WO2012005354A1 - フォトクロミック材料 - Google Patents
フォトクロミック材料 Download PDFInfo
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- WO2012005354A1 WO2012005354A1 PCT/JP2011/065702 JP2011065702W WO2012005354A1 WO 2012005354 A1 WO2012005354 A1 WO 2012005354A1 JP 2011065702 W JP2011065702 W JP 2011065702W WO 2012005354 A1 WO2012005354 A1 WO 2012005354A1
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- 0 CC([C@]1(c2c-3c(*)c(*)c(*)c2C)[n]2c-3nc(*)c2*)=C(*)C(*)=C(*)C1=C1N=C(*)C(*)=N1 Chemical compound CC([C@]1(c2c-3c(*)c(*)c(*)c2C)[n]2c-3nc(*)c2*)=C(*)C(*)=C(*)C1=C1N=C(*)C(*)=N1 0.000 description 8
- FYOQNPUWPICRGU-LXOGZNDWSA-N C/C=C\C(C=CC1=C(N=C2c3ccccc3)N=C2c2ccccc2)=C(Cc2ccc(ccc-3c45)c4c2)C15[n]1c-3nc(-c2ccccc2)c1-c1ccccc1 Chemical compound C/C=C\C(C=CC1=C(N=C2c3ccccc3)N=C2c2ccccc2)=C(Cc2ccc(ccc-3c45)c4c2)C15[n]1c-3nc(-c2ccccc2)c1-c1ccccc1 FYOQNPUWPICRGU-LXOGZNDWSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/20—Spiro-condensed systems
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Definitions
- the present invention relates to a photochromic material, and more particularly to a photochromic material made of a novel biimidazole compound.
- Photochromic materials generally have a function (light control function) that causes an isomerization reaction by irradiating light and reversibly changes color (transmittance of visible light).
- a material generated after light irradiation is also called a photochromic material.
- the photochromic material is used as a display material such as glasses for preventing glare, an optical switch, or ink having a display / non-display switching ability.
- applications as recording materials such as optical disks and holograms are also being studied.
- a color change due to a photochromic material is generally expressed by a reversible chemical change of the material due to light irradiation.
- typical photochromic materials spiropyran compounds, spirooxazine compounds, naphthopyran compounds, fulgide compounds, diarylethene compounds, and the like are known (for example, Non-Patent Document 1 below).
- Non-Patent Document 2 a compound having a new structure having high-speed photoresponsiveness has also been reported (for example, Non-Patent Document 2 below).
- Photochromic materials can be broadly divided into those that exhibit a phenomenon called positive photochromism that develops color (colored) with the structural changes caused by light irradiation, and conversely, changes from a colored body (colored body) to a colorless body by light irradiation. Some exhibit a phenomenon called negative photochromism (reverse photochromic material).
- Patent Document 1 spirobenzopyran derivatives
- Patent Document 2 dimethyldihydropyrene derivatives
- Patent Document 3 diarylethene derivatives
- the light control function is required to have characteristics such as color, color density and color speed suitable for the application. Therefore, it is necessary to develop various types of derivatives and compounds having a new molecular skeleton. Therefore, a photochromic material having a new structure has been demanded.
- An object of the present invention is to provide a photochromic material having a new structure that exhibits a reversible structural change (color change) by light irradiation or after light irradiation, when left under light shielding.
- the present inventors have found a completely new photochromic molecule. Specifically, the present inventors have found a new compound exhibiting negative photochromism by introducing a bulky substituent into R 4 and R 5 of the general formula (1-1) having biimidazole as a basic skeleton. It was. This molecule was a colored body in a stable state or an initial state, and exhibited a photochromic property (reverse photochromic property) that isomerizes to a decolored material when irradiated with visible light.
- a photochromic property reverse photochromic property
- R 4 and R 5 each independently represent a halogen atom or an alkyl group
- R 1 to R 3 and R 6 to R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a fluoroalkyl group, A hydroxyl group, an alkoxyl group, an amino group, an alkylamino group, a carbonyl group, an alkylcarbonyl group, a nitro group, a cyano group or an aryl group
- Ar 1 to Ar 4 each independently represents a substituted or unsubstituted aryl group.
- R 4 together with R 3 may form a fused substituted or unsubstituted aryl ring
- R 5 together with R 6 may form a fused substituted or unsubstituted aryl ring.
- the present invention is a photochromic material comprising the biimidazole compound represented by the general formula (1-1).
- the photochromic material of the present invention represented by the general formula (1-1) can be changed to an isomer represented by the general formula (3-1) by light irradiation.
- the photochromic material represented by the general formula (1-1) is a color former and has a low transmittance.
- the isomer represented by the general formula (3-1) is a decolorant. Therefore, according to the photochromic material of the present invention, it is possible to adjust the color tone of the photochromic material by light irradiation.
- the photochromic material of the present invention represented by the general formula (1-1) changes from a colored body to a decolored body by light irradiation. That is, the photochromic material of the present invention represented by the general formula (1-1) is an inverse photochromic material. In FIG. 1, ⁇ represents heat energy.
- R 4 together with R 3 forms a condensed substituted or unsubstituted aryl ring
- a photochromic material in which R 5 forms a substituted or unsubstituted aryl ring condensed with R 6 is generally represented by the general formula (3-1) by irradiation with light as shown in FIG. Can be an isomer.
- such a photochromic material does not become the isomer (II) shown in FIG. 1 even when left in a light-shielded state (see FIG. 3).
- the present inventors have also found a new compound having photochromism by introducing a bulky substituent into R 24 and R 25 of the following general formula (2-1) using biimidazole as a basic skeleton.
- This molecule is stable and pale yellow, isomerizes to a colorless structure when irradiated with light, and further isomerizes to a red chromophore after isomerization to a red chromophore.
- the photochromic characteristics to be changed are shown.
- R 24 and R 25 each independently represents an alkyl group or an alkyl group having a substituent
- R 1 to R 3 and R 6 to R 8 each independently represent a hydrogen atom, a halogen atom or an alkyl group
- Ar 1 to Ar 4 are each independently substituted or unsubstituted
- the present invention is a photochromic material comprising the biimidazole compound represented by the general formula (2-1).
- the photochromic material of the present invention represented by the general formula (2-1) can be changed to the isomer (II-2) by light irradiation.
- the isomer (II-2) is changed into the photochromic material represented by the isomer (I-2) and the general formula (2-1) by heat energy.
- isomer (I-2) is a color former and has a low transmittance.
- the isomer (II-2) is a decolorant, but has a transmittance different from that of the photochromic material represented by the general formula (2-1). Therefore, according to the photochromic material of the present invention, the color tone of the photochromic material can be adjusted in two stages.
- ⁇ represents heat energy.
- FIG. 2 shows a diagram in which R 4 in FIG. 1 is substituted with R 24 and R 5 is substituted with R 25 .
- R 4 and R 5 each independently represent a halogen atom or an alkyl group
- R 1 to R 3 and R 6 to R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group.
- Ar 1 to Ar 4 each independently represents a substituted or unsubstituted aryl group; the .R 4 showing, together with R 3, may form a fused substituted or unsubstituted aryl ring, R 5 together with R 6, may form a fused substituted or unsubstituted aryl ring.
- the present invention is a photochromic material comprising the biimidazole compound represented by the general formula (3-1).
- the photochromic material of the present invention represented by the general formula (3-1) can maintain the structure represented by the general formula (3-1) by continuing the light irradiation.
- the photochromic material of the present invention can be changed into an isomer represented by the general formula (1-1) by changing a thermal energy by leaving it in a light-shielded state. It becomes possible to do.
- the isomer represented by the general formula (1-1) when the isomer represented by the general formula (1-1) is left in a light-shielded state, it can be changed to the isomer (II) by a change in thermal energy.
- a photochromic material in which R 5 forms a substituted or unsubstituted aryl ring condensed with R 6 can usually be an isomer represented by the general formula (1-1) when in a light-shielded state. Even if the isomer represented by the general formula (1-1) is further left in a light-shielded state, it does not become the isomer (II) shown in FIG. 1 (see FIG. 3).
- the following effect (1), (2) or (3) can be obtained.
- the color tone easily changes from a colored body to a decolored body by irradiation with visible light.
- the transmittance can be easily increased by light irradiation to change the color tone from light yellow to colorless, and then the transmittance is lowered by heat energy to change to a color former, or the photochromic of the present invention Or return to material.
- (3) The color tone can be easily changed from the decolored body to the color body by shielding the light.
- the above properties can be applied to all uses where photochromic molecules are used. Specific applications include optical switches, printing materials, recording materials, and hologram materials.
- the photochromic material of the present invention has a completely different structure from conventional photochromic molecules, it can provide a new option for device development using photochromism.
- FIG. 2 is a view showing a structure that can be taken by light irradiation or light shielding by the photochromic material of the present invention represented by the general formula (1-1) or (3-1). It is a figure which shows the structure which the photochromic material of this invention represented by General formula (2-1) can take by light irradiation or light shielding.
- R 4 forms a condensed substituted or unsubstituted aryl ring together with R 3
- R 5 forms a substituted or unsubstituted aryl ring condensed together with R 6.
- 2 is a graph showing an ultraviolet-visible absorption spectrum of the compound [1-1] according to Example 1-1 in a normal state and during excitation light irradiation.
- 4 is a graph showing an ultraviolet-visible absorption spectrum during normal state and excitation light irradiation of the compound [1-2] according to Example 1-2.
- 2 is a graph showing an ultraviolet-visible absorption spectrum during normal state and excitation light irradiation of the compound [1-3] according to Example 1-3.
- 4 is a graph showing an ultraviolet-visible absorption spectrum during normal state and excitation light irradiation of the compound [1-4] according to Example 1-4.
- 6 is a graph showing an ultraviolet-visible absorption spectrum of the compound [1-5] according to Example 1-5 in a normal state and during excitation light irradiation.
- 6 is a graph showing an ultraviolet-visible absorption spectrum of a compound [1-6] according to Comparative Example 1-1 in a normal state and during excitation light irradiation.
- 6 is a graph showing an ultraviolet-visible absorption spectrum of the compound [2-3] according to Example 2-1 in a normal state, during irradiation with excitation light, and in a state where the compound [2-3] is left under light shielding after irradiation with excitation light.
- 3 is a graph showing an ultraviolet-visible absorption spectrum of a compound [2-1] according to Example 3-1 in a light irradiation state and a light shielding state.
- 4 is a graph showing an ultraviolet-visible absorption spectrum of a compound [3-1] according to Example 3-2 in a light irradiation state and a light shielding state.
- 4 is a graph showing an ultraviolet-visible absorption spectrum of a compound [3-2] according to Example 3-3 in a light irradiation state and a light shielding state.
- 4 is a graph showing an ultraviolet-visible absorption spectrum of a compound [3-3] according to Example 3-4 in a light irradiation state and a light shielding state.
- 6 is a graph showing an ultraviolet-visible absorption spectrum of a compound [3-4] according to Example 3-5 in a light irradiation state and a light shielding state. 6 is a graph showing an ultraviolet-visible absorption spectrum of a compound [1-6] according to Comparative Example 3-1 in a light irradiation state and a light shielding state.
- a spiro ring is introduced by introducing a sterically bulky substituent into both the R 4 and R 5 sites of the biimidazole compound represented by the general formula (1-1). A structure with a structure is obtained.
- Examples of the bulky substituent at both sites of R 4 and R 5 include a halogen atom or an alkyl group.
- the substituent may be the smallest methyl group among the alkyl groups. That is, the photochromic material may be represented by the following general formula (1-2).
- R 4 together with R 3 forms a condensed substituted or unsubstituted aryl ring
- R 5 together with R 6 forms a condensed substituted or unsubstituted aryl ring.
- the aryl ring is preferably a benzene ring.
- the photochromic material in this case is represented by the following general formula (1-3). (Wherein R 1 to R 2 and R 7 to R 14 are each independently a hydrogen atom, a halogen atom, an alkyl group, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, an amino group, an alkylamino group, a carbonyl group, or an alkylcarbonyl group. A group, a nitro group, a cyano group or an aryl group, Ar 1 to Ar 4 each independently represents a substituted or unsubstituted aryl group.)
- the photochromic material of the present invention includes, for example, a 2,2′-diformylbiphenyl derivative represented by the following general formula (1-4) and a diarylethane represented by the following general formulas (1-5) and (1-6) It can be obtained by reacting a dione derivative in the presence of a nitrogen compound to obtain an intermediate containing an imidazole ring and then subjecting the intermediate to an oxidation reaction.
- a 2,2′-diformylbiphenyl derivative represented by the general formula (1-4) instead of the 2,2′-diformyl-1,1′-binaphthalene derivative may be used.
- the 2,2'-diformylbiphenyl derivative does not include 2,2'-diformylbiphenyl. This is because if 2,2'-diformylbiphenyl is contained, the photochromic material of the present invention cannot be obtained.
- the photochromic material of the present invention can also be obtained by reacting two formyl groups with different diarylethanedione derivatives.
- the production method of the photochromic material of the present invention may take any synthetic route as long as the structure molecule of the present invention can be obtained, and is not limited by the synthetic route.
- R 4 and R 5 each independently represent a halogen atom or an alkyl group
- R 1 to R 3 and R 6 to R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a fluoroalkyl group, A hydroxyl group, an alkoxyl group, an amino group, an alkylamino group, a carbonyl group, an alkylcarbonyl group, a nitro group, a cyano group or an aryl group
- Ar 1 to Ar 4 each independently represents a substituted or unsubstituted aryl group.
- R 4 together with R 3 may form a fused substituted or unsubstituted aryl ring
- R 5 together with R 6 may form a fused substituted or unsubstituted aryl ring.
- Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group.
- Ar 3 Ar 4 each independently represents a substituted or unsubstituted aryl group.
- the 2,2′-diformylbiphenyl derivative used as a raw material for synthesizing the photochromic molecule of the present invention represented by the general formula (1-1) may have a sterically large substituent at the 6,6 ′ positions. preferable.
- Examples of such 2,2′-diformylbiphenyl derivatives include 6,6′dimethyl-2,2′-diformylbiphenyl, 6,6′diethyl-2,2′-diformylbiphenyl, and 6,6 ′.
- the 2,2′-diformyl-1,1′-binaphthalene derivatives include 2,2′-diformyl-1,1′-binaphthalene, 3,3′-dibromo-2,2′-diformyl-1,1.
- the diarylethanedione derivatives represented by the general formulas (1-5) and (1-6) used for the raw material of the photochromic material of the present invention include, for example, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2 -Chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-iodobenzyl, 3-iodobenzyl, 4-iodobenzyl, 2-hydroxybenzyl, 3 -Hydroxybenzyl, 4-hydroxybenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2-phenoxybenzyl, 3-phenoxybenzyl, 4 -Phenoxybenzyl, 2-acetoxybenzyl 3-acetoxybenzyl
- the temperature for reacting the 2,2′-diformylbiphenyl derivative represented by the general formula (1-4) with the diarylethanedione derivatives represented by the general formulas (1-5) and (1-6) is as follows:
- the reaction temperature is usually 80 to 120 ° C., preferably 100 to 120 ° C. It is.
- the reaction temperature can be 20 ° C. to 75 ° C. in the presence of the catalyst.
- reaction time varies depending on the presence or absence of the catalyst and the catalyst used, it cannot be generally stated.
- the reaction temperature is 4 to 32 hours, preferably 12 to 24 hours. It's time.
- the reaction time can be 1 to 10 hours in the presence of the catalyst.
- Examples of the nitrogen compound include ammonium acetate and ammonia. Among them, ammonium acetate is preferable because it is difficult to volatilize when heated.
- any solvent can be used as long as it can dissolve the raw materials.
- a solvent for example, a polar solvent such as acetic acid and acetonitrile is preferable.
- the intermediate oxidation reaction can be performed, for example, by dissolving the intermediate in a solvent to prepare a solution and adding an oxidizing agent to the solution.
- the solvent is not particularly limited as long as it can dissolve the intermediate.
- a solvent for example, benzene, methylene chloride and the like can be used.
- the oxidizing agent can be used without particular limitation as long as it can oxidize the intermediate to obtain the photochromic material represented by the general formula (1-1).
- Examples of such an oxidizing agent include potassium ferricyanide and lead oxide. Among them, potassium ferricyanide is preferable. This is because potassium ferricyanide is more reactive.
- a base is further added to the above solution.
- a base for example, potassium hydroxide can be used.
- the oxidation reaction is preferably performed in an inert gas atmosphere under light-shielding conditions.
- the inert gas atmosphere is used to suppress the reaction with oxygen.
- nitrogen can be used as the inert gas.
- the oxidation reaction is preferably performed under light-shielding conditions in order to prevent the obtained photochromic material from being changed from a colored body to a colorless body by light.
- a sterically bulky substituent is introduced into both the R 24 and R 25 sites of the biimidazole compound represented by the general formula (2-1) to thereby form a spiro ring.
- a structure with a structure is obtained.
- Examples of the bulky substituent at both sites of R 24 and R 25 include an alkyl group or an alkyl group having a substituent.
- examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, and an alkylamino group.
- the bulky substituent at both sites of R 4 and R 5 may be the smallest methyl group of the alkyl groups. That is, the photochromic material may be represented by the following general formula (2-2).
- the photochromic material of the present invention includes, for example, a 2,2′-diformylbiphenyl derivative represented by the following general formula (2-3) and a diarylethane represented by the above general formulas (1-5) and (1-6)
- a dione derivative is reacted in the presence of a nitrogen compound to obtain an intermediate containing an imidazole ring, and then the intermediate is oxidized to produce the isomer (II-2) shown in FIG. It can be obtained by leaving II-2) under light shielding.
- the 2,2'-diformylbiphenyl derivative does not include 2,2'-diformylbiphenyl.
- the photochromic material of the present invention can also be obtained by reacting two formyl groups with different diarylethanedione derivatives.
- the production method of the photochromic material of the present invention may take any synthetic route as long as the structure molecule of the present invention can be obtained, and is not limited by the synthetic route.
- R 24 and R 25 each independently represents an alkyl group or an alkyl group having a substituent
- R 1 to R 3 and R 6 to R 8 each independently represent a hydrogen atom, a halogen atom or an alkyl group
- Ar 1 to Ar 4 are each independently substituted or unsubstituted
- the 2,2′-diformylbiphenyl derivative used as a raw material for synthesizing the photochromic material of the present invention represented by the general formula (2-1) has a sterically large substituent at the 6,6 ′ position. preferable.
- Such 2,2′-diformylbiphenyl derivatives include 6,6′-dichloro-2,2′-diformylbiphenyl, 6,6′-dibromo-2,2′-diformylbiphenyl, 6,6 '-Diiodo-2,2'-diformylbiphenyl, 4,4', 6,6'-tetrachloro-2,2'-diformylbiphenyl, 4,4 ', 6,6'-tetrabromo-2,2 '-Diformylbiphenyl, 4,4'-difluoro-6,6'-dichloro-2,2'-diformylbiphenyl, 4,4'-difluoro-6,6'-dibromo-2,2'-diformyl Biphenyl, 4,4′-difluoro-6,6′-diiodo-2,2′-diformyl
- diarylethanedione derivatives represented by the general formulas (1-5) and (1-6) used for the raw material of the photochromic material of the present invention include those described in the first embodiment, for example, 1,2-bis (2-Naphtyl) ethanedione, 1,2-bis (1-naphthyl) ethanedione, 1,2-bis ⁇ 2- (6-methoxynaphthyl) ⁇ ethanedione can be used.
- reaction time, the nitrogen compound, the solvent for the above reaction, the oxidation reaction for the intermediate, and the solvent used for the oxidation reaction for the intermediate are the same as in the first embodiment.
- the oxidizing agent is not particularly limited as long as it can oxidize the intermediate to obtain the isomer (II-2).
- examples of such an oxidizing agent include potassium ferricyanide and lead oxide. Among them, potassium ferricyanide is preferable. This is because potassium ferricyanide is more reactive.
- a base is further added to the above solution.
- a base for example, potassium hydroxide can be used.
- the oxidation reaction is preferably performed in an inert gas atmosphere under light-shielding conditions.
- the inert gas atmosphere is used to suppress the reaction with oxygen.
- nitrogen can be used as the inert gas.
- the oxidation reaction is preferably performed under light-shielding conditions in order to prevent the photoisomerization reaction.
- the isomer (II-2) changes to the photochromic material of the present invention represented by the general formula (2-1) when left under light shielding. Therefore, in order to obtain the photochromic material of the present invention, this isomer (II-2) may be left under light shielding. Note that since the three types of compounds shown in FIG. 2 undergo thermal isomerization reaction, the photochromic material represented by the general formula (2-1) does not always become the isomer (II-2) only by light irradiation. Alternatively, the isomer (I-2) and the general formula (2-1) may be mixed.
- the temperature of the isomer (II-2) under shading is usually 10 to 50 ° C., preferably 25 to 40 ° C.
- the standing time of the isomer (II-2) under light shielding is usually 50 to 100 hours, preferably 70 to 80 hours.
- the R 4 and R 5 sites of the biimidazole compound represented by the general formula (3-1) are sterically formed.
- a structure having a spiro ring structure is obtained.
- the photochromic material represented by the general formula (3-1) can maintain the structure represented by the general formula (3-1) by continuing the light irradiation, and as shown in FIG. By making the light-shielding state, it is possible to change into the isomer represented by the general formula (1-1) and the isomer (II).
- the isomer represented by formula (1-1) is a color former and has a low transmittance.
- the isomer (II) is also a color former, but has a transmittance different from that of the isomer represented by the general formula (1-1).
- the photochromic material represented by the general formula (3-1) is a decolored material and has a transmittance different from that of the isomer and the isomer (II) represented by the general formula (1-1). Therefore, the color tone of the photochromic material can be adjusted in two stages.
- the substituent may be the smallest methyl group among the alkyl groups. That is, the photochromic material may be represented by the following general formula (3-2).
- R 4 together with R 3 forms a condensed substituted or unsubstituted aryl ring
- R 5 together with R 6 forms a condensed substituted or unsubstituted aryl ring. It may be formed.
- the aryl ring is preferably a benzene ring.
- the photochromic material in this case is represented by the following general formula (3-3).
- the photochromic material represented by the following general formula (3-3) can usually be converted to an isomer represented by the general formula (1-1) by putting it in a light-shielding state.
- R 1 to R 2 and R 7 to R 14 are each independently a hydrogen atom, a halogen atom, an alkyl group, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, an amino group, an alkylamino group, a carbonyl group, or an alkylcarbonyl group.
- a group, a nitro group, a cyano group or an aryl group, Ar 1 to Ar 4 each independently represents a substituted or unsubstituted aryl group.
- the photochromic material of the present invention includes, for example, a 2,2′-diformylbiphenyl derivative represented by the above general formula (1-4) and a diarylethane represented by the above general formulas (1-5) and (1-6)
- a dione derivative is reacted in the presence of a nitrogen compound to obtain an intermediate containing an imidazole ring, and then the intermediate is oxidized to obtain an isomer represented by the general formula (1-1) shown in FIG. Thereafter, the isomer represented by the general formula (1-1) is irradiated with visible light.
- a 2,2′-diformylbiphenyl derivative represented by the general formula (1-4) a 2,2′-diformyl-1,1′-binaphthalene derivative may be used.
- the 2,2'-diformylbiphenyl derivative does not include 2,2'-diformylbiphenyl.
- the isomer represented by the general formula (1-1) cannot be obtained, and as a result, the photochromic material of the present invention cannot be obtained.
- the photochromic material of the present invention can also be obtained by reacting two formyl groups with different diarylethanedione derivatives.
- the production method of the photochromic material of the present invention may take any synthetic route as long as the structure molecule of the present invention can be obtained, and is not limited by the synthetic route.
- the 2,2′-diformylbiphenyl derivative used as a raw material for synthesizing the photochromic material of the present invention represented by the general formula (3-1) has a sterically large substituent at the 6,6 ′ position.
- Preferred is the same as in the first embodiment, and specific examples of such 2,2′-diformylbiphenyl derivatives are also the same as in the first embodiment.
- diarylethanedione derivatives represented by the general formulas (1-5) and (1-6) used for the raw material of the photochromic material of the present invention the same ones as in the first embodiment can be used.
- the temperature for reacting the 2,2′-diformylbiphenyl derivative represented by the general formula (1-4) with the diarylethanedione derivatives represented by the general formulas (1-5) and (1-6) is as follows: This is the same as in the first embodiment.
- reaction time, the nitrogen compound, the solvent for the reaction, the intermediate oxidation reaction, and the solvent used for the intermediate oxidation reaction are the same as in the first embodiment.
- the oxidizing agent can be used without particular limitation as long as it can oxidize the intermediate to obtain the isomer represented by the general formula (1-1).
- examples of such an oxidizing agent include potassium ferricyanide and lead oxide. Among them, potassium ferricyanide is preferable. This is because potassium ferricyanide is more reactive.
- a base is further added to the above solution.
- a base for example, potassium hydroxide can be used.
- the oxidation reaction is preferably performed in an inert gas atmosphere under light-shielding conditions.
- the inert gas atmosphere is used to suppress the reaction with oxygen.
- nitrogen can be used as the inert gas.
- the oxidation reaction is preferably performed under light-shielding conditions in order to prevent the obtained isomer represented by the general formula (1-1) from being changed from a colored body to a decolored body by visible light.
- the light irradiated to the isomer represented by the general formula (1-1) may be light in a wavelength range including the maximum absorption wavelength in the visible light wavelength range of the isomer represented by the general formula (1-1). That's fine.
- the light irradiation time depends on the light intensity, it is usually 10 to 600 seconds, preferably 30 to 300 seconds.
- the temperature at the time of light irradiation is preferably 30 ° C. or less, more preferably 0 ° C. or less. Further, when the temperature at the time of light irradiation is 30 ° C. or lower, the production efficiency of the photochromic material of the present invention from the isomer represented by the general formula (1-1) is further improved as compared with the case where it exceeds 30 ° C. .
- the temperature during light irradiation is preferably higher than the melting point of the solvent. That is, the light irradiation is preferably performed in a state where the solvent does not become a solid.
- the photochromic material represented by the general formula (3-1) is not necessarily present alone, but the general formula (1-1 ) And the general formula (3-1) may be mixed.
- the photochromic material represented by the general formula (3-1) is generated. Since the reaction to the isomer represented by the general structure, that is, the isomer represented by the general formula (1-1) proceeds by a thermal reaction, the isomer represented by the general formula (1-1) and the general formula (3) -1) can also be mixed.
- the photochromic material represented by the general formula (3-1) is not necessarily present alone, but the general formula (1- The isomer represented by 1), the isomer (II), and the general formula (3-1) may be mixed.
- Benzyl, 4,4′-dimethoxybenzyl, 4,4′-bis (dimethylamino) benzyl used in the following Synthesis Examples 1-1 to 1-6, 2-1, and 3-1 to 3-5, 4 Commercially available reagents (manufactured by Tokyo Chemical Industry Co., Ltd.) were used as 4,4'-dibromobenzyl, ammonium acetate, acetic acid, potassium ferricyanide, and potassium hydroxide. Moreover, the measurement by NMR was performed at 25 degreeC unless there was special description.
- Example 1-1 A 1.0 ⁇ 10 ⁇ 3 M benzene solution was prepared using the mixture containing the compound [1-1] synthesized in Synthesis Example 1-1. This solution is put in a four-sided quartz cell, irradiated with excitation light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics), and developed by UV-visible absorption spectrum analysis that observes the transmittance at the wavelength with the largest transmittance change in the visible light region. And the decolored body was measured. The results are shown in Table 1 and FIG. In FIG. 4, the solid line indicates a state where excitation light is irradiated, and the broken line indicates a normal state (state where excitation light is not irradiated). As shown in Table 1 and FIG. 4, the transmittance at the maximum absorption wavelength of 496 nm of the color former was increased from 60% to 93% by excitation light irradiation.
- Example 1-2 Using the compound [1-2] synthesized in Synthesis Example 1-2, a 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared. This solution is put in a four-sided quartz cell, irradiated with excitation light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics), and developed by UV-visible absorption spectrum analysis that observes the transmittance at the wavelength with the largest transmittance change in the visible light region. And the decolored body was measured. The results are shown in Table 1 and FIG. In FIG. 5, the solid line indicates a state where excitation light is irradiated, and the broken line indicates a normal state where light is not irradiated. As shown in Table 1 and FIG. 5, the transmittance at the maximum absorption wavelength of 493 nm of the color former increased from 17% to 88% by excitation light irradiation.
- Example 1-3 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-3] synthesized in Synthesis Example 1-3. This solution is put in a four-sided quartz cell, irradiated with excitation light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics), and developed by UV-visible absorption spectrum analysis that observes the transmittance at the wavelength with the largest transmittance change in the visible light region. And the decolored body was measured. The results are shown in Table 1 and FIG. In FIG. 6, the solid line indicates a state in which excitation light is irradiated, and the broken line indicates a normal state (a state in which excitation light is not irradiated). As shown in Table 1 and FIG. 6, the transmittance at the maximum absorption wavelength of 475 nm of the color former increased from 16% to 73% by excitation light irradiation.
- Example 1-4 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-4] synthesized in Synthesis Example 1-4. This solution is put in a four-sided quartz cell, irradiated with excitation light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics), and developed by UV-visible absorption spectrum analysis that observes the transmittance at the wavelength with the largest transmittance change in the visible light region. And the decolored body was measured. The results are shown in Table 1 and FIG. In FIG. 7, the solid line indicates a state where the excitation light is irradiated, and the broken line indicates a normal state (a state where the excitation light is not irradiated). As shown in Table 1 and FIG. 7, the transmittance at a maximum absorption wavelength of 544 nm of the color former was increased from 23% to 74% by excitation light irradiation.
- Example 1-5 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-5] synthesized in Synthesis Example 1-5. This solution is put in a four-sided quartz cell, irradiated with excitation light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics), and developed by UV-visible absorption spectrum analysis that observes the transmittance at the wavelength with the largest transmittance change in the visible light region. And the decolored body was measured. The results are shown in Table 1 and FIG. In FIG. 8, a solid line indicates a state in which excitation light is irradiated, and a broken line indicates a normal state (a state in which excitation light is not irradiated). As shown in Table 1 and FIG. 8, the transmittance at the maximum absorption wavelength of 486 nm of the color former was increased from 39% to 74% by excitation light irradiation.
- Compound [2-1] 30 mg, was dissolved in deuterated chloroform (5 ml) and allowed to stand for 1 day at 25 ° C. in the dark.
- Compound [2-1] the following compound [1-1] and compound [2- 3] was obtained.
- Compound [1-1] has characteristic peaks of methoxy group and methyl group from NMR analysis of the mixture, and compound [1-1] has characteristic absorption band at 496 nm from UV spectrum analysis. It is considered that the structure is represented by the formula.
- Example 2-1 A 1.0 ⁇ 10 ⁇ 3 M benzene solution was prepared using the compound [2-3] synthesized in Synthesis Example 2-1. The transmittance of this benzene solution was measured by ultraviolet-visible absorption spectrum analysis. The results are shown in FIG. Also, the benzene solution is put in a four-sided quartz cell, irradiated with UV-visible light from a UV spot light source L8333 (manufactured by Hamamatsu Photonics) as excitation light, and the transmittance of the benzene solution is measured by UV-visible absorption spectrum analysis in this state. did. The results are shown in FIG.
- the benzene solution was irradiated with UV-visible light from a UV spot light source L8333 (Hamamatsu Photonics Co., Ltd.) as excitation light, and then allowed to stand at 25 ° C. for 1 day under shading.
- the benzene solution in this state was analyzed by UV-visible absorption spectrum analysis. The transmittance was measured.
- FIG. 10 the broken line indicates a normal state (state in which excitation light is not irradiated), the solid line indicates a state in which excitation light is irradiated, and the alternate long and short dash line is irradiated with excitation light and then shielded at 25 ° C. Indicates the state left for one day. As shown in FIG.
- the transmittance of the compound [2-3] at the maximum absorption wavelength of 496 nm of the mixture containing the compound [1-1] as the color former is determined by leaving it under light shielding after irradiation with excitation light. 87% to 60%. From this, it was found that the compound [2-3] was changed to a mixture containing the compound [1-1] by leaving it under light shielding after irradiation with excitation light. Similarly, the transmittance of the compound [2-3] at 496 nm increased from 87% to 91% by irradiation with excitation light. From this, it was found that compound [2-3] was changed to compound [2-1] by irradiation with excitation light.
- Example 2-1 From the results shown in Example 2-1 and Comparative Example 1-1, by introducing a sterically bulky substituent into R 4 and R 5 of the biimidazole compound represented by the general formula (1), the photochromism is improved. It was confirmed that a molecule to be expressed was obtained.
- the NMR analysis was performed on the mixture, and the NMR analysis result of compound [1-1] alone was not obtained, but it was characterized by 496 nm in the characteristic peaks and UV spectrum of the methoxy group and methyl group. It is considered that the compound [1-1] in the mixture is represented by the following structural formula because it shows a typical absorption band.
- Example 3-1 A 1.0 ⁇ 10 ⁇ 3 M benzene solution was prepared using a mixture containing the compound [1-1] synthesized in Synthesis Example 3-1. This solution was put in a four-sided quartz cell and irradiated with visible light at 25 ° C. for 30 seconds. Then, the spectrum of the compound [2-1] (decolored product) was measured by ultraviolet-visible absorption spectrum analysis while continuously irradiating visible light. The results are shown in Table 2 and FIG. In FIG. 11, the solid line shows the spectrum of the compound [2-1]. Subsequently, with respect to the benzene solution containing the above compound [2-1], the light irradiation was stopped, and the mixture was allowed to stand at 25 ° C.
- Example 3-2 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-2] synthesized in Synthesis Example 3-2. This solution was put in a four-sided quartz cell and irradiated with visible light at 25 ° C. for 30 seconds. Then, the spectrum of the compound [3-1] (decolored product) was measured by ultraviolet-visible absorption spectrum analysis while continuously irradiating visible light. The results are shown in Table 2 and FIG. In FIG. 12, the solid line indicates the spectrum of the compound [3-1]. Subsequently, with respect to the benzene solution containing the above compound [3-1], the light irradiation was stopped and the mixture was allowed to stand at 25 ° C. for 10 minutes under light shielding.
- Example 3-3 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-3] synthesized in Synthesis Example 3-3. This solution was put in a four-sided quartz cell and irradiated with visible light at 25 ° C. for 30 seconds. At this time, the same UV spectrum change as in Example 3-2 was observed, confirming the formation of the following compound [3-2]. Then, the spectrum of the compound [3-2] (decolored product) was measured by ultraviolet-visible absorption spectrum analysis while continuously irradiating visible light. The results are shown in Table 2 and FIG. In FIG. 13, the solid line shows the spectrum of the compound [3-2].
- Example 3-4 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-4] synthesized in Synthesis Example 3-4. This solution was put in a four-sided quartz cell and irradiated with visible light at 25 ° C. for 30 seconds. At this time, the same UV spectrum change as in Synthesis Example 3-2 was observed, confirming the formation of the following compound [3-3]. Then, the spectrum of the compound [3-3] (decolored product) was measured by ultraviolet-visible absorption spectrum analysis while continuously irradiating with visible light. The results are shown in Table 2 and FIG. In FIG. 14, the solid line shows the spectrum of the compound [3-3].
- Example 3-5 A 2.0 ⁇ 10 ⁇ 4 M benzene solution was prepared using the compound [1-5] synthesized in Synthesis Example 3-5. This solution was put in a four-sided quartz cell and irradiated with visible light at 25 ° C. for 30 seconds. At this time, the same UV spectrum change as in Synthesis Example 3-2 was observed, confirming the formation of the following compound [3-4]. Then, the spectrum of the compound [3-4] (decolored product) was measured by ultraviolet-visible absorption spectrum analysis while continuously irradiating visible light. The results are shown in Table 2 and FIG. In FIG. 15, the solid line shows the spectrum of the compound [3-4].
- the photochromic material of the present invention exhibits the following photochromic properties (1), (2) or (3).
- the photochromic material of the present invention has a completely different structure from conventional photochromic molecules, it provides a new option for device development using photochromism.
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Abstract
Description
従って、新たな構造を有するフォトクロミック材料が求められていた。
具体的には、本発明者らは、ビイミダゾールを基本骨格とし、一般式(1-1)のR4およびR5に嵩高い置換基を導入することで負のフォトクロミズムを示す新しい化合物を見出した。この分子は安定状態又は初期状態では発色体であり、可視光を照射することで消色体へと異性化するフォトクロミック特性(逆フォトクロミック特性)を示した。
一般式(1-1)で表される本発明のフォトクロミック材料は、図1に示すように、光照射により、一般式(3-1)で表される異性体に変化することが可能となる。ここで、一般式(1-1)で表されるフォトクロミック材料は発色体であり、透過率が低い。一方、一般式(3-1)で表される異性体は消色体である。従って、本発明のフォトクロミック材料によれば、光照射によりフォトクロミック材料の色調を調整することが可能である。一般式(1-1)で表される本発明のフォトクロミック材料は、光照射により発色体から消色体に変化する。すなわち、一般式(1-1)で表される本発明のフォトクロミック材料は逆フォトクロミック材料である。尚、図1において、Δは熱エネルギーを表す。但し、一般式(1-1)で表される本発明のフォトクロミック材料のうち一般式(1-1)において、R4が、R3と共に、縮合した置換又は無置換のアリール環を形成し、且つR5が、R6と共に縮合した置換又は無置換のアリール環を形成しているフォトクロミック材料は通常、図3に示すように、光照射することで一般式(3-1)で表される異性体になり得る。しかし、このようなフォトクロミック材料は、遮光状態で放置しても、図1に示される異性体(II)にはならない(図3参照)。
(1)可視光照射により容易に発色体から消色体へと色調が変化する。
(2)光照射により容易に透過率を増加させて淡黄色から無色へと色調を変化させることができ、その後、熱エネルギーによって透過率を低下させて発色体に変化させたり、本発明のフォトクロミック材料に戻したりすることが可能である。
(3)遮光することにより容易に消色体から発色体へと色調を変化させることができる。
上記の性質はフォトクロミック分子が利用されているあらゆる用途への適用が考えられるものである。具体的な用途としては、光スイッチ、印刷用材料、記録材料、ホログラム材料などがある。
しかも、本発明のフォトクロミック材料は従来のフォトクロミズムを示す分子と全く構造が異なるので、フォトクロミズムを利用したデバイス開発に新しい選択肢を提供することもできる。
まず本発明の第1実施形態について説明する。
本発明のフォトクロミック材料の第1実施形態は、一般式(1-1)で表されるビイミダゾール化合物のR4、R5の両部位に立体的に嵩高い置換基を導入することでスピロ環構造を持った構造を得るものである。
次に、本発明の第2実施形態について説明する。
次に、本発明の第3実施形態について説明する。
まず本発明の第1実施形態に対応する実施例について具体的に説明する。
6,6’ジメチル-2,2’-ジホルミルビフェニル100mgと4,4’-ジメトキシベンジル270mgと酢酸アンモニウム960mgと酢酸4.0mlを混合し、110℃のオイルバスで16時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-I)を273mg得た。NMRの分析によって中間体(1-I)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ8.92(2H s)、8.38(2H d)、7.53(2H t)、7.46(4H d)、7,40(2H d)、6.94(4H d)、6.80(4H d)、6.75(4H d)3.78(12H s)、1.99(6H s)
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ジメトキシベンジル183mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで14時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-II)を158mg得た。NMRの分析によって中間体(1-II)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ8.78(2H d)、8.45(2H s)、8.19(2H d)、8.02(2H d)7.55-7.51(2H m)、7.42(4H d)、7.32-7.30(4H m)、6.78(4H d)6.69-6.64(8H m)、3.77(12H s)
1H‐NMR(500MHz CDCl3)δ8.24(1H d)、7.92(1H d)、7.90(1H d)、7.77(1H d)、7.50(2H d)、7.47-7.42(5H m)、7.30-7.20(4H m)、7.09-7.05(1H m)、6.93(1H d)、6.89(1H d)、6.85(2H d)、6.80(2H d)6.73(2H d)、6.54(2H d)、6.44(2H d)、3.82(3H s)、3.81(3H s)、3.73(3H s)、3.73(3H s)
2,2’-ジホルミル-1,1’-ビナフタレン100mgとベンジル149mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで14時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-III)を162mg得た。NMRの分析によって中間体(1-III)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ8.76(2H d)、8.69(2H s)、8.20(2H d)、8.04(2H d)7.56-7.51(2H m)、7.51-7.49(4H m)、7.33-7.31(4H m)、7.24-7.14(12H m)6.75-6.73(4H m)
1H‐NMR(500MHz CDCl3)δ8.26(1H d)、7.93(2H d)、7.80(1H d)、7.57(2H d)、7.47(2H d)、7.47(2H d)、7.44(3H d)、7.40(1H d)、7.35-7.31(4H m)、7.30-7.21(3H m)、7.19-7.15(3H m)、7.13-7.07(2H m)、7.01(2H t)、6.98(1H d)、6.94(1H d)、6.55(2H d)
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ビス(ジメチルアミノ)ベンジル210mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで18時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-IV)を114mg得た。NMRの分析によって中間体(1-IV)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ8.84(2H br.s)、8.28(2H br.s)、8.18(2H d)、8.00(2H d)7.51-7.48(2H m)、7.43(4H br.s)、7.30-7.28(4H m)、6.63(8H br.s)6.49(4H br.s)、2.91(24H s)
1H‐NMR(500MHz CDCl3)δ8.23(1H d)、7.91(1H d)、7.86(1H d)、7.74(1H d)、7.52-7.50(3H m)、7.47(4H d)、7.23(1H t)、7.19-7.17(3H m)、7.02-6.98(1H m)、6.89(1H d)、6.76(1H d)、6.62(2H d)、6.59-6.56(4H m)6.40(2H d)、6.33(2H d)、3.00(6H s)、2.99(6H s)、2.87(6H s)、2.86(6H s)
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ジブロモベンジル261mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで18時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-V)を249mg得た。NMRの分析によって中間体(1-V)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ8.82(2H s)、8.62(2H d)、8.19(2H d)、8.04(2H d)7.84-7.82(4H m)、7.69-7.67(4H m)、7.56(2H t)、7.35-7.29(8H m)、6.61(4H d)
1H‐NMR(500MHz CDCl3)δ8.21(1H d)、7.95(2H d)、7.83(1H d)、7.49(2H d)、7.43(2H d)、7.40-7.29(12H m)、7.23(2H d)、7.16(2H d)、7.08(1H d)、6.96(1H d)6.36(2H d)
2,2’-ジホルミルビフェニル50mgと4,4’-ジメトキシベンジル142mgと酢酸アンモニウム550mgと酢酸3.0mlを混合し、110℃のオイルバスで24時間加熱攪拌を行い反応させた後に28%アンモニア水6.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-VI)を136mg得た。NMRの分析によって中間体(1-VI)の生成を確認した。尚、NMRの分析結果は下記の通りである。
1H‐NMR(500MHz CDCl3)δ9.37(2H s)、8.31(2H d)、7.56(2H t)、7.48-7.38(8H m)、7,29(2H d)、7.00(2H br.s)、6.77(8H d)3.78(12H s)
1H‐NMR(500MHz CDCl3)δ8.06(2H d)、7.45(2H t)、7.42(8H d)、7,19(2H t)、6.99(2H d)、6.79(8H d)3.80(12H s)
FD-MS m/z=708(M+)
合成例1-1で合成した化合物[1-1]を含む混合物を用いて1.0×10-3Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、可視光領域で最も透過率変化の大きな波長の透過率を観測する紫外可視吸収スペクトル分析によって発色体と消色体の測定をした。結果を表1及び図4に示す。尚、図4において、実線は励起光を照射している状態を示し、破線は、通常の状態(励起光を照射していない状態)を示す。表1及び図4に示すように、発色体の最大吸収波長496nmの透過率は励起光照射により60%から93%まで増加した。
合成例1-2で合成した化合物[1-2]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、可視光領域で最も透過率変化の大きな波長の透過率を観測する紫外可視吸収スペクトル分析によって発色体と消色体の測定をした。結果を表1及び図5に示す。尚、図5において、実線は励起光を照射している状態を示し、破線は、光を照射しない通常の状態を示す。表1及び図5に示すように、発色体の最大吸収波長493nmの透過率は励起光照射により17%から88%まで増加した。
合成例1-3で合成した化合物[1-3]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、可視光領域で最も透過率変化の大きな波長の透過率を観測する紫外可視吸収スペクトル分析によって発色体と消色体の測定をした。結果を表1及び図6に示す。尚、図6において、実線は励起光を照射している状態を示し、破線は、通常の状態(励起光を照射しない状態)を示す。表1及び図6に示すように、発色体の最大吸収波長475nmの透過率は励起光照射により16%から73%まで増加した。
合成例1-4で合成した化合物[1-4]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、可視光領域で最も透過率変化の大きな波長の透過率を観測する紫外可視吸収スペクトル分析によって発色体と消色体の測定をした。結果を表1及び図7に示す。尚、図7において、実線は、励起光を照射している状態を示し、破線は、通常の状態(励起光を照射しない状態)を示す。表1及び図7に示すように、発色体の最大吸収波長544nmの透過率は励起光照射により23%から74%まで増加した。
合成例1-5で合成した化合物[1-5]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、可視光領域で最も透過率変化の大きな波長の透過率を観測する紫外可視吸収スペクトル分析によって発色体と消色体の測定をした。結果を表1及び図8に示す。尚、図8において、実線は励起光を照射している状態を示し、破線は、通常の状態(励起光を照射しない状態)を示す。表1及び図8に示すように、発色体の最大吸収波長486nmの透過率は励起光照射により39%から74%まで増加した。
合成例1-6で合成した化合物[1-6]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス製)による励起光を照射し、紫外可視吸収スペクトル分析によって励起光を照射しない状態の透過率と励起光を照射している状態の透過率を測定した。結果を表1及び図9に示す。尚、図9において、実線は励起光を照射している状態を示し、破線は、通常の状態(励起光を照射しない状態)を示す。表1及び図9に示すように、透過率は励起光を照射しても93%から変化しなかった。
6,6’ジメチル-2,2’-ジホルミルビフェニル100mgと4,4’-ジメトキシベンジル270mgと酢酸アンモニウム960mgと酢酸4.0mlを混合し、110℃のオイルバスで16時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-I)を273mg得た。NMRの分析によって中間体(1-I)の生成を確認した。
1H-NMR(500MHz CDCl3);7.43(2H s)、7.41(4H d)、7.36(4H d)、7.13(2H t)、6.83(2H d)、6.80(4H d)、6.75(4H d)、3.81(6H s)、3.77(6H s)、2.48(6H s)
13C-NMR(500MHz CDCl3);169.9、164.9、161.14、161.09、136.1、135.4、134.9、131.2、130.6、128.3、126.7、125.4、125.0、121.6、113.5、113.3、106.7、55.3、55.2、21.3
1H-NMR(500MHz CDCl3);7.96(1H d)、7.64(1H d)、7.58(1H d)、7.39(1H t)、7.35(1H d)、7.28(2H d)、7.26(1H d)、7.19(1H t)、7.16(2H d)、7.11(1H d)、6.90(2H d)、6.85(1H d)、6.73(2H d)、6.71(2H d)、6.70(1H d)、6.67(2H d)、3.90(3H s)、3.83(3H s)、3.76(3H s)、3.71(3H s)、2.28(3H s)、2.23(3H s)
合成例2-1で合成した化合物[2-3]を用いて1.0×10-3Mのベンゼン溶液を調製した。このベンゼン溶液について紫外可視吸収スペクトル分析によって透過率を測定した。結果を図10に示す。また上記ベンゼン溶液を四面石英セルに入れ、UVスポット光源L8333(浜松ホトニクス(株)製)による紫外可視光を励起光として照射し、この状態でベンゼン溶液について紫外可視吸収スペクトル分析によって透過率を測定した。結果を図10に示す。また上記ベンゼン溶液にUVスポット光源L8333(浜松ホトニクス(株))による紫外可視光を励起光として照射した後、遮光下25℃で1日間放置し、その状態のベンゼン溶液について紫外可視吸収スペクトル分析によって透過率を測定した。結果を図10に示す。尚、図10において、破線は通常の状態(励起光を照射しない状態)を示し、実線は、励起光を照射している状態を示し、一点鎖線は励起光を照射後、遮光下25℃で1日間放置した状態を示す。図10に示すように、発色体である化合物[1-1]を含む混合物の最大吸収波長496nmにおける化合物[2-3]の透過率は、励起光の照射後、遮光下で放置することにより、87%から60%まで低下していた。このことから、化合物[2-3]は、励起光の照射後、遮光下で放置することにより、化合物[1-1]を含む混合物に変化していることが分かった。また同様に化合物[2-3]の496nmにおける透過率は、励起光の照射により、87%から91%まで増加していた。このことから、化合物[2-3]は、励起光の照射により、化合物[2-1]に変化していることが分かった。
6,6’ジメチル-2,2’-ジホルミルビフェニル100mgと4,4’-ジメトキシベンジル270mgと酢酸アンモニウム960mgと酢酸4.0mlを混合し、110℃のオイルバスで16時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-I)を273mg得た。NMRの分析によって中間体(1-I)の生成を確認した。
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ジメトキシベンジル183mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで14時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-II)を158mg得た。NMRの分析によって中間体(1-II)の生成を確認した。
1H-NMR(500MHz CDCl3);7.97(2H d)、7.87(2H d)、7.82(2H d)、7.56(2H t)、7.46-7.42(8H m)、7.41(2H t)、7.23(2H d)、6.89(4H d)、6.75(4H d)、3.88(6H s)、3.79(6H s)
13C-NMR(500MHz CDCl3);170.5、165.4、160.7、160.6、137.9、134.0、133.3、132.5、131.4、131.3、130.6、130.5、128.0、125.3、124.6、124.5、123.8、122.4、113.2、112.7、106.3、55.3、55.2
2,2’-ジホルミル-1,1’-ビナフタレン100mgとベンジル149mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで14時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-III)を162mg得た。NMRの分析によって中間体(1-III)の生成を確認した。
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ビス(ジメチルアミノ)ベンジル210mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで18時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-IV)を114mg得た。NMRの分析によって中間体(1-IV)の生成を確認した。
2,2’-ジホルミル-1,1’-ビナフタレン100mgと4,4’-ジブロモベンジル261mgと酢酸アンモニウム750mgと酢酸4.0mlを混合し、110℃のオイルバスで18時間加熱攪拌を行い反応させた後に28%アンモニア水8.0mlを加えて固体を析出させながら中和して、固体を水洗浄後にろ過して真空乾燥機で乾燥した。乾燥した固体をシリカゲルカラムで分離精製した後に溶媒を濃縮して中間体(1-V)を249mg得た。NMRの分析によって中間体(1-V)の生成を確認した。
合成例3-1で合成した化合物[1-1]を含む混合物を用いて1.0×10-3Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって化合物[2-1](消色体)のスペクトルを測定した。結果を表2及び図11に示す。尚、図11において、実線は化合物[2-1]のスペクトルを示すものである。
続いて、上記化合物[2-1]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で1日間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図11に示す。尚、結果は、図11において破線で示した。上記ベンゼン溶液は、NMR分析から、メトキシ基とメチル基の特徴的なピークを持ち、UVスペクトル分析から496nmに特徴的な吸収帯を持っていた。このことから、上記ベンゼン溶液が化合物[1-1]を含むことは明らかと考えられる。
表2及び図11に示すように、発色体の最大吸収波長496nmにおける消色体の透過率は、遮光状態で放置することで、93%から60%まで低下することが分かった。
合成例3-2で合成した化合物[1-2]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって化合物[3-1](消色体)のスペクトルを測定した。結果を表2及び図12に示す。尚、図12において、実線は化合物[3-1]のスペクトルを示すものである。
続いて、上記化合物[3-1]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で間10分間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図12に示す。尚、結果は、図12において破線で示した。
表2及び図12に示すように、発色体の最大吸収波長493nmにおける化合物[3-1](消色体)の透過率は88%から17%まで低下していることが分かった。また、図12において破線で示すスペクトルは、化合物[1-2]のスペクトルと同様であった。このことから、化合物[3-1]は、遮光下で放置することにより、化合物[1-2]に変化することが分かった。
合成例3-3で合成した化合物[1-3]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。このとき、実施例3-2と同様のUVスペクトル変化が見られたことから下記化合物[3-2]の生成が確認された。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって化合物[3-2](消色体)のスペクトルを測定した。結果を表2及び図13に示す。尚、図13において、実線は化合物[3-2]のスペクトルを示すものである。
続いて、上記化合物[3-2]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で10分間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図13に示す。尚、結果は、図13において、破線で示した。
表2及び図13に示すように、発色体の最大吸収波長475nmにおける化合物[3-2](消色体)の透過率は、遮光下で放置することにより、73%から16%まで低下していることが分かった。また、図13において破線で示すスペクトルは、化合物[1-3]のスペクトルと同様であった。このことから、化合物[3-2]は、遮光下で放置することにより、化合物[1-3]に変化することが分かった。
合成例3-4で合成した化合物[1-4]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。このとき、合成例3-2と同様のUVスペクトル変化が見られたことから下記化合物[3-3]の生成が確認された。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって化合物[3-3](消色体)のスペクトルを測定した。結果を表2及び図14示す。尚、図14において、実線は化合物[3-3]のスペクトルを示すものである。
続いて、上記化合物[3-3]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で間10分間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図14に示す。尚、結果は、図14において、破線で示した。
表2及び図14に示すように、発色体の最大吸収波長544nmにおける化合物[3-3](消色体)の透過率は、遮光下で放置することにより、74%から23%まで低下していることが分かった。また、図14において破線で示すスペクトルは、化合物[1-4]のスペクトルと同様であった。このことから、化合物[3-3]は、遮光下で放置することにより、化合物[1-4]に変化することが分かった。
合成例3-5で合成した化合物[1-5]を用いて2.0×10-4Mのベンゼン溶液を調製した。この溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。このとき、合成例3-2と同様のUVスペクトル変化が見られたことから下記化合物[3-4]の生成が確認された。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって化合物[3-4](消色体)のスペクトルを測定した。結果を表2及び図15に示す。尚、図15において、実線は化合物[3-4]のスペクトルを示すものである。
続いて、上記化合物[3-4]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で10分間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図15に示す。尚、結果は、図15において破線で示した。
表2及び図15に示すように、発色体の最大吸収波長486nmにおける消色体の透過率は、遮光下で放置することにより、74%から39%まで低下していることが分かった。また、図15において破線で示すスペクトルは、化合物[1-5]のスペクトルと同様であった。このことから、化合物[3-4]は、遮光下で放置することにより、化合物[1-5]に変化することが分かった。
合成例1-6で合成した化合物[1-6]を用いて2.0×10-4Mのベンゼン溶液を調製した。このベンゼン溶液を四面石英セルに入れ、可視光を25℃で30秒時間照射した。
そして、可視光を引き続き照射したまま、紫外可視吸収スペクトル分析によって上記ベンゼン溶液についてスペクトルを測定した。結果を表2及び図16に示す。尚、結果は、図16において、実線で示した。
続いて、上記化合物[1-6]を含むベンゼン溶液について、光照射を止め、遮光下、25℃で10分間放置した。そして、その状態のベンゼン溶液について、紫外可視吸収スペクトル分析によってスペクトルを測定した。結果を表2及び図16に示す。尚、結果は、図16において破線で示した。
表2及び図16に示すように、500nmにおける消色体の透過率は、遮光下で放置しても、93%から変化しないことが分かった。このことから、化合物[1-6]は、遮光下で放置しても、何ら変化しないことが分かった。
(1)赤色から紫色を呈しており、可視光に感受性を持ちその光を吸収して透過率を大きく上げるフォトクロミック特性
(2)光を吸収して透過率を大きく下げるフォトクロミック特性
(3)遮光下で放置することで、透過率を大きく下げるフォトクロミック特性
上記(1)~(3)の特性を利用して、これまで応用が提案されてきた光スイッチ、印刷用材料、記録材料などの分野で利用できる。例えば、光メモリ素子のマスク層材料として用いれば、再生信号を劣化させることなく高密度記録されたビットから良好な再生信号を得ることが可能となる。しかも、本発明のフォトクロミック材料は従来のフォトクロミズムを示す分子と全く構造が異なるので、フォトクロミズムを利用したデバイス開発に新しい選択肢を提供する。
Claims (8)
- 下記一般式(1-1)で表されるビイミダゾール化合物からなることを特徴とするフォトクロミック材料。
- 下記一般式(3-1)で表されるビイミダゾール化合物からなることを特徴とするフォトクロミック材料。
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AU2011274914A AU2011274914B2 (en) | 2010-07-09 | 2011-07-08 | Photochromic material |
US13/807,461 US8748629B2 (en) | 2010-07-09 | 2011-07-08 | Photochromic material |
EP11803688.8A EP2592130B1 (en) | 2010-07-09 | 2011-07-08 | Photochromic material |
CN201180021083.7A CN102906215B (zh) | 2010-07-09 | 2011-07-08 | 光致变色材料 |
KR1020127025504A KR20130091243A (ko) | 2010-07-09 | 2011-07-08 | 포토크로믹 재료 |
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JP2010157036A JP5598125B2 (ja) | 2010-07-09 | 2010-07-09 | 逆フォトクロミック材料 |
JP2011-080843 | 2011-03-31 | ||
JP2011080844 | 2011-03-31 | ||
JP2011080843A JP5640868B2 (ja) | 2011-03-31 | 2011-03-31 | フォトクロミック材料 |
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EP4177646A1 (en) | 2021-11-08 | 2023-05-10 | Carl Zeiss Vision International GmbH | Spectacle lens and method for manufacturing a spectacle lens |
Citations (3)
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WO2010061579A1 (ja) * | 2008-11-28 | 2010-06-03 | 関東化学株式会社 | 架橋型ヘキサアリールビスイミダゾール新規化合物およびその誘導体、該化合物の製造方法、ならびに該製造方法に用いられる前駆体化合物 |
JP2011132265A (ja) * | 2009-11-24 | 2011-07-07 | Aoyama Gakuin | セキュリティインク |
JP2011144289A (ja) * | 2010-01-15 | 2011-07-28 | Mitsubishi Gas Chemical Co Inc | フォトクロミック材料の消色速度の調節方法 |
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JPH04128834A (ja) | 1990-09-20 | 1992-04-30 | Toppan Printing Co Ltd | 光記録媒体 |
JPH079766A (ja) | 1993-06-07 | 1995-01-13 | Minnesota Mining & Mfg Co <3M> | 繰り返し使用可能な感熱発色材料 |
KR100422447B1 (ko) | 2001-10-09 | 2004-03-11 | 삼성전자주식회사 | 고속 반도체 장치에 채용하기 적합한 레벨 컨버터를가지는 신호컨버팅 장치 및 신호컨버팅 방법 |
JP5273640B2 (ja) * | 2007-09-10 | 2013-08-28 | 国立大学法人九州大学 | 熱不可逆性逆フォトクロミック分子材料 |
WO2009115572A2 (en) * | 2008-03-21 | 2009-09-24 | Novartis Ag | Novel heterocyclic compounds and uses therof |
CN101619060A (zh) * | 2008-06-30 | 2010-01-06 | 莱西肯医药有限公司 | 杂环化合物、包括其的组合物和它们的使用方法 |
CN101676293B (zh) * | 2008-09-18 | 2012-11-21 | 宁波大学 | 一种联咪唑有机膦化合物及其制备方法 |
JP5674305B2 (ja) | 2009-12-11 | 2015-02-25 | 三菱瓦斯化学株式会社 | フォトクロミック材料 |
-
2011
- 2011-07-08 WO PCT/JP2011/065702 patent/WO2012005354A1/ja active Application Filing
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WO2010061579A1 (ja) * | 2008-11-28 | 2010-06-03 | 関東化学株式会社 | 架橋型ヘキサアリールビスイミダゾール新規化合物およびその誘導体、該化合物の製造方法、ならびに該製造方法に用いられる前駆体化合物 |
JP2011132265A (ja) * | 2009-11-24 | 2011-07-07 | Aoyama Gakuin | セキュリティインク |
JP2011144289A (ja) * | 2010-01-15 | 2011-07-28 | Mitsubishi Gas Chemical Co Inc | フォトクロミック材料の消色速度の調節方法 |
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JOURNAL OF PHYSICAL CHEMISTRY LETTERS, vol. 1, no. 7, 16 March 2010 (2010-03-16), pages 1112 - 1115 * |
MACROMOLECULES, vol. 43, no. 8, 26 March 2010 (2010-03-26), pages 3764 - 3769, XP008154281 * |
See also references of EP2592130A4 * |
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AU2011274914B2 (en) | 2013-07-18 |
KR20130091243A (ko) | 2013-08-16 |
EP2592130A1 (en) | 2013-05-15 |
US8748629B2 (en) | 2014-06-10 |
EP2592130B1 (en) | 2015-01-21 |
US20130102775A1 (en) | 2013-04-25 |
EP2592130A4 (en) | 2014-03-26 |
CN102906215B (zh) | 2014-11-05 |
AU2011274914A1 (en) | 2013-01-17 |
CN102906215A (zh) | 2013-01-30 |
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