WO2011070942A1 - フォトクロミック材料 - Google Patents

フォトクロミック材料 Download PDF

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Publication number
WO2011070942A1
WO2011070942A1 PCT/JP2010/071345 JP2010071345W WO2011070942A1 WO 2011070942 A1 WO2011070942 A1 WO 2011070942A1 JP 2010071345 W JP2010071345 W JP 2010071345W WO 2011070942 A1 WO2011070942 A1 WO 2011070942A1
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Prior art keywords
photochromic
copolymer
methoxy group
bonded
group
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PCT/JP2010/071345
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English (en)
French (fr)
Japanese (ja)
Inventor
二朗 阿部
敦大 鴇田
建 堀野
豊嗣 大嶋
篤志 木本
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三菱瓦斯化学株式会社
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Priority to EP10835864.9A priority Critical patent/EP2511307B1/de
Priority to KR1020127017749A priority patent/KR20120129886A/ko
Priority to CN201080055566.4A priority patent/CN102652143B/zh
Priority to US13/514,620 priority patent/US9040647B2/en
Priority to AU2010329226A priority patent/AU2010329226B2/en
Publication of WO2011070942A1 publication Critical patent/WO2011070942A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • the present invention includes, for example, optical materials such as sunglasses and light modulation elements, device materials such as recording materials and display bodies, and inks and coating agents that can be switched between display / non-display and coloring / decoloring.
  • optical materials such as sunglasses and light modulation elements
  • device materials such as recording materials and display bodies
  • inks and coating agents that can be switched between display / non-display and coloring / decoloring.
  • the present invention relates to a photochromic dye used for printing materials.
  • Photochromic materials exhibiting photochromism that develops and discolors by photoreaction have been used mainly for light-control dyes for sunglasses.
  • recording materials such as optical disks and display materials such as holograms.
  • Spiropyran compounds, naphthopyran compounds, fulgide compounds, diarylethene compounds, etc. have been used as light control materials for sunglasses, but the decolorization reaction rate at room temperature is low, for example, even if they move indoors from outdoors However, there is a drawback that the recovery of the front view is delayed without discoloring even if entering the tunnel while driving.
  • Non-Patent Document 1 first generation HABI
  • Non-Patent Document 2 second generation HABI
  • the present inventors have an extremely fast decoloring reaction and a half-life of the color former.
  • the problem with the radical dissipation-suppressing photochromic molecule is that the time to return to the decoloring body when the dimming material is exposed to excitation light and becomes a colored body is in milliseconds. Since it is very short, there is a problem that the colored body does not accumulate and the color density is low (it is difficult to color). Therefore, in order to improve the color density or to achieve a desired color density, a method for reducing the reaction rate from the color former to the decolorant is required.
  • the present invention has been made in view of the above, and a method for reducing a decolorization reaction rate, a method for improving sensitivity to excitation light, and a color tone control method in order to develop a photochromic material having a practical reaction rate and color density. And photochromic materials made by these methods.
  • the present inventors first made extensive studies on a method for controlling the photoresponse speed of a high-speed photoresponsive photochromic molecule.
  • the photochromic molecule represented by the general formula (I) is a chromophore when two imidazole rings become imidazolyl radicals and they are in a substantially parallel state, and the two imidazolyl radicals are bonded together so that one imidazole ring is almost the same as the other. It is considered to be a decoloring body when taking a vertical arrangement. Thus, it has been considered that the decolorization reaction rate can be lowered by bonding at least one of the imidazole rings to the polymer main chain to make it difficult to return to the vertical state.
  • a photochromic molecule homopolymer 1-1 having the following structure was synthesized by polymerizing the photochromic molecule represented by the general formula (I). As shown in FIG. 1, this polymer has a longer half-life of the color former than the monomer, and it can be seen that the decolorization reaction rate is effectively reduced.
  • the photochromic molecule represented by the general formula (I) can be copolymerized with methyl methacrylate or a photosensitizer having a polymerizable functional group represented by the general formula (II). As shown, it was found that the half-life can be increased similarly to the above homopolymer, and the effect of reducing the decoloring reaction rate can be obtained.
  • the photochromic molecule represented by the general formula (I) is erased by introducing an electron donating functional group into any or all of R 4 to R 7. It has been found that the ultraviolet-visible absorption of the photochromic molecule of the chromophore is increased even on the long wavelength side, and it has become possible to obtain a photochromic molecule capable of generating a colored body efficiently even by irradiation with visible light.
  • the homopolymer synthesized by polymerizing photochromic molecules in which R 4 to R 7 are methoxy groups that generate a colored body with high sensitivity even under visible light irradiation is polymerized. It was clarified that the material is a combination of the effect of reducing the decoloring reaction rate and the effect of good visible light sensitivity.
  • R 4 ⁇ all R 7 are all photochromic molecules and R 4 ⁇ R 7 are absorption spectra of the color-forming material of the copolymer of the photochromic molecules of each a methoxy group is hydrogen
  • R 4 ⁇ R 7 are absorption spectra of the color-forming material of the copolymer of the photochromic molecules of each a methoxy group is hydrogen
  • the polymer containing the photochromic molecule of the present invention By using the polymer containing the photochromic molecule of the present invention, it is possible to reduce the decoloring reaction rate of the high-speed photochromic molecule or to control the color tone, and to improve the color density and control the color tone Can be provided.
  • R 4 ⁇ R 7 are homopolymers and R 4 ⁇ R 7 of the photochromic molecules of methoxy group is a comparison of the transient absorption measurements of the monomers of the photochromic molecules of methoxy groups.
  • 6 is an absorption spectrum of a color former of a copolymer of a photochromic molecule in which R 4 to R 7 are hydrogen and a photochromic molecule in which R 4 to R 7 are methoxy groups.
  • R 4 to R 7 are transient absorption measurements of a colored product of a copolymer of a hydrogen photochromic molecule and R 4 to R 7 are methoxy group photochromic molecules, and R 4 to R 7 are methoxy group photochromic molecule homopolymers.
  • R 4 ⁇ R 7 is a comparison of chromogenic absorption spectrum of the film the film and R 4 ⁇ R 7 produced is produced in homopolymer of the photochromic molecules of a methoxy group at the homopolymer of the photochromic molecules of hydrogen. It is the transient absorption measurement result of the film of the homopolymer 1-1. It is a transient absorption measurement of a film of a copolymer of compound 1-10, compound 1-7 and methyl methacrylate. It is the transient absorption measurement result of the film of the homopolymer 1-2. It is a comparison of the ultraviolet visible absorption spectrum of a homopolymer and a copolymer.
  • the present invention is characterized by synthesizing a polymer or oligomer by polymerizing the photochromic molecular monomer represented by the general formula (I).
  • a photopolymeric monomer is polymerized to synthesize a homopolymer, or a photosensitizing compound represented by the general formula (II) having a photochromic molecule and another polymerizable monomer or polymer group, and It is also possible to synthesize a copolymer by mixing.
  • This copolymer may be a block copolymer or a random copolymer.
  • the photochromic monomer molecule represented by the general formula (I) will be described.
  • the photochromic molecule of the present invention is a derivative of hexaarylbisimidazole (HABI) and has a skeleton in which the 2-position of the imidazole group is bonded with paracyclophane and the triphenylimidazole group is dimerized.
  • HABI hexaarylbisimidazole
  • R 1 and R 2 each independently represents hydrogen or a methyl group.
  • R 3 to R 8 are each independently hydrogen or various substituents. When R 3 or R 8 is not hydrogen but a substituent, the substitution position is preferably a para position. When R 4 to R 7 are not hydrogen but a substituent, the substitution position is preferably a para position, and when two substituents are bonded to one ring, a meta position and a para position are preferred.
  • this substituent examples include an alkoxy group, amino group, alkylamino group, alkyl group, hydroxyl group, halogen, cyano group, and nitro group.
  • molecules having an alkoxy group or an alkylamino group can absorb the visible light region efficiently, and the photochromic molecule itself has a low decoloration reaction rate, so that the color density can be increased in sunlight. preferable.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
  • the alkylamino group is preferably a dimethylamino group, a diethylamino group, a dipropylamino group, or a dibutylamino group.
  • n is preferably 2 to 20, more preferably 4 to 20, and particularly preferably 6 to 20.
  • m is preferably 2 to 20, more preferably 4 to 20, and particularly preferably 6 to 20.
  • polymerization initiator for radical polymerization various common compounds can be used, but high temperature reaction is not preferable in order to prevent damage to the photochromic molecule. From this point of view, it is preferable to use 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) or the like. However, it is not limited to this exemplified compound.
  • radical polymerizable monomer to be copolymerized examples include compounds having groups such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, acrylonitrile, and vinyl acetate.
  • the photosensitizing compound may be any photosensitizing compound having a polymerization group, and examples thereof include compounds represented by the general formula (II). Specifically, benzyl, methoxybenzyl, benzophenone, methoxybenzophenone, aminobenzophenone, dimethylaminobenzophenone, xanthone, thioxanthone, acetophenone, butyrophenone, propiophenone, anthrone, fluorene, triphenylene, anthraquinone, pyrene, naphthalene, anthracene, phenanthrene, Examples include chrysene, coronene, biphenyl, and benzaldehyde.
  • the polymerizable functional group is not particularly limited as long as it causes a polymerization reaction.
  • acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, styrene, alkylstyrene, acrylonitrile, acrylamide, methacrylamide, acetic acid examples include vinyl, butadiene, epoxy, propylene oxide, vinyl chloride and the like.
  • the solvent used in the polymerization of the photochromic molecular monomer according to the present invention examples include THF and toluene.
  • the polymerization temperature is preferably 30 to 150 ° C., more preferably 30 to 100 ° C., particularly preferably 30 to 60 ° C.
  • the reaction time varies depending on the reaction temperature and the required molecular weight, but 2 hours to One week is preferable, more preferably 1 to 5 days, and particularly preferably 2 to 4 days.
  • the photochromic material according to the present invention polymerizes the photochromic molecular monomer represented by the general formula (I) to form a polymer or oligomer, thereby controlling an excessively large decoloring reaction rate when the monomer is used.
  • the decolorization reaction speed can be adjusted to various uses.
  • the amount of light absorption is increased and the photosensitivity is improved by copolymerization with a photosensitizer, compared to the case of a photochromic molecule alone.
  • a photosensitizer By introducing an electron-donating functional group into the photochromic molecule, as shown in FIG. 4, ultraviolet-visible absorption increases even on the long wavelength side, and the visible light sensitivity can be increased.
  • Example 1 Homopolymer of photochromic polymer> An example of a method for synthesizing the photochromic molecular monomer represented by the general formula (I) is shown below.
  • ⁇ Test 1 of homopolymer of Example 1> 0.5 mg of the homopolymer 1-1 synthesized as described above was measured and dissolved in 10 mL of dichloromethane. This solution was placed in a four-sided quartz cell and the transient absorption of the polymer was measured by time-resolved spectroscopy. As a result, as shown in FIG. 1, the half-life of the color former is longer in the polymer than in the monomer state, and the reaction rate from the color former to the decolored body has been effectively slowed down. I understood.
  • the transient absorption of the colored body of the photochromic polymer (homopolymer 1-1) film was measured by time-resolved spectroscopy.
  • Excitation light with a wavelength of 355 nm (third harmonic of Nd-YAG laser) was irradiated to detect absorption at 400 nm.
  • FIG. 9 there is a component that is colored even after 800 milliseconds from the irradiation of excitation light, effectively reducing the reaction rate from the color former to the decolorant.
  • Example 2 Copolymer of photochromic polymer> 40 mg of compound 1-10, 4 mg of compound 1-7, 3.74 mg of methyl methacrylate and 0.7 mg of 2,2′-azobis (2,4-dimethylvaleronitrile) were dissolved in 267 ⁇ L of THF to form a frozen ampule. The tube was frozen and degassed 10 times, and then sealed. This solution was warmed to 40 ° C. and reacted for 3 days with stirring. Thereafter, the reaction solution was dissolved in dichloromethane and dropped into methanol for reprecipitation purification.
  • the precipitated solid was recovered by filtration to obtain 33.3 mg of a copolymer of a photochromic molecule (Compound 1-10), a photosensitizing compound (Compound 1-7), and methyl methacrylate.
  • the weight average molecular weight measured by GPC was 19,500.
  • ⁇ Test 1 of copolymer of Example 2 0.5 mg of a random copolymer of photochromic molecule (compound 1-10), photosensitizing compound (compound 1-7) and methyl methacrylate synthesized as described above was measured and dissolved in 10 mL of dichloromethane. This solution was placed in a four-sided quartz cell and the transient absorption of the polymer was measured by time-resolved spectroscopy. As a result, as shown in FIG. 2, the copolymer also has a color former half-life similar to that of the homopolymer 1-1, and succeeded in effectively slowing the decoloring reaction rate than the monomer. I understood.
  • ⁇ Test 2 of copolymer of Example 2> In the same manner as in Test 2 of the homopolymer of Example 1, a photochromic polymer film was prepared, and then transient absorption measurement was performed. As a result, as shown in FIG. 10, even in the case of the copolymer film, there is a component that develops color even after elapse of 800 milliseconds after irradiation with excitation light, as in the case of the homopolymer. Has succeeded in effectively slowing down the reaction rate from to the decolored body.
  • Example 3 Homopolymer of photochromic polymer> First, 0.5 g of compound 1-4, 0.63 g of compound 1-11 and 2.19 g of ammonium acetate were dissolved in 8 mL of acetic acid, and then heated at 100 ° C. for 5 hours. The reaction solution was neutralized with aqueous ammonia, and the product was extracted with dichloromethane. The dichloromethane layer was concentrated and the product was separated by silica gel column chromatography to obtain 0.48 g of compound 1-12.
  • the transient absorption of the chromophore of the photochromic polymer (homopolymer 1-2) film was measured by time-resolved spectroscopy.
  • Excitation light with a wavelength of 355 nm (third harmonic of Nd-YAG laser) was irradiated to detect absorption at 400 nm.
  • FIG. 11 there are components that are colored even after 800 milliseconds from the irradiation of the excitation light, effectively reducing the reaction rate from the color former to the decolorant. Successful.
  • a method for reducing the decoloring reaction rate of photochromic molecules by polymerizing photochromic molecules has been shown. If this method is used, the decolorization reaction rate is too fast and the colored body does not accumulate, and the decolorization reaction rate of the photochromic molecules having a low color density can be reduced, so that it is possible to provide a photochromic molecular material with good coloring.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2010/071345 2009-12-11 2010-11-30 フォトクロミック材料 WO2011070942A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP10835864.9A EP2511307B1 (de) 2009-12-11 2010-11-30 Photochromes material
KR1020127017749A KR20120129886A (ko) 2009-12-11 2010-11-30 포토크로믹 재료
CN201080055566.4A CN102652143B (zh) 2009-12-11 2010-11-30 光致变色材料
US13/514,620 US9040647B2 (en) 2009-12-11 2010-11-30 Photochromic material
AU2010329226A AU2010329226B2 (en) 2009-12-11 2010-11-30 Photochromic material

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JP2009281966A JP5674305B2 (ja) 2009-12-11 2009-12-11 フォトクロミック材料
JP2009-281966 2009-12-11

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US (1) US9040647B2 (de)
EP (1) EP2511307B1 (de)
JP (1) JP5674305B2 (de)
KR (1) KR20120129886A (de)
CN (1) CN102652143B (de)
AU (1) AU2010329226B2 (de)
WO (1) WO2011070942A1 (de)

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WO2015147126A1 (ja) * 2014-03-28 2015-10-01 関東化学株式会社 ペンタアリールビイミダゾール化合物および該化合物の製造方法
JP2021001129A (ja) * 2019-06-20 2021-01-07 Dic株式会社 イミダゾール化合物

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CN102576112B (zh) 2009-10-21 2014-12-31 三菱瓦斯化学株式会社 功能性片材和使用该功能性片材的透镜
WO2012005354A1 (ja) 2010-07-09 2012-01-12 三菱瓦斯化学株式会社 フォトクロミック材料
CN104687695A (zh) * 2015-03-12 2015-06-10 周士志 一种具有感光效果的箱包
CN113667256B (zh) * 2021-08-30 2023-03-03 湖北高碳光电科技有限公司 用于头戴式光学显示器的光致变色材料、其制备和应用

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WO2015147126A1 (ja) * 2014-03-28 2015-10-01 関東化学株式会社 ペンタアリールビイミダゾール化合物および該化合物の製造方法
JP2015189765A (ja) * 2014-03-28 2015-11-02 関東化学株式会社 ペンタアリールビイミダゾール化合物および該化合物の製造方法
US9834723B2 (en) 2014-03-28 2017-12-05 Kanto Kagaku Kabushiki Kaisha Pentaarylbiimidazole compound and production method for said compound
JP2021001129A (ja) * 2019-06-20 2021-01-07 Dic株式会社 イミダゾール化合物
JP7472438B2 (ja) 2019-06-20 2024-04-23 Dic株式会社 イミダゾール化合物

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CN102652143A (zh) 2012-08-29
CN102652143B (zh) 2014-10-29
US20120245317A1 (en) 2012-09-27
JP5674305B2 (ja) 2015-02-25
KR20120129886A (ko) 2012-11-28
AU2010329226A8 (en) 2012-07-19
EP2511307A4 (de) 2013-09-04
US9040647B2 (en) 2015-05-26
JP2011122089A (ja) 2011-06-23
AU2010329226B2 (en) 2014-05-22

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