WO2024085208A1 - 化合物、重合性組成物、重合体、ホログラム記録媒体、光学材料、並びに光学部品 - Google Patents

化合物、重合性組成物、重合体、ホログラム記録媒体、光学材料、並びに光学部品 Download PDF

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WO2024085208A1
WO2024085208A1 PCT/JP2023/037815 JP2023037815W WO2024085208A1 WO 2024085208 A1 WO2024085208 A1 WO 2024085208A1 JP 2023037815 W JP2023037815 W JP 2023037815W WO 2024085208 A1 WO2024085208 A1 WO 2024085208A1
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ring
formula
compound
group
substituent
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French (fr)
Japanese (ja)
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修治 山下
椋 名倉
晃子 矢部
一真 井上
憲 佐藤
淳 遠田
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Mitsubishi Chemical Corp
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Priority to EP23879851.6A priority Critical patent/EP4606785A4/en
Priority to CN202380071361.2A priority patent/CN119998258A/zh
Priority to JP2024551848A priority patent/JPWO2024085208A1/ja
Publication of WO2024085208A1 publication Critical patent/WO2024085208A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/48—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H2001/026—Recording materials or recording processes
    • G03H2001/0264—Organic recording material
    • 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 a compound that has a high refractive index, high transparency, easy polymerization properties, and excellent chemical stability, as well as excellent solubility in various solvents.
  • the present invention also relates to a holographic recording medium, an optical material, and an optical component that use a polymerizable composition containing the compound or a polymer thereof.
  • glass has been widely used as an optical material.
  • optical lenses even lenses with the same focal length are manufactured using a material with a high refractive index, which allows the lens to be made thinner, with the advantages of being lighter and allowing greater freedom in the design of the optical path.
  • High refractive index optical lenses are also effective in making optical imaging devices more compact, with higher resolution and a wider angle.
  • plastic materials have the advantages of being easier to reduce in weight, easier to improve in mechanical strength, and easier to process and mold.
  • peripheral technologies there is an increasing demand for improved performance of plastic optical materials.
  • materials for optical lenses are required to be easy to polymerize (easy polymerizability), have good curability and solubility in various solvents, and have a high refractive index for the polymerized product.
  • Patent Document 2 and Patent Document 3 describe that a holographic recording medium with high diffraction efficiency and light transmittance can be obtained by using a high refractive index aromatic acrylate compound substituted with a large number of aromatic rings.
  • a high refractive index aromatic acrylate compound substituted with a large number of aromatic rings it is known that there is generally a trade-off between the increase in molecular weight due to the introduction of aromatic substituents and the solubility in various media, and that increasing the number of aromatic substituents significantly reduces the solubility.
  • Even the polymerizable compounds in the examples of Patent Document 2 and Patent Document 3 have insufficient solubility in solvents to exhibit holographic recording performance that is practical.
  • Patent Document 4 describes that the solubility is improved by introducing an alkylene linker into a phenol substituted with many aromatic rings.
  • the examples are limited to disubstituted phenols.
  • Patent Document 5 which relates to an acrylate monomer for holograms having a polyaromatic substituted phenol and an aniline, the total number of carbon atoms in the aromatic substituents that exhibit a high refractive index is limited to 24 or less.
  • Patent Document 6 describes an acrylate compound with a glycerin skeleton that has two benzothiazole rings in one molecule, and its refractive index is 1.63.
  • Patent Document 7 describes a diacrylate monomer having a pentaerythritol skeleton and one or two naphthylthio groups per molecule, but this compound also has a refractive index of 1.62 to 1.65. These materials cannot be said to have a sufficient refractive index for applications requiring an ultra-high refractive index exceeding 1.65.
  • Patent Document 8 and Patent Document 9 describe monomers having a dibenzothiophenethio group and a refractive index exceeding 1.65. Furthermore, Patent Document 10 and Patent Document 11 describe ultra-high refractive index acrylate compounds having a dibenzocarbazole group and a refractive index exceeding 1.7. However, since these compounds contain alkylthio groups or alkylcarbazole groups that are easily oxidized by oxygen, there are concerns that discoloration or color changes may occur when heated in air, stored for a long period of time, or exposed to light, and they cannot be said to be materials with high chemical stability.
  • the objective of the present invention is to provide a compound that is useful as an optical material or optical component and has a high refractive index, high transparency, easy polymerization, chemical stability, high solubility in various solvents, and storage stability of the solution.
  • the present inventors have found that by linking a polymerizable group via a linking group to a high refractive index structure in which three or more aromatic substituents are intentionally introduced into one benzene ring so as to increase the molecular weight, it is possible to overcome the trade-off between the increase in molecular weight due to the introduction of a large number of aromatic substituents and the decrease in solubility in various media.
  • This has resulted in a compound that solves the problems of the present invention, and the polymerizable composition and polymer thereof have a high refractive index, high transparency, easy polymerizability, and chemical stability while also achieving improved solvent solubility.
  • the present inventors have found that by using a compound represented by the following formula (1) or a compound represented by the following formula (2), a high-performance holographic recording medium having high diffraction efficiency can be obtained, and have completed the present invention.
  • the gist of the present invention is as follows:
  • n represents an integer of 1 to 3.
  • L1 represents an (n+1)-valent linking group which may be branched (excluding linear saturated aliphatic hydrocarbon groups).
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-1 represents an aromatic ring group which may have a substituent.
  • m is an integer of 3 to 5, and multiple R 1-1 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-1 's represented by -(R 1-1 )m is 25 to 70.
  • the benzene ring having R 1-1 in the formula may further have a substituent other than R 1-1 .
  • R2 represents a hydrogen atom or a methyl group.
  • n represents an integer of 1 to 3.
  • L represents an (n+1)-valent linear saturated aliphatic hydrocarbon group which may have a substituent.
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-2 represents an aromatic ring group represented by the following formula (2-1).
  • m is an integer of 3 to 5, and multiple R 1-2 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-2 's represented by -(R 1-2 )m is 25 to 70.
  • the benzene ring having R 1-2 in the formula may further have a substituent other than R 1-2 .
  • R2 represents a hydrogen atom or a methyl group.
  • R 3 represents a substituent.
  • R3s When a plurality of R3s are present in formula (2-1), they may be bonded to each other to form a ring fused to the naphthalene ring in formula (2-1), and the fused ring may further have a substituent.
  • p represents 0 or an integer that is the upper limit of the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).
  • * represents a bond to the benzene ring in formula (2).
  • a holographic recording medium comprising the polymerizable composition described in [9].
  • a large-capacity memory including the holographic recording medium described in [10].
  • n represents an integer of 1 to 3.
  • L1 represents an (n+1)-valent linking group which may be branched (excluding linear saturated aliphatic hydrocarbon groups).
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-1 represents an aromatic ring group which may have a substituent.
  • m is an integer of 3 to 5, and multiple R 1-1 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-1 's represented by -(R 1-1 )m is 25 to 70.
  • the benzene ring having R 1-1 in the formula may further have a substituent other than R 1-1 .
  • R2 represents a hydrogen atom or a methyl group.
  • n represents an integer of 1 to 3.
  • L represents an (n+1)-valent linear saturated aliphatic hydrocarbon group which may have a substituent.
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-2 represents an aromatic ring group represented by the following formula (2-1).
  • m is an integer of 3 to 5, and multiple R 1-2 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-2 's represented by -(R 1-2 )m is 25 to 70.
  • the benzene ring having R 1-2 in the formula may further have a substituent other than R 1-2 .
  • R2 represents a hydrogen atom or a methyl group.
  • q represents the number of repetitions of the structure represented by formula (P1-1) or formula (P1-2).
  • R 3 represents a substituent.
  • R3s When a plurality of R3s are present in formula (2-1), they may be bonded to each other to form a ring fused to the naphthalene ring in formula (2-1), and the fused ring may further have a substituent.
  • p represents 0 or an integer that is the upper limit of the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).
  • * represents a bond to the benzene ring in formula (2).
  • a large-capacity memory including the holographic recording medium described in [18].
  • AR glasses including the optical element described in [22].
  • the present invention provides a high refractive index compound that is useful as an optical material and has a high refractive index, high transparency, easy polymerization property, chemical stability, high solubility, and storage stability of the solution.
  • the compound of the present invention is particularly useful as a reactive compound for use in optical lenses, hard coat layers of optical members, and holographic recording media. By using the compound of the present invention, it is possible to realize optical materials and optical components having high diffraction efficiency, high light transmittance, high chemical stability, and excellent processability.
  • FIG. 1 is a schematic diagram showing an outline of the configuration of an apparatus used for holographic recording.
  • (meth)acrylate is a general term for acrylate and methacrylate.
  • (meth)acryloyl group is a general term for acryloyl group and methacryloyl group. The same applies to "(meth)acrylic”.
  • the phrase "optionally having a substituent” means that the group may have one or more substituents.
  • n represents an integer of 1 to 3.
  • L1 represents an (n+1)-valent linking group which may be branched (excluding linear saturated aliphatic hydrocarbon groups).
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-1 represents an aromatic ring group which may have a substituent.
  • m is an integer of 3 to 5, and multiple R 1-1 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-1 's represented by -(R 1-1 )m is 25 to 70.
  • the benzene ring having R 1-1 in the formula may further have a substituent other than R 1-1 .
  • R2 represents a hydrogen atom or a methyl group.
  • a compound according to another embodiment of the present invention is represented by the following formula (2).
  • the compound represented by the following formula (2) may be referred to as "compound (2).”
  • n represents an integer of 1 to 3.
  • L represents an (n+1)-valent linear saturated aliphatic hydrocarbon group which may have a substituent.
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • R 1-2 represents an aromatic ring group represented by the following formula (2-1).
  • m is an integer of 3 to 5, and multiple R 1-2 may be the same or different. However, in the formula, the total number of carbon atoms constituting the multiple R 1-2 's represented by -(R 1-2 )m is 25 to 70.
  • the benzene ring having R 1-2 in the formula may further have a substituent other than R 1-2 .
  • R2 represents a hydrogen atom or a methyl group.
  • R 3 represents a substituent.
  • R3s When a plurality of R3s are present in formula (2-1), they may be bonded to each other to form a ring fused to the naphthalene ring in formula (2-1), and the fused ring may further have a substituent.
  • p represents 0 or an integer that is the upper limit of the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).
  • * represents a bond to the benzene ring in formula (2).
  • the compound of the present invention is characterized in that it has a structure in which a polymerizable group is bonded via a specific linking group L1 or L to a high molecular weight phenol compound or aniline compound having three or more aromatic ring groups (aromatic substituents) and a total of 25 to 70 carbon atoms in the three or more aromatic ring groups.
  • organic compounds with aromatic ring groups are sometimes used to improve the refractive index.
  • organic compounds with highly planar aromatic ring groups generally have poor solubility in various solvents, making them difficult to use as high-concentration solutions to achieve a high refractive index. Even if a high-concentration solution can be prepared, the organic compounds tend to precipitate out of the storage solution over time due to their high crystallinity.
  • aromatic organic compounds used in optical materials with a refractive index of more than 1.65 have multiple aromatic rings as substituents, and as their molecular weight increases, their solubility in various solvents tends to decrease.
  • one phenol skeleton or aniline skeleton has many aromatic ring groups densely packed together, which generates molecular twist between each substituent, and can reduce the crystallinity of the compound of the present invention.
  • the more aromatic ring groups R 1-1 or R 1-2 with a high refractive index are substituted, the higher the refractive index of the compound of the present invention becomes and the larger the molecular weight becomes.
  • the symmetry and planarity of the entire molecule also tend to be low, and high solubility in solvents can be achieved.
  • the flexibility of the compound of the present invention can be significantly improved while exhibiting high polymerizability as a (meth)acrylate monomer, and the refractive index of the polymer can be increased and the chemical stability can be improved.
  • L 1 represents an optionally branched (n+1)-valent linking group other than the chain saturated aliphatic hydrocarbon group represented by L in formula (2) described below.
  • L 1 may have an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.
  • an unsaturated aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group which may have a substituent is preferred from the viewpoint of ease of synthesis and availability.
  • the number of carbon atoms of the unsaturated aliphatic hydrocarbon group or the cyclic aliphatic hydrocarbon group is preferably 1 to 8.
  • L 1 is preferably a (n+1)-valent linking group having an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.
  • These linking groups may have a substituent, and the number of carbon atoms (not including the number of carbon atoms of the substituent) is preferably 1 to 8. If the number of carbon atoms of the (n+1)-valent linking group is 8 or less, the refractive index of the compound (1) is unlikely to decrease, and the viscosity is decreased due to the small molecular weight, and the processability tends to improve.
  • the (n+1)-valent linking group constituting L 1 may be either a cyclic linking group or a chain linking group, or these structures may be combined. From the viewpoint of alleviating steric hindrance around the polymerizable (meth)acrylate, a chain linking group is preferable.
  • L1 may be a combination of two or more of these groups.
  • L1 may be -( CH2 ) 2C ( CH3 )-, -(CH2) 2C ( CH3 )(CO)- , -( CH2 ) 2C ( CH2CH3 )(CO)-, -( CH2 ) 3C ( CO ) - , -( CH2 ) 2C ( CH3 )NH(CO)-, or a linking group in which any hydrogen atom in the chain linking group is replaced with a bond to a polymerizable group.
  • the linking to the polymerizable group may be made by a branched structure.
  • L 1 preferably contains a cyclic group, and the ring contained in the cyclic group constituting L 1 may be a monocyclic structure or a condensed ring structure.
  • the number of rings contained in L 1 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.
  • the ring contained in L 1 does not necessarily need to be aromatic, but is preferably an aromatic hydrocarbon ring in order to maintain a high refractive index while keeping the size of the ring in the entire molecule small.
  • Examples of the aromatic hydrocarbon ring constituting L 1 include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.
  • the linking group L 1 may have a substituent.
  • substituents that L 1 may have include a halogen atom (chlorine atom, bromine atom, iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a
  • R 1-1 represents an aromatic ring group which may have a substituent.
  • the aromatic ring group is roughly classified into an aromatic hydrocarbon ring and an aromatic heterocycle.
  • Aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a biphenylene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • Aromatic heterocycles include aromatic heterocycles containing one heteroatom, such as a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a naphthothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, a pyrrole ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, etc.; aromatic heterocycles containing two or more heteroatoms, such as an imid
  • rings include a ring in which two or three rings are condensed, including an aromatic heterocycle containing two or more heteroatoms, such as a zolooxazole ring, an oxazolooxazole ring, an oxazoloimidazole ring, an oxazolopyridine ring, an oxazolopyridazine ring, an oxazolopyrimidine ring, an oxazolopyrazine ring, a naphthoxazole ring, a quinolinoxazole ring, a dioxazolopyrazine ring, a phenoxazine ring, a benzothiazole ring, a furothiazole ring, a thienothiazole ring, a thiazolothiazole ring, a thiazoloimidazole ring, a thienothiadiazole ring, a thiazolothiadia
  • the aromatic hydrocarbon ring constituting R 1-1 is preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a biphenylene ring, or a fluorene ring.
  • the aromatic hydrocarbon ring constituting R 1 is more preferably a benzene ring, a naphthalene ring, a phenanthrene ring, a biphenylene ring, or a fluorene ring.
  • the aromatic hydrocarbon ring constituting R 1-1 is further preferably a 1-naphthalene ring, a 9-phenanthrene ring, or a 9-anthracene ring.
  • a sulfur-containing aromatic heterocycle is preferred since it tends to increase the refractive index of compound (1).
  • the sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle.
  • the heteroatom may have an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom.
  • the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.
  • Sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, a thiopyran ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; aromatic heterocycles containing two or more sulfur atoms, such as a thianthrene ring; aromatic heterocycles containing two or more heteroatoms, such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazoloimidazole ring, a thiazolopyr
  • the sulfur-containing aromatic heterocycle may be a single ring or a fused ring. From the viewpoint of increasing the refractive index, a fused ring is preferred.
  • the number of rings constituting the fused ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, from the viewpoint of facilitating the acquisition of raw materials and synthesis.
  • the sulfur-containing aromatic heterocycle is preferably a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, or a thianthrene ring.
  • the aromatic heterocycle constituting R 1-1 may be a nitrogen-containing aromatic heterocycle from the viewpoint of ease of synthesis.
  • the nitrogen-containing aromatic heterocycle has at least a nitrogen atom as a heteroatom constituting the aromatic heterocycle.
  • the heteroatom may have an oxygen atom, a sulfur atom, or an oxygen atom and a sulfur atom.
  • the number of heteroatoms constituting the nitrogen-containing aromatic heterocycle is preferably 1 to 3, and more preferably 1 to 2.
  • Nitrogen-containing aromatic heterocycles include aromatic heterocycles containing one nitrogen atom, such as a pyrrole ring, an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a phenoxazine ring, a phenothiazine ring, a thienoxazole ring, a thiazolooxazole ring, an oxazolooxazole ring, a furothiazole ring, a thienothiazole ring, and a thiazolothiazole ring
  • aromatic heterocycles containing two or more nitrogen atoms include a tetrazole ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiadiazole ring, a benzimidazole ring, an oxazoloimidazole ring, an oxazolopyridine ring, an oxazolopyridazine ring, an oxazolopyrimidine ring, an oxazolopyrazine ring, a quinolinoxazole ring, a dioxazolopyrazine ring, a thiazoloimidazole ring, a thienothiadiazole ring, a thiazolothiadiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring,
  • the nitrogen-containing aromatic heterocycle may be a single ring or a condensed ring.
  • a condensed ring is preferred.
  • the number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5 in terms of facilitating raw material availability and synthesis.
  • the nitrogen-containing aromatic heterocycle is preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring, and more preferably a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a thiadiazole ring.
  • the aromatic heterocycle constituting R 1-1 may be an oxygen-containing aromatic heterocycle.
  • the oxygen-containing aromatic heterocycle tends to improve the heat resistance and weather resistance of the polymer made from compound (1).
  • the oxygen-containing aromatic heterocycle has at least an oxygen atom as a heteroatom constituting the aromatic heterocycle.
  • the heteroatom may have a nitrogen atom, a sulfur atom, or a nitrogen atom and a sulfur atom. From the viewpoint of ensuring heat resistance, the number of oxygen atoms constituting the oxygen-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.
  • oxygen-containing aromatic heterocycles include aromatic heterocycles containing one oxygen atom, such as a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, a phenoxazine ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, a naphthoxazole ring, a thienoxazole ring, a thiazolooxazole ring, an oxazoloimidazole ring, and a furothiazole ring; and aromatic heterocycles containing two or more oxygen atoms, such as a dibenzodioxine ring, an oxazolooxazole ring, and a dioxazolopy
  • the oxygen-containing aromatic heterocycle may be a single ring or a condensed ring. From the viewpoint of increasing the refractive index, a condensed ring is preferred.
  • the number of rings constituting the condensed ring is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 5, from the viewpoint of facilitating the acquisition of raw materials and synthesis.
  • the oxygen-containing aromatic heterocycle is preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, an oxazole ring, an isoxazole ring, a benzoxazole ring, a benzisoxazole ring, or a naphthoxazole ring, and more preferably a dibenzofuran ring, a benzonaphthofuran ring, a dinaphthofuran ring, or a benzoxazole ring.
  • the aromatic rings constituting these R 1-1 may have a substituent.
  • substituents include a halogen atom such as chlorine, bromine, or iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a dialkylaminoethyl group formed by bonding alkyl groups having 1 to 4 carbon atoms,
  • an alkyl group having 1 to 8 carbon atoms preferred are an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a nitro group.
  • the aromatic rings constituting R 1-1 further have a group containing an aromatic ring as a substituent.
  • the aromatic ring contained in the substituent has the same meaning as the aromatic ring constituting R 1-1 .
  • the aromatic rings contained in these substituents may be directly bonded to the aromatic ring constituting R 1-1 at any position, may be bonded via an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent, or may be bonded via an arbitrary linking group. It is more preferable that the substituent is directly bonded to the aromatic ring constituting R 1-1 .
  • the refractive index of compound (1) tends to be higher.
  • the definition of the sulfur-containing aromatic heterocycle is the same as in R 1-1 .
  • a fused ring is more preferable, and in particular, a benzothiazole ring, a dibenzothiophene ring, a benzothiophene ring, a benzonaphthothiophene ring, a dinaphthothiophene ring, and a thianthrene ring are preferable.
  • the number of aromatic rings that R 1-1 has as a substituent is not particularly limited, but from the viewpoints of ease of synthesis and solubility, 1 to 4 is preferred, and 1 or 2 is more preferred.
  • the aromatic ring constituting R 1-1 is preferably a fused aromatic ring which may have a substituent, or a monocyclic aromatic ring substituted with an aromatic ring group, and more preferably a fused aromatic heterocycle which may have a substituent, or an aromatic hydrocarbon ring having an aromatic heterocycle as a substituent.
  • the aromatic ring constituting R 1-1 may have two or more selected from the above-mentioned aromatic hydrocarbon rings, sulfur-containing aromatic heterocycles, nitrogen-containing aromatic heterocycles, and oxygen-containing aromatic heterocycles.
  • a plurality of R 1-1 exists because m is 3 to 5, and the plurality of R 1-1 may be the same or different.
  • the total number of carbon atoms constituting the 3 to 5 R 1-1 groups present in formula (1) is 25 to 70. If the total number of carbon atoms is 25 or more, the refractive index of compound (1) can be expected to be high. On the other hand, if the total number of carbon atoms is 70 or less, compound (1) can be easily synthesized. From the above viewpoints, the total number of carbon atoms in the m R 1-1 groups in formula (1) is preferably 25 to 64, and more preferably 30 to 56.
  • m represents an integer of 3 to 5. This m can be appropriately selected.
  • R 1-1 is preferably bonded to the ortho-position and para-position with respect to the bonding position of X on the benzene ring.
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • X is preferably an oxygen atom.
  • the intermediate compound in synthesizing compound (1) tends to have excellent chemical stability, is less likely to be oxidized, and coloration is easily avoided, which is preferable.
  • X is preferably a nitrogen atom which may have a substituent.
  • X is a nitrogen atom having no substituent, it is possible to form multipoint hydrogen bonds with various solvents and holographic recording media, and it is more preferable since it is expected to provide a low haze material with little turbidity.
  • R 2 represents a hydrogen atom or a methyl group. This R 2 can be appropriately selected.
  • R 2 is preferably a hydrogen atom.
  • R 2 is preferably a methyl group.
  • n represents an integer of 1 to 3. This n can be appropriately selected. For example, n can be set to 2 or 3 from the viewpoint of making compound (1) easily polymerizable.
  • n 2 or 3
  • the benzene ring in formula (1) may have a substituent other than R 1-1 .
  • substituents that the benzene ring may have include a halogen atom such as fluorine, chlorine, bromine, or iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, an alkoxyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group,
  • the benzene ring has no substituent other than R 1-1 .
  • the benzene ring preferably has, as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, or a nitro group.
  • compound (1) preferably has a molecular weight of 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less. From the viewpoint of reducing the shrinkage rate during polymerization, compound (1) preferably has a molecular weight of 500 or more, more preferably 600 or more, and even more preferably 650 or more.
  • Compound (1) can appropriately introduce a molecular twist in which the dihedral angle of the linking site with the central benzene ring is 1 degree or more into the monomer and polymer by bonding three or more highly planar aromatic ring groups to the benzene ring of one phenol compound or aniline compound.
  • the aromatic ring group R 1-1 is an aromatic ring group having a substituent or ring structure at the ortho position of the linking site with the central benzene skeleton, such as a 1-naphthyl group, a 9-phenanthrenyl group, a 1-thianthrenyl group, a 4-dibenzofuranyl group, or a 4-dibenzothiophenyl group
  • the dihedral angle tends to be larger. This allows high solubility in various media to be achieved while suppressing aggregation of the high refractive index structure, and can be used as a polymerizable monomer having an ultra-high refractive index.
  • R 1-1 is a 1-naphthyl group, a 9-phenanthrenyl group, or a 9-anthracenyl group
  • R 1-1 has a hydrogen atom at the peri-position of the linking site to the benzene ring that is the central skeleton, and therefore forms a mixture of multiple atropisomers, and has high solubility both as a monomer and as a polymer, which is more preferable.
  • the above molecular twisting has the effect of suppressing excessive conjugation extension between the substituent R 1-1 and the central benzene skeleton, and suppressing the increase in the absorption wavelength of the compound (1), which can realize, for example, a colorless and transparent optical material in the visible light region and improve the stability of the compound against heating, light irradiation, oxidation, etc.
  • it is very important to improve the electron density per volume in the monomer and polymer, that is, to shorten the intermolecular distance in order to improve the refractive index.
  • the intermolecular distance may be shortened compared to a derivative without a linker due to molecular interactions such as van der Waals forces and hydrogen bonds. This can be expected to further increase the refractive index of the same high refractive index structure.
  • L is a chain-like saturated aliphatic hydrocarbon group which may have a substituent, from the viewpoints of ease of synthesis and availability.
  • the number of carbon atoms in the chain-like saturated aliphatic hydrocarbon group (not including the number of carbon atoms in the substituent) is preferably 1 to 8. If the number of carbon atoms in the chain-like saturated aliphatic hydrocarbon group is 8 or less, the refractive index of compound (2) is unlikely to decrease, and the viscosity is decreased due to the small molecular weight, which tends to improve processability.
  • the linear saturated aliphatic hydrocarbon group constituting L may be an alkylene group having 1 to 8 carbon atoms.
  • L may be a combination of two or more alkylene groups having 1 to 8 carbon atoms.
  • the linking group L may have a substituent.
  • substituent that L may have include a halogen atom (chlorine atom, bromine atom, iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyeth
  • R 1-2 represents an aromatic ring group represented by the following formula (2-1).
  • R 3 represents a substituent.
  • R3s When a plurality of R3s are present in formula (2-1), they may be bonded to each other to form a ring fused to the naphthalene ring in formula (2-1), and the fused ring may further have a substituent.
  • p represents 0 or an integer that is the upper limit of the maximum number of substitutions that can be made on the naphthalene ring represented by formula (2-1).
  • * represents a bond to the benzene ring in formula (2).
  • R 1-2 is preferably a 1-naphthalenyl group which may have a substituent , or may be a group represented by the following formula (2-1-1):
  • the structure represented by the above formula (2-1-1) is one in which adjacent R 3s in formula (2-1) are bonded to each other and condensed to the naphthalene ring in formula (2-1) to form a ring.
  • R 1-2 is a 9-phenanthrenyl group. From the viewpoints of availability and maintaining good solubility, R 1-2 is preferably a 1-naphthyl group or a 9-phenanthrenyl group. These may further have a substituent. In this case, examples of the substituent include those described below as the substituents that the benzene ring in formula (2) may have in addition to R 1-2 .
  • R 3 in formula (2-1) examples include those exemplified as R 1-1 in formula (1) or the substituent that R 1-1 may have. Of these, R3 is preferably a naphthyl group or a phenyl group, and more preferably a phenyl group. It is also preferred that R3 is absent, that is, the group represented by formula (2-1) is a 1-naphthyl group. When the compound (2) has a group represented by the formula (2-1), it is possible to provide a colorless and transparent material.
  • a plurality of R 1-2 exist because m is 3 to 5, and the plurality of R 1-2 may be the same or different.
  • the total number of carbon atoms constituting the 3 to 5 R 1-2 groups in formula (2) is 25 to 70. If the total number of carbon atoms is 25 or more, the refractive index of compound (2) can be expected to be high. On the other hand, if the total number of carbon atoms is 70 or less, compound (2) can be easily synthesized. From the above viewpoints, the total number of carbon atoms in m R 1-2 groups in formula (2) is preferably 25 to 64, and more preferably 30 to 56.
  • m represents an integer of 3 to 5. This m can be appropriately selected.
  • R 1-2 are preferably bonded to the ortho and para positions relative to the bonding position of X on the benzene ring.
  • X represents an oxygen atom or a nitrogen atom which may have a substituent.
  • X in formula (2) has the same definition as X in formula (1), and the preferred embodiments are also the same.
  • X is preferably an oxygen atom.
  • the intermediate compound in synthesizing compound (2) tends to have excellent chemical stability, is less likely to be oxidized, and coloration can be easily avoided, which is preferable.
  • X is preferably a nitrogen atom which may have a substituent.
  • X is a nitrogen atom having no substituent, it is possible to form multipoint hydrogen bonds with various solvents and holographic recording media, and it is more preferable since it is expected to provide a low haze material with little turbidity.
  • R 2 represents a hydrogen atom or a methyl group. This R 2 can be appropriately selected.
  • R 2 is preferably a hydrogen atom.
  • R 2 is preferably a methyl group.
  • n represents an integer of 1 to 3. This n can be appropriately selected. For example, n can be set to 2 or 3 from the viewpoint of making the compound (2) easily polymerizable.
  • n 2 or 3
  • Substituents other than R 1-2 on the benzene ring in formula (2) may have a substituent other than R 1-2 .
  • Examples of the substituent that the benzene ring may have include those described above as the substituent that the benzene ring in formula (1) may have.
  • the benzene ring has no substituents other than R 1-2 .
  • the benzene ring preferably has, as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an aromatic ring thio group having 6 to 10 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, or a nitro group.
  • the compound (2) preferably has a molecular weight of 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less. From the viewpoint of reducing the shrinkage rate during polymerization, the compound (2) preferably has a molecular weight of 500 or more, more preferably 600 or more, and even more preferably 650 or more.
  • Compound (2) can appropriately introduce a molecular twist in which the dihedral angle at the linking site with the benzene ring, which is the central skeleton, is 1 degree or more by bonding three or more highly planar aromatic ring groups to the benzene ring of one phenol compound or aniline compound, into the monomer and polymer.
  • the condensed ring group R 1-2 such as naphthylene group is a group having a substituent or a ring structure at the ortho position of the linking site with the central benzene skeleton, as typified by 1-naphthyl group and 9-phenanthrenyl group, the dihedral angle tends to be larger.
  • R 1-2 is a 1-naphthyl group, a 9-phenanthrenyl group, or a 9-anthracenyl group
  • a hydrogen atom is present at the peri position of the linking site with the benzene ring, which is the central skeleton, and thus the compound becomes a mixture of multiple atropisomers, which is more preferable because it has high solubility both as a monomer and as a polymer.
  • the above molecular twisting has the effect of suppressing excessive conjugation extension between the substituent R 1-2 and the central benzene skeleton, and suppressing the absorption wavelength of the compound (2) from becoming longer, which makes it possible to realize, for example, a colorless and transparent optical material in the visible light region and to improve the stability of the compound against heating, light irradiation, oxidation, etc.
  • the intermolecular distance may be shortened compared to a derivative without a linker due to molecular interactions such as van der Waals forces and hydrogen bonds. This can be expected to further increase the refractive index of the same high refractive index structure.
  • Compound (1) can be synthesized by combining various known methods. For example, it can be synthesized by reacting a compound represented by the following formula (3) (hereinafter, sometimes referred to as "compound (3)") with a carbonylating reagent such as an isocyanate having a polymerizable group.
  • a carbonylating reagent such as an isocyanate having a polymerizable group.
  • X, R 1 , R 2 , L 1 , m, and n are the same as those in the above formula (1).
  • Y 1 , Y 2 , and Y 3 represent a leaving group such as a halogen atom, a sulfonic acid group such as a methanesulfonic acid group, a tosylic acid group, or a trifluoromethanesulfonic acid group, a carboxyl group, a dimethylpyrazolyl group, or a 1-methylpropylideneaminooxy group.
  • the same symbols represent the same things.
  • compound (1) can be produced by reacting the hydroxyl or amino group, which is -XH, of compound (3) with an alkylating reagent compound having a polymerizable group represented by formula (i) (hereinafter, sometimes referred to as alkylating reagent (i)).
  • compound (1) can also be produced using a carbonylating reagent, such as an isocyanate represented by formula (ii) (hereinafter, sometimes referred to as carbonylating reagent (ii)).
  • alkylating reagents (i) examples include 2-methanesulfonylethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,3-dibromopropyl acrylate.
  • Examples of the carbonylation reagent (ii) include isocyanates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate, as well as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate.
  • isocyanates such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate, as well as
  • compound (1) can also be produced by subjecting a compound represented by formula (4) (hereinafter sometimes referred to as "compound (4)"), which is obtained by reacting compound (3) with a compound having a linking group represented by formula (iii) or formula (iv), to a polymerizable group-forming reaction with a (meth)acryloylating reagent represented by formula (v).
  • compound (4) a compound represented by formula (4) (hereinafter sometimes referred to as "compound (4)”), which is obtained by reacting compound (3) with a compound having a linking group represented by formula (iii) or formula (iv), to a polymerizable group-forming reaction with a (meth)acryloylating reagent represented by formula (v).
  • reaction of the active hydrogen of the hydroxyl group or amino group in formula (3) with the reagents represented by (i) to (iv) above, and the reaction of compound (4) with the reagent represented by formula (v) can be carried out by applying known methods.
  • compound (1) can be obtained by reacting compound (3) with isocyanates in the presence of a basic compound.
  • the basic compound may be one or more organic basic compounds (triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.), one or more inorganic basic compounds (sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.), or a combination of one or more organic basic compounds and one or more inorganic basic compounds.
  • organic basic compounds triethylamine, diisopropylethylamine, 1,1,3,3-tetramethylguanidine, diazabicycloundecene, diazabicyclononene, pyridine, imidazole, etc.
  • inorganic basic compounds sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, potassium tert-butoxide, etc.
  • organic solvents include dichloromethane, tetrahydrofuran (THF), dimethoxyethane, toluene, and N,N-dimethylformamide (DMF).
  • THF tetrahydrofuran
  • DMF N,N-dimethylformamide
  • One type of organic solvent may be used, or two or more types may be used in combination.
  • reaction product obtained in the synthesis reaction.
  • purifying and removing impurities low coloration can be achieved.
  • known techniques can be applied. For example, purification can be performed by extraction, column chromatography, recrystallization, distillation, etc. These purification methods may be performed alone or in combination.
  • compound (1) is a solid at room temperature, it is preferable to use a recrystallization method, since this makes it easier to remove colored substances.
  • recrystallization solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, t-butyl methyl ether, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; nitriles such as
  • Compound (3) which is the raw material compound used to produce compound (1), can be produced by the following reaction.
  • X, R 1-1 and m are as defined in the above formula (1).
  • Y 4 represents a leaving group such as a halogen atom or a trifluoromethanesulfonic acid group.
  • R 1-1 -M 1 represents an organometallic reagent capable of reacting with Y 4 to form a carbon-carbon bond, such as an organolithium reagent, an organomagnesium reagent, an organocerium reagent, an organosilicon reagent, an organoboron reagent or an organotin reagent.
  • compound (3) can be synthesized by simultaneously or sequentially linking a plurality of aromatic ring groups R1 through a linking reaction between an aromatic halide represented by formula (5) and an organic reagent represented by formula (vi).
  • compound (3) can be synthesized by directly utilizing the carbon-hydrogen bond in the aromatic hydrocarbon ring represented by formula (vii) and carrying out a cross-coupling reaction.
  • Compound (2) can be produced in the same manner as in the production of compound (1), except that the aromatic ring group R 1-1 in the production of compound (1) is changed to an aromatic ring group R 1-2 , and the linking group L 1 is changed to a linear saturated aliphatic hydrocarbon group L.
  • the polymerizable composition of the present invention contains the compound of the present invention, that is, compound (1) or compound (2), and a polymerization initiator.
  • the (meth)acrylate group of the compound of the present invention undergoes a polymerization reaction by the polymerization initiator, thereby giving a polymer of the present invention containing a structure represented by formula (P1-1) or the following formula (P1-2).
  • n, L 1 , X, R 1-1 , m and R 2 are each defined as the same as n, L 1 , X, R 1-1 , m and R 2 in formula (1).
  • n, L, X, R 1-2 , m and R 2 have the same meanings as n, L, X, R 1-2 , m and R 2 in formula (2).
  • q represents the number of repetitions of the structure represented by formula (P1-1) or formula (P1-2).
  • polymerization initiator is not particularly limited, and may be appropriately selected from known polymerization initiators depending on the polymerization method.
  • the polymerization method is not limited, and any known method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or partial polymerization can be used.
  • polymerization initiator contained in the polymerizable composition of the present invention examples include a radical polymerization initiator, a redox-based polymerization initiator, and an anionic polymerization initiator.
  • radical polymerization initiator examples include those generally called polymerization catalysts.
  • redox-based polymerization initiator examples include those generally called polymerization catalysts.
  • anionic polymerization initiator examples include those generally called polymerization catalysts.
  • the photopolymerization initiator that aids in the polymerization of the polymerizable composition of the present invention can be any known photoradical polymerization initiator.
  • photopolymerization initiators include benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone ⁇ , benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-mo 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl)-
  • photopolymerization initiators may be used alone, or two or more may be used in any combination and ratio.
  • the content of the photopolymerization initiator in the polymerizable composition of the present invention is usually 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more, when the total of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass.
  • the upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If the content of the photopolymerization initiator is too high, the polymerization may proceed too rapidly, which may not only increase the birefringence of the cured body but also deteriorate the hue. On the other hand, if the content is too low, the polymerizable composition may not polymerize sufficiently.
  • thermal polymerization initiator that assists the polymerization of the polymerizable composition of the present invention
  • any known thermal radical polymerization initiator can be used.
  • organic peroxides and azo compounds can be mentioned. Among them, organic peroxides are preferred from the viewpoint that bubbles are unlikely to be generated in the polymer obtained by the polymerization reaction.
  • organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl peroxide, di-t-butyl peroxide, and the like.
  • ketone peroxides such as methyl ethyl ketone peroxide
  • peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohe
  • dialkyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutyl-2-ethylhexanoate.
  • peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate
  • peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl mono
  • azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride.
  • thermal polymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.
  • the content of the thermal polymerization initiator in the polymerizable composition of the present invention is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more, when the total of all radically polymerizable compounds in the polymerizable composition is 100 parts by mass.
  • the upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less. If the content of the thermal polymerization initiator is too high, the polymerization may proceed too rapidly, which may not only impair the optical uniformity of the obtained polymer but also deteriorate the hue. On the other hand, if the content is too low, the thermal polymerization may not proceed sufficiently.
  • the mass ratio is usually 100:1 to 1:100 (photopolymerization initiator: thermal polymerization initiator, the same applies hereinafter in this paragraph), and preferably 10:1 to 1:10. If there is too little thermal polymerization initiator, polymerization may be insufficient, and if there is too much, there is a risk of discoloration.
  • Redox Polymerization Initiators are radical initiators that utilize a redox reaction by combining a peroxide and a reducing agent, and can generate radicals even at low temperatures. They are usually used in emulsion polymerization, etc.
  • the redox polymerization initiator include a combination of dibenzoyl peroxide as a peroxide and aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine as a reducing agent; a combination of a hydroperoxide as a peroxide and a metal soap as a reducing agent; and a combination of a hydroperoxide as a peroxide and a thiourea as a reducing agent.
  • Water-soluble redox polymerization initiators use peroxides such as persulfates, hydrogen peroxide, and hydroperoxides in combination with water-soluble inorganic reducing agents (such as Fe2 + and NaHSO3 ) or organic reducing agents (such as alcohols and polyamines).
  • peroxides such as persulfates, hydrogen peroxide, and hydroperoxides in combination with water-soluble inorganic reducing agents (such as Fe2 + and NaHSO3 ) or organic reducing agents (such as alcohols and polyamines).
  • the preferred range for the content of the redox polymerization initiator in the polymerizable composition of the present invention is the same as that for the thermal polymerization initiator.
  • the polymerizable compound contained in the polymerizable composition of the present invention may contain any one of the compounds of the present invention alone, or may contain two or more of them in any combination and ratio. That is, the polymerizable composition of the present invention may contain one type of compound (1) alone, or may contain two or more of them in any combination and ratio. In addition, the polymerizable composition of the present invention may contain one type of compound (2) alone, or may contain two or more of them in any combination and ratio. Furthermore, the polymerizable composition of the present invention may contain one or more types of compound (1) and one or more types of compound (2).
  • the polymerizable composition of the present invention may contain polymerizable compounds other than the compound of the present invention.
  • the content of the compound of the present invention in the polymerizable composition of the present invention is preferably 1% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 95% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of the compound of the present invention is less than 1% by mass, the effect of using the compound of the present invention is not fully exerted, while if it exceeds 99% by mass, the curability tends to decrease.
  • polymerizable compounds other than the compounds of the present invention include anionic polymerizable monomers and radical polymerizable monomers. Any one of these polymerizable compounds may be used alone, or two or more may be used in any combination and ratio. Polymerizable compounds having two or more polymerizable functional groups in one molecule (sometimes called polyfunctional monomers) can also be used. When a polyfunctional monomer is used, a crosslinked structure is formed inside the polymer, which can improve thermal stability, weather resistance, solvent resistance, etc.
  • the content of the other polymerizable compound is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 5% by mass or less, based on 100% by mass of the total solid content of the polymerizable composition of the present invention. If the content of the other polymerizable compound is less than 0.1% by mass, the effect of imparting characteristics by adding the other polymerizable compound is not fully exerted, while if it exceeds 5% by mass, problems such as impaired optical properties and strength tend to occur.
  • anionically polymerizable monomers examples include hydrocarbon monomers and polar monomers.
  • hydrocarbon monomers examples include styrene, ⁇ -methylstyrene, butadiene, isoprene, vinylpyridine, vinylanthracene, and derivatives thereof.
  • polar monomers examples include methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc.); acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, etc.); vinyl ketones (e.g., methyl vinyl ketone, isopropyl vinyl ketone, cyclohexyl vinyl ketone, phenyl vinyl ketone, etc.); isopropenyl ketones (e.g., methyl isopropenyl ketone, phenyl isopropenyl ketone, etc.); and other polar monomers (e.g., acrylonitrile, acrylamide, nitroethylene, methylene malonic acid esters, cyanoacrylic acid esters, vinylidene cyanide, etc.).
  • methacrylic acid esters e.g., methyl methacrylate, ethyl meth
  • Any one of these anionically polymerizable monomers may be used alone, or two or more of them may be used in any combination and ratio.
  • the radical polymerizable monomer is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include (meth)acrylic acid esters, (meth)acrylamides, vinyl esters, and styrenes.
  • Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, (n- or i-)propyl (meth)acrylate, (n-, i-, sec- or t-)butyl (meth)acrylate, amyl (meth)acrylate, adamantyl (meth)acrylate, chloroethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, trime Tyrolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, hydroxybenzyl (meth)acrylate,
  • Examples of (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-butyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-tolyl(meth)acrylamide, N-(hydroxyphenyl)(meth)acrylamide, N-(sulfamoylphenyl)(meth)acrylamide, N-(phenylsulfonyl)(meth)acrylamide, N-(tolylsulfonyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.
  • vinyl esters examples include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, vinyl t-butylbenzoate, vinyl chlorobenzoate, vinyl 4-ethoxybenzoate, vinyl 4-ethylbenzoate, vinyl 4-methylbenzoate, vinyl 3-methylbenzoate, vinyl 2-methylbenzoate, vinyl 4-phenylbenzoate, and vinyl pivalate.
  • styrenes examples include styrene, p-acetylstyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-sec-butylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dichlorostyrene, 2,4-diisopropylstyrene, dimethylstyrene, p-ethoxystyrene, 2-ethylstyrene, 2-methoxystyrene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, p-methylstyrene, p-phenoxystyrene, p-phenylstyrene, and divinylbenzene.
  • Any of these radically polymerizable monomers may be used alone, or two or more of them may be used in any combination and ratio.
  • any of the anionically polymerizable monomers and radically polymerizable monomers exemplified above may be used, and two or more of them may be used in combination.
  • a radical polymerizable monomer as the other polymerizable compound to be used in combination with compound (1).
  • Other components include, for example, various additives such as solvents, antioxidants, plasticizers, UV absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any organic or inorganic fillers, diffusing agents, pigments, and wavelength conversion materials such as phosphors.
  • additives such as solvents, antioxidants, plasticizers, UV absorbers, sensitizers, chain transfer agents, defoamers, polymerization inhibitors, any organic or inorganic fillers, diffusing agents, pigments, and wavelength conversion materials such as phosphors.
  • the polymerizable composition of the present invention may contain a solvent to adjust the viscosity.
  • solvents depending on the physical properties of the polymerizable composition, include, for example, alcohols such as ethanol, propanol, isopropanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as hexane, pentane, and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; chain ethers such as dimethyl ether and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ket
  • solvents can be used alone or in combination.
  • water can also be used.
  • a solvent or dispersion medium
  • the amount thereof is not particularly limited, and may be adjusted to provide a polymerizable composition with a suitable viscosity depending on the polymerization method, processing method, and application.
  • an antioxidant and/or a light stabilizer as additives into the polymerizable composition.
  • antioxidants include phenolic antioxidants such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; and triphenyl phosphite, trisisodecyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl Phosphi
  • a preferred combination of a phenol-based antioxidant and a phosphorus-based antioxidant is a combination of at least one selected from tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane and n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate as the phenol-based antioxidant and tris(2,4-di-t-butylphenyl)phosphite as the phosphorus-based antioxidant.
  • the amount of antioxidant in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of the polymerizable composition, in order to improve the heat yellowing resistance of the resulting polymer.
  • HALS hindered amine light stabilizer
  • Specific examples of HALS include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl)carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and Adekastab L.
  • A-68 (manufactured by ADEKA CORPORATION), Adeka STAB LA-63P (manufactured by ADEKA CORPORATION), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF), etc. These can be used alone or in combination of two or more kinds.
  • the amount of the light stabilizer in the polymerizable composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of the polymerizable composition, in order to improve the heat yellowing resistance and weather resistance of the resulting polymer.
  • Antioxidants and light stabilizers can be used alone or in combination of two or more.
  • the polymerizable composition of the present invention may be produced by mixing the respective components, or by premixing the components other than the polymerization initiator and adding the polymerization initiator immediately before the polymerization reaction.
  • the polymerization method of the polymerizable composition of the present invention is not particularly limited, but includes a method of polymerization by irradiation with active energy rays and a method of polymerization by heating.
  • the active energy rays used are preferably electron beams or light in the wavelength range from ultraviolet to infrared.
  • the light source for example, if the active energy rays are ultraviolet rays, an ultra-high pressure mercury light source or a metal halide light source can be used, if they are visible light, a metal halide light source or a halogen light source can be used, and if they are infrared rays, a halogen light source can be used.
  • light sources such as lasers and LEDs can also be used.
  • the amount of irradiation of the active energy rays is appropriately set depending on the type of light source, the thickness of the coating film, etc., but is preferably appropriately set so that the reaction rate of the total amount of polymerizable functional groups of compound (1) and other polymerizable compounds is 80% or more, more preferably 90% or more.
  • the reaction rate is calculated from the change in absorption peak intensity of the polymerizable functional groups before and after the reaction by infrared absorption spectroscopy.
  • the polymerization may be further promoted by a heat treatment or annealing treatment, if necessary.
  • the heating temperature in this case is preferably in the range of 80 to 200° C.
  • the heating time is preferably in the range of 10 to 60 minutes.
  • the heating temperature is preferably in the range of 80 to 200° C., more preferably in the range of 100 to 150° C. If the heating temperature is lower than 80° C. If the heating temperature is higher than 200° C., the heating time must be long, which tends to be uneconomical. If the heating temperature is higher than 200° C., the energy costs are high and the heating time and cooling time are long, which tends to be uneconomical. .
  • Refractive index Generally, the overall density is increased by a polymerization reaction, so the refractive index of a polymer tends to be higher than that of its precursor compound before polymerization (called a monomer). By sufficiently progressing the polymerization reaction using a monomer with a high refractive index, the refractive index of the resulting polymer can be increased, so it is considered important to improve the refractive index of the polymer by designing the molecular structure of the monomer.
  • the refractive index shows a large value when evaluated with irradiation light of a short wavelength, but a sample that shows a relatively large refractive index at a short wavelength also shows a relatively large refractive index at a long wavelength, and this relationship is not reversed. Therefore, by evaluating and comparing the refractive index at a constant wavelength, it is possible to compare the inherent refractive index of the material. In the present invention, the value at an irradiation light wavelength of 587 nm is used as the standard.
  • the refractive index of the compound of the present invention and the polymer of the present invention is preferably 1.60 or more, more preferably 1.63 or more, and particularly preferably 1.65 or more. There is no particular upper limit to the refractive index of the compound of the present invention and the polymer of the present invention, but it is usually 2.0 or less.
  • the refractive index of the compound and polymer of the present invention is usually in the range of 1.65 or more and 1.78 or less, preferably 1.77 or less. If the refractive index is less than 1.65, the diffraction efficiency is low and the multiplicity is insufficient. If the refractive index is more than 1.78, the difference in refractive index with the matrix resin becomes too large, causing increased scattering and reducing transmittance, requiring more energy for recording and reproduction.
  • a refractive index of less than 1.60 is undesirable because the central portion of the optical lens, etc. becomes thicker and the lightweight nature that is a characteristic of plastics is lost.
  • the glass transition temperature of the polymer of the present invention is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, particularly preferably 120°C or higher, and preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. If it is below this range, the optical properties may change from the designed values under the usage environment, and the practically required heat resistance may not be satisfied. If it exceeds this range, the processability of the polymer may decrease, and a molded product with good appearance and high dimensional accuracy may not be obtained, and the polymer may become brittle, the mechanical strength may decrease, and the handleability of the molded product may deteriorate.
  • the compound, polymerizable composition, and polymer of the present invention have properties such as a high refractive index, easy processability, and high chemical stability, and therefore can be applied to various optical materials and optical components.
  • optical materials include optical overcoats, hard coat agents, adhesives for optical components, resins for optical fibers, and acrylic resin modifiers.
  • optical components include lenses, filters, diffraction gratings, prisms, light guides, cover glass for display devices, photosensors, photoswitches, LEDs, light-emitting elements, optical waveguides, optical splitters, optical fiber adhesives, substrates for display devices, substrates for color filters, substrates for touch panels, polarizing plates, display backlights, light guide plates, anti-reflection films, viewing angle expansion films, optical recording, optical shaping, optical relief printing, and the like. These layers can also be used as, for example, protective films for displays.
  • the compound and polymer of the present invention are particularly preferably applied to plastic lenses due to their high refractive index characteristics, including imaging lenses for cameras (vehicle-mounted cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.), eyeglass lenses, light beam focusing lenses, and light diffusing lenses.
  • Lenses using the compound and polymer of the present invention can be subjected to physical or chemical treatments such as surface polishing, antistatic treatment, hard coating treatment, antireflective coating treatment, dyeing treatment, etc., in order to improve the lenses, such as antireflection properties, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging properties, or imparting fashionability, if necessary.
  • the polymerizable composition of the present invention can be suitably used in the recording layer of a holographic recording medium.
  • the polymerizable composition of the present invention is preferably a photoreactive composition containing a matrix resin, a photopolymerization initiator, a radical scavenger, and other additives in addition to the compound of the present invention.
  • the details of the use as a material for a holographic recording medium are described below.
  • the polymerizable composition of the present invention preferably contains a matrix resin.
  • the matrix resin constituting the recording layer of the holographic recording medium is an organic material that does not change significantly chemically or physically when irradiated with light, and is mainly composed of a polymer of an organic compound.
  • the matrix resin constitutes the polymerizable composition of the present invention together with the polymerizable compound and the photopolymerization initiator described below, it is strongly required that the matrix resin has excellent compatibility with the polymerizable compound and the photopolymerization initiator. If the matrix resin has low compatibility with the other components, an interface is created between the materials, and light is refracted or reflected at the interface, causing light to leak to unnecessary areas, which may cause the interference fringes to be distorted or cut and recorded in inappropriate areas, resulting in degradation of information.
  • the compatibility of the matrix resin with the other components can be evaluated based on the scattered light intensity obtained by placing a detector in a direction different from the transmitted light with respect to the sample, as described in, for example, Japanese Patent No. 3737306.
  • the matrix resin of the polymerizable composition of the present invention may be a resin that is made of multiple materials that are soluble in a solvent in the polymerizable composition and that is three-dimensionally crosslinked after being formed into a usable state, such as the thermoplastic resin, thermosetting resin, and photocurable resin described below.
  • the three-dimensionally crosslinked resin is insoluble in solvents and is a reaction cured product of a polymerizable compound that is liquid at room temperature and a compound that is reactive to the polymerizable compound.
  • the three-dimensionally crosslinked resin acts as a physical obstacle and suppresses volumetric changes during recording. That is, in the recording layer after recording, the bright areas expand and the dark areas shrink, tending to cause unevenness on the surface of the holographic recording medium. In order to suppress this volumetric change, it is more preferable to use a polymerizable composition containing a three-dimensionally crosslinked resin matrix for the recording layer.
  • thermosetting resins are preferred as the matrix resin. Resin materials that can be used as the matrix resin will be described in detail below.
  • thermoplastic resin materials include chlorinated polyethylene, polymethyl methacrylate resin (PMMA), copolymers of methyl methacrylate and other alkyl acrylate esters, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate resin (PVAC), polyvinyl alcohol, polyvinyl formal, polyvinylpyrrolidone, cellulose resins such as ethyl cellulose and nitrocellulose, polystyrene resins, polycarbonate resins, etc. These may be used alone or in combination of two or more.
  • thermoplastic resins there are no particular restrictions on the solvents for these thermoplastic resins as long as they dissolve them, but examples include ketones such as acetone and methyl ethyl ketone, esters such as butyl acetate and propylene glycol methyl ether acetate, aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran and 1,2-dimethoxyethane, and amides such as N,N-dimethylacetamide and N-methylpyrrolidone. These may be used alone or in combination of two or more.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as butyl acetate and propylene glycol methyl ether acetate
  • aromatic hydrocarbons such as toluene and xylene
  • ethers such as tetrahydrofuran and 1,2-dimethoxyethane
  • amides such as N,N-dimethyl
  • thermosetting resin When using a thermosetting resin as the matrix resin, the curing temperature varies depending on the type of crosslinking agent and catalyst. Typical examples of combinations of functional groups that cure at room temperature include epoxy and amine, epoxy and thiol, and isocyanate and amine. Typical examples of combinations that use a catalyst include epoxy and phenol, epoxy and acid anhydride, and isocyanate and polyol.
  • the former is convenient because it reacts immediately after mixing, but when molding such as in holographic recording media is involved, it is difficult to adjust due to the lack of time.
  • the latter allows the curing temperature and curing time to be freely selected by appropriately selecting the type and amount of catalyst used, so it is suitable for curing while molding such as in holographic recording media.
  • Various types of resin raw materials are commercially available for these, from low molecular weight to high molecular weight, so they can be selected while maintaining compatibility with polymerizable reactive compounds and photoinitiators, adhesion to substrates, etc. Each of the raw materials will be described below. Each of the raw materials may be used alone or in combination of two or more.
  • epoxy examples include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin; alicyclic epoxy compounds having a cyclic aliphatic group with a 4- to 7-membered ring such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and phenol or cresol novolac type epoxy compounds.
  • polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and
  • the epoxy preferably has two or more epoxy groups in one molecule, but there are no particular restrictions on the type. If the number of epoxy groups is small, the hardness required for the matrix may not be obtained. There is no particular upper limit on the number of epoxy groups in one molecule, but it is usually 8 or less, and 4 or less is particularly preferred. If there are too many epoxy groups, it may take a long time to consume the epoxy groups, and the formation of the matrix resin may take too long.
  • the amine may be one containing a primary amino group or a secondary amino group.
  • examples of such amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine and derivatives thereof, alicyclic polyamines such as isophoronediamine, menthanediamine, N-aminoethylpiperazine and derivatives thereof, aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and derivatives thereof, polyamides such as condensates of dicarboxylic acids such as dimer acid and the above-mentioned polyamines, imidazole compounds such as 2-methylimidazole and derivatives thereof, and other dicyandiamide, adipic dihydrazide, etc.
  • thiols include thiol compounds such as dithiols such as 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzeneedithiol, 1,3-benzeneedithiol, 1,4-benzeneedithiol, 1,10-decanedithiol, 1,2-ethaneedithiol, 1,6-hexaneedithiol, and 1,9-nonanedithiol, and polythiols such as Thiokol (manufactured by Toray Fine Chemicals Co., Ltd.) and jER Cure QX40 (manufactured by Mitsubishi Chemical Corporation). Of these, commercially available fast-curing polythiols such as jER Cure QX40 are preferably used.
  • phenols include bisphenol A, novolak-type phenolic resins, and resol-type phenolic resins.
  • acid anhydride examples include monofunctional acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride and derivatives thereof, and examples of the difunctional acid anhydrides include pyromellitic anhydride, benzophenonetetracarboxylic anhydride and derivatives thereof.
  • the amount of amine, thiol, phenol, and acid anhydride used is usually 0.1 equivalent or more, preferably 0.7 equivalent or more, and usually 2.0 equivalent or less, preferably 1.5 equivalent or less, in terms of the ratio to the number of moles of epoxy groups. If the amount of amine, thiol, phenol, or acid anhydride used is too small or too large, the number of unreacted functional groups is large, and storage stability may be impaired.
  • thermosetting resin As a catalyst for curing the thermosetting resin, an anionic polymerization initiator or a cationic polymerization initiator can be used depending on the curing temperature and curing time.
  • Anionic polymerization initiators generate anions when exposed to heat or active energy rays, and examples include amines.
  • amines include amino group-containing compounds such as dimethylbenzylamine, dimethylaminomethylphenol, and 1,8-diazabicyclo[5.4.0]undecene-7, and their derivatives; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole, and their derivatives. These can be used alone or in combination depending on the curing temperature and curing time.
  • the cationic polymerization initiator generates cations by heat or irradiation with active energy rays, and examples thereof include aromatic onium salts. Specific examples include compounds consisting of an anion component such as SbF 6 -, BF 4 -, AsF 6 -, PF 6 -, CF 3 SO 3 -, B(C 6 F 5 ) 4 -, and an aromatic cation component containing atoms such as iodine, sulfur, nitrogen, and phosphorus. Among these, diaryliodonium salts, triarylsulfonium salts, and the like are preferred. These can be used alone or in combination depending on the curing temperature and curing time.
  • the amount of these thermosetting resin polymerization initiators used is usually 0.001% by mass or more, preferably 0.01% by mass or more, and usually 50% by mass or less, preferably 10% by mass or less, relative to the matrix resin. If the amount of these thermosetting resin polymerization initiators used is too small, the concentration of the thermosetting resin polymerization initiator will be too low, and the polymerization reaction may take too long. On the other hand, if the amount of thermosetting resin polymerization initiator used is too large, the polymerization reaction may not result in a continuous ring-opening reaction.
  • the isocyanate is preferably one having two or more isocyanate groups in one molecule, but the type is not particularly limited. If the number of isocyanate groups in one molecule is small, the hardness required for the matrix resin may not be obtained.
  • the upper limit of the number of isocyanate groups in one molecule is not particularly limited, but is usually 8 or less, and preferably 4 or less. If the number of isocyanate groups in one molecule is too large, it may take a long time to consume the isocyanate groups, and the formation of the matrix resin may take too long.
  • the upper limit of the number of isocyanate groups in one molecule is not particularly limited, but is usually about 20 or less.
  • isocyanates include aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate); aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene-1,5'-diisocyanate; and oligomers of these, with 3- to 7-mers being preferred.
  • aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate
  • alicyclic isocyanates such as isophorone diisocyanate and 4,4'
  • the molecular weight of the isocyanate is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is too small, the crosslinking density increases, so that the hardness of the matrix resin becomes too high, and the recording speed may decrease. If the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, so that the hardness of the matrix resin becomes too low, and the recorded contents may disappear.
  • polyol examples include polypropylene polyol, polycaprolactone polyol, polyester polyol, and polycarbonate polyol.
  • Polypropylene polyol is obtained by reacting propylene oxide with a diol or polyhydric alcohol.
  • the diol or polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.
  • polypropylene polyols include Sannix GP-400 and GP-1000 (all manufactured by Sanyo Chemical Industries, Ltd., trade names), Adeka Polyether G400, G700, and G1500 (all manufactured by ADEKA Corporation, trade names), and the like.
  • Polycaprolactone polyols can be obtained by reacting lactones with diols or polyhydric alcohols, such as ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -caprolactone.
  • diols or polyhydric alcohols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, polytetramethylene glycol, etc.
  • polycaprolactone polyols obtained from the reaction of ⁇ -caprolactone include Plaxel 205, Plaxel 205H, Plaxel 205U, Plaxel 205UT, Plaxel 210, Plaxel 210N, Plaxel 210CP, Plaxel 220, Plaxel 230, Plaxel 230N, Plaxel 240, Plaxel 220EB, and Plaxel 220EC.
  • polyester polyols include those obtained by polycondensing dicarboxylic acids or their anhydrides with polyols.
  • dicarboxylic acids examples include succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, maleic anhydride, isophthalic acid, terephthalic acid, and trimellitic acid.
  • polyols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, and polytetramethylene glycol.
  • polyester polyols examples include polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate.
  • Commercially available polyester polyols include the ADEKA New Ace F series, ADEKA New Ace Y series, and ADEKA New Ace NS series (product names manufactured by ADEKA Corporation), as well as Kuraray Polyol N-2010, P-4011, and P-1020 (all product names manufactured by Kuraray Co., Ltd.).
  • polycarbonate polyol examples include those obtained by a dealcoholization condensation reaction between glycols and dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, etc.), those obtained by a phenol removal condensation reaction between glycols and diphenyl carbonates, and those obtained by a glycol removal condensation reaction between glycols and carbonates (e.g., ethylene carbonate, diethyl carbonate, etc.).
  • glycols examples include aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.
  • polycarbonate polyols examples include poly(hexamethylene carbonate) polyol obtained by the condensation reaction of 1,6-hexanediol and diethyl carbonate, poly(pentylene carbonate) obtained by the condensation reaction of pentanediol and diethyl carbonate, and poly(butylene carbonate) obtained by the condensation reaction of 1,4-butanediol and diethyl carbonate.
  • polycarbonate polyols include Plaxel CD CD205, Plaxel CD CD210, Plaxel CD CD220 (all trade names manufactured by Daicel Corporation), Duranol T5651, Duranol T5652, Duranol T5650J (all trade names manufactured by Asahi Kasei Corporation), etc.
  • the molecular weight of the polyol described above is preferably 100 to 50,000 in number average molecular weight, more preferably 150 to 10,000, and even more preferably 150 to 5,000. If the number average molecular weight is too small, the crosslinking density increases, so that the hardness of the matrix resin becomes too high, and the recording speed may decrease. If the number average molecular weight is too large, the compatibility with other components decreases or the crosslinking density decreases, so that the hardness of the matrix resin becomes too low, and the recorded contents may be lost.
  • the matrix resin in the present embodiment may contain other components in addition to the above-mentioned components, as long as it is not contrary to the spirit of the present invention.
  • Such other components include, for example, compounds having hydroxyl groups, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, trimethylolpropane, polyethylene glycol, and polytetramethylene glycol, which are used to change the physical properties of the matrix resin.
  • compounds having hydroxyl groups such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexan
  • a suitable urethane polymerization catalyst may be included to promote the reaction of the isocyanate and polyol.
  • the urethane polymerization catalyst include onium salts such as bis(4-t-butylphenyl)iodonium perfluoro-1-butanesulfonic acid, bis(4-t-butylphenyl)iodonium p-toluenesulfonic acid, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonic acid, (4-bromophenyl)diphenylsulfonium triflate, (4-t-butylphenyl)diphenylsulfonium trifluoromethanesulfonic acid, diphenyliodonium perfluoro-1-butanesulfonic acid, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonic acid, di
  • bismuth catalysts and zirconium catalysts are preferred for improving storage stability.
  • bismuth catalyst there are no particular limitations on the bismuth catalyst, so long as it is a catalyst containing elemental bismuth and is a compound that promotes the reaction between isocyanate and polyol.
  • bismuth-based catalysts include tris(2-ethylhexanoate)bismuth, tribenzoyloxybismuth, bismuth triacetate, bismuth tris(dimethyldiocarbamate), bismuth hydroxide, triphenylbismuth(V) bis(trichloroacetate), tris(4-methylphenyl)oxobismuth(V), triphenylbis(3-chlorobenzoyloxy)bismuth(V), and the like.
  • bismuth carboxylate which is represented by the general formula Bi(OCOR) 3 (R is a linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aromatic group), is more preferred.
  • the above bismuth catalysts may be used alone or in any combination and ratio of two or more kinds.
  • zirconium catalyst there are no particular limitations on the zirconium catalyst, so long as it is a catalyst containing zirconium element and is a compound that promotes the reaction between isocyanate and polyol.
  • examples of such compounds include cyclopentadienyl zirconium trichloride, decamethyl zirconocene dichloride, 1,1'-dibutyl zirconocene dichloride, 1,1'-isopropylidene zirconocene dichloride, tetrakis(2,4-pentanedionato)zirconium, tetrakis(trifluoro-2,4-pentanedionato)zirconium, tetrakis(hexafluoro-2,4-pentanedionato)zirconium, zirconium butoxide, zirconium-t-butoxide, zirconium propoxide, zirconium isopropoxide, zirconium
  • compounds having organic ligands are preferred in terms of compatibility with other components, and are more preferred than compounds having an alkoxide or acetylacetonate (2,4-pentanedionato) structure.
  • Any one of the above zirconium compounds may be used alone, or two or more may be used in any combination and ratio.
  • the bismuth-based catalyst and the zirconium-based catalyst may be used alone or in combination.
  • the amount of urethane polymerization catalyst used is, in terms of the ratio to the matrix resin, usually 0.0001% by mass or more, preferably 0.001% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. If the amount of urethane polymerization catalyst used is too small, curing may take too long. On the other hand, if the amount used is too large, it may become difficult to control the curing reaction.
  • a urethane polymerization catalyst allows it to harden at room temperature, but it can also be hardened by raising the temperature.
  • the temperature at this time is preferably between 40°C and 90°C.
  • Photocurable resin When using a photocurable resin as the matrix resin, it is necessary to use a photoinitiator for the matrix resin that corresponds to the wavelength to be used for curing. Since curing during light irradiation can cause problems in molding and adhesion, it is desirable for the curing reaction to be stable around room temperature, which is the temperature at which the material is mainly used. Considering this, catalytic curing using a photoinitiator for the matrix resin is a desirable choice.
  • Functional groups that react with cations such as protons include epoxy and oxetanyl groups.
  • Specific examples of compounds that have these include polyglycidyl ether compounds of polyols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, trimethylolpropane, and glycerin, which have epoxy groups; alicyclic epoxy compounds having 4- to 7-membered cyclic aliphatic groups such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; bisphenol A epoxy compounds, hydrogenated bisphenol A epoxy compounds, bisphenol F epoxy compounds, and phenol or cresol novolac epoxy compounds.
  • Examples of compounds that have oxetanyl groups include 2-ethyl-2-oxetanyl ether of bisphenol A and 1,6-bis(2-ethyl-2-oxetanyloxy)hexane.
  • (poly)ethylene glycol refers to both “ethylene glycol” and its polymer, “polyethylene glycol.”
  • Functional groups that react with anions include epoxy groups and episulfide groups.
  • Specific examples of compounds that have an episulfide group include phenyl episulfide and diepisulfide methyl ether of bisphenol A.
  • the amount of the matrix resin photoinitiator used when photocuring the above-mentioned matrix resin is, in terms of the ratio to the polymerizable compound, usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 1% by mass or less, preferably 0.5% by mass or less. If the amount of matrix resin photoinitiator used is too small, curing may take too long. On the other hand, if the amount used is too large, it may be difficult to control the curing reaction.
  • the wavelength during curing is different from the wavelength during recording, and the difference in wavelength is at least 10 nm, and preferably 30 nm.
  • the selection of a photoinitiator for the matrix resin can be roughly predicted from the absorption wavelength of the initiator.
  • photopolymerization initiator that assists the polymerization of the compound of the present invention can be any known photoradical polymerization initiator. Examples include azo compounds, azide compounds, organic peroxides, organic borates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, acylphosphine oxides, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, and oxime esters. Among them, titanocene compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred as photopolymerization initiators because they undergo polymerization reactions with light in the visible range.
  • the type of the titanocene compound is not particularly limited, and may be appropriately selected from various titanocene compounds described in, for example, JP-A-59-152396 and JP-A-61-151197.
  • titanocene compounds include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, and dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl.
  • di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1-yl, etc.
  • acylphosphine oxide compounds include monofunctional initiators that have only one photocleavage site per molecule, and bifunctional initiators that have two photocleavage sites per molecule.
  • monofunctional initiators include triphenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.
  • bifunctional initiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide.
  • oxime ester compounds include 1-[4-(phenylthio)-2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, 4-(acetoxyimino)-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoic acid methyl ester, and 1-(9-ethyl-6-cyclohexanoyl-9H-carbazol-3-yl)-1-(O-acetyloxime)glutarate methyl ester.
  • the content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 0.5 ⁇ mol/g or more, in terms of the molar amount per unit weight of the polymerizable composition. More preferably, it is 1 ⁇ mol/g or more.
  • the content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 100 ⁇ mol/g or less, in terms of the molar amount per unit weight of the polymerizable composition. More preferably, it is 50 ⁇ mol/g or less.
  • the content of photopolymerization initiator is too low, the amount of radicals generated will be small, slowing down the photopolymerization rate and possibly reducing the recording sensitivity of the holographic recording medium.
  • the content of photopolymerization initiator is too high, the radicals generated by light irradiation will recombine with each other or undergo disproportionation, reducing the contribution to photopolymerization and possibly reducing the recording sensitivity of the holographic recording medium.
  • two or more photopolymerization initiators it is preferable that their total amount falls within the above range.
  • a radical scavenger may be added to accurately fix the interference light intensity pattern as a polymer distribution in the holographic recording medium.
  • the radical scavenger preferably has both a functional group that captures radicals and a reactive group that is covalently fixed to the matrix resin.
  • An example of the functional group that captures radicals is a stable nitroxyl radical group.
  • radical scavengers that are covalently fixed to the matrix resin include hydroxyl groups, amino groups, isocyanate groups, and thiol groups.
  • examples of such radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (TEMPOL), 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxyl, 3-hydroxy-8-azabicyclo[3.2.1]octane N-oxyl, and 5-HO-AZADO: 5-hydroxy-2-azatricyclo[3.3.1.1 3,7 ]decane N-oxyl.
  • TMPOL 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical
  • 3-hydroxy-9-azabicyclo[3.3.1]nonane N-oxyl 3-hydroxy-8-azabicyclo[3.2.1]octane N-oxyl
  • 5-HO-AZADO 5-hydroxy-2-azatricyclo[3.3.1.1 3,7 ]decane N-oxyl.
  • the content of the radical scavenger in the polymerizable composition of the present invention is preferably 0.5 ⁇ mol/g or more, more preferably 1 ⁇ mol/g or more, in terms of molar amount per unit weight of the polymerizable composition, and is preferably 100 ⁇ mol/g or less, more preferably 50 ⁇ mol/g or less.
  • the content of the radical scavenger is too low, the efficiency of capturing radicals will be low, and the polymer with a low degree of polymerization will tend to diffuse, resulting in an increase in components that do not contribute to signals.
  • the content of the radical scavenger is too high, the polymerization efficiency of the polymer will tend to decrease, making it impossible to record signals.
  • the polymerizable composition of the present invention may contain other components in addition to the above-mentioned components, so long as they do not deviate from the spirit of the present invention.
  • Other components include solvents, plasticizers, dispersants, leveling agents, defoamers, adhesion promoters, etc. for preparing the polymerizable composition, and, particularly when used in holographic recording media, chain transfer agents, polymerization terminators, compatibilizers, reaction aids, sensitizers, etc. for controlling the recording reaction.
  • additives that may be required to improve other characteristics include preservatives, stabilizers, antioxidants, UV absorbers, light stabilizers, etc. These components may be used alone or in any combination and ratio of two or more.
  • the polymerizable composition of the present invention may contain a compound that controls the excitation of the photopolymerization initiator.
  • a compound that controls the excitation of the photopolymerization initiator examples include a sensitizer and a sensitizer assistant.
  • any one can be selected from various known sensitizers, but generally, colored compounds such as dyes are often used as sensitizers to absorb visible and ultraviolet laser light.
  • specific examples of preferred sensitizers in systems using green lasers include compounds described in JP-A-5-241338, JP-A-2-69, JP-B-2-55446, etc.
  • compounds described in JP-A-2000-10277, JP-A-2004-198446, etc. may be used. Any one of these sensitizers may be used alone, or two or more may be used in any combination and ratio.
  • the resulting holographic recording medium is required to be colorless and transparent, it is preferable to use a cyanine dye as a sensitizer. Since cyanine dyes are generally easily decomposed by light, post-exposure is performed, i.e., the holographic recording medium is left under indoor light or sunlight for several hours to several days, whereby the cyanine dye in the holographic recording medium is decomposed and no longer absorbs in the visible range, resulting in a colorless and transparent holographic recording medium.
  • the amount of sensitizer needs to be increased or decreased depending on the thickness of the recording layer to be formed, but it is preferable that the ratio to the photopolymerization initiator as described above in 6-2. is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. If too little sensitizer is used, the initiation efficiency decreases and recording may take a long time. On the other hand, if too much sensitizer is used, the absorption of the light used for recording and playback increases, and it may become difficult for the light to reach the depth direction. When two or more sensitizers are used in combination, the total amount of them should be within the above range.
  • the polymerizable composition of the present invention may contain a plasticizer in order to improve the reaction efficiency and adjust the physical properties of the recording layer of the holographic recording medium.
  • plasticizers include phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and diundecyl phthalate; adipates such as bis(2-ethylhexyl) adipate, diisononyl adipate, and di-n-butyl adipate; sebacates such as dioctyl sebacate and dibutyl sebacate; phosphates such as tricresyl phosphate; citric acid esters such as acetyl tributyl citrate; trimellitic acid esters such as trioctyl trimellitate; epoxidized soybean oil, chlorinated paraffin, alkoxylated (poly)alkylene glycol esters such as acetoxymethoxypropane; and terminally alkoxylated polyalkylene glycols such as dimethoxypolyethylene glycol.
  • phthalates such as dioc
  • plasticizers containing fluorine elements such as those exemplified in Japanese Patent No. 6069294.
  • plasticizers containing fluorine elements include 2,2,2-trifluoroethyl butyl carbamate, bis(2,2,2-trifluoroethyl)-(2,2,4-trimethylhexane-1,6-diyl) biscarbamate, bis(2,2,2-trifluoroethyl)-[4-( ⁇ [(2,2,2-trifluoroethoxy)carbonyl]amino ⁇ -methyl)octane-1,8-diyl] biscarbamate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl butyl carbamate, and 2,2,2-trifluoroethyl phenyl carbamate.
  • plasticizers are usually used in a ratio of 0.01% to 50% by mass, and preferably 0.05% to 20% by mass, relative to the total solid content of the polymerizable composition. If the plasticizer content is less than this, the effects of improving reaction efficiency and adjusting physical properties will not be achieved, and if it is more than this, the transparency of the recording layer will decrease and bleeding out of the plasticizer will become noticeable.
  • a leveling agent can be used in the polymerizable composition of the present invention.
  • the leveling agent include sodium polycarboxylate, ammonium polycarboxylate, amine polycarboxylate, silicon-based leveling agent, acrylic-based leveling agent, ester compound, ketone compound, fluorine compound, etc. Any one of these may be used alone, or two or more of them may be used in any combination and ratio.
  • a chain transfer agent can be used in the polymerizable composition of the present invention.
  • the chain transfer agent include phosphinates such as sodium phosphite and sodium hypophosphite, mercaptans such as mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, and thiophenol, aldehydes such as acetaldehyde and propionaldehyde, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as trichloroethylene and perchloroethylene, terpenes such as terpinolene, ⁇ -terpinene, ⁇ -terpinene, and ⁇ -terpinene, 1,4-cyclohexadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,4-heptadiene, and 1,4-cyclohexad
  • non-conjugated dienes such as 1,4-hexadiene, 2-methyl-1,4-pentadiene, 3,6-nonanedien-1-ol, and 9,12-octadecadienol
  • linoleic acids such as linoleic acid, ⁇ -linolenic acid, methyl linolenate, ethyl linolenate, isopropyl linoleate, and linoleic acid anhydride
  • linoleic acids such as linoleic acid, methyl linoleate, ethyl linoleate, isopropyl linoleate, and linoleic acid anhydride
  • eicosapentaenoic acids such as eicosapentaenoic acid and ethyl eicosapentaenoate
  • the amount of these additives used is preferably in the range of usually 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 30% by mass or less, more preferably 10% by mass or less, based on the total solid content of the polymerizable composition of this embodiment. When two or more additives are used in combination, the total amount of them satisfies the above range.
  • composition ratio of each component in the polymerizable composition The content of each component in the polymerizable composition of the present invention is arbitrary as long as it is not contrary to the gist of the present invention.
  • the ratio of each component shown below is preferably in the following range based on the molar amount per unit mass of the polymerizable composition.
  • the content of the polymerizable compound including the compound of the present invention is preferably 5 ⁇ mol/g or more, more preferably 10 ⁇ mol/g or more, and even more preferably 100 ⁇ mol/g or more.
  • the content of the polymerizable compound is preferably 1000 ⁇ mol/g or less, more preferably 500 ⁇ mol/g or less, and even more preferably 300 ⁇ mol/g or less.
  • the total content of these is usually 0.1% by mass or more, preferably 10% by mass or more, more preferably 35% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less. By making this content equal to or greater than the above lower limit, it becomes easier to form a recording layer.
  • the ratio of the number of isocyanate-reactive functional groups of the polyol to the number of isocyanate groups of the isocyanate is preferably 0.1 or more, more preferably 0.5 or more, and usually 10.0 or less, preferably 2.0 or less. By keeping this ratio within the above range, there are fewer unreacted functional groups, and storage stability is improved.
  • the content of the urethane polymerization catalyst is preferably determined taking into consideration the reaction rate of the isocyanate and the polyol, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 1% by mass or less. It is also preferable to use 0.003% by mass or more.
  • the total amount of other components other than those mentioned above should be 30% by mass or less, preferably 15% by mass or less, and more preferably 5% by mass or less.
  • the method for producing the polymerizable composition containing a polymerizable compound, a matrix resin, and a photopolymerization initiator is not particularly limited, and the order of mixing, etc. can be appropriately adjusted.
  • the polymerizable composition contains components other than those described above, the components may be mixed in any combination and order.
  • the polymerizable composition can be obtained, for example, by the following method, but the present invention is not limited thereto.
  • all components other than the isocyanate and the urethane polymerization catalyst are mixed to obtain a photoreactive composition (liquid A).
  • the mixture of the isocyanate and the urethane polymerization catalyst is obtained as liquid B.
  • all of the components other than the isocyanate may be mixed with the polymerizable compound and the photopolymerization initiator to form a photoreactive composition (liquid A).
  • dehydrate and degas each liquid it is preferable to dehydrate and degas each liquid. If dehydration and degassing are insufficient, air bubbles may form during the production of the holographic recording medium, making it impossible to obtain a uniform recording layer. During this dehydration and degassing process, heating and decompression may be performed as long as the individual components are not damaged.
  • the production of the polymerizable composition by mixing liquid A and liquid B is preferably carried out immediately before molding the holographic recording medium. At this time, it is possible to use a conventional mixing technique. When mixing liquid A and liquid B, degassing may be carried out as necessary to remove residual gas. Furthermore, liquid A and liquid B are preferably subjected to a filtration process to remove foreign matter and impurities, either individually or after mixing, and it is even more preferable to filter each liquid separately.
  • an isocyanate-functional prepolymer obtained by reacting an isocyanate having an excess of isocyanate groups with a polyol can be used as the matrix resin.
  • an isocyanate-reactive prepolymer obtained by reacting an isocyanate with a polyol having an excess of isocyanate-reactive functional groups can be used as the matrix resin.
  • the holographic recording medium of the present invention using the polymerizable composition of the present invention includes a recording layer and, if necessary, a support and other layers.
  • the holographic recording medium has a support, and the recording layer and other layers are laminated on the support to constitute the holographic recording medium.
  • the recording layer or other layers have the strength and durability required for the medium, the holographic recording medium does not need to have a support.
  • other layers include a protective layer, a reflective layer, an anti-reflective layer (anti-reflective film), and the like.
  • the recording layer of the holographic recording medium of the present invention is a layer formed by the polymerizable composition of the present invention, and is a layer in which information is recorded. Information is usually recorded as a hologram.
  • the polymerizable compound (hereinafter referred to as polymerizable monomer) contained in the recording layer undergoes a chemical change such as polymerization in part due to holographic recording or the like. Therefore, in the holographic recording medium after recording, a part of the polymerizable monomer is consumed, and exists as a compound after reaction such as a polymerized product.
  • the thickness of the recording layer which may be determined appropriately taking into consideration the recording method, etc., but is preferably at least 1 ⁇ m, more preferably at least 10 ⁇ m, and preferably at most 1 cm, more preferably at most 3 mm.
  • the thickness of the recording layer is preferably at least 1 ⁇ m, more preferably at least 10 ⁇ m, and preferably at most 1 cm, more preferably at most 3 mm.
  • the shrinkage rate of the recording layer due to exposure when recording and reproducing information is preferably 0.25% or less from the viewpoint of recording reproducibility.
  • Support There are no particular limitations on the details of the support, and any support can be used as long as it has the strength and durability required for the holographic recording medium.
  • the shape of the support is not limited, but is usually formed into a flat plate or film.
  • Transparent materials for the support include organic materials such as acrylic, polyethylene terephthalate, polyethylene naphthoate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycycloolefin, and cellulose acetate; and inorganic materials such as glass, silicon, and quartz.
  • organic materials such as acrylic, polyethylene terephthalate, polyethylene naphthoate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, polycycloolefin, and cellulose acetate
  • inorganic materials such as glass, silicon, and quartz.
  • polycarbonate, acrylic, polyester, amorphous polyolefin, and glass are preferred, with polycarbonate, acrylic, amorphous polyolefin, polycycloolefin, and glass being particularly preferred.
  • opaque support materials include metals such as aluminum, and the above-mentioned transparent supports coated with metals such as gold, silver, and aluminum, or with dielectrics such as magnesium fluoride and zirconium oxide.
  • the thickness of the support is preferably in the range of 0.05 mm or more and 1 mm or less. If the thickness of the support is equal to or more than the lower limit above, the mechanical strength of the holographic recording medium can be obtained and warping of the substrate can be prevented. If the thickness of the support is equal to or less than the upper limit above, advantages such as an increase in the amount of light transmission and reduction in the weight and cost of the holographic recording medium can be obtained.
  • the surface of the support may be subjected to a surface treatment.
  • This surface treatment is usually performed to improve the adhesion between the support and the recording layer.
  • Examples of surface treatments include subjecting the support to a corona discharge treatment, or forming an undercoat layer on the support in advance.
  • Examples of compositions for the undercoat layer include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, etc.
  • the surface treatment of the support may be carried out for purposes other than improving adhesion.
  • Examples include reflective coating treatments that form a reflective coating layer made of a metal such as gold, silver, or aluminum; and dielectric coating treatments that form a dielectric layer made of magnesium fluoride, zirconium oxide, or the like. These layers may be formed as a single layer, or two or more layers.
  • These surface treatments may be applied for the purpose of controlling the gas and moisture permeability of the substrate.
  • the support sandwiching the recording layer may also be given the function of suppressing the gas and moisture permeability, thereby improving the reliability of the holographic recording medium.
  • the support may be provided on only one of the upper and lower sides of the recording layer of the holographic recording medium of the present invention, or on both sides. However, when supports are provided on both the upper and lower sides of the recording layer, at least one of the supports is configured to be transparent so as to transmit active energy rays (excitation light, reference light, reproduction light, etc.).
  • a transmission type or reflection type hologram can be recorded.
  • a support having reflective properties is used on one side of the recording layer.
  • a reflection type hologram can be recorded.
  • the support may be provided with a pattern for data addresses.
  • the patterning method there are no limitations to the patterning method in this case, but for example, the support itself may be provided with projections and recesses, a pattern may be formed in the reflective layer described below, or a combination of these methods may be used.
  • the protective layer is a layer for preventing deterioration of the recording and reproducing characteristics of the recording layer.
  • the protective layer is a layer for preventing deterioration of the recording and reproducing characteristics of the recording layer.
  • any known material can be used.
  • a layer made of a water-soluble polymer, an organic/inorganic material, etc. can be formed as the protective layer.
  • the position where the protective layer is formed is not particularly limited, and it may be formed, for example, on the surface of the recording layer, between the recording layer and the support, or on the outer surface side of the support.
  • the protective layer may also be formed between the support and another layer.
  • the reflective layer is formed when the holographic recording medium is configured to be a reflective type.
  • the reflective layer may be formed between the support and the recording layer, or may be formed on the outer surface of the support, but it is usually preferable that the reflective layer is between the support and the recording layer.
  • any known material can be used, for example, a thin metal film or the like can be used.
  • an anti-reflection film may be provided on the side where the information light, reference light, and reproduction light enter and exit, or between the recording layer and the support.
  • the anti-reflection film improves the light utilization efficiency and suppresses the generation of noise.
  • any known antireflection film can be used as the antireflection film.
  • the manufacturing method of the holographic recording medium of the present invention can be manufactured by applying the polymerizable composition of the present invention onto a support without a solvent to form a recording layer.
  • any method can be used as the coating method. Specific examples include a spray method, a spin coating method, a wire bar method, a dip method, an air knife coating method, a roll coating method, a blade coating method, a doctor roll coating method, and the like.
  • a method of casting in a mold or a method of applying onto a release film and punching out a mold can be used.
  • the polymerizable composition of the present invention may be mixed with a solvent or additives to prepare a coating liquid, which is then applied onto a support and dried to form a recording layer.
  • any method can be used as the coating method, and for example, the same methods as those described above can be adopted.
  • the solvent used in the coating solution there are no restrictions on the solvent used in the coating solution, but it is usually preferable to use one that has sufficient solubility for the components used, provides good coating properties, and does not attack supports such as resin substrates.
  • a single solvent may be used, or two or more solvents may be used in any combination and ratio.
  • solvents examples include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; aromatic solvents such as toluene and xylene; alcohol-based solvents such as methanol, ethanol, propanol, n-butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketone alcohol-based solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; ether-based solvents such as tetrahydrofuran and dioxane; halogen-based solvents such as dichloromethane, dichloroethane, and chloroform; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cell
  • Propylene glycol solvents such as cholesteryl monobutyl ether acetate and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and methyl 3-methoxypropionate; perfluoroalkyl alcohol solvents such as tetrafluoropropanol, octafluoropentanol, and hexafluorobutanol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide; chain hydrocarbon solvents such as n-hexane
  • Examples of methods for producing holographic recording media include a method in which a polymerizable composition melted by heat is applied to a support, and then cooled and solidified to form a recording layer; a method in which a liquid polymerizable composition is applied to a support and then hardened by thermal polymerization to form a recording layer; and a method in which a liquid polymerizable composition is applied to a support and then hardened by photopolymerization to form a recording layer.
  • the holographic recording media thus produced can take the form of a free-standing slab or disc and can be used in three-dimensional image displays, diffractive optical elements, mass memories, and the like.
  • the holographic recording medium of the present invention using the polymerizable composition of the present invention has high refractive index modulation and is also useful as an AR glass light guide plate or an AR glass wave guide plate, where AR is an abbreviation of augmented reality.
  • object light When recording information, light capable of causing a chemical change in the polymerizable monomer, i.e., its polymerization and change in concentration, is used as object light (also called recording light).
  • an object beam is irradiated onto the recording layer together with a reference beam, causing the object beam and the reference beam to interfere with each other in the recording layer.
  • a specified reproduction light (usually a reference light) is irradiated onto the recording layer.
  • the irradiated reproduction light is diffracted according to the interference fringes.
  • This diffracted light contains the same information as the recording layer, so the information recorded in the recording layer can be reproduced by reading the diffracted light with an appropriate detection means.
  • the wavelength regions of the object light, the reproduction light, and the reference light are arbitrary depending on the respective applications, and may be either the visible light region or the ultraviolet region.
  • suitable ones include solid-state lasers such as ruby, glass, Nd-YAG, and Nd- YVO4 ; diode lasers such as GaAs, InGaAs, and GaN; gas lasers such as helium-neon, argon, krypton, excimer, and CO2; and lasers with excellent monochromaticity and directivity, such as dye-containing dye lasers.
  • the amount of irradiation of the object light, the reproduction light and the reference light there is no limit to the amount of irradiation of the object light, the reproduction light and the reference light, and the amount of irradiation is arbitrary as long as recording and reproduction are possible. If the amount of irradiation is extremely small, the chemical change of the polymerizable monomer may be too incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully expressed, and conversely, if the amount of irradiation is extremely large, the components of the recording layer (the components of the polymerizable composition of the present invention) may deteriorate.Therefore, the object light, the reproduction light and the reference light are usually irradiated in the range of 0.1 J/ cm2 or more and 20 J/ cm2 or less according to the composition of the polymerizable composition of the present invention used to form the recording layer, the type of photopolymerization initiator, and the amount of compounding.
  • Hologram recording methods include polarized collinear hologram recording and reference beam incident angle multiplexing hologram recording.
  • the hologram recording medium of the present invention is used as a recording medium, it is possible to provide good recording quality with either recording method.
  • a volume hologram is recorded in the holographic recording medium of the present invention in the same manner as in the case of the large-capacity memory application described above.
  • a specific reproduction light is irradiated onto the recording layer.
  • the irradiated reproduction light is diffracted according to the interference fringes.
  • the corresponding interference fringes are recorded according to the wavelength and incident angle of the reproduction light to be diffracted, diffraction can be caused for reproduction light over a wide wavelength range, and the display color gamut of AR glasses can be expanded.
  • the wavelength range of the object light and the reproduction light is arbitrary depending on the respective applications, and may be either the visible light range or the ultraviolet range.
  • the aforementioned laser is a suitable example.
  • the reproduction light is not limited to lasers, and display devices such as liquid crystal displays (LCDs) and organic electroluminescence displays (OLEDs) are also suitable examples.
  • the amount of irradiation of the object light, the reproduction light and the reference light there is no limit to the amount of irradiation of the object light, the reproduction light and the reference light, and the amount of irradiation is arbitrary as long as recording and reproduction are possible. If the amount of irradiation is extremely small, the chemical change of the polymerizable monomer may be too incomplete, and the heat resistance and mechanical properties of the recording layer may not be fully expressed, and conversely, if the amount of irradiation is extremely large, the components of the recording layer (the components of the polymerizable composition of the present invention) may deteriorate.Therefore, the object light, the reproduction light and the reference light are usually irradiated in the range of 0.1 J/ cm2 or more and 20 J/ cm2 or less according to the composition of the polymerizable composition of the present invention used to form the recording layer, the type of photopolymerization initiator, and the amount of compounding.
  • Performance index of holographic recording medium The performance of a holographic recording medium is indexed by total ⁇ n, which is calculated using the sum of the diffraction efficiencies over the entire multiplexed recording.
  • ⁇ n the diffraction efficiency of the hologram is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light. From the obtained diffraction efficiency, ⁇ n is calculated using the following formula according to Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum over the entire multiplexed recording is taken as total ⁇ n.
  • ⁇ is the diffraction efficiency
  • T is the thickness of the medium
  • ⁇ is the wavelength of the reference light
  • ⁇ is the angle of incidence of the reference light
  • a higher total ⁇ n is preferable because it means that more information can be recorded per unit volume. Also, in the case of AR glasses applications, a higher total ⁇ n is preferable because it means that the projected image from the projector can be delivered brighter to the pupil, power consumption can be reduced, and the viewing angle can be widened.
  • composition raw materials used in the examples and comparative examples are as follows.
  • Plaxel PCL-205U Polycaprolactone diol (molecular weight 530) (manufactured by Daicel Corporation)
  • Plaxel PCL-305 Polycaprolactone triol (molecular weight 550) (manufactured by Daicel Corporation)
  • TEMPOL 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (Tokyo Chemical Industry Co., Ltd.)
  • ⁇ Urethane polymerization catalyst Bismuth tris(2-ethylhexanoate) in octylic acid solution (active ingredient amount: 56% by mass)
  • the NMR measurement data of the compound S-1 was as follows. 1H -NMR (400MHz, CDCl3 , ⁇ , ppm) 8.26-8.16 (Ar, 5H), 8.15 (dd, Ar, 1H), 7.99 (brs, Ar, 2H), 7.90-7.83 (Ar, 3H), 7.70 (dd, Ar, 2H), 7.66-7.61 (Ar, 3H), 7.56 (dd, Ar, 1H), 7.50-7.43 (Ar, 6H), 5.39 (s, HO, 1H).
  • Liquid A was prepared by dissolving 0.261 g of compound M-1 as a polymerizable monomer, 0.0096 g of photopolymerization initiator HLI02, 3.30 mg of radical scavenger TEMPOL, and 2.6 mg of light stabilizer LA-63P in 2.53 g of Duranate (registered trademark) TSS-100.
  • This holographic recording medium was formulated so that the ratio of the number of isocyanate groups in solution A to the number of isocyanate-reactive groups in solution B was 1.0, and the polymerizable monomer was 58.3 ⁇ mol/g, the photopolymerization initiator was 3.05 ⁇ mol/g, and the radical scavenger was 3.05 ⁇ mol/g.
  • holographic recording and evaluation> Using the holographic recording medium prepared as the evaluation sample, holographic recording and evaluation of the holographic recording performance of the holographic recording medium were performed according to the procedure described below.
  • Holographic recording was performed using a semiconductor laser with a wavelength of 405 nm and an exposure power density of 10.2 mW/ cm2 per beam using the exposure device shown in FIG. 1, where two-beam plane wave holographic recording was performed.
  • the medium was rotated from -22.5° to 22.5°, and angle multiplex recording was performed at the same location.
  • the diffraction efficiency for each multiplex recording was measured.
  • ⁇ n was calculated from the obtained diffraction efficiency, and the sum of the entire multiplex recording was taken as total ⁇ n. This will be explained in detail below.
  • FIG. 1 is a diagram showing an outline of the device used for holographic recording.
  • S is a sample of a holographic recording medium
  • M1 to M3 all denote mirrors.
  • PBS denotes a polarizing beam splitter
  • L1 denotes a recording light laser light source that emits light with a wavelength of 405 nm (a single mode laser manufactured by TOPTICA Photonics ("L1" in Fig. 1) that can obtain light with a wavelength of about 405 nm).
  • L2 denotes a reproducing light laser light source that emits light with a wavelength of 633 nm.
  • PD1, PD2, and PD3 denote photodetectors. 1 denotes an LED unit.
  • a He-Ne laser capable of producing light with a wavelength of 633 nm (V05-LHP151 manufactured by Melles Griot: “L2” in the figure) was used to irradiate the hologram recording medium at an angle of 50.7°, and the diffracted light was detected using a photodiode and photosensor amplifier (S2281, C9329 manufactured by Hamamatsu Photonics: "PD1" in the figure) to determine whether the hologram was recorded correctly.
  • the angle at which the sample was moved relative to the optical axis was changed from -22.5° to 22.5° in 0.3° increments, and 151 multiplexed recordings were performed.
  • the LED unit (1 in the figure, central wavelength 405 nm) was turned on for a certain period of time to consume the remaining initiator and monomer. This process is called post-exposure.
  • the LED power was 100 mW/ cm2 , and irradiation was performed so that the cumulative energy was 12 J/ cm2 .
  • the diffraction efficiency of a hologram is given by the ratio of the intensity of the diffracted light to the sum of the intensity of the transmitted light and the intensity of the diffracted light.
  • Light (wavelength 405 nm) from mirror M1 in Figure 1 was irradiated, and the diffraction efficiency was measured from angles of -23° to 23°. From the obtained diffraction efficiency, ⁇ n was calculated using the following formula from Coupled Wave Theory (H. Kogelnik, The Bell System Technical Journal (1969), 48, 2909-2947), and the sum for the entire multiplex recording was taken as total ⁇ n.
  • ⁇ is the diffraction efficiency
  • T is the thickness of the medium
  • ⁇ is the wavelength of the reference light
  • ⁇ is the angle of incidence of the reference light (29.65°).
  • the refractive index of compound M-1 was measured by the following method.
  • the refractive indexes of the polymerizable monomers produced in the Examples and Comparative Examples were also measured by the same method.
  • a test solution was prepared by dissolving a sample in a mixed solution of 3-phenoxybenzyl acrylate and trimethylolpropane trimethacrylate in a mass ratio of 4:1 so as to give a predetermined concentration.
  • the test solutions were of two types, with sample concentrations of 10% by mass and 20% by mass.
  • the refractive index of each test solution was measured using a Kalnew precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-2000).
  • the temperature of the test solution was 23° C.
  • the measurement wavelength was a helium lamp d-line (587.6 nm). Based on the measurement results, a calibration curve showing the correlation between the sample concentration and the refractive index was created, and the refractive index when the sample concentration was 100 mass % was determined from the obtained calibration curve, and was taken as the refractive index of the sample.
  • Compound M-1 had a total ⁇ n of 0.0222 and a refractive index of 1.6818.
  • the NMR measurement data of the compound S-2 was as follows. 1H -NMR (400MHz, CDCl3 , ⁇ , ppm) 8.84-8.66 (Ar, 6H), 8.32 (dd, Ar, 1H), 8.11 (dd, Ar, 1H), 8.07 (dd, Ar, 1H), 8.04-7.86 (Ar, 8H), 7.75-7.57 (Ar, 12H), 5.18-5.13 (OH, 1H).
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-2 was used as the polymerizable monomer.
  • the total ⁇ n of compound M-2 was 0.0250, and the refractive index was 1.6898.
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-3 was used as the polymerizable monomer.
  • the total ⁇ n of compound M-3 was 0.0195, and the refractive index was 1.6891.
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-4 was used as the polymerizable monomer.
  • the total ⁇ n of compound M-4 was 0.0194, and the refractive index was 1.6894.
  • 2,4,6-Tribromophenol (2.3 g), naphthalene-2-boronic acid (3.7 g), and sodium carbonate (2.3 g) were suspended in 50 mL of toluene, 50 mL of ethanol, and 25 mL of water, and degassed by passing nitrogen gas through the solution. 2 mg of dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) was added to the reaction solution, and nitrogen gas was passed through the solution for an additional 5 minutes. The reaction solution was heated under a nitrogen atmosphere and stirred under reflux for 5 hours.
  • the NMR measurement data of the compound S-4 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.83-8.69 (Ar, 6H), 8.33-8.26 (Ar, 1H), 8.18-8.08 (Ar, 2H), 8.03-7.86 (Ar, 6H), 7.82-7.76 (Ar, 2H), 7.76-7.56 (Ar, 12H), 3.38-3.27 ( CH2 , 2H), 2.89-2.70 ( CH2 , 2H), 0.60, 0.51 (t, OH, total 1H).
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-10 was used as the polymerizable monomer.
  • the total ⁇ n of compound M-10 was 0.0160, and the refractive index was 1.7323.
  • the NMR measurement data of the compound S-5 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.85-8.66 (Ar, 6H), 8.34-8.25 (Ar, 1H), 8.18-8.07 (Ar, 2H), 8.04-7.85 (Ar, 6H), 7.82-7.56 (Ar, 14H), 3.43-3.29 (CH2, 2H ), 2.61, 2.42 ( CH2 , 2H), 0.97-0.75 ( CH2 , 2H), 0.45, 0.29 (t, OH, total 1H).
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound M-11 was used as the polymerizable monomer.
  • the total ⁇ n of compound M-11 was 0.0181, and the refractive index was 1.7316.
  • the NMR measurement data of compound L-1 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.30-8.10 (Ar, 4H), 7.88-7.82 (Ar, 3H), 7.82-7.75 (dd, Ar, 1H), 7.68-7.41 (Ar, 8H), 7.25 (d, Ar, 1H), 5.18 (s, OH, 1H).
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound R-1 was used as the polymerizable monomer.
  • the total ⁇ n of compound R-1 was 0.0115, and the refractive index was 1.6762.
  • a holographic recording medium was prepared and evaluated in the same manner as in Example 1, except that compound R-2 was used as the polymerizable monomer.
  • the total ⁇ n of compound R-2 was 0.0070, and the refractive index was 1.7056.
  • the NMR measurement data of the compound L-2 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.28-8.14 (Ar, 6H), 8.07 (s, Ar, 2H), 7.93-7.81 (Ar, 3H), 7.77-7.71 (Ar, 2H), 7.68-7.54 (Ar, 4H), 7.53-7.42 (Ar, 6H), 3.35 (t, CH2 , 2H), 3.09-3.01 ( CH2 , 2H), 0.91 (t, OH, 1H).
  • the NMR measurement data of compound L-3 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.26-8.13 (Ar, 6H), 8.04 (s, Ar, 2H), 7.93-7.81 (Ar, 3H), 7.75-7.69 (Ar, 2H), 7.67-7.53 (Ar, 4H), 7.53-7.43 (Ar, 6H), 3.27 (t, CH2 , 2H), 2.97-2.90 ( CH2 , 2H), 1.02-0.92 ( CH2 , 2H), 0.86-0.75 ( CH2 , 2H), 0.71 (t, OH, 1H).
  • the NMR measurement data of compound R-4 was as follows. 1H NMR (400MHz, CDCl3 , ⁇ , ppm) 8.26-8.13 (Ar, 6H), 8.04 (s, Ar, 2H), 7.93-7.81 (Ar, 3H), 7.75-7.69 (Ar, 2H), 7.67-7.53 (Ar, 4H), 7.53-7.40 (Ar, 6H), 6.15 (dd, CH2 , 1H), 5.83 (dd, CH2 , 1H), 5.65 (dd, CH2 , 1H), 3.50 (t, CH2 , 2H), 3.27 (t, CH2 , 2H), 1.02-0.81 ( CH2 , 4H).
  • the refractive index of each polymerizable monomer was evaluated as follows: ⁇ (1.73 or more), ⁇ (1.68 or more and less than 1.73), ⁇ (1.65 or more and less than 1.68), ⁇ (less than 1.65). Samples that were not suitable for refractive index measurement were marked as - (measurable).
  • the total ⁇ n of the holographic recording media of Comparative Examples 1 and 2 was less than 0.015, whereas the total ⁇ n of the Examples of the present invention was 0.015 or more.
  • the total ⁇ n of the holographic recording media created using the polymerizable monomers of Examples 1 to 4 was 0.019 or more, making them extremely excellent materials for holographic recording.
  • the refractive index of the compounds in the examples is 1.68 or more, and compared to the compounds in the comparative examples, it is clear that they have the same or higher refractive index, making them excellent high refractive index materials.
  • the refractive index of the polymerizable monomers in Examples 10 and 11 exceeds 1.73, making them extremely useful as ultra-high refractive index materials.
  • the polymerizable monomers of Comparative Examples 1 to 4 had insufficient storage stability in Duranate TSS-100 and low solubility.
  • the polymerizable monomers corresponding to the compounds of the present invention all exhibited high solubility in TSS-100 and were materials with excellent storage stability.
  • the improved total ⁇ n can improve the recording capacity.
  • high transparency is required for the hologram recording medium, and the turbidity caused by the inclusion and generation of insoluble matter causes the absorption and scattering of the recording light, leading to a decrease in the performance of the hologram recording medium.
  • the light scattering caused by the insoluble matter reduces the light utilization efficiency and aesthetics.
  • the compound of the present invention which has both high total ⁇ n and composition stability, especially high solubility in the medium, it is possible to make an AR glass light guide plate with excellent light utilization efficiency, aesthetics, and long-term performance stability. From the above, it can be said that the compounds of the present invention used in the examples are superior to the compounds of the comparative examples.

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