WO2021101264A1 - Composé azobenzénique comprenant un groupe hétéroaromatique contenant de l'azote et composition d'enregistrement d'hologramme bleu comprenant celui-ci - Google Patents

Composé azobenzénique comprenant un groupe hétéroaromatique contenant de l'azote et composition d'enregistrement d'hologramme bleu comprenant celui-ci Download PDF

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WO2021101264A1
WO2021101264A1 PCT/KR2020/016356 KR2020016356W WO2021101264A1 WO 2021101264 A1 WO2021101264 A1 WO 2021101264A1 KR 2020016356 W KR2020016356 W KR 2020016356W WO 2021101264 A1 WO2021101264 A1 WO 2021101264A1
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polymer
hologram
mmol
recording
azobenzene
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Korean (ko)
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가재원
강혜주
이미혜
강이영
김학린
주경일
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한국화학연구원
경북대학교 산학협력단
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Publication of WO2021101264A1 publication Critical patent/WO2021101264A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/82—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer

Definitions

  • the present invention relates to an azobenzene compound containing nitrogen-containing heteroaromatics such as pyridine and pyrimidine, a blue hologram recording composition comprising the same, a hologram recording medium, a hologram recording material using the same, and a hologram recording or rewriting method.
  • nitrogen-containing heteroaromatics such as pyridine and pyrimidine
  • a blue hologram recording composition comprising the same, a hologram recording medium, a hologram recording material using the same, and a hologram recording or rewriting method.
  • a hologram is a hologram that allows you to see complete three-dimensional information of an object by recording all information on the wavelength, intensity, and phase difference that the light hits and reflects.
  • the etymology of hologram is a compound word of holos (total) and gramm a (information, message) in Greek, and it can be said that the whole information is recorded.
  • Holography is a technique discovered and named by Dennis Gabor, a British physicist born in Hungary in 1948. It is a method of recording and reproducing the generated interference pattern by interfering with the object wave reflected from the subject and the reference wave without subject information. .
  • holography was first discovered by Gabor, it was before lasers were developed, and holography was not attracted much attention due to unclear results, and after the 1960s, lasers capable of generating coherent light were developed. As a rain, a clear hologram became possible, and after that, research began in earnest.
  • Holograms are widely used in security and military fields because the recording process is complicated and it is not easy to duplicate.
  • holograms are engraved on large bills for the purpose of preventing counterfeiting, and ID cards such as passports and driver's licenses are also used to prevent forgery.
  • ID cards such as passports and driver's licenses are also used to prevent forgery.
  • the current hologram's largest market is for genuine certification marks attached to cosmetics, liquor, and clothing.
  • holograms have been used for restoration of relics and treasures and educational contents.
  • Materials for recording holograms used in various applications are materials whose refractive index changes by reacting with light.
  • Holographic recording materials developed to date include silver halide, dichromated gelatin (DCG), photoresist, photochromic, photopolymer, and photorefractive.
  • DCG dichromated gelatin
  • MTA material transfer agreements
  • NDA confidentiality agreements
  • hologram recording materials described above are mostly single recording materials that cannot be rewritten once recorded.
  • a rewritable material that can be used after writing and erasing holographic image information is absolutely necessary.
  • Professor Paigambarian's team at the University of Arizona implemented and reported the world's first updateable hologram (Non-Patent Document 1, JOURNAL OF DISPLAY TECHNOLOGY, VOL. 6, NO. 10, OCTOBER 2010, Materials for an Updatable Holographic 3D Display).
  • Azobenzene which has been used as a variety of dyes in industrial fields, is a molecule capable of trans-cis isomerization by light, and when it is isomerized by light, its geometric shape changes. Accordingly, not only its structure, but also optical properties such as light absorption, emission, and refractive index Due to this change, there have been a lot of research on the application of devices using it. There has been a lot of research on applying an azobenzene compound as a hologram rewritable material. However, the diffraction efficiency was low due to the discrepancy between the wavelength of the laser to be recorded and reproduced, the light irradiation of high energy was required for recording/rewriting, or the dynamic characteristics were remarkably low.
  • the present inventors were conducting research on a polymer compound capable of recording and rewriting holograms, while the polymer containing the azobenzene monomer according to the present invention has an equal absorption point of light isomerization at the holographic recording laser wavelength, and thus recording laser irradiation
  • the present invention was completed by finding out that it is possible to record and rewrite holograms with excellent dynamic characteristics.
  • An object of the present invention is to provide a nitrogen-containing heteroaromatic-containing azobenzene monomer.
  • Another object of the present invention is to provide a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.
  • Another object of the present invention is to provide a light refractive index modulating polymer composition
  • a light refractive index modulating polymer composition comprising a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.
  • Another object of the present invention is to provide a composition for recording a hologram comprising a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.
  • Another object of the present invention is to provide a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.
  • Another object of the present invention is to provide a hologram recording method using the polymer.
  • Another object of the present invention is to provide a hologram rewriting method on the hologram recording medium.
  • R 1 is hydrogen or a straight or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer of 1 to 4;
  • R 2 is 5 to 10 membered heteroaryl containing at least one nitrogen
  • L is a straight or branched C 1-20 alkylene unsubstituted or substituted with one or more fluoro
  • Q is a photocrosslinkable functional group containing at least one radically polymerizable double bond in the molecule.
  • It provides a light refractive index modulating polymer composition comprising the polymer.
  • a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.
  • It provides a hologram recording method comprising; irradiating a laser diffraction pattern on the thin film prepared in step 1 (step 2).
  • a hologram rewriting method comprising the step of irradiating the hologram recording medium with only the reference light used when recording the hologram on the hologram recording medium.
  • the azobenzene monomer compound of the present invention has an isomerization point near the wavelength (460 nm) of the blue laser, and contains a high birefringence moiety that can increase the refractive index change by irradiation with light.
  • the polymer can be usefully used as a hologram recording/rewriting material by blue laser irradiation.
  • FIG. 1 is a graph showing an ultraviolet-visible light absorption spectrum after cis-trans isomerization of a polymer compound according to the present invention.
  • FIG. 3 is a graph showing the diffraction efficiency of a hologram recorded with a blue laser of an azobenzene polymer film according to the present invention.
  • FIG. 4 is a diagram showing a conceptual diagram of Four wave mixing (FWM).
  • R 1 is hydrogen or a straight or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer of 1 to 4;
  • R 2 is 5 to 10 membered heteroaryl containing at least one nitrogen
  • L is a straight or branched C 1-20 alkylene unsubstituted or substituted with one or more fluoro
  • Q is a photocrosslinkable functional group containing at least one radically polymerizable double bond in the molecule.
  • R 1 is hydrogen or a straight or branched C 1-10 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer of 1 to 3;
  • R 2 is a 6 membered heteroaryl containing at least one nitrogen
  • L is a straight or branched C 1-10 alkylene unsubstituted or substituted with one or more fluoro
  • Q may be a photocrosslinkable functional group containing at least one radically polymerizable double bond in the molecule.
  • R 1 is hydrogen or a straight or branched C 1-5 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer of 1 to 2;
  • R 2 is pyridine or pyrimidine
  • L is a straight or branched C 1-6 alkylene unsubstituted or substituted with one or more fluoro
  • the azobenzene monomer represented by Formula 1 may be any one compound selected from the following compound group.
  • the monomer according to the present invention exhibits an equal absorption point at a wavelength of about 460 nm, which is a blue wavelength region, and thus may be usefully used as a composition for hologram recording a blue color.
  • the polymer may be formed by a polymerization reaction of a double bond of Q in the azobenzene monomer represented by Formula 1 and a vinyl group in the monomer having the vinyl acryl group.
  • the polymer according to the present invention may form a copolymer with an azobenzene monomer represented by Chemical Formula 1 and a monomer having a vinyl acryl group.
  • the monomer having a vinyl acryl group may include a monomer containing at least one unsaturated double bond that can be polymerized by a radical mechanism and a monomer containing a terminal or pendant ethylenically unsaturated bond.
  • a monomer capable of photopolymerization with a photocrosslinkable functional group which is Q of the azobenzene monomer represented by Formula 1, but a monomer having a vinyl acrylic group is preferred, for example, vinyl acrylate, vinyl meth Acrylate, vinyl ethyl acrylate, vinyl ethyl methacrylate, vinyl octyl methacrylate, vinyl hexyl methacrylate, vinyl butyl methacrylate, and the like.
  • the polymer according to the present invention may be a block copolymer in which the copolymerization arrangement of the azobenzene monomer A represented by Formula 1 and the monomer B having a vinyl acryl group forms a block chain such as AAAAAA-BBBBBB-, and a random chain such as ABAABABABBA- It may be a random copolymer to form.
  • the arrangement of the monomers can be appropriately used in consideration of the increase of the desired refractive index and physical properties.
  • the polymer according to the present invention is not particularly limited as long as the ratio of the azobenzene monomer represented by Formula 1 and the monomer having a vinyl acryl group is within a range in which a desired refractive index change is obtained before and after light irradiation to the polymer.
  • the azobenzene monomer is 0.5 to 20 mol%, preferably 1 to 15 mol%, and more preferably 1 to 10 mol% of the total monomer.
  • the azobenzene monomer represented by Formula 1 is less than 0.5 mol% of the total monomer, the degree of sensitivity to light is too low, and too much energy is required to record the hologram, and if it exceeds 20 mol%, the wavelength used when reproducing the hologram By absorbing light, the efficiency can be drastically reduced.
  • the polymer according to the present invention can be obtained through a conventional polymerization reaction of an azobenzene monomer represented by Formula 1 and a monomer having a vinyl acryl group, but using a radical initiator such as azobisisobutylonitrile (AIBN) It is preferably prepared through a radical polymerization reaction.
  • a radical initiator such as azobisisobutylonitrile (AIBN)
  • the polymer according to the present invention has a property that the azobenzene structure is cis-trans isomerized when blue wavelength light is irradiated, and the refractive index is modulated before and after the light irradiation, and at this time, the refractive index change is 0.01 to 0.04.
  • the present invention provides a light refractive index modulating polymer composition comprising an azobenzene polymer.
  • the light refractive index modulating polymer composition according to the present invention is an azobenzene polymer having a high birefringence portion capable of increasing the refractive index change by absorbing blue wavelength light and causing light isomerization, even with a small amount of light irradiation.
  • at least one additive selected from a photo initiator, a sensitizer, and a chain transfer agent may be included.
  • the present invention provides a method for controlling a refractive index including the step of modulating a refractive index by irradiating light to the light refractive index modulation polymer composition described above.
  • the refractive index control method of the present invention after performing an appropriate molding treatment using the light refractive index modulating polymer composition, light may be irradiated.
  • the preferred wavelength of light is about 460 nm, and the intensity of light is usually 1000 mJ/cm 2 to 100 mJ/cm 2 , preferably 50 ⁇ 300 mJ/cm 2 but is not limited thereto.
  • It provides a hologram recording composition comprising an azobenzene polymer.
  • the hologram recording composition according to the present invention comprises an azobenzene polymer having a high birefringence portion capable of absorbing blue wavelength light to cause light isomerization and increasing the refractive index change even with a small amount of light irradiation. It includes, and thereby it is possible to form a volume phase type hologram excellent in high diffraction efficiency, high transparency, and reproduction wavelength reproducibility.
  • the hologram recording composition according to the present invention is a conventional plasticizer, thickener, thermal polymerization inhibitor, chain transfer agent, etc. known in the art in order to improve the weather resistance, heat resistance, chemical stability, storage stability, etc. of the hologram recording medium. It may contain additives. At this time, the additive may be added so as not to deviate from the effect of the present invention due to non-reactivity with the monomer or polymer according to the present invention.
  • the hologram recording composition may absorb a wavelength of 400 to 600 nm.
  • a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.
  • the substrate is preferably an optically transparent material, and is not particularly limited, but, for example, a glass plate, a PET plate or film, a polycarbonate plate or film, a polymethyl methacrylate plate or film, and It may be the same plastic plate or film.
  • the thickness of the substrate may be 0.01 to 10 mm, and the substrate is usually flat, but if necessary, it may be curved or have an uneven structure on the surface.
  • It provides a hologram recording method comprising; irradiating a laser diffraction pattern on the thin film prepared in step 1 (step 2).
  • step 1 is a step of preparing a polymer including the azobenzene monomer into a thin film.
  • a method of manufacturing a polymer into a thin film is not particularly limited as long as it is a method of coating a polymer such as spin coating, bar coating, or dip coating on a substrate.
  • a polymer such as spin coating, bar coating, or dip coating on a substrate.
  • it may be prepared by coating on one side of the substrate, or may be prepared by coating a polymer in the form of a sandwich between the substrate and the substrate.
  • step 2 is a step of irradiating a laser diffraction pattern on the thin film prepared in step 1 above.
  • the diffraction pattern may be a diffraction pattern generated by an interference between a reference light and an object light when recording an analog hologram, or a diffraction pattern generated by a computer when recording a digital hologram.
  • a hologram rewriting method comprising the step of irradiating the hologram recording medium with only the reference light used when recording the hologram on the hologram recording medium.
  • the hologram can be rewritten by diffracting the reference light by the interference fringe.
  • This hologram rewriting method is well known in the art along with the hologram recording method, so a detailed description thereof will be omitted.
  • the azobenzene monomer compound of the present invention has an isomerization point near the wavelength (460 nm) of the blue laser, and contains a high birefringence moiety that can increase the refractive index change by irradiation with light.
  • the polymer can be usefully used as a hologram recording/rerecording material by blue laser irradiation, which is supported by Examples and Experimental Examples described later.
  • Step 4 Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene
  • Step 1 Preparation of 4-(6-hydrooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene
  • Step 2 Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene
  • Step 2 Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene
  • Step 2 Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.9 g, 77%) was obtained by washing with an excess of methanol three or more times.
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.93g, 78) was obtained by washing with an excess of methanol three or more times.
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.8g, 72%) was obtained by washing with an excess of methanol three or more times.
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.9 g, 77%) was obtained by washing with an excess of methanol three or more times.
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.9 g, 77%) was obtained by washing with an excess of methanol three or more times.
  • reaction mixture was precipitated in an excess of methanol to terminate the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, and filtered after reprecipitating in an excess of methanol.
  • An orange solid polymer (1.9 g, 77%) was obtained by washing with an excess of methanol three or more times.
  • the polymer compound is dissolved in a solvent such as chloroform, dichloromethane, acetonitrile, and THF, and UV-Vis.
  • a solvent such as chloroform, dichloromethane, acetonitrile, and THF, and UV-Vis.
  • the absorption spectrum was placed in a cell for measuring the absorption spectrum, and the absorption by wavelength from 300 nm to 800 nm was measured, and the results are shown in FIG. 1.
  • 1 is a graph showing absorbance according to wavelength of a polymer compound.
  • the polymer compound according to the present invention was dissolved in a solvent such as chloroform, dichloromethane, acetonitrile, and THF, and UV-Vis. After the trans isomer was converted into a cis isomer by putting it in a cell for measuring an absorption spectrum and irradiated with ultraviolet rays, the absorbance for each wavelength from 300 nm to 800 nm was measured, and the results are shown in FIG. 2.
  • FIG. 2 is a graph showing absorbance according to wavelength after ultraviolet irradiation of a polymer compound.
  • Example 8 which is a polymer compound according to the present invention, it can be seen that the isoabsorption point wavelength appears at a wavelength of 450 to 470 nm.
  • the polymer compound according to the present invention exhibits an isoabsorption point wavelength in a blue wavelength region that conventional hologram recording polymers could not produce, it can be usefully used as a composition for producing a hologram including a blue color.
  • the FWM measurement setup is largely composed of a part for recording a hologram on a film using a recording beam, and a part for measuring the diffraction efficiency value of the azobenzene polymer film in real time in synchronization with this.
  • the diffraction pattern was recorded using a 460 nm laser, and the reproduction beam was designed to be incident at the same angle from the opposite side to the laser beam incident in the normal direction of the film to measure the diffraction efficiency of the recorded hologram.
  • the reproduction beam incident on the sample is diffracted by the recorded hologram, and the intensity of the diffracted beam through the photodiode can be measured in real time.
  • the diffraction efficiency can be obtained from the ratio of the intensity of the incident beam and the intensity of the diffracted beam.
  • the conceptual diagram of FWM is shown in FIG. 4.
  • FIG. 3 is a graph showing the diffraction efficiency of a hologram recorded with a blue laser of an azobenzene polymer film according to the present invention.
  • the polymer containing the azobenzene monomer compound according to the present invention can be usefully used as a hologram recording/rerecording material by blue laser irradiation.
  • the azobenzene monomer compound of the present invention has an isomerization point near the wavelength of the blue laser (460 nm), and contains a high birefringence moiety that can increase the refractive index change by irradiation with light.
  • the polymer is useful as a material for recording/rewriting holograms by blue laser irradiation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un composé azobenzénique, une composition d'enregistrement d'hologramme comprenant celui-ci, un support d'enregistrement d'hologramme, un matériau d'enregistrement d'hologramme utilisant celui-ci et un procédé pour l'enregistrement d'un hologramme ou le réenregistrement d'un hologramme. Le composé monomère azobenzénique selon la présente invention présente une photoisomérisation à une grande longueur d'onde et a une partie à indice de biréfringence élevé qui permet d'amplifier un changement d'indice de réfraction même par une petite dose de rayonnement, et ainsi, un polymère comprenant le composé monomère azobenzénique peut être utilisé de manière utile en tant que matériau pour l'enregistrement/réenregistrement d'un hologramme par irradiation par laser.
PCT/KR2020/016356 2019-11-22 2020-11-19 Composé azobenzénique comprenant un groupe hétéroaromatique contenant de l'azote et composition d'enregistrement d'hologramme bleu comprenant celui-ci WO2021101264A1 (fr)

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