JPH01500303A - Optical device using photochromic compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Optical device using photochromic compound This invention relates to optical device using photochromic compound. The present invention relates to optical devices, particularly optical resonance devices, that utilize .

UK Patent Application No. 8519711 (Publication Publication No. 2180360) by the applicant ), the applicant has developed a photocatalyst that can be reversibly converted between a colored state and a bleached state. Optical synchronization that uses chromic compounds to provide multiple stable optical transmission states disclosed the sound device.

The apparatus disclosed in the above patent application uses a pair of light beams, namely a coloring light and a bleaching light. rays and vary their relative intensities to vary the light transmission of the device.

This time, we used only one type of light beam with one or more wavelengths to create a bistable state. We have created an optical resonance device that can switch between the two directions.

This type has a low quantum yield for bleaching by light in the visible region. This is achieved by selecting photochromic compounds.

According to the present invention, a plurality of partial light transmitting bright mirrors and a photochromic mirror disposed at the mirror opening are provided. A layer of photochromic material and a variable intensity light incident on the layer of photochromic material. A light source that provides a light beam and measures the transmission values of said incident light beam at different intensity levels. the photochromic material has the light and has the following general formula ( 1): In the formula, both X and Y are a spiro-adamantylidene group or a spiro carbocyclic group. or a heterocyclic group, or Xj3 and Y independently represent hydrogen, alkyl (preferably preferably lower alkyl having 1 to b carbon atoms) or phenyl, and ]<36 and R4 are each independently hydrogen, Al:1, aralkyl, aryl , halogen or a heterocyclic group, R1 is hydrogen, lower alkyl, aryl, alkyl koxy, alkyl- or dialkylamino, halcogne or double; or R1 is at the 5.6 or 7.8 position (indicating a fused benzene ring) An optical resonance device is provided comprising a bilane compound selected from the following.

Specific examples of compounds having the desired properties can be found in the applicant's English II, 1 Special Edition Publication No. 2180360A @, which has the following general formula (II), (I[I ) and (IV). discloses pyro-bilane, formula (n) represents a 2-benzobilane series, and formula ( 1) Jj and (IV) represent isomeric naphthopyrans.

(m In the benzopyran ring or naphthopyran ring, a wide range of ← E group placements are possible. be. For example, these rings are denoted by R3~Ro (or R3~Rto). Al: rule, aryl (rfi substituted phenyl, e.g. alkoxy (including phenyldjJ, and halophenyl), alkoxy, hydroxy, alkyl kylamino or dialkylamino (e.g. dimedylamino), alkylamino-ph phenyl, halogen or a complex group (e.g. furyl or chenyl) Can be substituted, but also hydroxy or alkoxy or alkyl- Alternatively, di-alkylamino may be a substituent at the R3 or R4 position. Can not. Preferred substituents are lower alkyl (eg methyl or ethyl), chlorine , bromine, hydroxy, phenyl, methoxy or methoxyphenyl group.

Additionally, the basic benzopyran or naphthopyran nucleus is aryl or heterocyclic. rings, such as thiophene or furan rings, and the beneficial effect of reducing fatigue reactions. In addition, the introduction of spiro-2-adamantane groups increases the quantum yield for coloring in the U, V, and region. It has a tendency to show rapid thermal fading at the highest temperatures.

According to the following procedure, adamantylidene spiropyran having the above general formula is converted to W. a@ can be done. I understand that chromene is another name for benzopyran. It will be. That is, 2H-chromene is another name for 2H-1-benzopyran.

condensation Adamantane (1 mol) and 0-hydroxyacetophenone (1,1 mol) and cyclic Dissolve the secondary amine (1.2 moles) in toluene (M per gram of each reactant) and Boil until no more water is produced (5-24 hours). Digi and The water is removed as an azeotrope with toluene using a Stark apparatus. Then, Toluene is removed under reduced pressure and residual enamines are removed from acetone or ethanol. Recrystallize.

娨水邵 Dissolve the enamine in a minimum amount of boiling methanol and add CO hydrochloric acid (enamine 10g Add 1 m> for each. Upon standing, chromanone often crystallizes out. chromano If the yield is low, heat the solution to a boil and add hot water until the solution becomes cloudy. Ru. Upon cooling, the chromanone separates.

1 yuan Sodium borohydride (1 g per 2.50 chromanone) in small portions in methanol of chromanone (3d per gram of chromanone). After the addition is complete, The reaction mixture is boiled (2 hours) and the methanol is removed under reduced pressure. Residue in water Mg5O4) was added, extracted with chloroform, dehydrated (Mg5O4) and the solvent was removed to obtain the crude product. Leave chromanol behind.

Station Solvated copper sulfate (CuSOa・5H20) is heated until water no longer occurs. It is heated strongly in a boiling tube using a Bunsen burner. The obtained anhydrous copper sulfate is 1 q per 2 g of chromanol that can be mixed with chromanol in the Scooter, and organic compounds Heat things with a Bunsen burner until they melt. After cooling, the reaction mixture was diluted with chloroform. to remove the solvent and extract the residual chromene from acetone or ethanol. Recrystallize. Decolorization with activated carbon may be required.

Furthermore, in the present invention, compounds included in general formulas (n), (III) and (IV) , and the adamantylidene group becomes a spiro-carbocyclic or a spiro-polycyclic group. or the group R1aj and ]<2 (where R1 and R2 are hydrogen, al4- Structurally similar benzopyran 33 substituted with -b or aryl group) J: A naphthopyran compound can also be used. For example, the above structure The benzopyran compound corresponding to > is the following (II included) In each 14 structure (na), R1 and R2 independently represent hydrogen, al-1-nyl, phenyl. phenyl and substituted phenyl (alkyl, alkoxy, nitro and primary, secondary) or tertiary amino, or substituted with a nitrogen-containing heterocyclic substituent) It's also possible. The method for producing the species compound of formula (I[a)] UK application no. 8614680@ It is described in. Adamantylidene is IJRtcl; and R2 (here R1 and R2 have the above meanings) and the above structures (■) and (II Compounds similar to those of I> can also be prepared. specific compound or group An example of has the following structures (A>, (B), (C) and (D>).

In the above structural formula (I[a), at least one of R1 and R2 is preferably Aryl groups with silicon-containing substituents in the ortho and/or para positions (e.g. Examples of suitable nitrogen-containing substituents are alkyl or sialic (phenyl). Amino and morpholino, piperidino, pyridino, pyrazolino or pyrrolidine It is a radical.

The above compounds are not necessarily limited to the applicant's UK Patent Application No. 8711511 and Helioff described in No. 8614680@ [1 does not necessarily have the Mism characteristic Although it does not have equally significant photochromic L1 mism characteristics, it is suitable for use in the present invention. The at-chromism compound may be selected from the above range of compounds. can. Many of the compounds encompassed by the above structural formulas are themselves novel compounds. Ru.

Alternatively, they can also be structured by modification of the Claisen rearrangement. This person The method provides a general method for the production of chromene derivatives and is limited only to the production of spiropyran. Not possible.

This Claisen rearrangement method provides a general method for producing chromene derivatives, and this method The phenol is converted into a suitable propalol under mild reaction conditions in the presence of a suitable catalyst in a solvent. It consists of heating with a gill derivative.

Unlike the reaction conditions commonly used for Claisen rearrangement, this method requires relatively low temperatures. in boiling xylene or toluene in the presence of a suitable catalyst. It will be done. Generally, the reaction temperature should not exceed about 180°C, preferably 160' C or lower. The reaction can generally be expressed as follows: In the above formula, (A) can be any phenol and (B) is a propalol. gyl alcohol derivatives, such as B L'J pargyl acetate. Ru. The reaction is catalyzed by luminol and occurs at a relatively low temperature with almost no side reactions. Advance rj in degrees. Any aliphatic or yJ aromatic carboxylic acid in place of acetate Compounds such as propionate or benzo, r-t can be used. Ru.

P[1 pargyl acetate J, with T-nol (in the presence of acidic alumina as a catalyst in a solvent) Increased yields can be obtained by heating. Surprisingly, these relatively lenient ordinances gives rise to Claisen rearrangement, whereas conventional reaction conditions (e.g. strong acid Step 1 (heating to 210°C) is the heat content of the reactant/or desired product. bring a solution.

This method involves combining any phenol with a suitable propargyl acetate or other propargyl acetate. enables convenient one-step synthesis of chromene using pargyl alcohol derivatives. Ru.

Propargyl acetate is produced by reacting a suitable ketone with lithium acetylide. can be manufactured. Lithium acetylide/ethylene diamine complex in a suitable solvent such as tetrahydrofuran or dimethyl sulfoxide. Add to the solution of ketone in the solution with stirring. The product is the corresponding propargyl alcohol alcohol, and this alcohol is reacted with acetyl chloride in a suitable solvent. This allows convenient conversion to acetate.

In the practice of the present invention, photochromic compounds are added to the matrix within the resonant cavity. It can be supported in a box and irradiated with light of a suitable wavelength. This compound was first It is converted to its colored state before being inserted into or into the cavity. Almost The conversion of the above photochromic compounds into colored forms is in the blue or ultraviolet region. This is done by irradiating the area with rays of light.

The resonant cavity is created by applying a selected photochromic material to a transparent matrix, e.g. hydrogenated hydrocarbons (e.g. FC series or commercially available from 3M Company) or an inert solvent such as the PP series (commercially available from ISO Chemicals). It can be produced by absorption from a saturated solution of the material in a reagent. Or this The material can also be mixed with polymer particles and hot pressed to obtain samples with a thickness of 2-3 mm. can.

In a particular example, a sheet of cured polycarbonate plastic (CR39 The product name is P. P. G. Limited) has the following formula (X): 160% of the compound was prepared from a saturated solution of this compound in PP9. Absorption was allowed for 30 minutes at °C. In the second example, J3 τ is made of powdered polystyrene. A mixture of N and Bilan (X) is heated to a thickness of 211 with transparent parallel sides. A photochromic support of IIll was obtained.

These plastic supports are then fitted with a pair of partially transmitting mirrors as shown in FIG. The Fubly Perot resonance kit was formed using the following method.

The cavity is then illuminated with a beam of “bleaching” wavelength 1:I-1’tl’. tuning the device through one or more resonances, typically Light in the green spectral region is used. A green laser with a wavelength of 514 nm is suitable. ing. Increasing the intensity of the bleaching light changes the refractive index of the compound and The cavity can be coned through resonance or more. each When resonance is reached, the transmission of light through the device switches to a higher level. bleaching light Decreasing the intensity of the line causes the cavity to modulate through several resonances and lower A switch to the transmission level occurs.

Figure 1 shows the application of a bleaching beam of increasing intensity, followed by a gradual decrease in the intensity of the bleaching beam. 3 is a graph showing the characteristics of a resonant cavity according to the present invention when Curve 1 is drifting. It shows the effect on the transmission of light through the device in which the incident intensity of the white light beam increases gradually. . As the incident intensity increases beyond the value A, the transmission increases rapidly. Because, Cavity resonance gain overcomes absorption loss of 7 otochromic compounds, making it suitable for bleaching This is because it increases the output of the cavity at the wavelength. At the incident intensity of B, the photo Bleached conditions occur primarily in Lomistic materials. As the incident intensity decreases, the transmission returns to the initial value according to curve 2, but a hysteresis tune occurs with uneven transmission. form a line.

Therefore, this device corresponds to a stable state pair, i.e. logic 0 (zero) a first state in curve 1 and a second state in curve 2 corresponding to logic 1; has. This is shown in Figure 1 at points on curves 51 and 21 that intersect line XX. 31.41. Parameters of photochromic materials and resonant cavities By appropriate selection, switching can be induced at different bleaching light intensities and even one or more bistable states can be produced, and the number of bistable states also increases with the photochromic ratio. depending on the beam material and cavity parameters as well as on the maximum intensity of the bleaching beam. will be determined.

The present invention is based on UK Patent Application No. 8519711 (Publication Publication No. 218 0360). The arrangement is shown in Figure 2. However, FIG. 2 is a schematic diagram of an optical resonance apparatus according to the present invention.

Referring to FIG. 2, the Fubly-Perott resonant cavity 1 at a suitable wavelength is , a photochrome made of a partially transmitting mirror 3 and supported by a light transmitting matrix. A layer of Mism material 5 is placed between the mirrors 3. Beam splitter 7 to 7 averypero A part of the bleaching light beam 9 is input from the laser by positioning it in front of the cavity 1. A part of the light beam 9 is directed to the detector 11 of the incident light intensity and a portion of the light beam 9 is directed to the detector 11 of the incident light intensity. cavity 1, where it is transmitted to cavity 1 containing the photochromic layer 5. The transmitted light is transmitted and collected by the transmitted light intensity detector 13. Detection means 11 and 13 Transmission of the photochromic layer at different incident intensities by comparing the output from Measure the level.

Write a series of logic bits into the cavity and write a photo using a large number of bits. The high resolution of chromic materials allows for storage. These logical bits are by deflecting the incident beam 9 or by moving the resonant cavity relative to the beam. You can also address it using

The above resonator is described in the above mentioned British Publication No. 2180360 by the applicant. It can be used for all applications other than permanent data storage. However, 1 obtained by requiring only a single bleaching beam of one or more wavelengths. The simplicity of operation is advantageous in switching operations. In addition, the above photochromis The material allows a sharp up-and-down movement at the switching point, which means fast switching speeds. Taste.

The bleaching light is a laser operating in the visible range, such as an argon-ion laser. It can be the same.

Ray incident intensity international search report ANNEX To THE INTERNATIONAL 5EWCHREPO RT 0NUS-A-440573320109/83 None

Claims (11)

[Claims] 1. Multiple partially light transmitting mirrors and photochromic material placed between these mirrors. a layer of photochromic material and provide a variable intensity light beam incident on the layer of photochromic material. a light source and detection means for measuring transmission values of said incident light beam at different intensity levels; and the photochromic material is bleached by light of a wavelength corresponding to the light beam. and the following general formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, both X and Y are spiro-a] represents a damantylidene group or a spirocarbocyclic or heterocyclic group, or and Y are independently hydrogen, alkyl (preferably lower carbon atoms having 1 to 5 carbon atoms) alkyl) or phenyl, and R3 and R4 are each independently hydrogen. , represents an alkyl, aralkyl, aryl, halogen or heterocyclic group, and R1 is hydrogen, lower alkyl, aryl, alkoxy, alkyl- or dialkyl - represents amino, halogen or heterocycle, or R1 is in the 5, 6 or 7, 8 position Optical resonance selected from pyran compounds showing a fused benzene ring at the position Device. 2. 2. The resonance device according to claim 1, wherein one of X and Y is lower alkyl. 3. Claim 1 or 2, wherein one of X and Y is a phenyl group Resonator. 4. The phenyl group is a primary, secondary or tertiary amino group or a nitrogen-containing heterocyclic group resonance according to claim 3, substituted in the ortho and/or para position by Device. 5. Any one of claims 1 to 4, wherein R3 and R4 are both hydrogen. Resonator device according to item 1. 6. Photochromic compounds have the following structural formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein, X and Y have the same meaning as described in claim 1, and R1 to R12 each independently hydrogen, alkyl, aryl, aralkyl, alkoxy, hydride. Roxy, alkyl- or dialkyl-amino, alkylaminophenyl, ha rogene or a heterocyclic group, where R3 or R4 is alkoxy, hydro or alkyl- or dialkyl- or dialkyl-amino] The resonance device according to any one of claims 1 to 5, which is topiran. 7. A first detection means is provided to receive the light transmitted by the cavity; 2. A detection means is provided to receive light from the light source that has not passed through the cavity, and Comparing the relative intensities measured by the first and second detection means, Claims 1 to 3 determine the transmission value of the photochromic layer at a predetermined intensity. 7. The resonance device according to any one of Item 6. 8. Claims 1 to 3, wherein the resonant cavity is a Fabry-Perot etalon. Resonator device according to any one of clause 7. 9. Claims having at least two levels of transmission depending on the intensity of the incident light beam. The resonance device according to any one of items 1 to 8. 10. Equipped with deflection means for moving the incident light beam relative to the layer of photochromic material. and irradiating different points in the layer according to any one of claims 1 to 9. Resonator device according to item 1. 11. Claims wherein the deflection means comprises means for moving the cavity relative to the beam of light. 11. Resonator device according to item 10.