating.
The refractive index at the D-line light wavelength was 1.39, the light transmittance was 95.3%, and the water contact angle was 92 °. The reflectance of the antireflection thin film formed on polyethylene terephthalate was 0.4%.
［実施例９］
５−（パーフルオロデシル）−ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのトリフルオロメチルベンゼン溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２のトリフルオロメチルベンゼン溶液を添加し、７０℃にて開環メタセシス重合を行った後、トリフルオロメチルベンゼン溶液をメタノールに加えて析出させ、濾過を行うことによって粉体状の水素添加前のポリマーを得た。次いで、該水素添加処理前のポリマーをＴＨＦ溶液として、該ポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。
[Example 9]
5- (perfluoro decyl) - bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene of trifluoromethylbenzene solution, Mo (N-2,6-Pr i 2 C 6 H 3 ) (CHCMe 2 Ph) (OCMe (CF 3 ) 2 ) 2 in trifluoromethylbenzene solution was added and subjected to ring-opening metathesis polymerization at 70 ° C., and then the trifluoromethylbenzene solution was added to methanol for precipitation. By filtering, a powdery polymer before hydrogenation was obtained. Next, the polymer before the hydrogenation treatment was treated as a THF solution, and the olefin part of the polymer was subjected to a hydrogenation reaction at 160 ° C. with palladium carbon to obtain a THF solution of a fluorine-containing cyclic olefin polymer.
次いで、得られたフッ素含有環状オレフィンポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによってフッ素含有環状オレフィンポリマーの粉体を得た。該粉体状のポリマーの水素添加率は９９．４％、フッ素含有率は６５質量％、重量平均分子量（Ｍｗ）は５２０００、分子量分布（Ｍｗ／Ｍｎ）は、１．８１であった。
次いで、粉体状のフッ素含有環状オレフィンポリマーをメチルエチルケトンに溶解させ、０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリエチレンテレフタレート上に厚さ１２０ｎｍの反射防止膜を作成した。Ｄ線光波長における屈折率は１．３５、光線透過率は９５．８％、水接触角は１００°であった。また、ポリカーボネートに形成した反射防止薄膜の反射率は０．４％であった。
Next, the obtained fluorine-containing cyclic olefin polymer THF solution was filtered through a 0.1 μm membrane filter, precipitated in methanol, and filtered to obtain a fluorine-containing cyclic olefin polymer powder. The hydrogenation rate of the powdery polymer was 99.4%, the fluorine content was 65% by mass, the weight average molecular weight (Mw) was 52000, and the molecular weight distribution (Mw / Mn) was 1.81.
Subsequently, the powdery fluorine-containing cyclic olefin polymer was dissolved in methyl ethyl ketone, filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 120 nm was formed on polyethylene terephthalate by spin coating. The refractive index at the D-ray light wavelength was 1.35, the light transmittance was 95.8%, and the water contact angle was 100 °. Moreover, the reflectance of the antireflection thin film formed on the polycarbonate was 0.4%.
［実施例１０］
８−トリフルオロメチルテトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセンと１，５−ヘキサジエンのＴＨＦ溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２のＴＨＦ溶液を添加し、温度７０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。得られた水素添加後のポリマーの水素添加率は９９．５％、フッ素含有率は２５質量％、重量平均分子量（Ｍｗ）は８００００、分子量分布（Ｍｗ／Ｍｎ）は、２．１２であった。
[Example 10]
8-trifluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10] -3-dodecene and 1,5-hexadiene in THF, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2 of A THF solution was added, and ring-opening metathesis polymerization was performed at a temperature of 70 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain a THF solution of a fluorine-containing cyclic olefin polymer. The resulting hydrogenated polymer had a hydrogenation rate of 99.5%, a fluorine content of 25% by mass, a weight average molecular weight (Mw) of 80000, and a molecular weight distribution (Mw / Mn) of 2.12. .
次いで、得られた水素添加後のポリマーのＴＨＦ溶液を、０．１μｍのメンブレンフィルターで濾過した後に、メタノールに析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。
次いで、得られた粉体状のフッ素含有環状オレフィンポリマーをメチルエチルケトンに溶解させ、０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリエチレンテレフタレート上に厚さ１０５ｎｍの反射防止膜を作成した。Ｄ線光波長における屈折率は１．４８、光線透過率は９３．９％、水接触角は９３°であった。また、ポリカーボネートに形成した反射防止薄膜の反射率は０．６％であった。
Next, the obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, precipitated in methanol, and filtered to obtain a powdery fluorine-containing cyclic olefin polymer.
Next, the obtained powdery fluorine-containing cyclic olefin polymer was dissolved in methyl ethyl ketone, filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 105 nm was formed on polyethylene terephthalate by spin coating. The refractive index at the D-line light wavelength was 1.48, the light transmittance was 93.9%, and the water contact angle was 93 °. Moreover, the reflectance of the antireflection thin film formed on the polycarbonate was 0.6%.
［比較例１］
特許文献１の実施例１に従って、パーフルオロアリルビニルエーテルとジイソプロピルパーオキシジカーボネートから、脂環式のパーフルオロポリマーを合成した。得られたポリマーに、トルエン、ＴＨＦ、シクロヘキサノン、メチルエチルケトン、酢酸エチル、パーフルオロ（２−ブチルテトラヒドロフラン）をそれぞれ添加し、さらにスターラーチップを加えて１２時間撹拌を行った。
パーフルオロ（２−ブチルテトラヒドロフラン）を添加したサンプルだけが溶解した。
[Comparative Example 1]
According to Example 1 of Patent Document 1, an alicyclic perfluoropolymer was synthesized from perfluoroallyl vinyl ether and diisopropyl peroxydicarbonate. Toluene, THF, cyclohexanone, methyl ethyl ketone, ethyl acetate and perfluoro (2-butyltetrahydrofuran) were added to the obtained polymer, and a stirrer chip was further added, followed by stirring for 12 hours.
Only the sample to which perfluoro (2-butyltetrahydrofuran) was added dissolved.
［比較例２］
比較例１で合成したポリマーの物性を評価した。繰り返し構造単位中のフッ素含有率は６７質量％、Ｄ線波長光における屈折率は１．３４であった。
また、該ポリマーをパーフルオロ（２−ブチルテトラヒドロフラン）溶液に調製し、０．１μｍのメンブレンフィルターで濾過した後に、スピンコートによってポリカーボネート上に厚さ１９５ｎｍの反射防止膜を作成した。反射率は、０．９％であった。
また、スピンコート前のポリカーボネートの水接触角は８０°、その上にスピンコートして得られた反射防止薄膜の水接触角は１１２°であった。
[Comparative Example 2]
The physical properties of the polymer synthesized in Comparative Example 1 were evaluated. The fluorine content in the repeating structural unit was 67% by mass, and the refractive index in D-line wavelength light was 1.34.
The polymer was prepared in a perfluoro (2-butyltetrahydrofuran) solution, filtered through a 0.1 μm membrane filter, and then an antireflection film having a thickness of 195 nm was formed on the polycarbonate by spin coating. The reflectance was 0.9%.
The water contact angle of the polycarbonate before spin coating was 80 °, and the water contact angle of the antireflection thin film obtained by spin coating on the polycarbonate was 112 °.
［比較例３］
実施例１において、フッ素含有環状オレフィン単量体を８−フルオロテトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセンに代えたこと以外は、実施例１と同様に重合反応と水素添加反応を行った。水素添加処理よって得られたポリマーの水素添加率は９９．２％、フッ素含有率は１１質量％、重量平均分子量（Ｍｗ）は５４０００、分子量分布（Ｍｗ／Ｍｎ）は、２．１０であった。次いで、得られた水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のポリマーを得た。得られた粉体状のポリマーのＤ線光波長における屈折率は１．５２、水接触角は９１°であった。
[Comparative Example 3]
In Example 1, the fluorine-containing cyclic olefin monomer was substituted with 8-fluorotetracyclo [4.4.0.1 2,5 . The polymerization reaction and the hydrogenation reaction were carried out in the same manner as in Example 1 except that 1 7,10 ] -3-dodecene was used. The hydrogenation rate of the polymer obtained by the hydrogenation treatment was 99.2%, the fluorine content was 11% by mass, the weight average molecular weight (Mw) was 54000, and the molecular weight distribution (Mw / Mn) was 2.10. . Next, the obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then added to methanol for precipitation, followed by filtration to obtain a powdery polymer. The obtained powdery polymer had a refractive index of 1.52 and a water contact angle of 91 ° at the D-line light wavelength.
［比較例４］
実施例１において、フッ素含有環状オレフィン単量体を８，８−ジフルオロテトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセンに代えたこと以外は、実施例１と同様に重合反応と水素添加反応を行った。得られた水素添加後のポリマーの水素添加率は９９．５％、フッ素含有率は１９質量％、重量平均分子量（Ｍｗ）は４３０００、分子量分布（Ｍｗ／Ｍｎ）は、２．０１であった。
次いで、得られた水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のポリマーを得た。得られた粉体状のポリマーのＤ線光波長における屈折率は１．５１、水接触角は９０°であった。
[Comparative Example 4]
In Example 1, the fluorine-containing cyclic olefin monomer was replaced with 8,8-difluorotetracyclo [4.4.0.1 2,5 . The polymerization reaction and the hydrogenation reaction were carried out in the same manner as in Example 1 except that 1 7,10 ] -3-dodecene was used. The resulting hydrogenated polymer had a hydrogenation rate of 99.5%, a fluorine content of 19% by mass, a weight average molecular weight (Mw) of 43,000, and a molecular weight distribution (Mw / Mn) of 2.01. .
Next, the obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then added to methanol for precipitation, followed by filtration to obtain a powdery polymer. The obtained powdery polymer had a refractive index of 1.51 at a D-ray light wavelength and a water contact angle of 90 °.
［実施例１１］
５−（トリフルオロメチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのＴＨＦ溶液に、Ｍｏ（Ｎ−２，６−Ｍｅ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２のＴＨＦ溶液を添加し、６０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。
得られた水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。該粉体状のポリマーの水素添加率は１００％、フッ素含有率は３５質量％、重量平均分子量（Ｍｗ）は１９００００、分子量分布（Ｍｗ／Ｍｎ）は、１．７７であった。また、熱安定性の評価結果は０．０５％であった。この粉体状のポリマーを１２０℃で射出成形した試料片のアッベ数は６９であった。さらにまた、屈折率は、１．４５、光線透過率は９４．０％、水接触角は９５°、ヘイズは０．８％であった。
[Example 11]
To a THF solution of 5- (trifluoromethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene, Mo (N-2,6-Me 2 C 6 H 3 ) (CHBu t ) A solution of (OCMe (CF 3 ) 2 ) 2 in THF was added, and ring-opening metathesis polymerization was performed at 60 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain a THF solution of a fluorine-containing cyclic olefin polymer.
The obtained THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then added to methanol for precipitation, followed by filtration to obtain a powdery fluorine-containing cyclic olefin polymer. The powdered polymer had a hydrogenation rate of 100%, a fluorine content of 35% by mass, a weight average molecular weight (Mw) of 190000, and a molecular weight distribution (Mw / Mn) of 1.77. The evaluation result of thermal stability was 0.05%. The Abbe number of a sample piece obtained by injection molding of this powdery polymer at 120 ° C. was 69. Furthermore, the refractive index was 1.45, the light transmittance was 94.0%, the water contact angle was 95 °, and the haze was 0.8%.
［実施例１２］
５，５，６−トリフルオロ−６−（トリフルオロメチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンの酢酸エチル溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２の酢酸エチル溶液を添加し、７０℃にて開環メタセシス重合を行った。得られたポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーの酢酸エチル溶液を得た。該水素添加後のポリマーの酢酸エチル溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。該粉体状のポリマーの水素添加率は１００％、フッ素含有率は５２質量％、重量平均分子量（Ｍｗ）は１２００００、分子量分布（Ｍｗ／Ｍｎ）は、１．７１であった。また、熱安定性の評価結果は０．０３％であった。この粉体状のポリマーを１７０℃で射出成形した試料片のアッベ数は８０であった。さらにまた、屈折率は、１．４１、光線透過率は９４．２％、水接触角は９４°、ヘイズは０．７％であった。
[Example 12]
To an ethyl acetate solution of 5,5,6-trifluoro-6- (trifluoromethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene, Mo (N-2,6-Pr An ethyl acetate solution of i 2 C 6 H 3 ) (CHCMe 2 Ph) (OCMe (CF 3 ) 2 ) 2 was added, and ring-opening metathesis polymerization was performed at 70 ° C. The olefin part of the obtained polymer was hydrogenated with palladium carbon at 160 ° C. to obtain an ethyl acetate solution of a fluorine-containing cyclic olefin polymer. The ethyl acetate solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, and then precipitated by adding to methanol, followed by filtration to obtain a powdery fluorine-containing cyclic olefin polymer. The powdered polymer had a hydrogenation rate of 100%, a fluorine content of 52% by mass, a weight average molecular weight (Mw) of 120,000, and a molecular weight distribution (Mw / Mn) of 1.71. Moreover, the evaluation result of thermal stability was 0.03%. The Abbe number of a sample piece obtained by injection molding this powdery polymer at 170 ° C. was 80. Furthermore, the refractive index was 1.41, the light transmittance was 94.2%, the water contact angle was 94 °, and the haze was 0.7%.
［実施例１３］
５，６−ジフルオロ−５−（トリフルオロメチル）−６−（ペンタフルオロエチル）ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのメタキシレンヘキサフルオライド溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２のメタキシレンヘキサフルオライド溶液を添加し、６０℃にて開環メタセシス重合を行った。得られたポリマーのメタキシレンヘキサフルオライド溶液をメタノールに加えて析出させ、濾過を行うことによって粉体状のポリマーを得た。
[Example 13]
To a meta-xylene hexafluoride solution of 5,6-difluoro-5- (trifluoromethyl) -6- (pentafluoroethyl) bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene, (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2 metaxylene hexafluoride solution was added and subjected to ring-opening metathesis polymerization at 60 ° C. . A metaxylene hexafluoride solution of the obtained polymer was added to methanol for precipitation, followed by filtration to obtain a powdery polymer.
次いで、得られた粉体状のポリマーをＴＨＦ溶液として、該ポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。粉体状のフッ素含有環状オレフィンポリマーの水素添加率は１００％、フッ素含有率は６０質量％、重量平均分子量（Ｍｗ）は１３９０００、分子量分布（Ｍｗ／Ｍｎ）は、１．８７であった。また、熱安定性の評価結果は０．０５％であった。この粉体状のフッ素含有環状オレフィンポリマーを１７０℃で射出成形した試料片のアッベ数は８５であった。さらにまた、屈折率は１．３９、光線透過率は９５．４％、水接触角は、９５°、ヘイズは０．７％であった。 Subsequently, the obtained powdery polymer was used as a THF solution, and the olefin part of the polymer was subjected to hydrogenation reaction at 160 ° C. with palladium carbon to obtain a THF solution of a fluorine-containing cyclic olefin polymer. The THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, precipitated in methanol, and filtered to obtain a powdery fluorine-containing cyclic olefin polymer. The hydrogenation rate of the powdery fluorine-containing cyclic olefin polymer was 100%, the fluorine content rate was 60% by mass, the weight average molecular weight (Mw) was 139000, and the molecular weight distribution (Mw / Mn) was 1.87. The evaluation result of thermal stability was 0.05%. The Abbe number of a sample piece obtained by injection-molding this powdery fluorine-containing cyclic olefin polymer at 170 ° C. was 85. Furthermore, the refractive index was 1.39, the light transmittance was 95.4%, the water contact angle was 95 °, and the haze was 0.7%.
［実施例１４］
５，６−ビス（ノナフルオロブチル）−ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのトリフルオロメチルベンゼン溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＣＭｅ２Ｐｈ）（ＯＣＭｅ（ＣＦ３）２）２のトリフルオロメチルベンゼン溶液を添加し、６０℃にて開環メタセシス重合を行った。
得られたポリマーのトリフルオロメチルベンゼン溶液をメタノールに加えて析出させ、濾過を行うことによって粉体状のポリマーを得た。該粉体状のポリマーをＴＨＦ溶液とし、該ポリマーのオレフィン部を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。
水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。粉体状のフッ素含有環状オレフィンポリマーの水素添加率は１００％、フッ素含有率は６４質量％、重量平均分子量（Ｍｗ）は８９０００、分子量分布（Ｍｗ／Ｍｎ）は、１．８１であった。また、熱安定性の評価結果は０．０５％であった。さらに粉体状のフッ素含有環状オレフィンポリマーを１５０℃で射出成形した試料片のアッベ数は８９であった。また、屈折率は１．３６、光線透過率は９６．１％、ヘイズは０．８％、水接触角は９５°であった。
[Example 14]
5,6-bis (nonafluorobutyl) - bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene of trifluoromethylbenzene solution, Mo (N-2,6-Pr i 2 C A trifluoromethylbenzene solution of 6H 3 ) (CHCMe 2 Ph) (OCMe (CF 3 ) 2 ) 2 was added, and ring-opening metathesis polymerization was performed at 60 ° C.
A trifluoromethylbenzene solution of the obtained polymer was added to methanol for precipitation, followed by filtration to obtain a powdery polymer. The powdery polymer was used as a THF solution, and the olefin portion of the polymer was subjected to a hydrogenation reaction at 160 ° C. with palladium carbon to obtain a THF solution of a fluorine-containing cyclic olefin polymer.
The THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, precipitated in methanol, and filtered to obtain a powdery fluorine-containing cyclic olefin polymer. The hydrogenation rate of the powdery fluorine-containing cyclic olefin polymer was 100%, the fluorine content was 64% by mass, the weight average molecular weight (Mw) was 89000, and the molecular weight distribution (Mw / Mn) was 1.81. The evaluation result of thermal stability was 0.05%. Further, the Abbe number of a sample piece obtained by injection molding a powdery fluorine-containing cyclic olefin polymer at 150 ° C. was 89. The refractive index was 1.36, the light transmittance was 96.1%, the haze was 0.8%, and the water contact angle was 95 °.
［実施例１５］
５，６−ジフルオロ−５−トリフルオロメチル−６−ヘプタフルオロイソプロピル−ビシクロ［２．２．１］ヘプト−２−エンと１，５−ヘキサジエンのトリフルオロメチルベンゼン溶液に、Ｍｏ（Ｎ−２，６−Ｐｒｉ ２Ｃ６Ｈ３）（ＣＨＢｕｔ）（ＯＣＭｅ（ＣＦ３）２）２のトリフルオロメチルベンゼン溶液を添加し、７０℃にて開環メタセシス重合を行った。得られたポリマーのトリフルオロメチルベンゼン溶液をメタノールに加えて析出させ、濾過を行うことによって粉体状のポリマーを得た。
得られた粉体状のポリマーをＴＨＦ溶液として、開環メタセシス重合体の二重結合を、パラジウムカーボンによって１６０℃で水素添加反応を行い、フッ素含有環状オレフィンポリマーのＴＨＦ溶液を得た。水素添加後のポリマーのＴＨＦ溶液を０．１μｍのメンブレンフィルターで濾過した後に、メタノールに加えて析出させ、濾過を行うことによって粉体状のフッ素含有環状オレフィンポリマーを得た。粉体状のフッ素含有環状オレフィンポリマーの水素添加率は１００％、フッ素含有率は６２質量％、重量平均分子量（Ｍｗ）は１０５０００、分子量分布（Ｍｗ／Ｍｎ）は、１．８３であった。また、熱安定性の評価結果は０．０３％であった。さらに粉体状のフッ素含有環状オレフィンポリマーを１９０℃で射出成形した試料片のアッベ数は９４であった。また、屈折率は１．３４、光線透過率は９５．９％、ヘイズは０．８％、水接触角は９６°であった。
[Example 15]
To a solution of 5,6-difluoro-5-trifluoromethyl-6-heptafluoroisopropyl-bicyclo [2.2.1] hept-2-ene and 1,5-hexadiene in a trifluoromethylbenzene solution, Mo (N-2 , 6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2 of trifluoromethylbenzene was added and was subjected to ring-opening metathesis polymerization at 70 ° C.. A trifluoromethylbenzene solution of the obtained polymer was added to methanol for precipitation, followed by filtration to obtain a powdery polymer.
Using the obtained powdery polymer as a THF solution, the double bond of the ring-opening metathesis polymer was hydrogenated with palladium carbon at 160 ° C. to obtain a THF solution of a fluorine-containing cyclic olefin polymer. The THF solution of the polymer after hydrogenation was filtered through a 0.1 μm membrane filter, precipitated in methanol, and filtered to obtain a powdery fluorine-containing cyclic olefin polymer. The hydrogenation rate of the powdery fluorine-containing cyclic olefin polymer was 100%, the fluorine content rate was 62% by mass, the weight average molecular weight (Mw) was 105000, and the molecular weight distribution (Mw / Mn) was 1.83. Moreover, the evaluation result of thermal stability was 0.03%. Further, the Abbe number of a sample piece obtained by injection molding a powdery fluorine-containing cyclic olefin polymer at 190 ° C. was 94. The refractive index was 1.34, the light transmittance was 95.9%, the haze was 0.8%, and the water contact angle was 96 °.
［比較例５］
比較例１で得たポリマーの熱安定性の評価結果は、０．１％であった。
[Comparative Example 5]
The evaluation result of the thermal stability of the polymer obtained in Comparative Example 1 was 0.1%.
［比較例６］
ポリ（４−メチル−１−ペンテン）を３００℃にてプレス成形し、厚さ１ｍｍの板を成形した。得られた成形板のヘイズ測定結果は２．５％であった。
[Comparative Example 6]
Poly (4-methyl-1-pentene) was press-molded at 300 ° C. to form a plate having a thickness of 1 mm. The haze measurement result of the obtained molded plate was 2.5%.
本発明の特定の構造を有するフッ素含有環状オレフィンポリマーを含む光学部品材料は、特に、カメラ、ビデオカメラ等に使用する撮像レンズ、プロジェクションテレビ等に使用する投影用レンズ、レーザープリンターに使用するｆθレンズやマイクロレンズアレイ等の光学レンズおよび、反射防止膜として使用することができ、工業的価値は極めて高い。
The optical component material containing a fluorine-containing cyclic olefin polymer having a specific structure according to the present invention includes an imaging lens used for a camera, a video camera, a projection lens used for a projection television, and an fθ lens used for a laser printer. Can be used as an optical lens such as a microlens array or an antireflection film, and has an extremely high industrial value.
Claims (6)
An optical lens obtained by molding the optical component material according to claim 1.
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