WO2015068839A1 - Composé polymérisable, composition de résine l'utilisant, résine durcie et matériau optique - Google Patents

Composé polymérisable, composition de résine l'utilisant, résine durcie et matériau optique Download PDF

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WO2015068839A1
WO2015068839A1 PCT/JP2014/079728 JP2014079728W WO2015068839A1 WO 2015068839 A1 WO2015068839 A1 WO 2015068839A1 JP 2014079728 W JP2014079728 W JP 2014079728W WO 2015068839 A1 WO2015068839 A1 WO 2015068839A1
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group
carbon atoms
meth
polymerizable compound
acrylate
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PCT/JP2014/079728
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Japanese (ja)
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一嘉 正木
清水　健博
敏男 安藤
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新日鉄住金化学株式会社
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Priority to JP2015546716A priority Critical patent/JP6869636B2/ja
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    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • 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
    • C08F220/38—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
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to 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
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • 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
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component

Definitions

  • the present invention relates to a polymerizable compound having a high refractive index and excellent in transparency, handling properties, and the like, a resin composition using the same, a cured resin and an optical material, particularly a holographic recording material and a holographic recording medium It is about.
  • optical resins have been actively used in various optical fields, and (meth) acrylic resins such as polymethylmethacrylate are well known as materials thereof.
  • optical resin materials typified by (meth) acrylic resins have lightness, safety, and design properties, but have a disadvantage of low refractive index. Therefore, in recent years, there has been an increasing demand for optical resins having a high refractive index, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT prism lens sheets, aspherical lenses, optical fibers.
  • Studies on optical waveguides, optical recording materials, and the like have been actively conducted.
  • optical recording materials particularly holographic recording materials
  • the development of high refractive index materials for achieving a high degree of refractive index modulation, a large M # (M number), and high sensitivity has become a major issue.
  • a high refractive index monomer as a raw material polymerizable compound (hereinafter also referred to as a monomer). It is theoretically known that introduction of halogen atoms (chlorine, bromine, iodine), sulfur atoms and heavy metal atoms is effective.
  • monomers having an aromatic ring in the molecular structure for example, those having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene and anthracene in addition to a benzene ring are known (Patent Documents 1 and 2, etc.).
  • the refractive index of a monomer having a single benzene ring in the molecular structure is not sufficient.
  • monomers having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, and anthracene in the molecular structure are expected to have a high refractive index, but in most cases become a high-viscosity liquid or a crystalline solid. There is a problem that handling property is lowered. Furthermore, there is a problem that not only the transparency is lowered but also the photocurability and the weather resistance are lowered by increasing the absorption wavelength.
  • a monomer having a diphenyl sulfide structure in the molecular structure has a higher refractive index than a monomer having a single benzene ring.
  • the higher the viscosity and the longer the absorption wavelength the less the monomer having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, anthracene, etc., handling properties such as solubility, transparency, photocurability, weather resistance
  • the advantage that there are few problems of the fall of can be expected.
  • Patent Documents 3 to 6, etc. So far, several polymerizable compounds having a diphenyl sulfide structure in the molecular structure have been synthesized (Patent Documents 3 to 6, etc.). However, even the polymerizable compounds disclosed in the patent documents listed here are insufficient in terms of high refractive index, transparency and handling properties, and further creation of improved polymerizable compounds is required. ing.
  • Holographic recording is performed by recording interference fringes generated by simultaneously irradiating reference light together with signal light having image information on a recording medium as a diffraction grating (hereinafter also referred to as a grating).
  • the reproduction from the recording medium is performed by irradiating the recording medium on which the image information is recorded with reference light and reading out the image information as reproduction signal light from the diffraction grating.
  • the above-mentioned image information can be recorded and reproduced as a single page in a batch, and multiple pages can be recorded at the same location on the medium. Therefore, bit-by-bit used in conventional CDs, DVDs, and Blu-ray discs. This technology is expected as a high transfer rate and large capacity optical recording system that replaces the bit recording system.
  • a holographic recording material As a holographic recording material, a photopolymer in which a recording polymerizable compound and a photopolymerization initiator are dispersed in a matrix resin is used in consideration of the convenience of recording medium production and diversity of raw material selection. There are many cases.
  • a holographic recording medium using a photopolymer a write-once type in which interference fringes are recorded as a refractive index modulation diffraction grating is generally used.
  • M # is an index representing the multiplex recording performance, and is a numerical value represented by the following formula (I) when the diffraction efficiency of the i-th page is ⁇ i in the m-multiplex recorded signal.
  • a high recording sensitivity is required because it is necessary to obtain a sufficient diffraction efficiency with a short recording exposure in order to achieve a high transfer rate.
  • Holographic recording is performed by irradiating a photopolymer with interference fringes (light contrast) obtained by crossing coherent light. Photopolymerization occurs in the bright part of the interference fringes during light irradiation, and the polymerizable compound is consumed to produce a polymer. The polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes so as to compensate for the concentration gradient of the polymerizable compound generated at this time. In this way, the interference fringe pattern is fixed in the photopolymer as a refractive index distribution (Non-Patent Document 1).
  • the matrix resin and the polymerizable compound are advantageous to select so that the difference in refractive index is as large as possible.
  • the polymerizable compound should have a refractive index as high as possible. It is desirable to use it.
  • examples of the high refractive index polymerizable compound include condensed (hetero) aryl groups and bromine-substituted aryl groups such as N-vinylcarbazole, bromostyrene, and tribromophenyl acrylate described in Patent Documents 7 to 9. There are those that have.
  • Patent Documents 10 to 12 report that a holographic recording material and a recording medium having high diffraction efficiency and sensitivity can be obtained by using a polymerizable compound having a sulfur-containing fused ring structure.
  • the difference in refractive index and the compatibility are in a trade-off relationship.
  • the refractive index of the polymerizable compound is improved to improve the diffraction efficiency, the matrix resin and the polymerizable compound or a polymer thereof are not affected. Compatibility is deteriorated.
  • Even the polymerizable compounds disclosed in the patent documents listed here are insufficient from the viewpoint of diffraction efficiency, light transmittance, and compatibility, and the creation of further improved polymerizable compounds is demanded.
  • JP-A-5-170702 JP 2004-83855 A Japanese Patent Laid-Open No. 2-113005 JP 2005-145861 A JP 2010-186979 A Korean Patent No. 1254325 (KR2012-40799A) JP-A-10-105030 Japanese Patent Laid-Open No. 11-352303 JP 2005-502918 A JP 2005-43507 A JP 2005-114848 A JP 2010-18606 A
  • the diffraction efficiency of the holographic recording medium is proportional to the recording density per medium surface, and the value can be expressed by the refractive index modulation degree from the Kogelnik theory of the following equation (II).
  • ⁇ is the diffraction efficiency
  • ⁇ n is the refractive index modulation degree
  • ⁇ is the reproduction wavelength
  • ⁇ B is the reproduction angle.
  • the degree of modulation of the refractive index is the difference in refractive index between the light irradiated part and the non-irradiated part.
  • the holographic recording medium before recording is uniformly dispersed in a state where the polymerizable compound is compatible with the matrix resin.
  • this holographic recording medium is irradiated with interference fringes for recording, photopolymerization starts in the bright part of the interference fringes, and the polymerizable compound is consumed to produce a polymer.
  • the polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes, and the polymerization continues, and the polymerization causes an increase in density.
  • the concentration of the polymerizable compound decreases in the dark part of the interference fringes.
  • the refractive index of the polymerizable compound when the refractive index of the polymerizable compound is higher than the refractive index of the matrix resin, the refractive index increases with respect to the non-irradiated portion due to the increase in density due to polymerization and the concentration of the polymerizable compound in the light irradiated portion.
  • the refractive index in the non-irradiated portion, the refractive index is further lowered than the state before recording due to the decrease in the polymerizable compound concentration. Therefore, a refractive index difference is formed between the light irradiation part and the non-irradiation part.
  • the refractive index of the polymerizable compound When the refractive index of the polymerizable compound is lower than the refractive index of the matrix resin, the refractive index increases in the light-irradiated part than in the non-irradiated part due to polymerization. The width is suppressed. Furthermore, since the refractive index increases due to a decrease in the concentration of the polymerizable compound in the non-irradiated part, the difference in refractive index between the light-irradiated part and the non-irradiated part is larger than that when the polymerizable compound has a higher refractive index than the matrix resin. Smaller.
  • the refractive index of the polymerizable compound is larger than the refractive index of the matrix resin and that the difference is large.
  • M # increases as the multiplicity increases. Further, M # is calculated from the diffraction efficiency, and it can be seen from the formula (II) that the diffraction efficiency increases as the refractive index modulation degree increases. From these facts, the diffraction efficiency can be increased as the difference in the refractive index between the light-irradiated portion and the non-irradiated portion is increased, and further, improvement in M # can be achieved.
  • the present invention provides a polymerizable compound having a high refractive index, a high light transmittance, and a low viscosity, and a resin composition, a cured resin and an optical material using the polymerizable compound, and further when used as a holographic recording material. It is an object to provide a holographic recording material containing the polymerizable compound capable of obtaining a large M # and high sensitivity, and a holographic recording medium capable of realizing a large capacity (high density) and a high transfer rate using the material. To do.
  • R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms.
  • X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent,
  • the substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon number 6 to 10 arylthio groups.
  • R 6 is a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, an optionally substituted vinylaryl group or a vinylaryloyl group.
  • the -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be.
  • the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.
  • R 1 ⁇ R 5 it is -S-Ar 1, or two or but three R 1 ⁇ R 5, more excellent If it is -S-Ar 1 It becomes a polymerizable compound.
  • the present invention also includes a resin composition characterized by containing the polymerizable compound, a resin cured product obtained by curing the resin composition, and the resin composition or resin cured product. It is an optical material characterized by this.
  • the present invention relates to a holographic recording material containing the polymerizable compound.
  • the holographic recording material may be a holographic recording material containing A) the polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.
  • one of R 1 to R 5 is —S—Ar 1
  • two or three of R 1 to R 5 are —S—Ar 1
  • a refractive index n D at 25 ° C. of the compound of 1.60 or more gives a better holographic recording material.
  • Examples of the matrix resin include isocyanate-hydroxyl polyadducts, and examples of the matrix resin forming material include materials containing polyisocyanate and polyol.
  • the present invention also provides a holographic recording medium comprising a recording layer containing the holographic recording material.
  • the polymerizable compound of the present invention is higher in refractive index, transparency and handling than conventional polymerizable compounds, glass substitute materials for lens applications, and protective film materials for color filters for liquid crystal displays.
  • Resin compositions useful for various optical materials such as coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, and curing Can give things.
  • the optical material as used in the present invention means a material used for light transmitting or reflecting light, and is preferably an optical material for light transmission such as for lenses and light transmission films. More preferably, it is an optical material for lens use.
  • the polymerizable compound used in the holographic recording material of the present invention is compatible with the refractive index modulation and compatibility, and without causing turbidity or scattering, the holographic recording material using the polymerizable compound is , Large M #, high sensitivity.
  • the polymerizable compound of the present invention is represented by the general formula (1).
  • R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms.
  • one, two or three of R 1 to R 5 are the arylthio group.
  • the number of monovalent groups other than hydrogen atoms or arylthio groups in R 1 to R 5 is 0 to 4, preferably 0 to 2, and more preferably 0 or 1.
  • a monovalent group other than a hydrogen atom or an arylthio group for example, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkyloxy group having 1 to 2 carbon atoms, or an alkylthio group having 1 to 2 carbon atoms
  • an aryloxy group having 6 to 7 carbon atoms, an aryloxy group having 6 to 7 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms preferably a bromine atom, methyl group, methoxy group, methylthio group, phenyl group, phenoxy A group, a benzyl group, a 1-phenylethyl group, or a 2-phenylpropan-2-yl group is more preferable.
  • X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms.
  • the oxyalkylene group, thioalkylene group, alkyleneoxy group or alkylenethio group is represented by YC n H 2n or C n H 2n Y, Y is O or S, and n is a number from 1 to 4. It is.
  • the alkylene group, oxyalkylene group (or alkyleneoxy group), and thioalkylene group (or alkylenethio group) may have a substituent.
  • preferred substituents include a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 6 carbon atoms.
  • 10 aryloxy group or arylthio group having 6 to 10 carbon atoms, and the aryl group, aryloxy group or arylthio group may have a substituent which Ar1 described later may have.
  • R 6 represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group.
  • the vinyl aryl group preferably has 8 to 20 carbon atoms, and the vinyl aryloyl group preferably has 9 to 20 carbon atoms.
  • a vinyl aryl group Preferred examples of the substituent for the case of having a substituent include the substituents cited as preferred substituents in the description of X 1.
  • Ar 1 of -S-Ar 1 represents a ring members 6-14 aryl group or ring members 5-14 heterocyclic aryl group may have a substituent, and two or more rings condensed You may do it.
  • Ar 1 may be a monocyclic structure or a condensed ring structure, and the number of rings constituting Ar 1 is 1 to 4, preferably 1 to 3, and more preferably 1 to 2.
  • the coloring is small in order to ensure not only a decrease in transparency but also photocurability and weather resistance. From this point, Ar 1 is an aryl group. It is preferable that The substituent in the case of having a substituent will be described later.
  • —S—Ar 1 When used as a holographic recording material, the number of —S—Ar 1 is one, R 1 , R 2 , R 4 , R 5 are hydrogen atoms, and R 3 is —S—Ar 1 .
  • Ar 1 is a phenyl group, it is desirable to exclude those in which X 1 is a direct bond and R 6 is a vinyl group.
  • ⁇ Aryl group> 6-16 preferably 6 carbon atoms such as benzene, indene, naphthalene, azulene, fluorene, acenaphthene, anthracene, phenanthrene, fluoranthene, pyrene, and the like -14 aryl groups.
  • the number of carbon atoms is more preferably 6 to 10, and particularly preferably a benzene ring group and a naphthalene ring group.
  • the benzene ring group is a group formed by taking one H from benzene, and the other groups are the same.
  • the heteroatom contained in the heteroaryl group is not particularly limited, and each atom such as S, O, N, and P can be used, but each atom of S, O, and N is preferable from the viewpoint of ensuring compatibility, Each atom of S or O is more preferable, and S atom is particularly preferable from the viewpoint of improving the refractive index. From the viewpoint of high transmittance and compatibility, the number of heteroatoms is preferably 1 to 3, more preferably 1 to 2, in the heteroaryl group.
  • Ar 1 may have a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group, an alkylthio group, a phenyloxy group, and a phenylthio group.
  • Preferred substituents are a chlorine atom, a bromine atom, an alkylthio group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms.
  • the polymerizable compound represented by the general formula (1) can be produced by a known method.
  • a compound in which R 6 is a vinyl group can be produced, for example, by a dehydration reaction using a compound having a hydroxyethyl group as a precursor.
  • a compound in which R 6 is a (meth) acryloyl group can be produced, for example, by a reaction between a compound having active hydrogen and (meth) acrylic acids.
  • a compound in which R 6 is a glycidyl group can be produced, for example, by a reaction between a compound having active hydrogen and epichlorohydrin.
  • the molecular weight of the polymerizable compound represented by the general formula (1) described above is usually 1000 or less, preferably 800 or less, from the viewpoint of shrinkage reduction due to crosslinking during light irradiation or recording sensitivity and compatibility. More preferably, it is 600 or less, especially 500 or less, and is usually 200 or more, preferably 220 or more, more preferably 250 or more.
  • the polymerizable compound represented by the general formula (1) has a refractive index n D at 25 ° C. of 1.50 or more, preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.62 or more. It is.
  • n D refractive index
  • the refractive index n D is 1.60 or more. It is preferable.
  • the refractive index is excessively high, the difference in refractive index from the matrix resin becomes too large, which may cause scattering.
  • a refractive index shows a large value when evaluated at a short wavelength
  • a sample showing a relatively large refractive index at a short wavelength shows a relatively large refractive index even at a long wavelength, and its order is not reversed. . Therefore, the refractive index can be evaluated at a wavelength other than the recording wavelength, and the value at the recording wavelength can be predicted.
  • the compound When the polymerizable compound is solid and it is difficult to directly measure the refractive index, the compound is dissolved in an appropriate solvent to form a solution, and the refractive index of this solution is measured.
  • the refractive index can be obtained by extrapolation.
  • the polymerizable compound represented by the general formula (1) has a viscosity at 60 ° C. of 5000 mPa ⁇ s or less, preferably 3000 mPa ⁇ s or less, more preferably 1000 mPa ⁇ s or less, and particularly preferably 500 mPa ⁇ s or less. is there.
  • the resin composition of the present invention contains the polymerizable compound, but preferably contains a polymerization initiator.
  • the polymerization initiator may be a known polymerization initiator and is not particularly limited as long as the polymerization is initiated by heating or irradiation with ultraviolet rays.
  • a thermal radical polymerization initiator a photo radical polymerization initiator, etc. may be mentioned.
  • a radical photopolymerization initiator is preferred because it can be rapidly cured at room temperature.
  • thermal radical polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert -Butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1 -Peroxyketals such as bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxides such as p-menthane hydroperoxide, ⁇ , ⁇ '-bis (tert-butylperoxy) ) Diiso Dialkyl peroxides such as propylbenzene, dicum
  • diacyl peroxides peroxycarbonates, peroxyesters, and azo compounds are preferable from the viewpoints of curability, transparency, and heat resistance.
  • photo radical polymerization initiator examples include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl.
  • ⁇ -hydroxyacetophenones such as propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1 ⁇ -aminoacetophenones such as-(4-morpholinophenyl) -butan-1-one and 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1- [ Oxime esters such as 4- (phenylthio) phenyl] -1,2-octadione and 2- (O-benzoyl) oxime Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as fin oxide, 2- (o-
  • thermal and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
  • the photosensitizer is not particularly limited, and specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphine such as triphenylphosphine, ⁇ -thiodiglycol and the like Thioethers are exemplified, and the blending amount is recommended to be about 0.01 to 5% by weight with respect to the total amount of the resin composition.
  • examples of the polymerization initiator include a thermal cationic polymerization initiator and a photo cationic polymerization initiator.
  • a photocationic polymerization initiator is preferred because it can be rapidly cured at room temperature.
  • thermal cationic polymerization initiator examples include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o-cyanopyridinium hexafluoroantimonate.
  • pyridinium salts such as cinnamyl-o-cyanopyridinium hexafluoroantimonate and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.
  • benzylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.
  • Examples of the cationic photopolymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfone Triarylsulfonium such as phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate Salts, triphenyl acetate Triarylselenonium salt
  • triarylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.
  • thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
  • the amount of the polymerization initiator used is 0.01 to 10% by weight based on the total amount of the resin composition, although it varies depending on the presence or absence of the polymerization inhibitor and the type and amount of the polymerization inhibitor used. More preferably, it is 0.02 to 5% by weight, and further preferably 0.03 to 3% by weight. However, since the amount used varies greatly depending on the type of polymerization initiator used, it is necessary to appropriately determine the optimum conditions.
  • a known polymerization inhibitor can be added for storage of the resin composition.
  • the type and amount of addition vary greatly depending on the type and amount of polymerization initiator and polymerizable compound to be used, it is necessary to appropriately determine the optimum conditions.
  • the resin composition of this invention can contain other polymeric compounds (henceforth other polymeric compounds) other than the polymeric compound represented by General formula (1) as needed. . Even when other polymerizable compounds are included, the polymerizable compound represented by the general formula (1) is preferably 10% by weight or more, more preferably 50% by weight based on the total amount of the resin composition. % Or more.
  • the other polymerizable compound a known polymerizable compound may be used, and any of monofunctional, bifunctional, polyfunctional, and polymerizable oligomers may be used. You may use together.
  • the polymerizable compound by heat or light it is preferable to use either a thermally polymerizable compound or a photopolymerizable compound depending on the application.
  • a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinylaryl group
  • a known radical polymerizable compound can be used as the other polymerizable compound.
  • Examples of monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and butoxyethyl (meth) acrylate.
  • bifunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth).
  • trifunctional or higher polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxy.
  • (Meth) acrylate-based polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate , Cyclopentadiene oligomer (meth) acrylate, silicone oligomer (meth) acrylate, and the like.
  • Another polymerizable oligomer is a copolymer obtained by copolymerizing a bifunctional compound having two unsaturated double bonds and a chain transfer agent, and a reaction derived from the bifunctional compound in the side chain.
  • An oligomer having a pendant structure having a sex group can be mentioned.
  • Preferred functional groups at this time are a vinyl group and an allyl group, and the bifunctional compound includes a branched structure, an alicyclic structure, or a substituent having an unsaturated double bond in a monocyclic or condensed aromatic ring. May be partially substituted with oxygen, nitrogen, or sulfur atoms.
  • a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention
  • a known cationic polymerizable compound can be used as the other polymerizable compound.
  • Examples of the cationic polymerizable compound used as the other polymerizable compound include alkenyl ethers such as vinyl ether compounds and propenyl ether compounds, alkenyl thioethers such as vinyl thioether compounds and propenyl thioether compounds, vinyl ester compounds, and O-propenyl ester compounds.
  • N-alkenylamides such as N-vinylamide compounds and N-propenylamide compounds
  • cyclic ethers such as epoxy (oxirane) compounds, oxetane compounds and oxolane compounds
  • cyclic compounds such as ethylene sulfide (thiirane) compounds Thioethers, cyclic acetal compounds, lactone compounds, spiroorthoester compounds, N-vinylimidazole compounds, N-vinylcarbazole compounds, etc.
  • Rukoto can.
  • vinyl ether compounds, epoxy compounds, and oxetane compounds are preferable.
  • Particularly preferable other polymerizable compounds include a resin composition having a high refractive index and a low viscosity, which contains a polymerizable functional group capable of copolymerization and is a compound represented by the following general formula (2). It is suitable for giving.
  • Y represents an n-valent ring-containing group having 2 to 7, preferably 2 to 5, 5- or 6-membered rings, where n is an integer of 2 to 4.
  • the plurality of rings of the ring-containing group are (a) those directly connected to each other by a single bond, (b) an alkylene group having 1 to 3 carbon atoms, an oxygen atom (ether group), a sulfur atom (sulfide group)
  • the rings are bonded via any of the above, or (c) the rings are condensed, and have two or more types of bonds (a), (b) and (c) above. It may be what you are doing.
  • Y is not particularly limited, but an n-valent ring-containing group having a structure represented by the following formulas (Y-1) to (Y-17) is preferable.
  • the compound represented by the general formula (2) is obtained by substituting these n-valent ring-containing groups with n atomic groups -ZA.
  • n-valent ring-containing groups having the structures of the above formulas (Y-1) to (Y-11) are preferable from the viewpoint of improving the refractive index, and the above formulas (Y-12) to (Y An n-valent ring-containing group having the structure of Y-17) is preferred from the viewpoint of reducing the viscosity.
  • Z represents a direct bond, an oxygen atom, a sulfur atom, or an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group, a thioalkylene group, an alkyleneoxy group, or an alkylenethio group.
  • A represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinylaryl group or a vinylaryloyl group.
  • n is an integer of 2 to 4, but a compound in which n is 2 is more preferable because of the availability of materials.
  • the type and content of the other polymerizable compound represented by the general formula (2) can be appropriately determined depending on the type and amount of the other constituents in the resin composition, but preferably to obtain a sufficient effect. In addition, 5% by weight, preferably 10% by weight or more is added to the total amount of the resin composition.
  • fillers such as fillers, fibers, coupling agents, flame retardants, mold release agents, and foaming agents can be added to the resin composition of the present invention as necessary.
  • the filler used in this case is polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron powder. , Talc, mica, kaolin clay and the like.
  • the fiber include cellulose fiber, glass fiber, carbon fiber, and aramid fiber.
  • the coupling agent include a silane coupling agent and a titanium coupling agent.
  • Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds.
  • Examples of the release agent include stearates, silicones, waxes and the like.
  • Freon, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or freon, dichloroethane, butane, pentane, etc. are vinyl chloride-vinylidene chloride copolymer or styrene- (meth) acrylic. Examples thereof include expandable thermoplastic resin particles filled in an acid ester copolymer shell.
  • the resin composition of the present invention can be dissolved in a solvent and diluted for use.
  • specific examples of the diluent solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and the amount used is based on the total amount of the resin composition and the diluent solvent. It is preferable that it is 70 weight% or less, More preferably, it is 60 weight% or less.
  • other polymerizable compounds having a low viscosity can also be used as a reactive diluent for reducing the viscosity of the resin composition.
  • the low viscosity is 500 mPa ⁇ s or less, preferably 200 mPa ⁇ s or less.
  • the resin composition of the present invention can be easily made into a cured resin or molded product by a method similar to a conventionally known method. For example, a thermal polymerization initiator or a photopolymerization initiator is added to the polymerizable compound of the present invention, and other polymerizable compounds and other additives are further added as necessary, and an extruder, kneader, roll, stirrer, etc. And mixed well to obtain a resin composition.
  • the resin composition is molded using a roll coater, a cast after casting or a transfer molding machine, and further heated to 60 to 200 ° C. or irradiated with light. A cured product can be obtained.
  • a prepreg obtained by impregnating the resin composition of the present invention into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding to obtain a cured product.
  • a thermal polymerization initiator is added to the polymerizable compound of the present invention, another polymerizable compound or other additive is further added as necessary, a solvent is further added, and the resin composition diluent is stirred.
  • a glass cloth laminate can be produced by impregnating a glass cloth and heating and semi-drying (devolatilization) and prepressing the prepreg obtained by heating at 60 to 200 ° C.
  • the substrate is preferably a transparent material.
  • the substrate is opaque with respect to the wavelength of the light to be reflected / diffused.
  • the resin composition thus obtained and its cured product are excellent in high refractive index, excellent in transparency, handling properties, etc., glass substitute materials for lens applications, protective film materials for color filters for liquid crystal displays, optical It is suitably used for various optical materials such as coating materials for product protection, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, and optical recording materials for hologram recording media.
  • the holographic recording material of the present invention comprises A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.
  • the polymerizable compound the polymerizable compound represented by the general formula (1) is used.
  • A) polymerizable compound, B) matrix resin or matrix resin forming component, and C) photopolymerization initiator are also referred to as A component, B component, and C component, respectively.
  • the matrix resin As the matrix resin, a resin that can be dissolved in a solvent may be used, or a three-dimensionally cross-linked resin may be used, and a three-dimensional cross-linked resin is preferably used from the viewpoint of recording characteristics.
  • the holographic recording material may be blended with a matrix resin, but may be blended as a matrix resin forming component (such as a monomer) that forms the matrix resin. When the matrix resin forming component is blended, it is preferable that polymerization of the polymerizable compound does not occur when forming the matrix resin.
  • the three-dimensional crosslinked resin examples include isocyanate-hydroxyl polyadducts, isocyanate-amine polyadducts, isocyanate-thiol polyadducts, epoxy-amine polyadducts, epoxy-thiol polyadducts, episulfide-amine polyadducts, and Episulfide-thiol polyadduct, etc. can be mentioned, and it is an isocyanate-hydroxyl polyadduct capable of reacting under a relatively mild temperature condition, having excellent optical characteristics of the resulting matrix resin, and having a relatively low odor. It is preferable.
  • the polyisocyanate component constituting the isocyanate-hydroxyl polyadduct a compound having two or more isocyanate groups in one molecule or a mixture thereof is used.
  • a compound having two or more hydroxyl groups in one molecule or a mixture thereof is used as the polyol component constituting the isocyanate-hydroxyl polyadduct.
  • diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, heptanediol, tetramethylene glycol; bisphenols;
  • triols such as methylolpropane, butanetriol, pentanetriol, hexanetriol and decanetriol; compounds obtained by modifying the hydroxyl group of these compounds with a polyethyleneoxy chain or a polypropyleneoxy chain.
  • the matrix resin may contain a unit derived from a reactive aromatic compound having an aromatic ring and having a polymerization reactive group and a hydroxyl group as a part of the constituent unit of the matrix resin.
  • it can be part of the structural unit of the matrix resin via the hydroxyl group, and an aromatic ring is present in the matrix resin, so that the hollow resin containing the high refractive index polymerizable compound having the aromatic ring is present.
  • the compatibility is high and turbidity hardly occurs, and a relatively large amount of polymerizable compound can be contained.
  • the refractive index difference between the matrix resin and the polymerizable compound or polymer thereof can be increased, and as a result, the refractive index modulation can be increased.
  • a plurality of diffraction gratings can be formed with high contrast by the refractive index modulation structure, and a plurality of page information corresponding to the plurality of diffraction gratings can be obtained. It can be recorded and played back with a high SNR.
  • Examples of the reactive aromatic compound include those represented by the formula (5), (6) or (7).
  • Ar5 represents a monovalent or divalent group having one or more aromatic rings
  • Z 1 and Z 2 each independently represents a hydrogen atom or a methyl group
  • L 1 represents an oxygen atom, a sulfur atom or — (OZ 3 ) nO—
  • Z 3 is an alkylene group having 1 to 4 carbon atoms, n is an integer of 1 to 4
  • L 2 is a divalent divalent alkyl group which may have an aromatic ring.
  • m represents an integer of 1 to 2.
  • Z 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • L 3 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group having 1 to 4 carbon atoms. Or represents a 9,9-fluorenylene group.
  • Z 1 and L 1 are the same as in formula (5).
  • L 2 represents a single bond or a divalent group which may have an aromatic ring.
  • Z 1 , Z 2 , and L 1 are the same as in formula (6).
  • Examples of the reactive aromatic compound represented by the formula (5) or (6) include (meth) acrylic acid adducts, 3-butenoic acid adducts, and vinyl benzoic acid adducts of bisphenol A type epoxy resins. , Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, bisphenol F type epoxy resin (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid adduct, Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, (meth) acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether, 3-butenoic acid adduct, Vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9,9- (Meth) acrylic acid adducts, 3-butenoic acid
  • the reactive aromatic compound is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, based on the total of the matrix resin or the matrix resin forming component (including the reactive aromatic compound), More preferably, it is 0.3-5% by mass. If the content of the reactive aromatic compound is too high, the viscosity of the precursor becomes high and the production of the holographic recording material may become complicated. On the other hand, if the reactive aromatic compound is not contained or if the content is too low, the compatibility between the matrix resin and the polymerizable compound or polymer thereof is lowered, and the holographic recording material may be turbid. .
  • Examples of the compound having a polymerization reactive group and a hydroxyl group represented by the formula (7) include 9,9-bis (4-hydroxy) among the reactive aromatic compounds represented by the formula (5) or (6).
  • the main component of the acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is that R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
  • the main components of the methacrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether are as follows: R 1 in formula (7) is a methyl group, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
  • R 1 in formula (7) is a hydrogen atom
  • R 2 is a hydrogen atom
  • L 1 is an oxygen atom
  • L 2 is a compound represented by a methylene group.
  • the main component of the vinyl benzoic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is as follows: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a phenylene group.
  • Component A polymerizable compound
  • the blending amount of the polymerizable compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 10% by mass with respect to the entire holographic recording material. Moreover, if necessary, a small amount of other polymerizable compounds can be used in combination for the purpose of adjusting the refractive index.
  • the photopolymerization initiator is not particularly limited as long as it initiates polymerization of the polymerizable compound of component A by irradiation with ultraviolet rays or the like.
  • a radical photopolymerization initiator can be used.
  • any known radical radical polymerization initiator can be used.
  • Examples include azo compounds, azide compounds, organic peroxides, organoborates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, ⁇ -hydroxyketone compounds. , ⁇ -aminoketone compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are used. Any one of these may be used alone, or two or more may be used in any combination and ratio. Of these, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are preferable because a polymerization reaction occurs in the visible light region without requiring a sensitizer.
  • titanocene compound is not particularly limited, but specific examples thereof include biscyclopentadienyl-Ti-dichloride, biscyclopentadienyl-Ti-diphenyl, biscyclopentadienyl-Ti-bis (2 , 3,4,5,6-pentafluorophenyl), biscyclopentadienyl-Ti-bis (2,3,5,6-tetrafluorophenyl), biscyclopentadienyl-Ti-bis (2,4 , 6-trifluorophenyl), biscyclopentadienyl-Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2,4-difluorophenyl), bis (methylcyclopentadi) Enyl) -Ti-bis (2,3,4,5,6-pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,
  • the acyl phosphine oxide compound is not particularly limited, but specific examples include triphenyl phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,6-dichlorobenzoyl diphenyl.
  • Phosphine oxide bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichloro) And benzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and the like.
  • the type of the oxime ester compound is not particularly limited, but specific examples thereof include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -2- (O-benzoyloxime) -3-cyclopentyl-1,2-propanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] And -2- (O-acetyloxime) -4-cyclopentyl-1,2-butanedione.
  • any one of these various photo radical polymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.
  • a photocationic polymerization initiator can be used as the photopolymerization initiator.
  • Any known cationic photopolymerization initiator can be used as the cationic photopolymerization initiator.
  • Examples include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenonium salts, dialkylphenacyl sulfonium salts, dialkyl-4-hydroxy salts, sulfonic acid esters, and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio.
  • the holographic recording material of the present invention includes a photosensitizer, a plasticizer, a compatibilizer, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, a polymerization inhibitor, a radical scavenger, and a surfactant as necessary.
  • a silane coupling agent, an antifoaming agent, a release agent, a stabilizer, an antioxidant, a flame retardant and the like may be further included. These additives may be used alone, or two or more of them may be used in any combination and ratio.
  • a matrix resin forming component for example, a polyisocyanate component and a polyol component constituting an isocyanate-hydroxyl polyadduct, a polymerizable compound, a photopolymerization initiator, and, if necessary, represented by the formula (5)
  • a reactive aromatic compound is blended.
  • a matrix resin is formed by causing polymerization by a reaction other than a reaction in which the polymerizable reactive group of the polymerizable compound or the reactive aromatic compound is polymerized with respect to the matrix resin forming component.
  • the matrix resin can be formed by polymerizing a matrix resin forming component in the presence of a polymerizable compound and a photopolymerization initiator.
  • a holographic recording material contains a high refractive index polymerizable compound in addition to a low refractive index matrix resin, and forms a diffraction grating as a refractive index modulation structure in the medium by polymerizing the polymerizable compound during recording. It is preferable.
  • the holographic recording material includes (1) matrix forming components (isocyanate, polyol, reaction catalyst (tin-containing catalyst), etc.), (2) polymerizable compound, (3) photopolymerization initiator, (4) other components, Are mixed and dissolved as appropriate, and (1) only the matrix-forming components are allowed to react independently.
  • a polymerizable compound (3) a photopolymerization initiator, (4) other components Is basically unaffected and is preferably dispersed in the matrix resin as it is.
  • a material in which the holographic recording material is sandwiched between two substrates is called a holographic recording medium.
  • a photopolymerization initiator is cleaved to form polymerization initiation species (radicals, etc.), and (2) polymerization Compound is polymerized.
  • the polymerizable compound or the photopolymerization initiator decreases due to reaction, the performance as a holographic recording material is lowered. Therefore, it is preferable to form a matrix resin without reducing these. Therefore, it is preferable to mix a reaction catalyst or adjust the reaction temperature so that polymerization in a reaction form different from the reaction in which the polymerizable compound is polymerized preferentially occurs.
  • reaction catalyst for example, as a catalyst for isocyanate-hydroxyl polyaddition reaction, a tin-containing catalyst, a titanium-containing catalyst, a zinc-containing catalyst, a zirconium-containing catalyst, an aluminum-containing catalyst, a cobalt-containing catalyst, a nickel-containing catalyst, a copper-containing catalyst, and Various metal-containing catalysts such as iron-containing catalysts can be used. Of these, tin-containing catalysts are preferred from the viewpoint of reaction rate.
  • a tin-containing catalyst such as dimethyltin dilaurate or dibutyltin dilaurate can be used.
  • Non-metal-containing catalysts include 1,4-diazabicyclo [2,2,2] octane (DABCO), imidazole derivatives, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine. Tertiary amine compounds such as can be used. These catalysts may be used alone or in combination of two or more.
  • the holographic recording medium of the present invention includes a recording layer containing the holographic recording material described above.
  • the holographic recording medium of the present invention can have other layers such as an upper substrate, a lower substrate, and a reflective film as necessary.
  • the holographic recording medium of the present invention may be either a transmission type or a reflection type.
  • each substrate and recording layer that can be included in the holographic recording medium of the present invention.
  • the substrate material glass, ceramics, resin and the like are usually used, but resin is preferable from the viewpoint of moldability and cost.
  • the resin include polycarbonate resin, acrylic resin, polycycloolefin resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, ABS resin, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, and urethane resin.
  • polycarbonate resin, acrylic resin, and polycycloolefin resin are particularly preferable in terms of moldability, optical characteristics, and cost.
  • a substrate provided with a reflective layer in advance can also be used according to the recording / reproducing method.
  • the recording layer is made of the holographic recording material, and information can be recorded using the holographic recording.
  • those obtained by subjecting the surface of the recording layer to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate.
  • the holographic recording medium of the present invention is preferably used for holographic recording / reproduction, but any method can be used for the holographic recording / reproduction method.
  • a holographic recording / reproducing method based on the two-beam interference method, a coaxial holographic recording / reproducing method in which reference light and information light are arranged on the same axis and condensed are preferably used.
  • FIG. 3 shows a schematic configuration diagram of an optical system for multiple recording.
  • Laser light emitted from a laser generator (a semiconductor laser having a wavelength of 405 nm) 1 is reflected by a mirror 2 and is a half-wave plate (HWP).
  • HWP half-wave plate
  • the beam diameter is enlarged by the beam expander 5, and then passed through the shutter 6 to be stopped.
  • the beam diameter is narrowed by 7 (opening diameter 6 mm ⁇ ), and reaches the PBS 9 through the HWP 8.
  • the laser light is divided into two, and one of the divided lights passes through the shutter 10, is reflected by the mirror 11, and is applied to the holographic recording medium S as the recording signal light Ls.
  • the other light split by the PBS 9 passes through the quarter wave plate (QWP) 12 and is reflected by the mirror 13, and then passes through the QWP 12 and PBS 9 again to irradiate the holographic recording medium S as the recording reference light Lw. Is done.
  • the angle ⁇ of the rotary stage 14 to which the holographic recording medium S is attached is set to a predetermined value, the shutter 6 is opened for a predetermined time and exposed, and the first hologram is recorded on the holographic recording medium S. .
  • ⁇ is set to the next predetermined value
  • the shutter 6 is opened for a predetermined time and exposed, and a second hologram is recorded in the same location of the holographic recording medium S.
  • multiplex recording can be performed by repeating the above operation until a predetermined multiplicity is reached.
  • HWP3 is for adjusting the power of the entire optical system
  • HWP8 is for adjusting the power ratio of the signal light and the reference light.
  • the QWP 12 is for adjusting the polarization axis of the recording reference light Lw (or reproduction reference light Lr described later).
  • FIG. 4 is a schematic configuration diagram of the reproducing optical system, and the same symbols as those in FIG. 3 have the same meaning.
  • Laser light emitted from the laser generator 1 reaches the PBS 9 via the mirror 2, the HWP 3, the PBS 4, the beam expander 5, the shutter 6, and the diaphragm 7.
  • the PBS 9 the laser light is divided into two, and one of the divided lights is blocked by the shutter 10.
  • the other light divided by the PBS 9 is reflected by the mirror 13 through the QWP 12, and then passes again through the QWP 12 and the PBS 9, and the beam diameter is narrowed by the aperture 15 (opening diameter 2.7 mm ⁇ ), and the reproduction reference light Lr To the holographic recording medium S.
  • the angle ⁇ of the rotary stage 14 to which the holographic recording medium S is attached is set to a value corresponding to a predetermined (reproduced) hologram, the shutter 6 is opened for a predetermined time, and the reproduction reference light Lr is irradiated onto the medium.
  • the intensity of the light (reproduced signal light) diffracted by the recorded hologram is measured by the optical power meter 16, and the intensity of the light transmitted through the medium (transmitted light) is measured by the optical power meter 17.
  • Example 1 1- (I): Synthesis of 4-acetyldiphenyl sulfide 25.0 g (0.136 mol) of diphenyl sulfide was dissolved in 300 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. 149 mol) was added slowly and the mixture was stirred for 15 minutes. A solution prepared by dissolving 11.9 g (0.149 mol) of acetyl chloride in 50 ml of dichloromethane was added dropwise, stirred for 30 minutes, warmed to room temperature, and further stirred for 1 hour.
  • the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography to obtain 3.0 g of the objective compound as a colorless transparent liquid (yield 48%).
  • DMF dimethylformamide
  • the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 68.7 g of a crude product.
  • the obtained crude product was used in the next reaction without further purification.
  • DMF dimethylformamide
  • Example 9 9- (I): Synthesis of 4- (2-naphthylthio) -2-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), 2-naphthalenethiol 25 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Subsequently, after 17.2 g (0.156 mol) of thiophenol was added little by little, the mixture was further stirred at 130 ° C. for 1 hour.
  • DMF dimethylformamide
  • the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml).
  • the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 20.1 g of a crude product.
  • the obtained crude product was used in the next reaction without further purification.
  • Example 10 10- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), thiophenol 17.2 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 25 g (0.156 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour.
  • DMF dimethylformamide
  • DMF dimethylformamide
  • the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml).
  • the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 94.1 g of a crude product.
  • the obtained crude product was used in the next reaction without further purification.
  • the refractive index of each of the compounds obtained in Examples 1 to 11 was determined according to the following procedure. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm. Since the compound obtained in Example 4 was a solid, the refractive index of a compound dissolved in a solvent having a known refractive index was measured using the above apparatus, and the value extrapolated to 100% of the substrate The refractive index of the compound was used. In this case, N-methylpyrrolidone was used as a solvent, and the substrate concentrations were 10% by mass, 20% by mass, and 30% by mass. The results of refractive index measurement are shown in Table 1.
  • ultraviolet / visible absorption spectra were measured according to the following procedures.
  • the above compound was dissolved in acetonitrile to make a 0.001% by weight solution, and an absorption spectrum was measured in a wavelength region of 500 to 200 nm using an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation.
  • FIG. 1 is an ultraviolet / visible absorption spectrum of the compounds obtained in Examples 1 to 3, 9, and 11. In any sample, it was confirmed that there was no absorption in the visible region of 400 nm or more, and the transparency was high.
  • FIG. 2 is an infrared absorption spectrum of the compounds obtained in Examples 1 to 3.
  • the inset in FIG. 2 is an enlarged view of the wave number range of 500 to 1000 cm ⁇ 1 .
  • Example 12 99.5 parts by weight of 2,4-bis (phenylthio) styrene obtained in Example 2 as a polymerizable compound and 0.5 parts by weight of azobisisobutyronitrile as a thermal radical polymerization initiator are stirred and mixed at 40 ° C. Thus, a resin composition was obtained. Furthermore, this resin composition was introduced into a gap formed by bonding two glass substrates (50 mm ⁇ 50 mm) coated with a release agent through silicon film spacers (thickness 1.0 mm). After heat treatment at 60 ° C. for 15 hours, the glass substrate was peeled off to obtain a colorless and transparent sheet-like resin cured product.
  • Example 13 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate obtained in Example 3 was used as the polymerizable compound. It was.
  • Example 14 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 4,4′-bis (phenylthio) phenylmethyl acrylate obtained in Example 8 was used as the polymerizable compound.
  • Example 15 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12, except that 2- (2-naphthylthio) -4-phenylthiostyrene obtained in Example 10 was used as the polymerizable compound.
  • Example 16 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained in Example 11 was used as the polymerizable compound.
  • Comparative Example 1 A pale yellow transparent sheet-like cured resin was obtained in the same manner as in Example 9 except that phenylthioethyl acrylate (manufactured by BIMAX, BX-PTEA) was used as the polymerizable compound.
  • Comparative Example 2 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 9, except that benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester BZ) was used as the polymerizable compound.
  • Comparative Example 3 A light yellow transparent sheet-like resin cured product was obtained in the same manner as in Example 9 except that ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
  • ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
  • Samples having a length of 20 mm, a width of 5 mm, and a thickness of 1.0 mm were cut out from the sheet-like resin cured products obtained in Examples 12 to 16 and Comparative Examples 1 to 3, and the refractive index was measured. The results are shown in Table 2.
  • an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm.
  • the polymerizable compound of the present invention, the resin composition using the same, and the cured product thereof are excellent in high refractive index and excellent in transparency, and are used for glass substitute materials for lens applications, liquid crystal displays, and the like.
  • Suitable for various optical materials such as protective film materials for color filters, coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, etc. Used for.
  • holographic recording materials examples are shown below.
  • the abbreviations and the like in the preparation examples of the holographic recording material are as follows.
  • Matrix resin forming catalyst Dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Photopolymerization initiator 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -2- (O-
  • Example 17 Compound having a polymerizable reactive group containing 34.2 parts (parts by mass) of HMDI, 45.8 parts of G-400, 10.0 parts of OFHDO, and 0.06 parts of matrix resin-forming catalyst as matrix resin-forming components 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2 parts obtained as a polymerizable compound in Example 2 , 4-bis (phenylthio) styrene (3.0 parts by mass), photopolymerization initiator (0.05 parts), and plasticizer (6.0 parts) were blended to prepare a holographic recording material.
  • matrix resin-forming catalyst 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2
  • This holographic recording material was introduced into the gap between two glass substrates (30 mm ⁇ 30 mm) bonded together via a silicon film spacer (thickness 0.5 mm).
  • Holographic recording medium in which a matrix resin is formed by heat treatment at 60 ° C. for 2 hours in a nitrogen atmosphere, and a recording layer made of a holographic recording material is formed between two glass substrates to a thickness of 0.5 mm Got.
  • Example 18 As a matrix resin forming component, 33.7 parts of HMDI, 44.9 parts of G-400, and 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate obtained in Example 4 as a polymerizable compound A holographic recording medium was obtained in the same manner as in Example 17 except that 4.4 parts were used.
  • Example 19 As the matrix resin forming component, 33.9 parts of HMDI, 45.2 parts of G-400, and 4.0 parts of 2,4-bis (2-naphthylthio) styrene obtained in Example 5 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as Example 17 except for the above.
  • Example 20 As a matrix resin forming component, 33.8 parts of HMDI, 45.5 parts of G-400, and 3.5 parts of 4- (2-naphthylthio) -2-phenylthiostyrene obtained in Example 9 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as in Example 17 except that it was used.
  • Table 3 shows the compositions of the holographic recording material precursors of Examples 17 to 20 and Comparative Examples 4 and 5.
  • the number of the compounding amount in Table 3 is part by mass.
  • Holographic recording / reproduction evaluation was performed using a holographic recording / reproduction evaluation machine based on the two-beam interference method. Multiple recording was performed using angle multiplexing.
  • Diffraction efficiency ( ⁇ ) [diffracted light intensity / (transmitted light intensity + diffracted light intensity)] ⁇ 100 (%)
  • M # M number
  • the recording sensitivity was calculated by the formula (III), and the maximum value was defined as the maximum sensitivity.
  • ⁇ diffraction efficiency E is exposure energy [mJ / cm 2 ]
  • L is the media thickness [cm] Represents.
  • FIG. 5 is an integrated value of M # with respect to the recording exposure energy. It can be seen that the media according to Examples 17 to 20 all have a higher M # than the media according to Comparative Examples 4 and 5 and are excellent in multiplex recording properties.
  • FIG. 6 shows the sensitivity to the recording exposure energy. All the media according to Examples 17 to 20 have higher sensitivity than the media according to Comparative Examples 4 and 5, and a high data transfer rate can be realized.
  • Table 4 shows the results of numerical comparison of M # obtained by plane wave measurement, maximum sensitivity, refractive index of polymerizable compound, and number of molecules per gram of material.
  • the polymerizable compound since the polymerizable compound is responsible for forming a refractive index modulation structure when holographic recording is performed, increasing the content improves M # and sensitivity, but on the other hand, it tends to cause polymerization shrinkage. Become. Generally, it is known that the polymerization shrinkage of vinyl monomers is proportional to the inverse of the molecular weight. By aligning the number of molecules of the polymerizable compound contained in the material, it is possible to polymerize with the same shrinkage of the recording medium. The performance between compounds can be compared. It can be seen from Table 4 that when the shrinkage ratios are set to the same level, the medium according to the example clearly has higher M # and sensitivity than the medium according to the comparative example.

Abstract

　L'invention concerne un composé polymérisable ayant un grand indice de réfraction, un facteur élevé de transmission de la lumière et une faible viscosité, une composition de résine l'utilisant, une résine durcie, et un matériau optique. Composé polymérisable représenté par la formule générale (1). Ici, R1-R5 sont chacun un atome d'hydrogène ou un groupe monovalent tel qu'un groupe arylthio, un groupe alkyle ou analogues, mais dont 1-3 sont des groupes arylthio représentés par –S-Ar1 ; X1 est une liaison directe, un atome d'oxygène ou un groupe divalent tel qu'un groupe alkylène ou analogues ; R6 est un groupe polymérisable tel qu'un groupe glycidyle, un groupe acryloyle ou analogues ; et l'Ar1 du -S-Ar1 est un groupe aryle ou un groupe hétéroaryle.
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JP2017190326A (ja) * 2016-04-08 2017-10-19 三菱ケミカル株式会社 （メタ）アクリル酸エステル及びその製造方法、並びにその（共）重合体
JP2018104696A (ja) * 2016-12-26 2018-07-05 旭硝子株式会社 重合性化合物、硬化性組成物および硬化物
JP2020113355A (ja) * 2019-01-15 2020-07-27 学校法人神奈川大学 光学材料、光学素子、及び物品の屈折率を変化させる方法
CN113845622A (zh) * 2021-10-13 2021-12-28 常州邦瑞新材料科技有限公司 一种高折射率高辉度的贴合膜用棱镜树脂及其制备方法
US11529230B2 (en) 2019-04-05 2022-12-20 Amo Groningen B.V. Systems and methods for correcting power of an intraocular lens using refractive index writing
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US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11667742B2 (en) 2019-05-03 2023-06-06 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
US11678975B2 (en) 2019-04-05 2023-06-20 Amo Groningen B.V. Systems and methods for treating ocular disease with an intraocular lens and refractive index writing
US11708440B2 (en) 2019-05-03 2023-07-25 Johnson & Johnson Surgical Vision, Inc. High refractive index, high Abbe compositions
US11795252B2 (en) 2020-10-29 2023-10-24 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
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JP2017190326A (ja) * 2016-04-08 2017-10-19 三菱ケミカル株式会社 （メタ）アクリル酸エステル及びその製造方法、並びにその（共）重合体
JP2018104696A (ja) * 2016-12-26 2018-07-05 旭硝子株式会社 重合性化合物、硬化性組成物および硬化物
JP7056141B2 (ja) 2016-12-26 2022-04-19 Ａｇｃ株式会社 重合性化合物、硬化性組成物および硬化物
JP7215718B2 (ja) 2019-01-15 2023-01-31 学校法人神奈川大学 光学材料、光学素子、及び物品の屈折率を変化させる方法
JP2020113355A (ja) * 2019-01-15 2020-07-27 学校法人神奈川大学 光学材料、光学素子、及び物品の屈折率を変化させる方法
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11931296B2 (en) 2019-04-05 2024-03-19 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11564839B2 (en) 2019-04-05 2023-01-31 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
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US11958923B2 (en) 2019-05-03 2024-04-16 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and abbe number
US11667742B2 (en) 2019-05-03 2023-06-06 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
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