WO2007105699A1 - Compose de dithienylcyclopentene, polymere de styrene comportant un dithienylcyclopentene, materiau photochromique et element photonique - Google Patents

Compose de dithienylcyclopentene, polymere de styrene comportant un dithienylcyclopentene, materiau photochromique et element photonique Download PDF

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WO2007105699A1
WO2007105699A1 PCT/JP2007/054868 JP2007054868W WO2007105699A1 WO 2007105699 A1 WO2007105699 A1 WO 2007105699A1 JP 2007054868 W JP2007054868 W JP 2007054868W WO 2007105699 A1 WO2007105699 A1 WO 2007105699A1
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compound
mmol
reaction
yield
solution
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Seiya Kobatake
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Osaka Industrial Promotion Organization
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • 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
    • C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • 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
    • C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • 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
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom

Definitions

  • Dicenylcyclopentene compound Dicenylcyclopentene compound, styrene polymer having diphenylcyclopentene, photochromic material, and optical functional device
  • the present invention relates to a novel diphenylcyclopentene compound, a styrene polymer having a novel diacetylcyclopentene, a photochromic material including these compounds, and an optical functional device including the material.
  • a photochromic compound is a compound that reversibly generates two structural isomers having different colors by light irradiation.
  • Such photochromic compounds are broadly classified into those that are thermally stable at room temperature (P-type photochromism) and those that are thermally unstable at room temperature (T-type photochromism). Is done. For example, diarylmethene compounds and fulgide compounds exhibit P-type photochromism, and spiropyran azobenzene exhibits T-type photochromism.
  • a diarylethene compound or a fulgide compound is a compound in which both two kinds of heterogeneous substances generated by light irradiation are relatively thermally stable. For this reason, application in fields such as optical recording is expected (see, for example, Patent Documents 1 and 2).
  • a photochromic compound is a substance that reversibly generates two structural isomers having different colors by light irradiation.
  • diarylethene compounds are expected to be applied to optical memories and display materials that are thermally stable and have high repeated durability.
  • a diaryruthene compound represented by the following chemical formula ( ⁇ ) fades with visible light. For this reason, this compound has a problem that it cannot be used in the presence of room light.
  • a diallethene is synthesized in which a colored body does not fade even under room light and returns to an original colorless body by heating.
  • a diallethene compound represented by the following chemical formula (IV) developed by the present inventors does not fade with visible light (see, for example, Non-Patent Document 1, Patent Documents 3 and 4).
  • Patent Document 1 Japanese Patent Laid-Open No. 10-45732
  • Patent Document 2 JP-A-9 71585
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-255489
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-255490
  • Non-patent literature l Morimitsu, Shibata, Kobatake, Irie, J. Org. Chem. 2002, 67, p. 4574-4578
  • Patent Documents 1 and 2 are not easy to return from a colored state to an uncolored state. Therefore, it is necessary to provide a compound that can be easily rewritten when used as a display material.
  • the present invention has been made in view of the above-mentioned problems, and the object thereof is that both of the two isomers generated by light irradiation are thermally relatively stable and have no color state.
  • An object of the present invention is to provide a display material that can be easily returned to a colored state.
  • Another object of the present invention is to provide a dicenylcyclopentene-based material that reacts irreversibly with ultraviolet light.
  • Still another object of the present invention is to provide a novel di-cyclopentene-based material that is colored red.
  • Another object of the present invention is to provide a novel photochromic material that reversibly shows photochromism by light and that irreversibly loses its colored state by heating.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a polymer, photochromic, which exhibits photochromism in a solid state and can contain a photochromic component uniformly and in a high density in the polymer. It is to provide a material and an optical functional element. Another object of the present invention is to obtain a polymer having high heat resistance. Means for solving the problem
  • the present invention is a diacetylcyclopentene compound represented by the following general formula (I).
  • R 1 represents a hydrogen (H) or fluorine (F) atom
  • R 2 represents a hydrogen (H) or methyl group
  • R 3 represents a methyl group, a methoxy group, a trimethylsilyl group
  • R 4 and R 5 may be the same or different and each represents hydrogen (H) or an amino group capable of protonation.
  • the present invention is a photochromic material containing the above-mentioned dichelcyclopentene compound.
  • the present invention may be an optical functional device including the photochromic material.
  • the present invention is a styrene polymer having a repeating unit represented by the following general formula ( ⁇ ).
  • R represents a cyclohexyloxy group.
  • the present invention is also a photochromic material containing the styrene polymer.
  • the present invention may be an optical functional device including the photochromic material.
  • the present invention provides a display material in which both of the two isomers generated by light irradiation are thermally relatively stable and can be easily returned to a non-colored state. be able to.
  • the present invention exhibits photochromism in a solid state, It is possible to provide a display material that is uniform and highly dense.
  • FIG. 1 is a diagram showing the state of spectrum change of a coloring reaction and a decoloring reaction by light irradiation of a compound (la-H) in acetonitrile.
  • FIG. 2 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added to (a) compound (la—H) and (b) compound (lb—H) in acetonitrile. is there.
  • FIG. 3 is a graph showing the protonation rate of amino groups when an acid is added to compound (la—H) and compound (lb—H).
  • FIG. 4 is a diagram showing the thermal fading reaction of compound (lb—H) and compound (2b—H) at 60 ° C.
  • FIG. 5 is a graph showing the progress of thermal fading at 30 ° C., 50 ° C. and 60 ° C., although 3 equivalents of trifluoromethanesulfonic acid is added to the compound (lb-H).
  • Figure 6 is a logarithmic plot of the change in absorption spectrum from the data in Figure 5.
  • FIG. 7 is a graph showing the temperature dependence of the velocity coefficient obtained for the slope force of the primary plot of FIG.
  • FIG. 8 is a diagram showing the state of spectrum change of the coloring reaction and decoloring reaction of compound (la-F) by light irradiation in acetonitrile.
  • FIG. 9 is a graph showing a change in spectrum when trifluoromethanesulfonic acid is added to a compound (la-F) in acetonitrile.
  • FIG. 10 is a diagram showing the protonation rate of amino groups when acid is added to compound (la-F) in acetonitrile.
  • FIG. 11 is a diagram showing the thermal fading reaction of compound (lb-F) and compound (2b-F) at 80 ° C.
  • FIG. 12 is a logarithmic plot of the change in absorption spectrum from the data in FIG.
  • FIG. 13 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient of the compound (lb-F) and the compound (2b-F).
  • FIG. 14 is a diagram showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′-H) in acetonitrile.
  • FIG. 15 is a diagram comparing the photostability of the diphenylcyclopentene compounds (lb′—H) and (1 b—H) and the dithiylberberfluorocyclopentene compounds of this example. is there.
  • FIG. 16 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added to a compound (la′—H) and a compound (lb′—H) in acetonitrile.
  • FIG. 17 is a diagram showing a fading reaction at 25 ° C. under a certain place of compound (lb′—H).
  • FIG. 18 is a view showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′-F) in acetonitrile.
  • FIG. 19 is a view showing a change in spectrum when trifluoromethanesulfonic acid is added to the compound (la′-F) and the compound (lb′-F) in acetonitrile.
  • FIG. 20 shows the results when the compound (la′-F) of this example was added with trifluoromethanesulfonic acid and then irradiated with ultraviolet light and left at 40 ° C. and 60 ° C. under some conditions. Absorption spectrum change
  • FIG. 21 is a diagram showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′′F) in hexane.
  • FIG. 22 is a diagram showing a thermal fading reaction of compound (lb ′ ,, 1 F) at 50 ° C. in hexane.
  • FIG. 23 is a graph showing the attenuation of absorbance of compound (lb ′, 1F) in hexane at 30-60 ° C.
  • FIG. 24 is a logarithmic plot of the change in absorption spectrum from the data in FIG.
  • FIG. 25 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the gradient force of the primary plot of FIG.
  • FIG. 26 is a diagram showing an outline of synthesizing a styrene monomer having the di-cyclopentene of the present invention.
  • FIG. 27 shows a DSC curve obtained by measuring the differential scanning calorimetry of the polymer (poly (la-M)). It is a figure.
  • FIG. 28 is a diagram showing a change in ultraviolet-visible absorption spectrum when ultraviolet light is irradiated in a toluene solution of a polymer (poly (la-M)) and in a film.
  • FIG. 29 is a graph showing a change in reaction rate when ultraviolet light is irradiated in a toluene solution of a polymer (poly (la-M)) and in a film.
  • FIG. 30 shows 110 ° C., 120 ° C., 130 in a polymer (poly (lb-M)) film. It is a figure which shows progress of thermal fading in C, 140 degreeC, and 150 degreeC.
  • FIG. 31 is a plot of the change in absorption spectrum logarithmically from the data in FIG.
  • FIG. 32 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the gradient force of the primary plot of FIG.
  • FIG. 33 is a graph showing changes in Tg when 1-adamantyl methacrylate is prepared as a copolymer.
  • FIG. 34 is a view showing a DSC curve of a copolymer Poly ((la-M) -co- (1-adamantyl methacrylate)).
  • FIG. 35 is a view showing a thermogravimetric analysis curve of a copolymer Poly ((la-M) -co- (1-adamantyl methacrylate)).
  • Fig.36 shows the thermal fading coefficient of polymer (Poly (lb-M)) ( ⁇ ) and copolymer (Poly ((la-M) -co- (1-adamantyl methacrylate)) ( ⁇ )
  • Poly (lb-M) poly ((la-M) -co- (1-adamantyl methacrylate)
  • the diphenylcyclopentene compound of the present invention is represented by the following general formula a).
  • R 1 represents a hydrogen (H) or fluorine (F) atom
  • R 2 represents a hydrogen (H) or methyl group
  • R 3 represents a methyl group, a methoxy group, a trimethylsilyl group
  • R 4 and R 5 may be the same or different and each represents hydrogen (H) or an amino group capable of protonation.
  • the amino group is not particularly limited as long as it can be protonated in the presence of an acid.
  • Specific examples include an amino group substituted with an alkyl group.
  • Preferred alkyl groups are those having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, tert-butyl group, pentyl group. Group, octyl group and the like.
  • the di-cyclopentene compound represented by the general formula (I) is! By changing ⁇ ⁇ , (1) a compound that can switch between P-type photochromism and T-type photochromism in the presence of acid, (2) a compound that can be heated and decolored by adding acid, (3) Different compounds can be obtained from blue to red.
  • the compound (2b-H) is a compound that exhibits a T-type photochromium whose state caused by light irradiation is thermally unstable at room temperature.
  • Compound (2a-H) can also be obtained by placing compound (la-H) in the presence of an acid and protonating the amino group.
  • the amino group is deprotonated in the presence of an alkyl group to produce the compound (la-H). That is, the di-cyclocyclopentene compound of the present invention undergoes a series of reactions by light irradiation, heat treatment, and acid / alkali treatment, as shown in the following chemical formula.
  • the dichelcyclopentene compound of the present invention has P-type photochromism and T
  • the type photochromism can be switched by having an amino group capable of protonation in the molecule. That is, in the present invention, the role of an amino group capable of protonation is important.
  • Compound (2b ′) differs from the optical properties of compound (lb ′).
  • the amino group is deprotonated in the presence of alkali to produce the compound (lb ′).
  • the compound (2b ′) becomes a separate compound by heating and is almost colorless.
  • the compound (2a ′) is irradiated with ultraviolet rays, the compound (2b ′) is irreversibly generated.
  • Compound (2a ′) can also be obtained by placing compound (la ′) in the presence of an acid and protonating the amino group.
  • the amino group is deprotonated in the presence of alkali to produce the compound (la ′). That is, the diphenylcyclopentene compound of the present invention undergoes a series of reactions by light irradiation, heat treatment, acid and alkali treatment as shown in the following chemical formula.
  • Such an irreversible photochromic material can be used for a temperature sensor, for example.
  • the diphenylcyclopentene compound represented by the general formula (I) can be produced by a known method as shown in Examples.
  • the diphenylcyclopentene compound of the present invention causes a photoreaction and exhibits photochromism
  • a material containing the compound can be used as a photochromic material useful for various optical functional elements, for example.
  • the dichelcyclopentene compound of the present invention can switch between P-type photochromism and T-type photochromism, so that recording and erasing of information can be easily repeated. Can do.
  • An optical functional element such as an optical memory element or an optical switching element can be produced by using such a mechanism and a change in optical characteristics accompanying the mechanism.
  • a thin film is formed using a photochromic material containing the di-cyclopentene-based compound of the present invention, and an optical switching element is manufactured using the thin film.
  • the element can be miniaturized, which is preferable.
  • a thin film is formed using a photochromic material containing a diphenylcyclopentene compound of the present invention, and an optical memory element is produced using this as a recording layer.
  • the photon mode recording on the recording layer makes it possible to significantly improve the recording density, which is preferable.
  • By using a multiphoton absorption reaction, three-dimensional recording is also possible, so the recording capacity can be improved. It is possible and more preferable.
  • the dichelcyclopentene compound of the above (2) since it is not decolored by visible light, it can be used as an irreversible optical recording element.
  • the dichelcyclopentene compound (2) can be decolorized by heating, and can be used as a heating sensor.
  • dicenylcyclopentene compound of the present invention can be confirmed by a general organic analysis technique such as nuclear magnetic resonance sputtering, mass spectrometry, and high performance liquid chromatography.
  • the amount of the acid used is 1 molar equivalent or more, preferably 1 to 5 molar equivalents, more preferably, with respect to the di-cyclopentapentene compound of the present invention. Or 2 to 4 molar equivalents.
  • the acid to be used trifluoromethanesulfonic acid, acetic acid, hydrochloric acid and the like are used.
  • triethylamine or the like is used as the base to be used.
  • the acid may be used in the state of being dissolved in a solvent such as acetonitrile, or the solvent may not be used.
  • a solvent such as acetonitrile
  • heating from room temperature to about 150 ° C. is preferable because the reaction is accelerated.
  • no solvent is used, two isomers are reversibly produced when irradiated with light in the state where the diphenylcyclopentene compound of the present invention and an acid coexist.
  • the presence of acid does not have a significant effect on this reaction.
  • heating may be performed. By heating, the acid is Surrounds the periphery of the otochromic material and protonates the amino group. Upon cooling, the acid leaves the photochromic material. Thereby, a photochromic material can be decolored.
  • the styrene polymer having dicenylcyclopentene of the present invention has a repeating unit represented by the following general formula (II), and is obtained by radical polymerization of a compound represented by the following general formula (V). It is done.
  • R represents a cyclohexyloxy group.
  • R represents a cyclohexyloxy group.
  • the styrene polymer having di-cyclocyclopentene of the present invention comprises a compound represented by the general formula (V) in the presence of 2, 2'-azobisisobutyl nitrile (AIB N) as a radical polymerization initiator. Obtained by radical polymerization under pressure.
  • AIB N 2, 2'-azobisisobutyl nitrile
  • the solvent used for the polymerization include cyclohexane and toluene.
  • the number average molecular weight of the polymer photochromic material of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 40,000, and polydispersity (weight average molecular weight and number average). The ratio to the molecular weight is about 1.6 to 2.1, and the glass transition temperature (Tg) is 104 ° C.
  • the styrene polymer having the dicyclocyclopentene of the present invention is obtained by irradiating light with two polymers (Poly (la-M) and Poly (lb-M)) as shown in the following reaction formula (VI). Generate reversibly. It has the property of reversibly changing optical properties such as light absorption coefficient, refractive index, optical rotation or dielectric constant according to this change due to the change in molecular structure due to photochemical reaction. In addition, by heating Poly (lb— M) at a temperature higher than 100 ° C, Poly (la— M) Is generated. That is, the styrene polymer having the dicyclocyclopentene of the present invention undergoes a reversible reaction by light irradiation and heat treatment.
  • R represents a cyclohexyloxy group.
  • the polymer photochromic material of the present invention may contain other copolymerization components as long as the photochromism is not inhibited. By including other copolymerization components in this way, a polymer having a high Tg can be obtained. Usually, when other copolymerization monomers are included, the photochromism of the photochromic material of the present invention tends to decrease, and therefore the content of other copolymerization components may be appropriately adjusted depending on the balance between photochromism and Tg.
  • a copolymer having a high Tg can be obtained by copolymerizing the dicyclocyclopentene of the present invention with 1-adamantyl methacrylate, N-1-adamantyl maleimide, or the like.
  • the optical recording medium of the present invention can be obtained by forming a recording layer containing a polymer photochromic material having a repeating unit represented by the general formula ( ⁇ ) of the present invention on a substrate.
  • the substrate is appropriately selected from those usually used which may be transparent or opaque to the light used. Specific materials for the substrate include power such as glass, plastic, paper, plate-like or foil-like metal such as aluminum. Among these, plastic is preferred from various points of view. Examples of plastics include acrylic resin, methallyl resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, and polysulfone resin. .
  • the recording layer is formed on the substrate by dissolving the polymer photochromic material of the present invention in a suitable solvent together with a nonder resin if necessary, and using a doctor blade method, a casting method, a spinner method, an immersion method. By such means, it is applied so as to form a thin film having a film thickness of 2 nm to 50 ⁇ m, preferably 10 nm to 30 ⁇ m.
  • the binder resin used include phenol resin, polycarbonate resin, polystyrene resin, and (meth) acrylic resin such as methyl poly (meth) acrylate. In general, it leads to a decrease in the concentration of the galleureten structure.
  • noinder resin it is most desirable to use noinder resin but not more than the same amount as that of the polymer photochromic material of the present invention, more preferably less than half.
  • the solvent include toluene, xylene, black benzene, methyl ethyl ketone, and ethyl acetate.
  • the content of the polymer photochromic material of the present invention in the formed recording layer is not particularly limited, but can be appropriately determined in consideration of the absorbance of the substance, the intensity of light emission, and the like.
  • the recording layer may be provided on only one side of the substrate or on both sides. Further, a protective film such as an ultraviolet curable resin can be provided on the recording layer for the purpose of improving the weather resistance. Recording on the optical recording medium of the present invention is performed by irradiating the converged light on the recording layer provided on the substrate.
  • Diceryl cyclopentene (la-H) having a jetylamino group at one end of the synthesized molecule showed a thermally stable photochromism in a neutral acetonitrile solution.
  • the colorless (la-H) solution was irradiated with ultraviolet light, the solution turned purple (lb-Pi) and changed to a spectrum having an absorption maximum at 540 nm.
  • FIG. 1 is a diagram showing a state of spectrum change between a coloring reaction and a decoloring reaction. From this result, it was found that the diphenylcyclopentene compound of the present invention exhibits a normal photochromism that causes a coloring reaction by ultraviolet irradiation and a fading reaction by visible light irradiation.
  • Fig. 2 is a diagram showing the change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, it can be seen that if about 3 equivalents of trifluoromethanesulfonic acid is added to the compound (la-H), the spectral change is eliminated.
  • FIG. 3 is a diagram showing the proton ratio of an amino group when an acid is added. From this figure, it was found that in the acetonitrile, the amino group was almost protonated when about 3 equivalents of trifluoromethanesulfonic acid was added.
  • FIG. 4 is a diagram showing a thermal fading reaction at 60 ° C.
  • the lb graph is for trifluoromethanesulfonic acid without addition, and 2b is 10 equivalents of trifluoromethanesulfonic acid. It is added.
  • the compound (lb-H) obtained by irradiating the compound (la-H) with ultraviolet light, which contains 10 equivalents of trifluoromethanesulfonic acid was heated at 60 ° C for 2 hours. On standing, the solution returned to almost colorless, and its absorption spectrum coincided with the absorption spectrum of (2a-H) having an absorption maximum at 281 nm. In addition, the solution of 2b returned to colorless even after being left at room temperature for 3 days.
  • (2b-H) was found to show a heat return reaction at room temperature.
  • the compound (lb—H) did not show a heat return reaction at 60 ° C. as well as at room temperature. From this result, it became clear that the diphenylcyclopentene compound of the present invention can switch between P-type photochromism and T-type photochromism by adding acid.
  • Figure 5 shows the compound (lb—H) with 3 equivalents of trifluoromethanesulfonic acid. It is a figure which shows progress of thermal fading in C, 50 degreeC, and 60 degreeC. From this figure, it can be seen that the progression of thermal fading is promoted by heating.
  • Figure 6 is a logarithmic plot of the change in absorption spectrum from the data in Figure 5.
  • FIG. 7 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the slope of the primary plot of FIG. From this figure, it was estimated that the thermal fading speed increased due to heating, and fading occurred at several seconds (about 6 seconds) at 120 ° C.
  • Diacetylcyclopentene (la-F) having a jetylamino group at one end of the synthesized molecule reacts as shown in the following chemical formula.
  • experimental examples will be described based on the following chemical formula.
  • FIG. 8 is a diagram showing the state of spectrum change between the coloring reaction and the decoloring reaction. From this result, it was found that the diphenylcyclopentene compound of the present invention exhibits a normal photochromism that causes a coloring reaction by ultraviolet irradiation and a fading reaction by visible light irradiation.
  • FIG. 9 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, it can be seen that if about 3 equivalents of compound (la-F) and about 6 equivalents of trifluoromethanesulfonic acid are added to compound (lb-F), the spectral change is eliminated.
  • FIG. 10 is a diagram showing the proton ratio of an amino group when an acid is added. From this figure, it can be seen that in diphenylcyclopentene, if about 6 equivalents of trifluoromethanesulfonic acid is added, the amino groups of both compounds (la-F) and (lb-F) are almost protonated. Wakatsuta o
  • FIG. 11 is a diagram showing a thermal fading reaction at 80 ° C.
  • the white circles in the figure are those without trifluoromethanesulfonic acid (lb-F), and the black circles are those with 10 equivalents of trifluoromethanesulfonic acid (2b-F).
  • the compound (lb-F) obtained by irradiating the compound (la-F) with ultraviolet light, which is obtained by adding 10 equivalents of trifluoromethanesulfonic acid (2b-F),
  • the solution was allowed to stand at 80 ° C for 10 hours, the solution returned to almost colorless, and the absorption spectrum coincided with the absorption spectrum of (la-F) having an absorption maximum at 293 nm.
  • the diphenylcyclopentene compound of the present invention has a heat regeneration function by adding an acid.
  • FIG. 12 is a logarithmic plot of the change in absorption spectrum from the data in FIG. Figure 13 shows the logarithm of the rate coefficient obtained at various temperatures for the compound (lb-F) and trifluoromethanesulfonic acid 10 equivalents (2b-F). From this figure, the compound (lb-F) is stable at 30 ° C for several years, and when 10 equivalents of trifluoromethanesulfonic acid is added, the thermal fading rate increases with heating, and at 160 ° C, it takes several tens of seconds. It was estimated that the color would fade.
  • the flask was charged with 12 g of 2-methoxy-4-methylthiophene (0. 92 mol), 200 mL of hexane and 20 mL of acetic acid, and cooled to 0 ° C. with an ice-water bath.
  • N-chlorosuccinimide (13.5 g, 0.1 mol) was added little by little, and the mixture was stirred for 3 hours in an ice-water bath. After completion of the reaction, the reaction mixture was neutralized with an aqueous sodium hydroxide solution, then extracted with ether, and the organic layer was washed with an aqueous sodium chloride solution.
  • the mixture was stirred at ° C. for 1 hour to synthesize 1,2-bis (2-black-mouth-3-methyl-5-methoxy-4-cell) cyclopentene.
  • FIG. 15 is a comparison of the photostability of the dichelcyclopentene compound (lb ′, 1 H) of this example and the dicherel perfluorocyclopentene compound.
  • the conventional diphenylperfluorocyclopentene system is colored blue ( ⁇ in the figure)
  • the dichelcyclopentene compound of this example is colored in red ( ⁇ in the figure).
  • the ⁇ in the figure is the dicenyl cyclopentene compound (1b-H) of Example 1 that reacts reversibly with visible light.
  • the photostability of the dicenylcyclopentene compound of this example is about 10 times higher than that of the conventional dithiylberylfluorocyclopentene compound.
  • FIG. 16 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, 1— (2-methoxy-4-methyl-5-p-N, N—jetylaminophenol 3 chael) 2— (2-methoxy-1-methyl-5-phenyl 5-phenyl 3 ) Addition of 2 to 3 equivalents of trifluoromethanesulfonic acid to cyclopentene (Fig. 16 (a)) and this UV-irradiated product (Fig. 16 (b)) reveals that the spectral change is eliminated. . [0089] [Fade reaction]
  • Figure 17 shows 1— (2-methoxy-4-methyl-5-p-N, N-deethylaminophenol-3 chael)-2- (2-methoxy-4-methyl-5-phenol
  • This is the change in absorption spectrum when trifluoromethanesulfonic acid is added to (Cheel) cyclopentene and then irradiated with ultraviolet light, and then left at 25 ° C under certain conditions.
  • the gradually fading force spectrum has shifted to a long wavelength and has not returned to the open ring.
  • the solution after fading is light stable. With increasing temperature, the fading response increased.
  • the di-cyclopentene compound of this example has light stability after color development. In addition, since it fades due to heat, it was found that application to a heating sensor is possible.
  • the yield was 210 mg and the yield was 32%.
  • FIG. 19 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, 1— (2-methoxy—4-methyl-5—p—N, N—jetylaminophenol 3 chas) 2— (2-methoxy-1-methyl-5-methyl 5-ferol 3 che -L) It can be seen that the addition of 2 to 3 equivalents of trifluoromethanesulfonic acid to perfluorocyclopentene eliminates the spectral change.
  • FIG. 20 shows the change in absorption spectrum when dichloromethane sulfonic acid is added to the dicyclocyclopentene of this example and then irradiated with ultraviolet light and left at 60 ° C. in the dark.
  • the force of fading reaction has not progressed to the open ring.
  • the solution after fading is light stable
  • Examples 3 and 4 show that these diphenyl cyclopentene compounds do not cause a reversible reaction with visible light under neutral and acidic conditions. It can also be seen that when the material is heat faded under acidic conditions, it changes to a different substance.
  • Diarylethene having a trimethylsilyl group was synthesized according to the following scheme.
  • Table 1 shows. In other words, at temperatures below 10 ° C, it will not fade safely for several months, and at temperatures above 30 ° C it will fade in several hours.
  • a material having such a property can be used as a temperature sensor for temperature management in a place where a temperature change may occur. For example, when long-term frozen storage (1 month) is required, color is irradiated with ultraviolet light at a low temperature. If it is kept frozen, it will not fade, but it will fade if it is above 30 ° C for several hours. In this way, frozen storage is maintained for a long time Can be used as a temperature sensor.
  • FIG. 26 shows an outline for synthesizing the styrene polymer having dicenylcyclopentene of the present invention shown below.
  • Monomer la- M 0.151g (. 0 178mmol) , Azobisuisobuchi port - tolyl (AIBN) 1. 57mg (9.68X10 _3 mmol), toluene (0.50 ml) placed in a glass tube, after Datsukifu tube, at 60 ° C Polymerized for 10 hours.
  • the polymerization mixture was precipitated in methanol to isolate the polymer. It refine
  • Aromatic H Aromatic H
  • the glass transition point (Tg) was determined from the change in the differential scanning calorific value of the polymer obtained above. The results are shown in FIG. From this measurement, it was found that the Tg of the polymer obtained was 104 ° C.
  • FIG. 28 is a diagram showing the state of spectrum change of the coloring reaction in the toluene solution and in the film. From this result, it was proved that the styrene polymer having diceryl cyclopentene of the present invention causes a coloring reaction by ultraviolet irradiation.
  • the polymer irradiated with ultraviolet light (Poly (lb-M)) faded when heated to a high temperature of 100 ° C or higher, which was relatively stable in room light.
  • the photochromism of photocoloring and heating regeneration can be repeated when the faded film is irradiated with ultraviolet light.
  • Figure 30 shows the polymer 110 (Poly (lb-M)). C, 120. C, 130. C, 140. C, 150.
  • FIG. 4 is a diagram showing the progress of thermal fading in C. From this figure, it can be seen that the process of thermal fading is promoted by heating. From this figure, it can be seen that at 150 ° C, the color faded completely within 10 minutes.
  • Fig. 31 is a logarithmic plot of the change in absorption spectrum from the data in Fig. 30.
  • FIG. 32 is a graph in which the speed coefficient is obtained from the slope of the primary plot of FIG.
  • the amount of la- M in the copolymer 61 mole 0/0
  • the amount of la- M in the copolymer 49 mole 0/0
  • the glass transition point (Tg) was determined from the change in the differential scanning calorific value of the polymer obtained above. The results are shown in FIG. From this measurement, it was found that the Tg of the polymer obtained above had no glass transition point below 230 ° C.
  • FIG. 36 is a graph showing the temperature dependence of the thermal fading reaction coefficient of the polymer (Poly (lb-M)) and the copolymer (Poly ((lb-M) -co-14)). This figure shows that the thermal fading rates of Poly (lb—M) and Poly ((1 b-M) co-14) are almost equal. Based on the above, it was possible to synthesize a polymer having a glass transition point of 200 ° C. or higher with a high density introduction of a di-cyclopentene dye having photo-coloring and heating regeneration functions.
  • the present invention provides a display material in which both of the two isomers generated by light irradiation are thermally relatively stable and can be easily returned to a non-colored state. Is possible.
  • the present invention it is possible to provide a novel photochromic material that reacts in addition and reverse with ultraviolet light, exhibits photochromism, and decolors in addition and reverse by heating.
  • the present invention can provide a display material that exhibits photochromism in a solid state and contains a photochromic component that is uniform in poly and high density.

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Abstract

La présente invention concerne un matériau d'affichage qui, lors d'un rayonnement de lumière, génère deux isomères chacun relativement stables à la chaleur et qui, dans un état coloré, peut être facilement ramené à un état incolore; un matériau photochromique qui réagit de manière irréversible par l'action d'un rayonnement ultraviolet; un nouveau matériau photochromique qui prend une couleur rouge; un nouveau matériau photochromique qui réagit de manière irréversible par l'action d'un rayonnement ultraviolet pour montrer un photochromisme et est décoloré de manière irréversible par chauffage; et un polymère qui, dans un état solide, montre un photochromisme et qui peut contenir un ingrédient photochromique de manière uniforme à une densité élevée. Le matériau d'affichage est un composé de dithiénylcyclopentène représenté par la formule générale suivante (I). Le polymère est un polymère de styrène comportant un dithiénylcyclopentène représenté par la formule générale suivante (II).
PCT/JP2007/054868 2006-03-11 2007-03-12 Compose de dithienylcyclopentene, polymere de styrene comportant un dithienylcyclopentene, materiau photochromique et element photonique WO2007105699A1 (fr)

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JP2014015552A (ja) * 2012-07-10 2014-01-30 Osaka City Univ ジアリールエテン化合物を含むフォトクロミック材料および光機能素子
US9708528B2 (en) 2014-06-13 2017-07-18 The University Of Hong Kong Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and the production thereof
JPWO2018038145A1 (ja) * 2016-08-25 2019-06-24 公立大学法人大阪市立大学 ジアリールエテン化合物
JP2019151632A (ja) * 2018-03-05 2019-09-12 公立大学法人大阪市立大学 ジアリールエテン化合物、フォトクロミック材料、及び表示媒体
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EP2003497B1 (fr) * 2007-06-13 2010-07-28 Xerox Corporation Papier d'impression sans encre sur lequel une image peut être formulée plusieurs fois et procédée
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US7645560B1 (en) 2008-09-08 2010-01-12 Xerox Corporation Inkless reimageable printing paper and method
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US9708528B2 (en) 2014-06-13 2017-07-18 The University Of Hong Kong Robust photochromic compounds with silicon- or phosphorus-containing heterocyclic ring and the production thereof
JPWO2018038145A1 (ja) * 2016-08-25 2019-06-24 公立大学法人大阪市立大学 ジアリールエテン化合物
JP7364202B2 (ja) 2016-08-25 2023-10-18 公立大学法人大阪 ジアリールエテン化合物
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