Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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
  • G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
• • 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
• • 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
• • 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
  • G11B7/24038—Multiple laminated recording layers
• • 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
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
  • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
  • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
• • 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
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
  • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
  • G11B2007/25701—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials
  • G11B2007/25703—Resins
• • 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
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
  • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
  • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component

Definitions

• the present disclosure relates to an optical recording medium, an information recording method, and an information reading method.
• Three-dimensional recording which records information on a multilayer body, is known as a technique for increasing the recording capacity of optical information recording media.
• a laser light with a short wavelength is used to achieve a finer focused spot.
• This laser light includes a laser light having a center wavelength of 405 nm, which is the standard for Blu-ray (registered trademark) discs.
• optical recording media using laser light having a center wavelength of 405 nm are known.
• An optical recording medium includes, for example, a recording layer and a dielectric layer located on the recording layer (for example, Patent Document 1).
• an optical recording medium including a recording layer made of an optical information recording material can perform hologram recording.
• An optical recording medium in one aspect of the present disclosure includes: a recording layer; a dielectric layer located on the recording layer and including a porous organic structure; Equipped with.
• the present disclosure provides an optical recording medium with improved recording sensitivity.
• FIG. 1 is a cross-sectional view showing a schematic configuration of an optical recording medium according to an embodiment of the present disclosure.
• FIG. 2A is a flowchart regarding a method for recording information using an optical recording medium according to an embodiment of the present disclosure.
• FIG. 2B is a flowchart regarding a method for reading information using an optical recording medium according to an embodiment of the present disclosure.
• FIG. 3 is a graph showing the solid state 13 C-NMR spectrum of the intrinsically microporous polymer used in the examples.
• Multilayer optical recording media are attracting particular attention as low-cost, large-capacity optical recording media.
• a multilayer optical recording medium is, for example, a recording device in which recording layers containing a dye and dielectric layers containing a polymer are alternately laminated.
• the dye in the recording layer has, for example, nonlinear optical properties.
• the polymer of the dielectric layer is typically a non-porous polymer.
• the recording layer includes, for example, a resin and a dye that generates heat by absorbing light.
• heat is generated when the dye absorbs recording light.
• the generated heat propagates to the resin, and the shape of the resin changes, thereby forming recording marks.
• the recording sensitivity of an optical recording medium can be evaluated based on the light irradiation energy required to form recording marks. Note that the recording sensitivity can also be evaluated based on the pulse width that correlates with the light irradiation energy.
• the optical recording medium does not have a dielectric layer and the recording layer is in contact with air, the heat generated in the recording layer is effectively used by the recording layer due to the heat insulating effect of the air. In this case, since the resin is easily deformed, the recording sensitivity is good. However, if a non-porous dielectric layer is laminated on the recording layer, the heat insulation effect of air cannot be obtained, and the recording layer tends to dissipate heat. As described above, an optical recording medium having a laminated structure has a problem of a decrease in recording sensitivity.
• An optical recording medium having a laminated structure is manufactured, for example, by alternately laminating a recording layer containing a nonlinear light-absorbing dye and a non-porous dielectric layer.
• a recording layer containing a nonlinear light-absorbing dye and a non-porous dielectric layer is stacked, the thermal properties and strength of the recording layer change, and the recording sensitivity at the excitation wavelength may decrease significantly.
• one way to realize a low-cost, high-capacity optical recording medium is to introduce a dielectric layer that has high optical transparency to the recording and reproducing wavelength on top of the recording layer containing a nonlinear light-absorbing dye.
• a dielectric layer that has high optical transparency to the recording and reproducing wavelength on top of the recording layer containing a nonlinear light-absorbing dye.
• a dielectric layer containing a porous organic structure suppresses a decrease in recording sensitivity.
• this dielectric layer is suitable for suppressing a decrease in recording sensitivity when using light having a wavelength in a short wavelength range.
• the short wavelength range means a wavelength range including 405 nm, for example, a wavelength range of 390 nm or more and 420 nm or less.
• a dielectric layer containing a porous organic structure is suitable for suppressing a decrease in recording sensitivity when using light having a wavelength around 405 nm.
• the optical recording medium according to the first aspect of the present disclosure includes: a recording layer; a dielectric layer located on the recording layer and including a porous organic structure; Equipped with.
• the dielectric layer has pores due to the porous organic structure. According to the heat insulating effect of the air in the pores, for example, heat generated in the recording layer during a recording operation can be suppressed from being released from the recording layer. Since the heat generated in the recording layer is effectively used in the recording layer, the recording sensitivity of the optical recording medium is improved.
• the porous organic structure may have a specific surface area of 50 m 2 /g or more.
• the porous organic structure may have an average pore diameter of 0.3 nm or more and 50 nm or less.
• the porous organic structure has an average pore diameter of 0.3 nm or more and 3 nm or less. Good too.
• optical recording media according to the second to fourth aspects have improved recording sensitivity.
• the porous organic structure may be an intrinsically microporous polymer.
• the intrinsic microporous polymer described in the fifth aspect has, for example, a twisted and rigid main chain skeleton, and entanglement of the main chain skeletons is suppressed. Therefore, dielectric layers containing inherently microporous polymers tend to have nanometer-sized pores.
• the nanometer-sized pore structure tends to suppress light scattering of recording and reproducing light. This pore structure is suitable for improving the recording sensitivity of optical recording media because the air in the pores produces a heat insulating effect.
• the intrinsic microporous polymer may include a structural unit represented by the following formula (1).
• R 1 to R 18 are each independently at least one selected from the group consisting of H, B, C, N, O, F, Si, P, S, Cl, Br, and I.
• X is F, Cl, Br or I, independently of each other.
• the intrinsic microporous polymer may include a structural unit represented by the following formula (2).
• the pi-conjugated system of the main chain skeleton is short.
• This intrinsically microporous polymer tends to suppress absorption of recording and reproducing light.
• a cation is generated by introducing a substituent such as a hydrogen atom or an alkyl group to the nitrogen atom.
• the intrinsically microporous polymer has a cationic main chain skeleton.
• This inherently microporous polymer has hydrophilic properties and is soluble in highly polar solvents. In this case, it is easy to form a dielectric layer by applying a coating liquid containing an intrinsically microporous polymer to a hydrophobic recording layer.
• the recording layer may include an organic compound having nonlinear optical properties.
• the nonlinear optical characteristic may be a two-photon absorption characteristic.
• the recording capacity of the optical recording medium can be easily increased.
• the information recording method includes: Prepare a light source that emits light having a wavelength of 390 nm or more and 420 nm or less, condensing the light from the light source and irradiating the recording layer in the optical recording medium according to any one of the first to ninth aspects; Including.
• information can be recorded on the optical recording medium at high recording density.
• the method for reading information according to the eleventh aspect of the present disclosure is, for example, a method for reading information recorded by the recording method according to the tenth aspect, comprising:
• the reading method is Measuring the optical properties of the recording layer by irradiating the recording layer in the optical recording medium with light, reading information from the recording layer; Including.
• the optical property may be the intensity of light reflected by the recording layer.
• information can be easily read from the optical recording medium.
• FIG. 1 is a cross-sectional view showing a schematic configuration of an optical recording medium 100 according to an embodiment of the present disclosure.
• the optical recording medium 100 includes a recording layer 10 and a dielectric layer 20.
• the dielectric layer 20 is located on the recording layer 10, and is in direct contact with the recording layer 10, for example.
• the optical recording medium 100 has a laminated structure of a recording layer 10 and a dielectric layer 20.
• Dielectric layer 20 includes a porous organic structure.
• the optical recording medium 100 may include multiple recording layers 10.
• the plurality of recording layers 10 are arranged, for example, in the thickness direction of the optical recording medium 100.
• the number of recording layers 10 is not particularly limited, and is, for example, 2 or more and 1000 or less.
• the optical recording medium 100 including the plurality of recording layers 10 functions as a three-dimensional optical memory.
• a specific example of the optical recording medium 100 is a three-dimensional optical disc.
• the dielectric layer 20 may be, for example, an intermediate layer located between the two recording layers 10.
• the optical recording medium 100 may include multiple dielectric layers 20.
• the plurality of recording layers 10 and the plurality of dielectric layers 20 may be arranged alternately.
• a plurality of recording layers 10 and a plurality of dielectric layers 20 may be alternately stacked.
• each of the plurality of recording layers 10 is disposed between two dielectric layers 20 and is in direct contact with each of the two dielectric layers 20.
• the number of dielectric layers 20 is not particularly limited, and is, for example, 3 or more and 1001 or less.
• dielectric layer 20 includes a porous organic structure.
• a porous organic structure means an organic compound having a porous structure.
• the coating method is a method of producing a thin film by applying a coating solution containing a porous organic structure and drying the obtained coating film.
• Dielectric layer 20 does not include pores formed using, for example, a foaming agent. In other words, dielectric layer 20 is, for example, substantially foam-free.
• porous organic frameworks include polymers of intrinsic microporosity (PIM), metal organic frameworks (MOF), covalent organic frameworks (COF), and hydrogen bonds. Examples include hydrogen-bonded organic frameworks (HOF).
• PIM refers to a porous structure having a porous structure created by suppressing the entanglement of main chain skeletons of polymers.
• the intrinsic microporous polymer includes, for example, a structural unit represented by the following formula (1).
• R 1 to R 18 are each independently at least one selected from the group consisting of H, B, C, N, O, F, Si, P, S, Cl, Br, and I. Contains atoms.
• R1 to R18 each independently include a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a group containing an oxygen atom, a group containing a nitrogen atom, a group containing a sulfur atom, and a silicon atom. group, a group containing a phosphorus atom, or a group containing a boron atom.
• halogen atom examples include F, Cl, Br, I, and the like.
• a halogen atom may be referred to as a halogen group.
• the number of carbon atoms in the hydrocarbon group is not particularly limited, and is, for example, 1 or more and 20 or less, may be 1 or more and 10 or less, or may be 1 or more and 5 or less.
• the hydrocarbon group may be linear, branched, or cyclic.
• hydrocarbon group examples include an aliphatic saturated hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic unsaturated hydrocarbon group.
• the aliphatic saturated hydrocarbon group may be an alkyl group.
• Examples of aliphatic saturated hydrocarbon groups include -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 , -C(CH 3 ) 3 , -CH2CH ( CH3 ) 2 , -( CH2 ) 3CH3 , -( CH2 ) 4CH3 , -C( CH2CH3 ) ( CH3 ) 2 , -CH2C (CH 3 ) 3 , -(CH 2 ) 5 CH 3 , -(CH 2 ) 6 CH 3 , -(CH 2 ) 7 CH 3 , -(CH 2 ) 8 CH 3 , -(CH 2 ) 9 CH
• Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
• a halogenated hydrocarbon group means a group in which at least one hydrogen atom contained in the hydrocarbon group is substituted with a halogen atom.
• the halogenated hydrocarbon group may be a group in which all hydrogen atoms contained in the hydrocarbon group are substituted with halogen atoms.
• Examples of the halogenated hydrocarbon group include a halogenated alkyl group and a halogenated alkenyl group.
• halogenated alkyl group examples include -CF 3 , -CH 2 F, -CH 2 Br, -CH 2 Cl, -CH 2 I, -CH 2 CF 3 and the like.
• the group containing an oxygen atom is, for example, a substituent having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group, an ether group, an acyl group, and an ester group.
• Examples of the substituent having a hydroxyl group include a hydroxyl group itself and a hydrocarbon group having a hydroxyl group. In this substituent, the hydroxyl group may be deprotonated to be in the -O - state.
• Examples of the hydrocarbon group having a hydroxyl group include -CH 2 OH, -CH(OH)CH 3 , -CH 2 CH(OH)CH 3 and -CH 2 C(OH)(CH 3 ) 2 .
• Examples of the substituent having a carboxyl group include the carboxyl group itself and a hydrocarbon group having a carboxyl group. In this substituent, the carboxyl group may be deprotonated to be in the -CO 2 - state.
• Examples of the hydrocarbon group having a carboxyl group include -CH 2 CH 2 COOH, -C(COOH)(CH 3 ) 2 and -CH 2 CO 2 - .
• Examples of the substituent having an aldehyde group include the aldehyde group itself and a hydrocarbon group having an aldehyde group.
• Examples of the substituent having an ether group include an alkoxy group, a halogenated alkoxy group, an alkenyloxy group, an oxiranyl group, and a hydrocarbon group having at least one of these functional groups. At least one hydrogen atom contained in the alkoxy group may be substituted with a group containing at least one atom selected from the group consisting of N, O, P, and S.
• alkoxy groups include methoxy, ethoxy, 2-methoxyethoxy, butoxy, 2-methylbutoxy, 2-methoxybutoxy, 4-ethylthiobutoxy, pentyloxy, hexyloxy, and heptyloxy groups.
• halogenated alkoxy group examples include -OCHF 2 , -OCH 2 F, and -OCH 2 Cl.
• hydrocarbon group having a functional group such as an alkoxy group include -CH 2 OCH 3 , -C(OCH 3 ) 3 , 2-methoxybutyl group, and 6-methoxyhexyl group.
• Examples of the substituent having an acyl group include the acyl group itself and a hydrocarbon group having an acyl group.
• Examples of the acyl group include -COCH 3 and the like.
• Examples of the substituent having an ester group include an alkoxycarbonyl group, an acyloxy group, and a hydrocarbon group having at least one of these functional groups.
• Examples of the alkoxycarbonyl group include -COOCH 3 , -COO(CH 2 ) 3 CH 3 and -COO(CH 2 ) 7 CH 3 .
• Examples of the acyloxy group include -OCOCH 3 and the like.
• the hydrocarbon group having a functional group such as an acyloxy group include -CH 2 OCOCH 3 and the like.
• the nitrogen atom-containing group is, for example, a substituent having at least one member selected from the group consisting of an amino group, an imino group, a cyano group, an azide group, an amide group, a carbamate group, a nitro group, a cyanamide group, an isocyanate group, and an oxime group. It is the basis.
• substituent having an amino group examples include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group, and a hydrocarbon group having at least one of these functional groups. .
• the amino group may be protonated.
• the tertiary amino group examples include -N(CH 3 ) 2 and the like.
• Hydrocarbon groups having functional groups such as primary amino groups include -CH 2 NH 2 , -CH 2 N(CH 3 ) 2 , -(CH 2 ) 4 N(CH 3 ) 2 , -CH 2 CH 2 Examples include NH 3 + , -CH 2 CH 2 NH(CH 3 ) 2 + , -CH 2 CH 2 N(CH 3 ) 3 + and the like.
• Examples of the substituent having an imino group include the imino group itself and a hydrocarbon group having an imino group.
• Examples of the substituent having a cyano group include the cyano group itself and a hydrocarbon group having a cyano group.
• Examples of the substituent having an azide group include the azide group itself and a hydrocarbon group having an azide group.
• Examples of the substituent having an amide group include the amide group itself and a hydrocarbon group having an amide group.
• Examples of the amide group include -CONH 2 , -NHCHO, -NHCOCH 3 , -NHCOCF 3 , -NHCOCH 2 Cl, -NHCOCH(CH 3 ) 2 and the like.
• Examples of the hydrocarbon group having an amide group include -CH 2 CONH 2 and -CH 2 NHCOCH 3 .
• Examples of the substituent having a carbamate group include the carbamate group itself and a hydrocarbon group having a carbamate group.
• Examples of the carbamate group include -NHCOOCH 3 , -NHCOOCH 2 CH 3 , -NHCO 2 (CH 2 ) 3 CH 3 and the like.
• Examples of the substituent having a nitro group include the nitro group itself and a hydrocarbon group having a nitro group.
• Examples of the hydrocarbon group having a nitro group include -C(NO 2 )(CH 3 ) 2 and the like.
• Examples of the substituent having a cyanamide group include the cyanamide group itself and a hydrocarbon group having a cyanamide group.
• the cyanamide group is represented by -NHCN.
• Examples of the substituent having an isocyanate group include the isocyanate group itself and a hydrocarbon group having an isocyanate group.
• Examples of the substituent having an oxime group include the oxime group itself and a hydrocarbon group having an oxime group.
• Groups containing a sulfur atom include, for example, a thiol group, a sulfide group, a sulfinyl group, a sulfonyl group, a sulfino group, a sulfonic acid group, an acylthio group, a sulfenamide group, a sulfonamide group, a thioamide group, a thiocarbamide group, and a thiocyano group. It is a substituent having at least one member selected from the group consisting of:
• Examples of the substituent having a thiol group include the thiol group itself and a hydrocarbon group having a thiol group.
• the thiol group is represented by -SH.
• Examples of the substituent having a sulfide group include an alkylthio group, an alkyldithio group, an alkenylthio group, an alkynylthio group, a thiacyclopropyl group, and a hydrocarbon group having at least one of these functional groups. . At least one hydrogen atom contained in the alkylthio group may be substituted with a halogen group.
• Examples of the alkylthio group include -SCH 3 , -S(CH 2 )F, -SCH(CH 3 ) 2 and -SCH 2 CH 3 .
• Examples of the alkyldithio group include -SSCH 3 and the like.
• alkynylthio group examples include -SC ⁇ CH and the like.
• hydrocarbon group having a functional group such as an alkylthio group examples include -CH 2 SCF 3 and the like.
• Examples of the substituent having a sulfinyl group include the sulfinyl group itself and a hydrocarbon group having a sulfinyl group.
• Examples of the sulfinyl group include -SOCH 3 and the like.
• Examples of the substituent having a sulfonyl group include the sulfonyl group itself and a hydrocarbon group having a sulfonyl group.
• Examples of the sulfonyl group include -SO 2 CH 3 and the like.
• Examples of the hydrocarbon group having a sulfonyl group include -CH 2 SO 2 CH 3 and -CH 2 SO 2 CH 2 CH 3 .
• substituent having a sulfino group examples include the sulfino group itself and a hydrocarbon group having a sulfino group.
• the sulfino group may be deprotonated to form -SO 2 - .
• substituent having a sulfonic acid group examples include the sulfonic acid group itself and a hydrocarbon group having a sulfonic acid group.
• the sulfonic acid group may be deprotonated to form -SO 3 - .
• Examples of the substituent having an acylthio group include the acylthio group itself and a hydrocarbon group having an acylthio group.
• Examples of the acylthio group include -SCOCH 3 and the like.
• Examples of the substituent having a sulfenamide group include the sulfenamide group itself and a hydrocarbon group having a sulfenamide group.
• Examples of the sulfenamide group include -SN(CH 3 ) 2 and the like.
• Examples of the substituent having a sulfonamide group include the sulfonamide group itself and a hydrocarbon group having a sulfonamide group.
• Examples of the sulfonamide group include -SO 2 NH 2 and -NHSO 2 CH 3 .
• Examples of the substituent having a thioamide group include the thioamide group itself and a hydrocarbon group having a thioamide group.
• Examples of the thioamide group include -NHCSCH 3 and the like.
• Examples of the hydrocarbon group having a thioamide group include -CH 2 SC(NH 2 ) 2 + and the like.
• Examples of the substituent having a thiocarbamide group include the thiocarbamide group itself and a hydrocarbon group having a thiocarbamide group.
• Examples of the thiocarbamide group include -NHCSNHCH 2 CH 3 and the like.
• Examples of the substituent having a thiocyano group include the thiocyano group itself and a hydrocarbon group having a thiocyano group.
• Examples of the hydrocarbon group having a thiocyano group include -CH 2 SCN and the like.
• the group containing a silicon atom is, for example, a substituent having at least one selected from the group consisting of a silyl group and a siloxy group.
• Examples of the substituent having a silyl group include the silyl group itself and a hydrocarbon group having a silyl group.
• Silyl groups include -Si(CH 3 ) 3 , -SiH(CH 3 ) 2 , -Si(OCH 3 ) 3 , -Si(OCH 2 CH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si (CH 3 ) 2 OCH 3 , -Si(N(CH 3 ) 2 ) 3 , -SiF(CH 3 ) 2 , -Si(OSi(CH 3 ) 3 ) 3 , -Si(CH 3 ) 2 OSi(CH 3 ) 3 etc.
• Examples of the hydrocarbon group having a silyl group include -(CH 2 ) 2 Si(CH 3 ) 3 and the like.
• Examples of the substituent having a siloxy group include the siloxy group itself and a hydrocarbon group having a siloxy group.
• Examples of the hydrocarbon group having a siloxy group include -CH 2 OSi(CH 3 ) 3 and the like.
• the group containing a phosphorus atom is, for example, a substituent having at least one selected from the group consisting of a phosphino group and a phosphoryl group.
• Examples of the substituent having a phosphino group include the phosphino group itself and a hydrocarbon group having a phosphino group.
• Phosphino groups include -PH 2 , -P(CH 3 ) 2 , -P(CH 2 CH 3 ) 2 , -P(C(CH 3 ) 3 ) 2 , -P(CH(CH 3 ) 2 ) 2 Examples include.
• Examples of the substituent having a phosphoryl group include the phosphoryl group itself and a hydrocarbon group having a phosphoryl group.
• Examples of the hydrocarbon group having a phosphoryl group include -CH 2 PO(OCH 2 CH 3 ) 2 and the like.
• the group containing a boron atom is, for example, a substituent having a boronic acid group.
• substituent having a boronic acid group include the boronic acid group itself and a hydrocarbon group having a boronic acid group.
• At least one selected from the group consisting of R 7 and R 8 may be an alkyl group such as a methyl group.
• At least one selected from the group consisting of R 17 and R 18 may be a hydrogen atom or an alkyl group such as a methyl group.
• R 1 to R 6 and R 9 to R 16 may be hydrogen atoms.
• X is F, Cl, Br or I independently of each other.
• X may be Cl.
• the intrinsic microporous polymer may include a structural unit represented by the following formula (2).
• the intrinsic microporous polymer contains, for example, the structural unit represented by the above formula (1) or the structural unit represented by the formula (2) as a main component.
• the intrinsic microporous polymer may be represented by the following formula (3) or (4).
• R 1 to R 18 and X are the same as described above for formula (1).
• n is an integer.
• the intrinsic microporous polymer containing the structural unit represented by the above formula (1) or the structural unit represented by the formula (2) tends to have a short pi-conjugated system in the main chain skeleton.
• This intrinsically microporous polymer tends to suppress absorption of recording and reproducing light.
• this intrinsically microporous polymer tends to suppress absorption of light having wavelengths in the short wavelength range.
• the porous organic structure has a porous structure. Therefore, when a nitrogen adsorption method is performed on a porous organic structure, the amount of nitrogen gas adsorbed tends to be large.
• the adsorption amount A of nitrogen gas determined by a nitrogen adsorption method for a porous organic structure is, for example, 50 cm 3 /g or more, and may be 100 cm 3 /g or more, or 200 cm 3 /g or more. It may be 250 cm 3 /g or more.
• the upper limit of the adsorption amount A is not particularly limited, and is, for example, 1000 cm 3 /g.
• the adsorption amount A of nitrogen gas can be determined by the following method. First, nitrogen gas adsorption and desorption measurements are performed on the powdered porous organic structure. The adsorption and desorption measurement of nitrogen gas is carried out at a temperature of 77 K and by adjusting the relative pressure P/P 0 in the range of 0 to 1. Based on the measurement results, an adsorption isotherm showing the relationship between the relative pressure P/P 0 and the amount of nitrogen gas adsorbed is created. At this time, the adsorption amount of nitrogen gas is converted to a value under standard temperature and pressure (STP). From the adsorption isotherm, the amount of nitrogen gas adsorbed when the relative pressure P/P 0 is 1 is read and specified as the adsorption amount A.
• STP standard temperature and pressure
• the specific surface area a of the porous organic structure is, for example, 50 m 2 /g or more, may be 100 m 2 /g or more, 300 m 2 /g or more, or 500 m 2 /g or more. It's okay.
• the upper limit of the specific surface area a is not particularly limited, and is, for example, 3000 m 2 /g.
• the specific surface area a is obtained by converting the adsorption isotherm data described above for the adsorption amount A using the BET (Brunauer-Emmett-Teller) method.
• the total pore volume v of the porous organic structure is, for example, 0.1 cm 3 /g or more, may be 0.2 cm 3 /g or more, or may be 0.3 cm 3 /g or more. , 0.4 cm 3 /g or more.
• the upper limit of the total pore volume v is not particularly limited, and is, for example, 1.0 cm 3 /g.
• the total pore volume v is obtained by converting the adsorption isotherm data described above for the adsorption amount A using the BJH (Barrett-Joyner-Halenda) method.
• the average pore diameter d of the porous organic structure is, for example, 50 nm or less, may be 30 nm or less, may be 10 nm or less, may be 5 nm or less, may be 3 nm or less, It may be 2 nm or less.
• a porous organic structure having a small average pore diameter d is suitable for suppressing light scattering of recording and reproducing light.
• the lower limit of the average pore diameter d is not particularly limited, and is, for example, 0.3 nm.
• the average pore diameter d may be 0.3 nm or more and 50 nm or less, or 0.3 nm or more and 3 nm or less.
• the average pore diameter d (nm) of the porous organic structure is calculated by substituting the specific surface area a (m 2 /g) and total pore volume v (cm 3 /g) of the porous organic structure into the following formula. can do.
• the average pore diameter d corresponds to the diameter of a cylindrical pore when all pores included in the porous organic structure are considered as one cylindrical pore.
• Average pore diameter d 4 ⁇ 10 3 ⁇ total pore volume v / specific surface area a
• the dielectric layer 20 includes, for example, a porous organic structure as a main component.
• the term “main component” refers to the component contained in the dielectric layer 20 in the largest amount by weight.
• Dielectric layer 20, for example, consists essentially of a porous organic structure. "Substantially consisting of” means to exclude other ingredients that alter the essential characteristics of the material referred to. However, the dielectric layer 20 may contain impurities in addition to the porous organic structure.
• the thickness of the dielectric layer 20 is not particularly limited, and is, for example, 5 nm or more and 100 ⁇ m or less. However, the thickness of the dielectric layer 20 may exceed 100 ⁇ m.
• the dielectric layer 20 containing a porous organic structure tends to have high light transmittance to recording/reproducing wavelengths, particularly wavelengths in the short wavelength range.
• the dielectric layer 20 also tends to have both high heat insulation properties and mechanical strength.
• the recording sensitivity of the optical recording medium 100 can be improved by the dielectric layer 20 having heat insulating properties.
• the recording layer 10 contains, for example, an organic compound C having optical properties.
• the optical property is typically a light absorption property.
• the organic compound C can change from a ground state to a transition state by absorbing light having a wavelength in a short wavelength range.
• the organic compound C may generate heat when returning from the transition state to the ground state.
• the organic compound C may have, for example, nonlinear optical properties, particularly nonlinear light absorption properties. Specifically, the organic compound C may have nonlinear optical properties with respect to light having a wavelength in a short wavelength range. An example of nonlinear optical properties is two-photon absorption properties. However, the organic compound C may have one-photon absorption characteristics for light having a wavelength in a short wavelength range. In this specification, the organic compound C having optical properties may be simply referred to as a dye.
• the organic compound C contains at least one selected from the group consisting of a carbon-carbon double bond, a carbon-nitrogen double bond, and a carbon-carbon triple bond.
• Organic compound C may further contain an aromatic ring.
• the aromatic ring contained in the organic compound C may be composed of carbon atoms, or may be a heteroaromatic ring containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. Examples of the aromatic ring contained in the organic compound C include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a furan ring, a pyrrole ring, a pyridine ring, and a thiophene ring.
• the organic compound C may contain a benzene ring as an aromatic ring.
• the number of aromatic rings contained in the organic compound C is not particularly limited, and may be, for example, 2 or more, 3 or more, or 5 or more.
• the upper limit of the number of aromatic rings is not particularly limited, and is, for example, 15.
• a plurality of aromatic rings may be connected by at least one bond selected from the group consisting of a carbon-carbon double bond, a carbon-nitrogen double bond, and a carbon-carbon triple bond.
• the plurality of aromatic rings contained in the organic compound C may be the same or different.
• a specific example of the organic compound C is a dye 28Ev represented by the following formula (5).
• Dye 28Ev is a compound that has two-photon absorption characteristics for light having a wavelength in a short wavelength range.
• organic compound C examples include coumarin 6 and the like.
• Coumarin 6 is a compound that has one-photon absorption characteristics for light having a wavelength in a short wavelength range.
• the content of organic compound C in the recording layer 10 is, for example, less than 50 wt%, may be 30 wt% or less, or may be 10 wt% or less.
• the lower limit of the content of organic compound C is not particularly limited, and is, for example, 2 wt%.
• the recording layer 10 may further contain a resin that functions as a binder.
• a resin that functions as a binder is polyvinylcarbazole.
• the content of the resin in the recording layer 10 is, for example, 50 wt% or more, may be 70 wt% or more, or may be 90 wt% or more.
• the upper limit of the resin content is not particularly limited, and is, for example, 98 wt%.
• the recording layer 10 is, for example, a thin film having a thickness of 1 nm or more and 100 ⁇ m or less. However, the thickness of the recording layer 10 may exceed 100 ⁇ m.
• the optical recording medium 100 can be manufactured, for example, by the following method. First, a coating liquid is prepared by mixing the material of the recording layer 10 with a solvent. As the solvent, for example, a low polarity solvent can be used. This coating liquid is applied to a substrate by a method such as spin coating, and the resulting coating film is dried to produce a thin recording layer 10.
• a solvent for example, a low polarity solvent can be used.
• This coating liquid is applied to a substrate by a method such as spin coating, and the resulting coating film is dried to produce a thin recording layer 10.
• a coating solution is prepared by mixing the porous organic structure with a solvent.
• a solvent for example, a highly polar solvent can be used.
• the dielectric layer 20 is produced by applying this coating liquid onto the recording layer 10 by a method such as spin coating and drying the obtained coating film. If necessary, the optical recording medium 100 can be obtained by alternately producing a plurality of recording layers 10 and a plurality of dielectric layers 20.
• this intrinsically microporous polymer has hydrophilic properties and is soluble in highly polar solvents. In this case, it is easy to form a dielectric layer by applying a coating liquid containing an intrinsically microporous polymer to a hydrophobic recording layer.
• the optical recording medium 100 of this embodiment uses, for example, light having a wavelength in a short wavelength range.
• the optical recording medium 100 uses light having a wavelength of 390 nm or more and 420 nm or less.
• the light used in the optical recording medium 100 has, for example, a high photon density near its focal point.
• the power density near the focal point of the light used in the optical recording medium 100 is, for example, 0.1 W/cm 2 or more and 1.0 ⁇ 10 20 W/cm 2 or less.
• the power density near the focal point of this light may be 1.0 W/cm 2 or more, 1.0 ⁇ 10 2 W/cm 2 or more, or 1.0 ⁇ 10 5 W/cm It may be 2 or more.
• a light source used in the optical recording medium 100 for example, a femtosecond laser such as a titanium sapphire laser, or a pulsed laser having a pulse width from a picosecond to a nanosecond such as a semiconductor laser can be used.
• a femtosecond laser such as a titanium sapphire laser
• a pulsed laser having a pulse width from a picosecond to a nanosecond such as a semiconductor laser
• FIG. 2A is a flowchart regarding a method of recording information using the optical recording medium 100.
• a light source that emits light having a wavelength of 390 nm or more and 420 nm or less is prepared.
• the light source for example, a femtosecond laser such as a titanium sapphire laser, or a pulsed laser having a pulse width from picoseconds to nanoseconds such as a semiconductor laser can be used.
• step S12 light from a light source is focused by a lens or the like and irradiated onto the recording layer 10 of the optical recording medium 100.
• the NA number of the lens used for condensing light is not particularly limited.
• a lens having an NA of 0.8 or more and 0.9 or less may be used.
• the power density of this light near the focal point is, for example, 0.1 W/cm 2 or more and 1.0 ⁇ 10 20 W/cm 2 or less.
• the power density near the focal point of this light may be 1.0 W/cm 2 or more, 1.0 ⁇ 10 2 W/cm 2 or more, or 1.0 ⁇ 10 5 W/cm It may be 2 or more.
• the recording area refers to a spot that exists in the recording layer 10 and can record information by being irradiated with light.
• a physical or chemical change occurs in the recording area irradiated with the above light, thereby changing the optical characteristics of the recording area.
• the wavelength of fluorescent light changes.
• the intensity of light reflected by the recording area or the intensity of fluorescent light emitted from the recording area is reduced. Thereby, information can be recorded in the recording layer 10, specifically in the recording area (step S13).
• FIG. 2B is a flowchart regarding a method for reading information using the optical recording medium 100.
• step S21 the recording layer 10 of the optical recording medium 100 is irradiated with light. Specifically, the recording area on the optical recording medium 100 is irradiated with light.
• the light used in step S21 may be the same as the light used to record information on the optical recording medium 100, or may be different.
• step S22 the optical characteristics of the recording layer 10 are measured. Specifically, the optical characteristics of the recording area are measured. In step S22, for example, the intensity of light reflected by the recording area or the intensity of fluorescent light emitted from the recording area is measured as the optical characteristic of the recording area.
• the optical characteristics of the recording area include the reflectance of light in the recording area, the absorption rate of light in the recording area, the refractive index of light in the recording area, and the wavelength of fluorescent light emitted from the recording area. may be measured.
• step S23 information is read from the recording layer 10, specifically from the recording area.
• the recording area where information is recorded can be found by the following method.
• the optical characteristics of the area irradiated with light are measured. Optical properties include, for example, the intensity of light reflected in the region, the reflectance of light in the region, the absorption rate of light in the region, the refractive index of light in the region, and the fluorescence emitted from the region. Examples include the intensity of the light, the wavelength of the fluorescent light emitted from the region, etc. Based on the measured optical characteristics, it is determined whether the area irradiated with light is a recording area.
• the method for determining whether the area irradiated with light is a recording area is not limited to the above method. For example, it may be determined that the area is a recording area if the intensity of light reflected in the area exceeds a specific value. Alternatively, it may be determined that the area is not a recording area if the intensity of the light reflected in the area is below a specific value. If it is determined that the area is not a recording area, similar operations are performed on other areas of the optical recording medium. This makes it possible to search for a recording area.
• the method of recording and reading information using the optical recording medium 100 can be performed by, for example, a known recording device.
• the recording device includes, for example, a light source that irradiates a recording area on the optical recording medium 100 with light, a measuring device that measures optical characteristics of the recording area, and a controller that controls the light source and the measuring device.
• the organic compound C when the recording layer 10 is irradiated with recording light, the organic compound C absorbs the recording light and changes from the ground state to the transition state. For example, heat is generated when the organic compound C returns from the transition state to the ground state. This heat causes, for example, the binder present in the recording area to change in quality, and recording marks are formed.
• the dielectric layer 20 has pores caused by the porous organic structure. According to the heat insulating effect of the air in the pores, for example, heat generated in the recording layer 10 when a recording operation is performed can be suppressed from being released from the recording layer 10. Since the heat generated in the recording layer 10 is effectively used in the recording layer 10, the recording sensitivity of the optical recording medium 100 is improved.
• the recording sensitivity of the optical recording medium 100 can be evaluated, for example, by the following method. First, recording light is irradiated onto the recording layer 10 of the optical recording medium 100 using a laser. As a result, the shape of the resin included in the recording layer 10 changes near the focal point where the light from the laser is focused. The minimum light irradiation energy required to cause this change is determined and considered as the minimum light irradiation energy necessary for recording. Based on this light irradiation energy, the recording sensitivity of the optical recording medium 100 can be evaluated. Note that the recording sensitivity may be evaluated based on the pulse width that correlates with the light irradiation energy. In the optical recording medium 100 of this embodiment, a recording operation can be performed using recording light with a relatively short pulse width compared to the conventional one.
• FIG. 3 is a graph showing a solid state 13 C-NMR spectrum of an intrinsically microporous polymer.
• the 1 H-NMR spectrum and solid state 13 C-NMR spectrum of the intrinsic microporous polymer were as follows. 1 H NMR (500 MHz, DMSO d6): ⁇ (ppm) 7.26-6.83 (br, m, 4H), 4.84-4.60 (br, s, 2H),4.24 (br, s, 4H), 3.47 (br, s), 1.83 (br, m), 1.42 (br, m, 4H).
• Solid 13 C NMR ⁇ (ppm) 158.6-136.7, 130.0-112.1, 80.8, 67.6, 58.2, 41.8, 39.5-32.3, 25.6- 14.9.
• the nitrogen gas adsorption amount A, specific surface area a, total pore volume v, and average pore diameter d were measured by the above-mentioned method. The results are shown in Table 1.
• a recording layer coating liquid containing a material for the recording layer was prepared. Specifically, 1 g of polyvinylcarbazole (PVK) and 105 mg of coumarin 6 dye were added to 20 mL of dichlorobenzene, and the mixture was heated and stirred at 80° C. for 12 hours to prepare a recording layer coating liquid.
• a dielectric layer coating liquid containing a material for the dielectric layer was prepared. Specifically, 200 mg of the precursor of the intrinsic microporous polymer represented by the above formula (6) and 1 mL of hydrochloric acid with a concentration of 12 mol/L are added to 5 mL of diacetone alcohol, and the mixture is stirred at room temperature for 1 hour. A coating solution for a dielectric layer was prepared. In the dielectric layer coating liquid, an intrinsic microporous polymer represented by formula (4) was synthesized.
• a recording layer coating liquid was applied onto the quartz substrate using a spin coater, and the coating film was dried to produce a recording layer. Furthermore, a dielectric layer coating liquid was applied onto the recording layer using a spin coater, and the coating film was dried to produce a dielectric layer. As a result, the optical recording medium of Example 1 in which the dielectric layer was laminated on the recording layer was obtained. In the optical recording medium of Example 1, the dielectric layer had pores caused by the inherent microporous polymer.
• Example 2 An optical recording medium of Example 2 was obtained by the same method as Example 1, except that 53 mg of the dye 28Ev represented by the above formula (5) was used in place of the coumarin 6 dye.
• Comparative example 1 The optical recording medium of Comparative Example 1 was prepared in the same manner as in Example 1, except that 1 g of cellulose acetate was added to 24 mL of diacetone alcohol and stirred at 80° C. for 12 hours to prepare a dielectric layer coating solution. Obtained. Note that since cellulose acetate does not have a porous structure, the dielectric layer in the optical recording medium of Comparative Example 1 did not have a porous structure. It is disclosed in Thin Solid Films, 2007, Vol. 515, p.3887-3892, for example, that a layer of cellulose acetate can be laminated on a layer containing polyvinylcarbazole.
• Comparative example 2 An optical recording medium of Comparative Example 2 was obtained by the same method as Comparative Example 1, except that 53 mg of the dye 28Ev represented by the above formula (5) was used in place of the coumarin 6 dye.
• the optical recording medium of the example equipped with the dielectric layer containing the intrinsic microporous polymer, which is a porous organic structure had a shorter minimum pulse width required for recording than the comparative example. , recording sensitivity was improved.
• optical recording medium of the present disclosure can be used for applications such as three-dimensional optical memory.

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