WO2021172552A1 - 硬化物、硬化性樹脂組成物、光学部材、レンズ、回折光学素子及び多層型回折光学素子、並びに、化合物 - Google Patents

硬化物、硬化性樹脂組成物、光学部材、レンズ、回折光学素子及び多層型回折光学素子、並びに、化合物 Download PDF

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WO2021172552A1
WO2021172552A1 PCT/JP2021/007485 JP2021007485W WO2021172552A1 WO 2021172552 A1 WO2021172552 A1 WO 2021172552A1 JP 2021007485 W JP2021007485 W JP 2021007485W WO 2021172552 A1 WO2021172552 A1 WO 2021172552A1
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group
carbon atoms
cured product
pol
hydrogen atom
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French (fr)
Japanese (ja)
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直澄 白岩
直之 師岡
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022503766A priority Critical patent/JP7274040B2/ja
Priority to CN202180011224.0A priority patent/CN115003708B/zh
Publication of WO2021172552A1 publication Critical patent/WO2021172552A1/ja
Priority to US17/881,333 priority patent/US12570901B2/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • C09K19/3861—Poly(meth)acrylate derivatives containing condensed ring systems
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • 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
    • C08F220/387—Esters containing sulfur and containing nitrogen and 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/24—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1814—Diffraction gratings structurally combined with one or more further optical elements, e.g. lenses, mirrors, prisms or other diffraction gratings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1833—Diffraction gratings comprising birefringent materials
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • the present invention relates to a cured product, a curable resin composition, an optical member, a lens, a diffractive optical element, a multilayer diffractive optical element, and a compound.
  • a glass material has been used for an optical member of an imaging module such as a camera, a video camera or a mobile phone with a camera, a videophone or a doorphone with a camera.
  • the glass material has optical characteristics suitable for the optical member of the image pickup module, can impart desired optical characteristics, and has excellent environmental resistance.
  • the cured resin product can be mass-produced and has excellent workability. Therefore, with the recent miniaturization of the imaging module, the cured resin product is used as an optical member to replace the glass material. It has become like.
  • the optical members are also required to be miniaturized.
  • the problem of chromatic aberration arises. Therefore, in an optical member using a cured resin product, it has been studied to correct the chromatic aberration by adjusting the Abbe number with a monomer or an additive of the curable composition.
  • Patent Document 1 by using a curable composition containing a compound (monomer) having an aromatic ring group such as benzodithiol and benzodithiazole, the Abbe number ( ⁇ D) is low and the partial dispersion ratio is partially dispersed. It is disclosed that a cured product having a high ( ⁇ g, F value) can be obtained.
  • a compound (monomer) having an aromatic ring group such as benzodithiol and benzodithiazole
  • the present invention provides a cured product having an aromatic ring having absorption in the near-ultraviolet region such as benzodithiol and benzodithiazole, which has excellent light resistance, and an optical member and a lens containing the cured product.
  • the task is to do.
  • Another object of the present invention is to provide a compound suitable for obtaining the cured product.
  • the present invention includes a curable resin composition suitable for obtaining the cured product, a cured product obtained from the curable resin composition, and a diffractive optical element and a multilayer diffractive optical element containing the cured product. The challenge is to provide.
  • Ar represents an aromatic ring group represented by any of the following general formulas (2-1) to (2-4).
  • L 1 and L 2 indicate -O-.
  • Sp a indicates a linking group having the shortest atomic number of 11 or more connecting Pol 1 and L 1
  • Sp b indicates a linking group having the shortest atomic number of 11 or more connecting Pol 2 and L 2 .
  • Pol 1 and Pol 2 show polymerizable groups.
  • the connecting portion of Sp a to L 1 and the connecting portion of Sp b to L 2 are both -CH 2-
  • the connecting portion of Sp a to Pol 1 and the connecting portion of Sp b to Pol 2 are both. Are all carbon atoms.
  • Q 1 represents -S-, -O- or> NR 11
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms
  • Z 1 , Z 2 and Z 3 are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms.
  • Z 1 and Z 2 may be bonded to each other to form an aromatic hydrocarbon ring or an aromatic heterocycle.
  • R 12 and R 13 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a x represents an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a y represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a x and A y may be combined with each other to form a ring.
  • Q 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * Indicates the bonding position with L 1 or L 2.
  • the connecting portion to Pol 1 or Pol 2 is a carbon atom.
  • Pol 1 and Pol 2 are (meth) acryloyloxy groups.
  • a compound represented by the following general formula (1) In the above formula, Ar represents an aromatic ring group represented by the following general formula (2-2).
  • L 1 and L 2 indicate -O-.
  • Sp a and Sp b are one or more linear alkylene groups having 11 to 30 carbon atoms or linear alkylene groups having 11 to 30 carbon atoms, excluding the linking portion to L 1 or L 2.
  • R 201 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • both the connecting portion of Sp a to Pol 1 and the connecting portion of Sp b to Pol 2 are carbon atoms.
  • Pol 1 and Pol 2 show polymerizable groups.
  • Z 1 and Z 2 are hydrogen atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms, monovalent. Shows are aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR 12 R 13 or -SR 12 having 6 to 20 carbon atoms.
  • Z 1 and Z 2 may be bonded to each other to form an aromatic hydrocarbon ring or an aromatic heterocycle.
  • R 12 and R 13 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Ar represents an aromatic ring group represented by any of the following general formulas (2-1) to (2-4).
  • L 1 and L 2 indicate -O-.
  • Sp a indicates a linking group having the shortest atomic number of 11 or more connecting Pol 1 and L 1
  • Sp b indicates a linking group having the shortest atomic number of 11 or more connecting Pol 2 and L 2 .
  • Pol 1 and Pol 2 show polymerizable groups.
  • the connecting portion of Sp a to L 1 and the connecting portion of Sp b to L 2 are both -CH 2-
  • the connecting portion of Sp a to Pol 1 and the connecting portion of Sp b to Pol 2 are both.
  • Q 1 represents -S-, -O- or> NR 11
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms.
  • Z 1 , Z 2 and Z 3 are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. Shows ⁇ 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR 12 R 13 or -SR 12 .
  • Z 1 and Z 2 may be bonded to each other to form an aromatic hydrocarbon ring or an aromatic heterocycle.
  • R 12 and R 13 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a x represents an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a y represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a x and A y may be combined with each other to form a ring.
  • Q 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * Indicates the bonding position with L 1 or L 2.
  • L P is a single bond or a divalent linking group
  • Ar P represents a phenyl group
  • R P1 is a hydrogen atom or a methyl group.
  • Ar P does not contain the above acidic group. * Indicates a joint.
  • ⁇ 13> The cured product of the curable resin composition according to any one of ⁇ 10> to ⁇ 12>.
  • the first diffractive optical element and the second diffractive optical element are included.
  • the first diffractive optical element is the diffractive optical element according to ⁇ 14>.
  • a multilayer diffractive optical element in which a surface having a diffraction grating shape in the first diffractive optical element and a surface having a diffraction grating shape in the second diffractive optical element face each other.
  • substituents, etc. there is no particular notice when there are a plurality of substituents or linking groups (hereinafter referred to as substituents, etc.) represented by a specific code or formula, or when a plurality of substituents, etc. are specified at the same time.
  • substituents, etc. may be the same or different from each other (regardless of the presence or absence of the expression "independently", the substituents, etc. may be the same or different from each other). This also applies to the regulation of the number of substituents and the like.
  • substituents, etc. may be connected to each other to form a ring unless otherwise specified.
  • the ring for example, an alicyclic ring, an aromatic ring, or a heterocycle may be further condensed to form a condensed ring.
  • the double bond may be any of E-type and Z-type in the molecule, or a mixture thereof.
  • the stereochemistry of such asymmetric carbons is independently the (R) form or the (R) form.
  • S Any of the bodies can be taken.
  • the compound may be a mixture of stereoisomers such as optical isomers or diastereoisomers, or racemates.
  • the labeling of a compound means that a part of the structure is changed within a range that does not impair the effect of the present invention.
  • a compound for which substitution or non-substitution is not specified may have an arbitrary substituent as long as the effect of the present invention is not impaired.
  • a substituent the same applies to a linking group and a ring
  • substitution or non-substitution is not specified in the present invention, it means that the group may have an arbitrary substituent as long as the desired effect is not impaired.
  • the term "alkyl group” means to include both an unsubstituted alkyl group and a substituted alkyl group.
  • this carbon number means the carbon number of the entire group unless otherwise specified in the present invention or the present specification. That is, when this group is in the form of further having a substituent, it means the total number of carbon atoms including this substituent.
  • the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • each component may be used alone or in combination of two or more.
  • the solid content in the curable composition used for producing the cured product of the present invention is the general formula (1).
  • it means a component remaining in the cured product obtained from the curable composition used for producing the cured product of the present invention. Usually, the remainder after removing the solvent is "solid content”. This also applies to the description of the content of each component in the curable resin composition of the present invention.
  • (meth) acrylate represents one or both of acrylate and methacrylate
  • (meth) acryloyl represents one or both of acryloyl and methacryloyl.
  • the monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1000 or less.
  • the term aliphatic hydrocarbon group represents a group obtained by removing one arbitrary hydrogen atom from a linear or branched alkane, a linear or branched alkene, or a linear or branched alkyne. ..
  • the aliphatic hydrocarbon group is preferably an alkyl group obtained by removing one arbitrary hydrogen atom from a linear or branched alkane.
  • alkyl group methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 3-methylbutyl group, hexyl group, 1 -Methylpentyl group, 4-methylpentyl group, heptyl group, 1-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, octyl group, 1-methylheptyl group, nonyl group, 1-methyloctyl group, decyl Examples thereof include a group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an o
  • alkyl group means a linear or branched alkyl group.
  • alkyl group examples include the above examples.
  • alkyl group in the group containing the alkyl group alkoxy group, alkoxycarbonyl group, etc.
  • linear alkylene group in the present invention there is a group obtained by removing one hydrogen atom bonded to the terminal carbon from the linear alkyl group among the above alkyl groups.
  • the alicyclic hydrocarbon ring means a saturated hydrocarbon ring (cycloalkane).
  • the alicyclic hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and the like.
  • the unsaturated hydrocarbon ring means a hydrocarbon ring having a carbon-carbon unsaturated double bond that is not an aromatic ring. Examples of unsaturated hydrocarbon rings include indene, indane, fluorene and the like.
  • the alicyclic hydrocarbon group means a cycloalkyl group obtained by removing one arbitrary hydrogen atom from a cycloalkane.
  • the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and the like, and a cycloalkyl having 3 to 12 carbon atoms. Groups are preferred.
  • the cycloalkylene group represents a divalent group obtained by removing two arbitrary hydrogen atoms from a cycloalkane. Examples of cycloalkylene groups include cyclohexylene groups.
  • aromatic ring means either or both of an aromatic hydrocarbon ring and an aromatic heterocycle.
  • the aromatic hydrocarbon ring means an aromatic ring in which a ring is formed only by carbon atoms.
  • the aromatic hydrocarbon ring may be a monocyclic ring or a condensed ring.
  • An aromatic hydrocarbon ring having 6 to 14 carbon atoms is preferable.
  • Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthylene ring, an anthracene ring, a phenanthrene ring and the like.
  • the aromatic hydrocarbon ring when the aromatic hydrocarbon ring is bonded to another ring, the aromatic hydrocarbon ring should be substituted on the other ring as a monovalent or divalent aromatic hydrocarbon group. Just do it.
  • the monovalent group when referred to as an aromatic hydrocarbon group, it represents a monovalent group obtained by removing one arbitrary hydrogen atom from the aromatic hydrocarbon ring.
  • an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthrasenyl group.
  • Examples thereof include 2-anthrasenyl group, 3-anthrasenyl group, 4-anthrasenyl group, 9-anthrasenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthril group and the like. Of these, a phenyl group is preferred.
  • aromatic hydrocarbon group for a divalent group represents a divalent group obtained by removing one arbitrary hydrogen atom from the monovalent aromatic hydrocarbon group.
  • divalent aromatic hydrocarbon group include a phenylene group, a biphenylene group, a naphthylene group, a phenanthylene group and the like, and a phenylene group is preferable, and a 1,4-phenylene group is more preferable.
  • the aromatic heterocycle means an aromatic ring in which a ring is formed by a carbon atom and a hetero atom.
  • the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the aromatic heterocycle may be a monocyclic ring or a condensed ring, and the number of atoms constituting the ring is preferably 5 to 20, more preferably 5 to 14.
  • the number of heteroatoms in the atoms constituting the ring is not particularly limited, but is preferably 1 to 3, and more preferably 1 to 2.
  • aromatic heterocycles examples include furan, thiophene, pyrrole, imidazole, isothiazole, isoxazole, pyridine, pyrazine, quinoline, benzofuran, benzothiazole, benzoxazole, and. Examples of the nitrogen-containing condensed aromatic ring described later can be mentioned.
  • the aromatic heterocycle when the aromatic heterocycle is bonded to another ring, the aromatic heterocycle may be substituted on the other ring as a monovalent or divalent aromatic heterocyclic group. ..
  • a monovalent group when referred to as an aromatic heterocyclic group, it represents a monovalent group obtained by removing one arbitrary hydrogen atom from the aromatic heterocycle.
  • monovalent aromatic heterocyclic groups include a furyl group, a thienyl group, a pyrrolyl group, an imidazolyl group, an isothiazolyl group, an isooxazolyl group, a pyridyl group, a pyrazinyl group, a quinolyl group and a benzofuranyl group (preferably a 2-benzofuranyl group).
  • Benthiazolyl group preferably 2-benzothiazolyl group
  • benzoxazolyl group preferably 2-benzoxazolyl group
  • a frill group a thienyl group, a benzofuranyl group, a benzothiazolyl group and a benzoxazolyl group are preferable, and a 2-furyl group and a 2-thienyl group are more preferable.
  • divalent aromatic heterocyclic group represents a divalent group obtained by removing two arbitrary hydrogen atoms from the aromatic heterocycle, and an example thereof is the above (monovalent).
  • examples thereof include a divalent group obtained by removing one arbitrary hydrogen atom from an aromatic heterocyclic group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the cured product of the present invention has excellent light resistance. Therefore, the optical member and lens of the present invention containing this cured product as a constituent member are excellent in light resistance and are unlikely to cause deterioration in performance even when used outdoors, for example.
  • the compound of the present invention is suitable as a main raw material for a cured product having the above-mentioned excellent light resistance.
  • the curable resin composition of the present invention is a cured product obtained from this composition and is used as a constituent member of one of the diffraction gratings to obtain a diffractive optical element and a multilayer diffractive optical element having excellent diffraction efficiency. be able to.
  • FIG. 1 is a graph for explaining the shape of the diffraction grating of the mold used in the second embodiment.
  • the horizontal axis is the pitch of the diffraction grating shape
  • the central portion in the cross section of the diffraction grating portion of the mold is 0 mm
  • the pitch from the central portion to the end portion (10 mm) is shown.
  • the vertical axis shows the step of the mold grating.
  • FIG. 2 is a schematic explanatory view of the multilayer diffractive optical element produced in Example 2.
  • the cured product of the present invention is a cured product of a curable composition containing a compound represented by the general formula (1) described later, and the birefringence ⁇ n of the cured product at a wavelength of 587 nm is 0.00 ⁇ ⁇ n ⁇ 0.01. Is.
  • the cured product of the present invention is obtained by advancing the polymerization reaction of the monomer containing the compound represented by the general formula (1) and curing it.
  • the cured product of the present invention may contain an unreacted monomer (for example, a compound represented by the general formula (1)) and the like.
  • the cured product of the present invention becomes a cured product that is three-dimensionally crosslinked by light irradiation or heating, and the monomer used is incorporated into the cured product, so its structure cannot be specified by analysis or the like.
  • the cured product of the present invention has an aromatic ring having a specific structure represented by Ar (hereinafter, abbreviated as “aromatic ring Ar”) derived from the compound represented by the general formula (1).
  • aromatic ring Ar a cured product obtained from a curable composition containing a compound represented by the general formula 1 of Patent Document 1 having an aromatic ring Ar has a refractive index dispersion characteristic. It has a low Abbe number ( ⁇ d), a high partial dispersion ratio ( ⁇ g, F value), and exhibits excellent optical characteristics. However, this cured product did not have sufficient light resistance.
  • the present inventors consider that the cause of the inferior light resistance is that after the aromatic ring Ar is excited by light absorption, the lowest excited triplet state T 1 undergoes a hydrogen abstraction reaction or the like and decomposes. , Diligently examined. As a result, expressed in a polymerizable group represented by the aromatic ring Ar and Pol 1 and Pol 2, linked by a particular linking group represented by L 1 -Sp a and L 2 -Sp b general formula (1) It has been found that the light resistance of the obtained cured product can be effectively enhanced by using the compound as a polymerizable monomer.
  • the birefringence ⁇ n (hereinafter, also referred to as birefringence ⁇ n (587 nm)) at a wavelength of 587 nm of the cured product of the present invention is 0.00 ⁇ ⁇ n ⁇ 0.01.
  • the birefringence ⁇ n (587 nm) is preferably 0.001 or less, and more preferably less than 0.001.
  • the lower limit of the birefringence ⁇ n (587 nm) may be 0.00001 or 0.0001.
  • the birefringence ⁇ n (587 nm) of the cured product can be obtained by the following method.
  • a film-shaped sample is prepared, and birefringence within a circle having a diameter of 10 mm including the center of the sample is measured using a birefringence evaluation device (for example, WPA-100, manufactured by Photonic Lattice Co., Ltd.) at a wavelength of 587 nm.
  • Birefringence ⁇ n (587 nm) can be obtained by obtaining the average value of birefringence.
  • the Abbe number ( ⁇ d) and partial dispersion ratio ( ⁇ g, F) of the cured product are values measured using a Carnew precision refractometer KPR-2000 (manufactured by Shimadzu Device Co., Ltd.). Specifically, the curable composition is injected into a transparent glass mold having a diameter of 20 mm and a thickness of 2 mm, and ultraviolet rays of 1000 mJ / cm 2 are irradiated from above the transparent glass mold in an atmosphere having an oxygen concentration of 1% or less. A cured product is formed (ultraviolet irradiation step), and the Abbe number ( ⁇ d) and partial dispersion ratio ( ⁇ g, F) of this cured product are measured.
  • the Abbe number ( ⁇ d) and partial dispersion ratio ( ⁇ g, F) of the cured product are calculated by the following formulas.
  • a heating step may be adopted instead of the ultraviolet irradiation step, or both the heating step and the ultraviolet irradiation step may be adopted.
  • ⁇ d (nd-1) / (nF-nC) ⁇ g
  • F (ng-nF) / (nF-nC)
  • nd represents the refractive index at the wavelength of 587.56 nm
  • nF represents the refractive index at the wavelength of 486.13 nm
  • nC represents the refractive index at the wavelength of 656.27 nm
  • ng represents the refractive index at the wavelength of 435.83 nm.
  • the Abbe number of the cured product of the present invention is not particularly limited, but is preferably 30 or less, more preferably 27 or less, further preferably 25 or less, and 23 or less. Is particularly preferable.
  • the Abbe number of the cured product of the present invention is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and 7 or more. It is particularly preferable to have.
  • the partial dispersion ratios ⁇ g and F of the cured product of the present invention are not particularly limited, but are preferably 0.65 or more, more preferably 0.70 or more, and 0.75 or more. Is particularly preferable.
  • the partial dispersion ratios ⁇ g and F of the cured product of the present invention are not particularly limited, but are preferably 2 or less, more preferably 1.8 or less, and 1.7 or less. Is particularly preferable.
  • the glass transition temperature (Tg) of the cured product of the present invention is not particularly limited, but is preferably 40 to 200 ° C, more preferably 50 to 180 ° C.
  • the glass transition temperature is measured by the method described in Examples described later.
  • the curable composition contains a compound represented by the general formula (1).
  • the cured product of the present invention is a cured product containing a curable composition containing a compound represented by the following general formula (1).
  • Ar represents an aromatic ring group represented by any of the following general formulas (2-1) to (2-4).
  • L 1 and L 2 indicate -O-.
  • Sp a indicates a linking group having the shortest atomic number of 11 or more connecting Pol 1 and L 1
  • Sp b indicates a linking group having the shortest atomic number of 11 or more connecting Pol 2 and L 2 .
  • Pol 1 and Pol 2 show polymerizable groups. However, both the connecting portion of Sp a to L 1 and the connecting portion of Sp b to L 2 are ⁇ CH 2 ⁇ . Further, both the connecting portion of Sp a to Pol 1 and the connecting portion of Sp b to Pol 2 are carbon atoms.
  • Ar is an aromatic ring group represented by any of the following general formulas (2-1) to (2-4).
  • Q 1 represents -S-, -O-, or> NR 11
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms
  • Z 1 , Z 2 and Z 3 are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms.
  • Z 1 and Z 2 may be bonded to each other to form an aromatic hydrocarbon ring or an aromatic heterocycle.
  • R 12 and R 13 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 21 represents a hydrogen atom or a substituent, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable.
  • a x represents an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a y represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an organic group having 1 to 30 carbon atoms having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocycle.
  • a x and A y may be combined with each other to form a ring.
  • Q 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * Indicates the bonding position with L 1 or L 2.
  • each substituent in the general formulas (2-1) to (2-4) are Y 1 relating to the compound (A) described in JP2012-21068A.
  • Q 1 and Q 2 can be applied to Y 1 , Z 1 and Z 2 , respectively, and A 1 , A 2 for the compound represented by the general formula (I) described in JP-A-2008-107767.
  • the descriptions relating to and X can be directly applied to A 1 , A 2 and X of the general formula (2-2), respectively , and A x , A y and A x, A y and the compound represented by the general formula (I) described in WO2013 / 018526 can be applied.
  • a x respectively general formula described for Q 1 (2-3), it can be applied to a y and Q 2, a a of the compound represented by the general formula (II) according to WO2013 / 018526, a b And Q 11 can be directly applied to A x , A y and Q 2 of the general formula (2-4), respectively.
  • Z 3 the description regarding Q 1 regarding compound (A) described in JP2012-21068 can be applied as it is.
  • X is preferably a carbon atom to which two substituents are bonded, and both A 1 and A 2 are preferably —S—.
  • a 1 and A 2 are preferably —S—.
  • X is preferably a carbon atom to which two substituents are bonded, and both A 1 and A 2 are preferably —S—.
  • a alicyclic hydrocarbon ring, an aromatic hydrocarbon ring or an aromatic heterocycle is preferable. Aromatic heterocycles are more preferred.
  • an unsaturated hydrocarbon ring is preferable as the ring when Ax and Ay are bonded to each other to form a ring.
  • Ar in the general formula (1) is preferably an aromatic ring group represented by the general formula (2-2).
  • the aromatic ring group represented by the general formula (2-2) the aromatic ring group represented by the following general formula (2-21) is preferable.
  • R z indicates a substituent
  • Z 1 and Z 2 are synonymous with Z 1 and Z 2 in the above general formula (2-2), respectively.
  • substituents indicated by R z include substituents that the linear alkylene group in Sp a and Sp b described later may have, such as an alkyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom and a cyano. Groups are preferred.
  • the two Rz may be the same or different. Further, two Rz may be bonded to form a ring.
  • the formed ring is preferably a 5-membered ring or a 6-membered ring, and nitrogen atom or oxygen is used as an atom constituting the ring. More preferably, it contains an atom.
  • the ring formed by combining two R z is more preferably a ring represented by any of the following structures.
  • * indicates the position of the carbon atom to which the two Rz are bonded in the general formula (2-21), respectively.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a linear alkyl group having 1 to 4 carbon atoms is more preferable.
  • an aromatic ring group represented by the general formula (2-21) an aromatic ring group in which at least one R z is a cyano group or an aromatic ring group in which two R z are bonded to form a ring.
  • an aromatic ring group represented by the following general formula (2-21a) in which both of the two Rz are cyano groups is more preferable.
  • the adhesion can be further improved.
  • Z 1 and Z 2 are synonymous with Z 1 and Z 2 in the above general formula (2-2), respectively.
  • Sp a , Sp b Sp a indicates a linking group having the shortest atomic number of 11 or more connecting Pol 1 and L 1
  • Sp b indicates a linking group having the shortest atomic number of 11 or more connecting Pol 2 and L 2 .
  • the connecting portion of Sp a to L 1 and the connecting portion of Sp b to L 2 are both -CH 2-
  • the connecting portion of Sp a to Pol 1 and the connecting portion of Sp b to Pol 2 are both.
  • the provisions of these connecting parts also apply to the subsequent descriptions relating to Sp a and Sp b.
  • Examples of the "shortest atoms is 11 or more linking groups" in the -L 2 -Sp b -Pol 2 shown below, -O- and is L 2, connecting the methacryloyloxy group is Pol 2
  • the shortest number of atoms is 10.
  • the shortest number of atoms is preferably 11 to 30, more preferably 11 to 25, further preferably 12 to 25, and particularly preferably 12 to 20.
  • the linking group represented by Sp a or Sp b is a linear alkylene group having 11 to 30 carbon atoms or a linear alkylene group having 11 to 30 carbon atoms, and the linking portion to L 1 or L 2 is used.
  • R 201 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the carbon number in the above-mentioned "linear alkylene group having 11 to 30 carbon atoms” means the carbon number in a state without a substituent. Therefore, as the carbon number in the linear alkylene group having 11 to 30 carbon atoms, the preferable carbon number described in the shortest atomic number can be applied. In connection with this, when the "linear alkylene group having 11 to 30 carbon atoms" has a substituent, an alkyl group can also be adopted as the substituent.
  • Examples of the substituent that the linear alkylene group in Sp a and Sp b may have include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an amide group and an amino group.
  • Examples thereof include a group, a halogen atom, a nitro group and a cyano group, and an alkyl group is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
  • the number of substituents is not particularly limited, and for example, it may have 1 to 4 substituents.
  • the linking group represented by Sp a or Sp b is a linear alkylene group having 11 to 30 carbon atoms or a linear alkylene group having 11 to 30 carbon atoms from the viewpoint of further improving the light resistance of the cured product.
  • the group is more preferable as the linking group represented by Sp a or Sp b, the adhesion can be further improved.
  • Sp a and Sp b may be the same or different, but are preferably the same.
  • the polymerizable group may be a group containing any one of a vinylidene structure, an oxylan structure and an oxetane structure. From the viewpoint of convenience in synthesizing the compound represented by the general formula (1), the polymerizable group has an oxygen atom at the linking portion to Sp a or Sp b, and has a vinylidene structure, an oxylan structure and an oxetane structure. It is preferable that the group contains any of the above, and examples thereof include polymerizable groups represented by any of the following formulas (Pol-1) to (Pol-6).
  • the (meth) acryloyloxy group represented by the above formula (Pol-1) or the above formula (Pol-2) is preferable, and the methacryloyloxy group represented by the above formula (Pol-2) is more preferable.
  • Either one of Pol 1 and Pol 2 is preferably a (meth) acryloyloxy group, and more preferably both are (meth) acryloyloxy groups.
  • Pol 1 and Pol 2 may be the same or different, and are preferably the same.
  • Pol 1 described in the specific example of the compound represented by the general formula (1) will be described later.
  • Examples thereof include a structure of -Sp a- L 1- or Pol 2- Sp b -L 2-.
  • Pol 1- Sp a- L 1- and Pol 2- Sp b- L 2- may be the same or different, but it is preferable that they are the same.
  • the structure represented by the following notation indicates an isopropylene structure.
  • This isopropylene structure may be any of two structural isomers in which a methyl group is bonded to one of the carbons constituting the ethylene group, and these structural isomers may be mixed.
  • the compound represented by the general formula (1) when a linear alkylene group has a structure in which a substituent is substituted, structural isomers having different substitution positions of the substituent may exist. ..
  • the compound represented by the general formula (1) may be a mixture of such structural isomers.
  • the compound represented by the general formula (1) is preferably a non-liquid crystal compound. That is, from the viewpoint of using the above-mentioned Sp a and Sp b as a lens material, it is preferable that both of them are linking groups having no ring structure.
  • Me represents a methyl group
  • Et represents an ethyl group
  • nPr represents an n-propyl group
  • iPr represents an isopropyl group
  • nBu represents an n-butyl group
  • tBu represents a t-butyl group.
  • the content of the compound represented by the general formula (1) in the curable composition is preferably 20 to 99% by mass, preferably 25% by mass to 98% by mass, from the viewpoint of adjusting the refractive index. Is more preferable, and 30 to 96% by mass is further preferable.
  • the curable composition may contain two or more compounds represented by the general formula (1).
  • the total content is preferably within the above range.
  • the curable composition may further contain other components in addition to the compound represented by the general formula (1).
  • other components include (meth) acrylate monomers, polymers having a radically polymerizable group in the side chain, and polymerization initiators.
  • the curable composition may contain a (meth) acrylate monomer.
  • the (meth) acrylate monomer may be a polyfunctional (meth) acrylate monomer having two or more (meth) acryloyl groups in the molecule, or a monofunctional (meth) acrylate monomer having one (meth) acryloyl group in the molecule. ) It may be an acrylate monomer.
  • the upper limit of the number of (meth) acryloyl groups contained in the (meth) acrylate monomer is not particularly limited, and may be, for example, 8 functional or less.
  • (meth) acrylate monomer examples include monomer 1 (phenoxyethyl acrylate), monomer 2 (benzyl acrylate), monomer 3 (tricyclodecanedimethanol diacrylate) and monomer 4 (dicyclopentanyl acrylate). Can be mentioned.
  • M-1 (1,6-hexanediol diacrylate), M-2 (1,6-hexanediol dimethacrylate), M-3 (benzyl acrylate), M-4 (isobornyl methacrylate), M- 5 (dicyclopentanyl methacrylate), M-6 (dodecyl methacrylate), M-7 (2-ethylhexyl acrylate), M-8 (2-hydroxyethyl acrylate), M-9 (hydroxypropyl acrylate), M- Examples thereof include 10 (4-hydroxybutyl acrylate), M-11 (2-ethylhexyl methacrylate) and M-12 (decyl methacrylate).
  • the (meth) acrylate monomer described in paragraphs 0037 to 0046 of JP2012-107191A can be mentioned.
  • the (meth) acrylate monomer is preferably 2-ethylhexyl methacrylate, decyl methacrylate or dodecyl methacrylate, and more preferably decyl methacrylate or dodecyl methacrylate from the viewpoint of excellent light resistance and permeability.
  • the molecular weight of the (meth) acrylate monomer is preferably 100 to 500.
  • the method for obtaining the (meth) acrylate monomer is not particularly limited, and the (meth) acrylate monomer may be obtained commercially or synthesized by a conventional method.
  • the (meth) acrylate monomer may be obtained commercially or synthesized by a conventional method.
  • the (meth) acrylate monomer may be obtained commercially or synthesized by a conventional method.
  • the (meth) acrylate monomer may be obtained commercially or synthesized by a conventional method.
  • the curable composition when it is necessary to increase the hardness and abrasion resistance of the surface of the cured product, contains a polyfunctional (meth) acrylate monomer having three or more (meth) acryloyl groups in the molecule. Is preferable. By including a polyfunctional (meth) acrylate monomer having three or more (meth) acryloyl groups in the molecule, the crosslink density of the cured product can be effectively improved, so that a high partial dispersion ratio can be maintained. Surface hardness and abrasion resistance can be increased.
  • the upper limit of the number of polyfunctional (meth) acrylate monomer (meth) acryloyl groups having three or more (meth) acryloyl groups in the molecule is not particularly limited, but is preferably 8 and more preferably 6. ..
  • A-TMPT monomer 5
  • A-TMMT monomer 6
  • AD-TMP monomer 7
  • A-DPH monomer 8
  • the content of the (meth) acrylate monomer in the curable composition is preferably 1 to 80% by mass, more preferably 2 to 50% by mass, and 3 to 3 to 50% by mass. 40% by mass is more preferable.
  • the curable composition when the curable composition contains a polyfunctional (meth) acrylate monomer having three or more (meth) acryloyl groups in the molecule, the curable composition
  • the content of the polyfunctional (meth) acrylate monomer having three or more (meth) acryloyl groups in the molecule in the substance is preferably 5 to 95% by mass, more preferably 10 to 80% by mass, and 25 to 70% by mass. % Is more preferable.
  • the content of the compound represented by the general formula (1) in the curable composition is preferably 5 to 95% by mass, more preferably 20 to 95% by mass, still more preferably 30 to 75% by mass.
  • Such a composition can be used as a composition for forming a hard coat.
  • the curable composition may contain a polymer having a radically polymerizable group in the side chain.
  • a polymer having a radically polymerizable group in the side chain for example, the description of the polymer having a radically polymerizable group in the side chain in [0088] to [095] of International Publication No. 2019/044863 is preferably applied. Can be done.
  • the curable composition preferably contains at least one of a thermal radical polymerization initiator and a photoradical polymerization initiator as the polymerization initiator.
  • the curable composition preferably contains a thermal radical polymerization initiator. By the action of this thermal polymerization initiator, the curable composition can be thermally polymerized to form a cured product exhibiting high heat resistance.
  • thermal radical polymerization initiator a compound usually used as a thermal radical polymerization initiator can be appropriately used according to the conditions of the thermal polymerization (thermosetting) step described later.
  • organic peroxides and the like can be mentioned, and specifically, the following compounds can be used.
  • the content of the thermal radical polymerization initiator in the curable composition is preferably 0.01 to 10% by mass, preferably 0.05 to 5.0% by mass. More preferably, it is more preferably 0.05 to 2.0% by mass.
  • the curable composition preferably contains a photoradical polymerization initiator.
  • a photoradical polymerization initiator a compound usually used as a photoradical polymerization initiator can be appropriately used according to the conditions of the photopolymerization (photocuring) step described later, and specifically, the following compounds are used. Can be done.
  • bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide bis (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4) 6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1-phenyl-2-hydroxy-2-methyl Propane-1-one, 1-hydroxycyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1,2-diphenylethanedione, methylphenylglycolate, 1 -[4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- ⁇
  • 1-hydroxycyclohexylphenylketone available as Irgacure 184 (trade name) from BASF
  • bis (2,4,6-trimethylbenzoyl) -phenylphosphenyl oxide available from BASF
  • Irgacure 819 (trade name) from BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (available as Irgacure 651 (trade name) from BASF), 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one or 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one is preferred. Can be used.
  • the content of the photoradical polymerization initiator in the curable composition is preferably 0.01 to 5.0% by mass, preferably 0.05 to 1.0% by mass. It is more preferably%, and further preferably 0.05 to 0.5% by mass.
  • the curable composition preferably contains both a photoradical polymerization initiator and a thermal radical polymerization initiator. In this case, the total content of the photoradical polymerization initiator and the thermal radical polymerization initiator is the curable composition. It is preferably 0.01 to 5% by mass, more preferably 0.05 to 1.0% by mass, and preferably 0.05 to 0.5% by mass with respect to the total mass of the product. More preferred.
  • the curable composition containing the compound represented by the general formula (1) is a polymer or monomer other than the above-mentioned components, a dispersant, a plasticizer, a heat stabilizer, a mold release agent, and the like. It may contain a solvent or the like.
  • the viscosity of the curable composition containing the compound represented by the general formula (1) is preferably 20,000 mPa ⁇ s or less, more preferably 15,000 mPa ⁇ s or less, and 13,000 mPa ⁇ s or less. It is more preferably 10,000 mPa ⁇ s or less, and particularly preferably 10,000 mPa ⁇ s or less.
  • the viscosity of the curable composition is preferably 2,000 mPa ⁇ s or more, more preferably 3,000 mPa ⁇ s or more, further preferably 4,000 mPa ⁇ s or more, and 5, It is particularly preferable that it is 000 mPa ⁇ s or more.
  • the cured product of the present invention is a cured product of a curable resin composition containing the compound represented by the above-mentioned general formula (1), and is indium tin oxide (also abbreviated as "ITO" in the present invention).
  • ITO indium tin oxide
  • a cured product containing particles is also preferably mentioned.
  • the curable resin composition of the present invention (hereinafter, also simply referred to as “the curable resin composition of the present invention”) used for preparing the cured product is a compound represented by the above-mentioned general formula (1) and Includes ITO particles.
  • the curable resin composition of the present invention contains other components that may be contained in the curable composition described above, and a polymer dispersion described later. It may contain an agent or the like. Regarding other components that may be contained in the above-mentioned curable composition, the description of the content of each component in the curable composition can be read as the content in the curable resin composition of the present invention. can.
  • the particle size of the ITO particles is preferably 5 to 50 nm. By setting the thickness to 50 nm or less, deterioration of the transmittance due to Rayleigh scattering can be prevented. Further, at 5 nm or more, ITO particles can be produced without technical difficulty.
  • the particle size of ITO particles can be determined by averaging the particle size measured by a transmission electron microscope (TEM). That is, the minor axis and the major axis of one particle of the electron micrograph taken by TEM are measured, and the average value thereof is obtained as the particle diameter of one particle.
  • TEM transmission electron microscope
  • the particle size of 500 particles is randomly obtained, and the average value (arithmetic mean) of these 500 particle sizes is calculated and used as the average primary particle size.
  • the curable resin composition of the present invention is prepared by mixing ITO particles dispersed in a solvent with the compound represented by the above general formula (1) and the polymer (dispersant) described later. Is preferable. After mixing, the solvent used for dispersing the ITO particles may or may not be removed from the curable resin composition by distillation or the like, but it is preferable that the solvent is removed.
  • the surface modification of the ITO particles is preferably performed using, for example, a monocarboxylic acid having 6 to 20 carbon atoms as the surface modification compound.
  • the surface modification of ITO particles with a monocarboxylic acid is performed by forming an ester bond with the oxygen atom on the surface of the ITO particle by the carboxy group derived from the monocarboxylic acid, or by coordinating the carboxy group with respect to the In or Ti atom. It is preferably done.
  • Examples of the monocarboxylic acid having 6 to 20 carbon atoms include oleic acid (18 carbon atoms), stearic acid (18 carbon atoms), palmitic acid (16 carbon atoms), myristic acid (14 carbon atoms) or decanoic acid (carbon carbon atoms). The number 10) is mentioned, and oleic acid (18 carbon atoms) is preferable.
  • the site derived from the surface-modified compound (for example, a group derived from a monocarboxylic acid having 6 to 20 carbon atoms) in the surface-modified ITO particles may be directly bonded to the ITO particles.
  • a part may be replaced with a group derived from a polymer described later, or all may be replaced with a group derived from a polymer described later.
  • both a site derived from a surface-modifying compound for example, a group derived from a monocarboxylic acid having 6 to 20 carbon atoms
  • a group derived from a polymer described later are bonded to the surface of ITO particles. It is preferable to have.
  • the solvent is preferably a solvent in which the component ( ⁇ p) of the polar term of the solubility parameter (SP value) is 0 to 6 MPa (1/2).
  • the component ( ⁇ p) of the polarity term of the SP value is a value calculated by the Hansen solubility parameter.
  • the Hansen solubility parameter is composed of intermolecular dispersion force energy ( ⁇ d), intermolecular polar energy ( ⁇ p), and intermolecular hydrogen bonding energy ( ⁇ h).
  • the Hansen solubility parameter shall be calculated using HSPiP (version 4.1.07) software.
  • the solvent is preferably toluene (1.4), xylene (1.0) or hexane (0), and more preferably toluene.
  • the value in parentheses is the value of ⁇ p, and the unit is MPa (1/2) .
  • the method for producing ITO particles is not particularly limited, and for example, the ITO particles can be produced according to the procedure described in ACS Nano 2016, 10, 6942-6951.
  • a dispersion liquid of surface-modified ITO particles can be obtained.
  • an alcohol obtained by heating a solution of a mixture of a monocarboxylic acid having 6 to 20 carbon atoms, an indium salt (for example, indium acetate) and a tin salt (for example, tin acetate) to a high temperature (long-chain alcohol such as oleyl alcohol). Can be dropped into and maintained at a high temperature to form particles.
  • Dispersion solution can be obtained.
  • the content ratio of ITO particles in the curable resin composition of the present invention is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 20 to 50% by mass.
  • the curable resin composition of the present invention preferably contains a polymer that functions as a dispersant in the curable resin composition (hereinafter, this polymer is also referred to as "polymer dispersant").
  • the polymer dispersant has a structural unit represented by the following general formula (P), and also has an acidic group at one end of the polymer chain.
  • L P is a single bond or a divalent linking group
  • Ar P represents an aryl group
  • R P1 is a hydrogen atom or a methyl group.
  • Ar P does not contain the above acidic group.
  • * Indicates a bond for incorporation into the polymer backbone.
  • the aryl group of Ar P a phenyl group, a 1-naphthyl group or a 2-naphthyl group is preferable.
  • Preferred examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group and an aryl group.
  • Methyl group which may take as R P1 is preferably free of the acid group as a substituent.
  • the polymer dispersant is a polymer having an acidic group indicating an adsorbing group for ITO particles at one end of the polymer chain and having a structural unit represented by the general formula (P) containing Ar P (aryl group). be.
  • the curable resin composition of the present invention contains the above polymer dispersant together with ITO particles and a compound represented by the general formula (1), so that the polymer dispersant has Ar P in the side chain and the general formula (1).
  • the compatibility of both components is enhanced by the ⁇ - ⁇ interaction with the aromatic ring of the compound represented by, the interaction between the acidic group of the polymer dispersant and the ITO particles, etc., and the dispersion stability of the composition is effective. It is thought that it can be enhanced.
  • the curable resin composition of the present invention can not only enhance the dispersibility at the time of preparing the curable resin composition, but also sufficiently enhance the medium- to long-term dispersion stability. ..
  • the acidic groups that the polymer dispersant has at one end of the polymer chain are carboxy group (-COOH), phosphono group (-PO (OH) 2 ), phosphonooxy group (-OPO (OH) 2 ), and hydrohydroxyphosphoryl group (-). It is preferably selected from PH (O) (OH)), sulfino group (-SO (OH)), sulfo group (-SO 2 (OH)) and sulfanyl group (-SH).
  • the other end of the polymer chain in the polymer dispersant is not particularly limited as long as the desired dispersibility can be obtained, but it is preferable that it does not have an acidic group, and the other end thereof is, for example, a hydrogen atom, an alkyl group, or the like. Can be done.
  • the polymer dispersant may contain a small amount of a polymer having an acidic group at both ends of the polymer chain in addition to the polymer having an acidic group at one end of the polymer chain.
  • the composition is stable even if the polymer having an acidic group at both ends is contained.
  • the polymer dispersant may contain an acidic group in the side chain of the polymer chain as long as the desired dispersibility can be obtained.
  • the side chain contains an acidic group, it is preferable not to include it because ITO particles tend to aggregate.
  • the acidic group exhibits an adsorption action on the surface of indium tin oxide particles by at least one of ionic bond, covalent bond, hydrogen bond and coordination bond.
  • the acidic group is more preferably a carboxy group, a phosphono group or a phosphonooxy group, and further preferably a carboxy group, from the viewpoint of further improving the dispersion stability in the medium to long term.
  • the carbon number of the alkylene portion is preferably 1 to 4, more preferably 1 to 2.
  • n is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 2, and particularly preferably 1.
  • L P is a single bond, an alkylene group or * - (alkylene -O) n -, more preferably a single bond, -CH 2 -, * - CH 2 O-or * -CH 2 CH 2 O-are more preferred.
  • L P * shows the side of the bond that does not bind to Ar P.
  • the main chain skeleton portion of the polymer dispersant may be linear or branched. Of these, it is preferably linear.
  • the polymer dispersant may have a structural unit represented by the following general formula (P2) in addition to the structural unit represented by the general formula (P) within a range in which the desired dispersibility can be obtained. good.
  • RP3 represents a hydrogen atom or a methyl group
  • RP2 represents a monovalent substituent
  • R P2 is not be -L P -Ar P in the above general formula (P).
  • * Indicates a bond for incorporation into the polymer backbone.
  • RP2 is preferably an alkyl group or an alicyclic hydrocarbon group, preferably an alkyl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.
  • Methyl group which may take as R P3 is preferably free of the acid group as a substituent.
  • the polymer dispersant preferably has a main chain structure and a side chain structure composed of a structural unit represented by the general formula (P), and the structural unit represented by the general formula (P) and the general formula (P2). ) Is also preferable. Further, within the range in which the desired dispersibility can be obtained, the structural units (formulas (P) and (P2)) that are different from the structural units represented by the general formulas (P) and (P2) are represented. It may have a structural unit derived from a monomer having an ethylenically unsaturated bond, which is not a structural unit to be formed. When the polymer dispersant is a copolymer, it may be either random or block.
  • the ratio of the general formula (P) to all the constituent units constituting the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, for example. From the viewpoint of further improving the dispersion stability in the medium to long term, the above ratio is more preferably 10 mol% or more, further preferably 15 mol% or more. The upper limit of this ratio is not particularly limited, and it is also preferable that all the structural units in the polymer dispersant are the structural units represented by the general formula (P).
  • the ratio of the general formula (P2) to all the structural units constituting the polymer dispersant is preferably 95 mol% or less, for example.
  • the lower limit of the ratio is not particularly limited and may exceed 0 mol%.
  • the structural unit constituting the polymer dispersant means a structural unit derived from the monomer component, and can be calculated from the content ratio of the monomer component.
  • the content of the structural unit represented by the general formula (P) in the polymer dispersant is not particularly limited, but is preferably 20% by mass or more, for example. From the viewpoint of further improving the dispersion stability in the medium to long term, the above ratio is more preferably 30% by mass or more, further preferably 50% by mass or more.
  • the upper limit of this ratio is not particularly limited, and it is also preferable that all the structural units in the polymer dispersant are the structural units represented by the general formula (P).
  • the polymer dispersant preferably has a structural portion represented by the following general formula (PA) at one end of the polymer chain as a structural portion containing the acidic group.
  • PA general formula
  • a P represents an acidic group
  • LL represents a single bond or x + 1 valent linking group
  • x is an integer of 1-8. * Indicates the bonding position of the polymer dispersant with the remaining sites.
  • Acidic group which can be taken as A P has the same meaning as acidic group described above, the preferred form also the same.
  • the LL is preferably a group consisting of an x + 1 valent alkane or a combination of an x + 1 valent alkane and —O—.
  • x is preferably an integer of 1 to 6, more preferably an integer of 2 to 4, and even more preferably an integer of 2.
  • the structure represented by the general formula (PA) is preferably a structure represented by the following general formula (PA1), and by having a carboxy group at a adjacent site, the adsorptivity to ITO particles is improved. From the viewpoint, it is more preferable that the structure is represented by the following formula (PA2).
  • LL and x in the above formula are synonymous with LL and x in the above general formula (PA). * Indicates the bonding position of the polymer dispersant with the remaining sites.
  • the acid value of the polymer dispersant is preferably 2.0 mgKOH / g or more and less than 100 mgKOH / g, more preferably 2.0 mgKOH / g or more and less than 70 mgKOH / g, and 10 mgKOH / g or more and less than 50 mgKOH / g. It is more preferable to have.
  • the acid value means the number of mg of potassium hydroxide required to neutralize the acidic component present in 1 g of the polymer.
  • the polymer dispersant can be sufficiently adsorbed and dispersed on the ITO particles. Further, when the acid value of the polymer dispersant is less than the above-mentioned preferable upper limit value, the number of adsorptive groups and the molecular size can be adjusted, and the viscosity of the curable resin composition can be adjusted to an appropriate range.
  • the weight average molecular weight of the polymer dispersant is not particularly limited, but is preferably 1000 to 30000, more preferably 1000 to 20000, and further preferably 1000 to 15000 from the viewpoint of further improving dispersion stability in the medium to long term. It is preferable, and 1000 to 13000 is particularly preferable.
  • 1000 to 10000 it is possible to suppress the mixing of bubbles generated during curing of the curable resin composition.
  • the fluidity is less likely to decrease even when an amount required for dispersing ITO particles is added to the curable resin composition, and when forming a cured product having a diffraction grating shape. In addition, air gaps are unlikely to occur at the steps of the mold.
  • polymer dispersant examples are listed below, but the structure is not limited to these. Although the specific examples shown below are all homopolymers, they may be copolymers and may have a structural unit other than the structural unit represented by the general formula (P). Further, the specific example shown below has a structural portion containing an acidic group at one end, and the other end is a methyl group, but a group other than the methyl group may be used. n it has the same meaning as n in L P in formula (P).
  • the polymer dispersant can be produced by a conventional method. For example, it can be produced by reacting a (meth) acrylate monomer with a compound capable of terminating the polymerization reaction of this monomer and having an acidic group. Examples of such a compound include mercaptosuccinic acid, mercaptooxalic acid or mercaptomalonic acid, and mercaptosuccinic acid is preferable. Further, for the polymer dispersant having a phosphonooxy group at one end, the method described in JP-A-6-20261 can be referred to.
  • the content of the polymer dispersant with respect to 100 parts by mass of the ITO particles is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and 4 to 20 parts by mass. More preferred.
  • the content ratio in the above-mentioned preferable range, it is possible to stably disperse the ITO particles in the curable resin composition and suppress the mixing of bubbles generated during curing.
  • the cured product of the present invention can be produced by a method including at least one of a step of photocuring and a step of thermosetting the above-mentioned curable composition.
  • the method for producing a cured product includes a step of forming a semi-cured product by irradiating the curable composition with light or heating the curable composition, and irradiating the obtained semi-cured product with light or semi-curing product. It is preferable to include a step of forming a cured product by heating the cured product. The same applies when the curable resin composition of the present invention is used instead of the curable composition described above.
  • step of forming a semi-cured product the “step of forming a cured product” and the “semi-cured product” are referred to as [0106] to [0117] and [0118] to [0118] in International Publication No. 2019/044863, respectively.
  • step of forming a semi-cured product the “step of forming a cured product” and “semi-cured product” in [0124] and [0125] can be applied as they are.
  • the cured product of the present invention Since the cured product of the present invention has a low birefringence and excellent light resistance, it can be used for various purposes. For example, it can be used as a coating layer such as a hard coat layer. Further, in addition to the above, the cured product of the present invention having a low Abbe number ( ⁇ d) and a high partial dispersion ratio ( ⁇ g, F) can be preferably used for an optical member, and is more suitable for an optical member requiring light resistance. It can be preferably used. Further, the cured product of the present invention containing ITO particles is preferably used as a material for manufacturing a diffractive optical element. In particular, it is used as a material for manufacturing a low Abbe number diffractive optical element in a multilayer diffractive optical element, and can provide excellent diffraction efficiency.
  • optical member The type of the optical member is not particularly limited, but it can be suitably used as an optical member that transmits light (so-called passive optical member).
  • optical functional device provided with such an optical member include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP (Overhead projector), liquid crystal projector, etc.), optical fiber communication device (optical waveguide, etc.).
  • OHP Overhead projector
  • optical fiber communication device optical waveguide, etc.
  • imaging devices such as cameras or videos, etc. are exemplified.
  • the passive optical member examples include a lens, a prism, a prism sheet, a panel (plate-shaped molded body), a film, an optical waveguide (film-shaped or fiber-shaped, etc.), an optical disk, an LED encapsulant, and the like.
  • the passive optical member may be provided with an arbitrary coating layer or an arbitrary additional function layer, if necessary.
  • the passive optical member includes a protective layer that prevents mechanical damage to the coated surface due to friction or wear, a light absorbing layer that absorbs light of an undesired wavelength that causes deterioration of inorganic particles or a substrate, and the like.
  • a transmission shielding layer, an antiglare layer, an antireflection layer, a low refractive index layer, or the like may be provided to suppress or prevent the permeation of reactive low molecules such as water or oxygen gas.
  • the coating layer include a transparent conductive film or gas barrier film composed of an inorganic oxide or inorganic nitride coating layer, a gas barrier film or a hard coat film composed of an organic material coating layer, and the like.
  • a coating method for forming the coating layer a known coating method such as a vacuum deposition method, a CVD method, a sputtering method, a dip coating method, or a spin coating method can be used.
  • the optical member may be a lens base material. That is, the cured product of the present invention may be used as a lens base material.
  • the term "lens substrate” means a single member capable of exerting a lens function.
  • the lens base material produced by using the cured product of the present invention exhibits a low Abbe number and a high partial dispersion ratio.
  • the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of the monomer constituting the curable composition, and further, high refractive index, light transmittance, It can be used as a lens base material having both lightness and lightness.
  • a film or member may be provided on or around the surface of the lens base material depending on the usage environment or application of the lens.
  • a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens base material.
  • the lens base material produced by using the cured product of the present invention is made into a composite lens in which one or more lens base materials selected from a glass lens base material, a plastic lens base material, and the like are laminated. Can be done.
  • the periphery of the lens base material may be fitted and fixed in a base material holding frame or the like.
  • these films or frames are members added to the lens base material, and are distinguished from the lens base material itself referred to in the present specification.
  • the lens base material When the lens base material is used as a lens, the lens base material itself may be used alone as a lens, or the above-mentioned film or frame, or other lens base material may be added and used as a lens.
  • the type or shape of the lens using the lens base material is not particularly limited, but the maximum thickness is preferably 0.1 to 10 mm. The maximum thickness is more preferably 0.1 to 5 mm, still more preferably 0.15 to 3 mm.
  • the lens base material preferably has a circular shape having a maximum diameter of 1 to 1000 mm. The maximum diameter is more preferably 2 to 200 mm, still more preferably 2.5 to 100 mm.
  • the lens base material is preferably used for an imaging lens such as a mobile phone or a digital camera, an imaging lens such as a television or a video camera, an in-vehicle lens, or an endoscopic lens.
  • a bonded lens can be manufactured by using the cured product of the present invention as an adhesive for adhering two lenses (hereinafter, also referred to as an adhesive for lenses). Since the cured product of the present invention has excellent light resistance, the bonded lens functions as a UV-cutting adhesive, and optics of a member located inside the adhesive, for example, a lens using a resin cured product. The member can be protected from ultraviolet rays and the like. In addition, the cured product of the present invention exhibits excellent adhesion even after a light irradiation test, and therefore can be suitably used as an adhesive.
  • the bonded lens can be obtained by superimposing two lenses via the curable composition and then curing the curable composition to form an adhesive layer made of the cured product of the present invention.
  • Curing is preferably performed after the above superposition and after removing air bubbles mixed in the curable composition.
  • Curing of the curable composition can be carried out by light irradiation or heating. Curing is preferably performed by at least light irradiation. Further, a step of further heating after performing light irradiation may be carried out.
  • the above description can be referred to as appropriate.
  • the thickness of the adhesive layer is preferably 10 to 50 ⁇ m, more preferably 20 to 30 ⁇ m.
  • a light resistance effect that is, an effect of absorbing ultraviolet rays (UV: ultraviolet) can be sufficiently obtained.
  • UV: ultraviolet ultraviolet
  • the thickness it is possible to increase the transmittance of visible light in the short wavelength region (400-430 nm) while exhibiting high adhesiveness.
  • the refractive index of the adhesive layer at a wavelength of 587 nm is preferably 1.51 or more, more preferably 1.53 or more, and even more preferably 1.55 or more. This is because the difference in the refractive index from the lens to be joined becomes small.
  • the cutoff wavelength is preferably 380 nm or less, more preferably 385 nm or less, and even more preferably 390 nm or less in the adhesive layer having a film thickness of 30 ⁇ m.
  • the wavelength at which the transmittance of the adhesive layer is 0.5% or less is defined as the cutoff wavelength.
  • the transmittance of the adhesive layer can be measured using a spectrophotometer (for example, UV-2550 manufactured by Shimadzu Corporation).
  • the refractive index and cutoff wavelength of the adhesive layer can be adjusted within the above ranges depending on the content of the compound component represented by the general formula (1) in the lens adhesive.
  • the diffractive optical element of the present invention is a diffractive optical element including a surface having a diffraction grating shape formed of the cured product of the present invention containing ITO particles, and the compound represented by the general formula (1) and the ITO particles Is formed by curing the curable resin composition of the present invention containing.
  • the diffractive optical element of the present invention preferably has a maximum thickness of 2 ⁇ m to 100 ⁇ m. The maximum thickness is more preferably 2 ⁇ m to 50 ⁇ m, and particularly preferably 2 ⁇ m to 30 ⁇ m.
  • the step (lattice thickness) of the diffraction grating shape (periodic structure) of the diffraction optical element is preferably 1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m.
  • the pitch of the diffraction grating shape of the diffractive optical element may be between 0.1 mm and 10 mm, and it is preferable that the pitch changes within the same diffractive optical element according to the required optical aberration.
  • the diffractive optical element can be manufactured, for example, by the following procedure.
  • the curable resin composition is sandwiched between the surface of a mold having a surface processed into a diffraction grating shape and a transparent substrate. After that, the curable resin composition may be pressurized and stretched to a desired range.
  • the curable resin composition is cured by irradiating light from the transparent substrate side in the sandwiched state. Then, the cured product is removed from the mold. After the mold is released, light may be further irradiated from the side opposite to the transparent substrate side.
  • the transparent substrate examples include flat glass and flat transparent resin ((meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, etc.).
  • the transparent substrate used in the above production may be included in the diffractive optical element as it is, or may be peeled off.
  • the surface of the mold processed into a diffraction grating shape is preferably treated with chromium nitride.
  • chromium nitride treatment include a method of forming a chromium nitride film on the surface of a mold.
  • the method for forming a chromium nitride film on the mold surface include a CVD (Chemical Vapor Deposition) method and a PVD (Physical Vapor Deposition) method.
  • the CVD method is a method of forming a chromium nitride film on the surface of a substrate by reacting a raw material gas containing chromium with a raw material gas containing nitrogen at a high temperature.
  • the PVD method is a method of forming a chromium nitride film on the surface of a substrate by using an arc discharge (arc type vacuum deposition method).
  • arc discharge arc type vacuum deposition method.
  • a cathode (evaporation source) made of chromium is placed in a vacuum vessel, and an arc discharge is caused between the cathode and the wall surface of the vacuum vessel via a trigger to evaporate the cathode.
  • the metal is ionized by arc plasma, a negative voltage is applied to the substrate, and a reaction gas (for example, nitrogen gas) is put into a vacuum vessel at about several tens of mTorr (1.33 Pa) to form an ionized metal and reaction gas. Is reacted on the surface of the substrate to form a film of the compound.
  • a reaction gas for example, nitrogen gas
  • the light used for light irradiation for curing the curable resin composition is preferably ultraviolet rays or visible light, and more preferably ultraviolet rays.
  • metal halide lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, sterilization lamps, xenon lamps, LED (Light Emitting Diode) light source lamps and the like are preferably used.
  • the illuminance of ultraviolet light used for light irradiation for curing the curable resin composition is preferably 1 to 100 mW / cm 2 , more preferably 1 to 75 mW / cm 2, and 5 to 50 mW / cm 2. It is more preferably cm 2. Ultraviolet light having different illuminance may be irradiated multiple times.
  • the exposure amount of ultraviolet light is preferably 0.4 to 10 J / cm 2 , more preferably 0.5 to 5 J / cm 2 , and even more preferably 1 to 3 J / cm 2 .
  • the atmosphere at the time of light irradiation is preferably an atmosphere in which air or an inert gas is replaced, and more preferably an atmosphere in which air is replaced with nitrogen until the oxygen concentration becomes 1% or less.
  • the multilayer diffractive optical element of the present invention includes a first diffractive optical element and a second diffractive optical element, and the first diffractive optical element is a diffractive optical element formed of the cured product of the present invention.
  • the surface of the first diffractive optical element having a diffraction grating shape and the surface of the second diffractive optical element having a diffraction grating shape face each other. It is preferable that the surfaces having the shapes of the diffraction gratings are in contact with each other.
  • the diffractive optical element formed by curing the curable resin composition of the present invention is used as the first diffractive optical element, and the second diffractive optical element formed of different materials faces each other in a lattice-shaped plane. It is preferable to stack them to form a multilayer diffractive optical element. At this time, it is preferable that the lattice-shaped surfaces are in contact with each other.
  • the second diffractive optical element With a material having a higher refractive index and a higher Abbe number than the first diffractive optical element, flare is suppressed and the chromatic aberration reducing action of the multilayer diffractive optical element is fully utilized. be able to.
  • the Abbe number ⁇ d of the second diffractive optical element is not particularly limited, but is preferably larger than 30, more preferably 35 or more, and further preferably 40 or more.
  • the Abbe number ⁇ d of the second diffractive optical element is not particularly limited, but is preferably 70 or less, more preferably 60 or less, and further preferably 50 or less. Among them, the Abbe number ⁇ d of the second diffractive optical element is preferably 35 to 60.
  • the refractive index nd of the second diffractive optical element is preferably 1.55 or more and 1.70 or less, and more preferably 1.56 or more and 1.65 or less. Further, the refractive index nd of the second diffractive optical element is larger than the refractive index nd of the first diffractive optical element used at the same time in the multilayer diffractive optical element, that is, the refractive index nd of the second diffractive optical element>. It is assumed that the refractive index nd of the first diffractive optical element is satisfied.
  • the material for forming the second diffractive optical element is not particularly limited as long as a cured product having a high refractive index and a high Abbe number can be obtained.
  • a curable resin composition containing a sulfur atom, a halogen atom, or a (meth) acrylate monomer having an aromatic structure or a curable resin composition containing zirconium oxide and a (meth) acrylate monomer can be used.
  • the multilayer diffractive optical element can be manufactured, for example, by the following procedure. For forming a second diffractive optical element between the diffraction grating-shaped surface (the surface obtained after the above-mentioned mold release) of the diffractive optical element formed by curing the curable resin composition of the present invention and the transparent substrate. Insert the material. After this, the material may be pressurized and stretched to a desired range. In the sandwiched state, light is irradiated from the transparent substrate side to cure the above material. Then, the cured product is removed from the mold. That is, as the multilayer diffractive optical element of the present invention, it is preferable that the first diffractive optical element, the second diffractive optical element, and the transparent substrate are arranged in this order.
  • Examples of the transparent substrate include the same examples as the transparent substrate used in the manufacture of the diffractive optical element (first diffractive optical element).
  • the transparent substrate used in the above production may be included in the multilayer diffractive optical element as it is, or may be peeled off.
  • the diffraction efficiency of the multilayer diffractive optical element is preferably high.
  • the diffraction efficiency of the primary light on the d-line (wavelength 587 nm), F-line (486 nm) and C-line (656 nm) of the multilayer diffractive optical element is preferably 95% or more.
  • the diffraction efficiency of the primary light can be calculated, for example, by the method described in Examples described later. Since the diffraction efficiency of the primary light of the multilayer diffractive optical element shows high diffraction efficiency in the d-line, F-line and C-line, the diffraction efficiency of the primary light in the entire visible light region becomes about 95% or more. Unnecessary diffracted light can be sufficiently suppressed, and a high-performance lens can be realized.
  • the maximum thickness of the multilayer diffractive optical element is preferably 50 ⁇ m to 20 mm.
  • the maximum thickness is more preferably 50 ⁇ m to 10 mm, and particularly preferably 50 ⁇ m to 3 mm.
  • the diffractive optical element and the multilayer diffractive optical element can be used as lenses, respectively.
  • a film or a member can be provided on the surface or the periphery of the lens depending on the usage environment and application of the lens.
  • a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens.
  • it can be a composite lens laminated on a glass lens or a plastic lens.
  • the periphery of the lens can be fitted into a base material holding frame or the like to be fixed.
  • these films or frames are members added to the lens and are distinguished from the lens itself referred to in the present specification.
  • the lens is preferably used for an imaging lens such as a mobile phone or a digital camera, an imaging lens such as a television or a video camera, and an in-vehicle lens.
  • EDAC 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • HEMA hydroxyethyl methacrylate
  • HPA hydroxypropyl acrylate
  • HPMA hydroxypropyl methacrylate
  • DMAc N, N-dimethylacetamide
  • THF tetrahydrofuran
  • Acetyl group Et Ethyl group
  • the compound (Y-2) was synthesized by the same method as the synthesis of the compound (I-6) except that the raw material compound 11-bromoundecanoic acid in the synthesis of the compound (I-6) was changed to 7-bromoenanthic acid.
  • Example 1 Preparation of curable composition
  • (1) Preparation of curable composition
  • the component (A) or the comparative compound, the component (B), and the photoinitiator so as to have the composition shown in the table below, and stirring to make them uniform.
  • a curable composition was prepared.
  • the cured product obtained from the curable composition described in the table below becomes a cured product that is three-dimensionally crosslinked by light irradiation, and the monomer used is incorporated into the cured product. Therefore, the structure is specified by analysis or the like. I could't.
  • a cured product sanded on a glass plate by irradiating 2 J / cm 2 ultraviolet rays using EXECURE3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere with an oxygen concentration of 1% or less.
  • EXECURE3000 trade name, manufactured by HOYA Corporation
  • the transmittance T1 (%) at 450 nm was measured using a spectrophotometer UV-2600 (trade name, manufactured by Shimadzu Corporation). After that, a UV light cut filter (transmittance of less than 1% with a wavelength of 390 nm or less) was placed on the cured product sample, and a xenon-accelerated weather resistance tester Q-SUN Xe-1 (trade name, manufactured by Q-Lab) was used. After irradiation for 360 hours under the condition of an illuminance of 0.4 W / m 2 (340 nm), the transmittance T2 (%) at 450 nm was measured.
  • the change in transmittance ( ⁇ T%) before and after the light irradiation test was calculated according to the following formula, and the light resistance ( ⁇ T%) was evaluated based on the following criteria.
  • "B" or higher is acceptable.
  • ⁇ T% T1-T2 ... (Equation) - ⁇ T% evaluation- AAA: ⁇ T% was less than 4%.
  • AA: ⁇ T% was 4% or more and less than 5%.
  • A: ⁇ T% was 5% or more and less than 8%.
  • B: ⁇ T% was 8% or more and less than 10%.
  • Adhesion test (1) Preparation of a cured product sample for adhesion test A curable composition is prepared by placing 10 ⁇ L of the curable composition prepared above on a circular flat glass (BK7) having a diameter of 30 mm and sandwiching it between glass plates of the same size. Spread out. A cured product sanded on a glass plate (adhesion test) by irradiating 2 J / cm 2 ultraviolet rays using EXECURE3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere with an oxygen concentration of 1% or less. A cured product sample) was obtained.
  • EXECURE3000 trade name, manufactured by HOYA Corporation
  • the curable resin composition prepared above is injected into a circular transparent glass mold having a diameter of 20 mm so that the thickness of the cured product is 2 mm, and a UV irradiation device (EXECURE3000 (commodity)) is used in an atmosphere having an oxygen concentration of 1% or less. Name), manufactured by HOYA Co., Ltd.) was irradiated with ultraviolet rays of 15 mW / cm 2 for 150 seconds to obtain a cured product sample for optical measurement.
  • a UV irradiation device EXECURE3000 (commodity)
  • the "birefringence ⁇ n" is within a circle having a diameter of 10 mm including the center of the cured product sample for optical measurement prepared above using a birefringence evaluation device (WPA-100 (trade name), manufactured by Photonic Lattice Co., Ltd.). The birefringence of was measured and the average value was measured.
  • WPA-100 trade name
  • nd refrtive index
  • ⁇ d Abbe number
  • ⁇ g, F partial dispersion ratio
  • the "refractive index (nd)” is the refractive index at a wavelength of 587.56 nm.
  • the “Abbe number ( ⁇ d)” and “partial dispersion ratio ( ⁇ g, F)” are values calculated by the following formulas from the measured refractive indexes at different wavelengths.
  • ⁇ d (nd-1) / (nF-nC) ⁇ g
  • F (ng-nF) / (nF-nC)
  • nd represents the refractive index at the wavelength of 587.56 nm
  • nF represents the refractive index at the wavelength of 486.13 nm
  • nC represents the refractive index at the wavelength of 656.27 nm
  • ng represents the refractive index at the wavelength of 435.83 nm.
  • the cured products obtained from 101 to 112 have a double refraction ⁇ n of 0.0003 to 0.0006, a refractive index of 1.55 to 1.60 at a wavelength of 587.56 nm, and an Abbe number. It was as low as 21 to 18, and the partial dispersion ratio was as high as 0.8 to 0.9, satisfying the abnormal dispersibility of the refractive index required for the chromatic aberration correction lens.
  • ⁇ Glass transition temperature> Preparation of a cured product sample for measuring the glass transition temperature
  • the curable composition prepared above is sandwiched between glass plates of the same size so as to have a thickness of 150 um on an 8 cm ⁇ 5 cm hydrophobized glass plate. So, the curable composition was spread.
  • EXECURE3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere with an oxygen concentration of 1% or less, after irradiating with 2 J / cm 2 ultraviolet rays, the glass plate is removed to remove the cured product single film (glass transition). A cured product sample for temperature measurement) was obtained.
  • each component in the table is as follows.
  • the blending amount ratio of each component is based on mass.
  • the component (B) means a (meth) acrylate monomer.
  • Curable Composition No. Each of the comparative cured products obtained from c01 or c02 has a linking group having 7 or 10 atoms as Sp a and Sp b in the general formula (1), respectively, and does not have a linking group having 11 or more atoms. In that respect, it is not a cured product specified in the present invention.
  • Curable Composition No. The comparative cured product obtained from c01 had ⁇ Abs of 15% or more and ⁇ T% of 15% or more before and after the light irradiation test, and the curable composition No.
  • the comparative cured product obtained from c02 had ⁇ Abs of 10% or more and ⁇ T% of 15% or more before and after the light irradiation test, and both were inferior in light resistance.
  • the curable composition No. None of the comparative compounds obtained from c03 or c04 is a cured product specified in the present invention in that the bond to Ar in the general formula (1) is an ester bond and not an ether bond.
  • the comparative cured products obtained from c03 or c04 had a ⁇ Abs of 10% or more and a ⁇ T% of 15% or more before and after the light irradiation test, and were inferior in light resistance.
  • Each component in the table is as follows.
  • the blending amount ratio of each component is based on mass.
  • the blending amount of ITO particles means the amount of solid content in the ITO particle dispersion liquid.
  • ITO particles (ITO-1) 75 ml of oleic acid (Sigma-Aldrich, technical grade, 90%) and 10.060 g (34.5 mmol) of indium acetate (Alfa Aesar, 99.99%) and 1.079 g (3) in a flask. .0 mmol) of tin acetate (IV) (manufactured by Alfa Aesar) was added. The mixture in this flask was heated at 160 ° C. for 1 hour in a nitrogen flow environment to give a clear yellow precursor solution.
  • ITO-1 oleic acid-coordinated ITO particles
  • concentration of the solid content (ITO particles + surface treatment component) in the dispersion was 5% by mass, and the ratio of the surface treatment component in the solid content was 5% by mass.
  • ITO particles (ITO-1) were observed by TEM (trade name: JFM-ARM300F2 GRAND, manufactured by JEOL Ltd.), the average primary particle size was 28.5 nm. Specifically, the measurement was performed based on the above-mentioned method for measuring the particle size of ITO particles.
  • Polymer dispersant (P-1) Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 10.8 g, t-butyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 9.2 g, mercapto humic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.95 g was dissolved in 23 mL of methyl ethyl ketone and heated to 70 ° C. under a nitrogen stream.
  • a polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-65
  • the polymer dispersant (P-1) is substantially composed of a polymer having a carboxy group at one end.
  • the weight average molecular weight (Mw) of the obtained polymer is 5900 in terms of standard polystyrene by the GPC (Gel Permeation Chromatography) method measured under the following measurement conditions, and the dispersity (Mw / Mn, Mn: number average molecular weight) is It was 1.70.
  • the number of mg of potassium hydroxide required to neutralize the free fatty acid present in 1 g of the obtained polymer was measured and the acid value was determined, it was 20 mgKOH / g.
  • Measuring instrument HLC-8320GPC (trade name, manufactured by Tosoh Corporation) Column: Connect TOSOH TSKgel SuperHZM-H (trade name, manufactured by Tosoh), TOSOH TSKgel SuperHZ4000 (trade name, manufactured by Tosoh), and TOSOH TSKgel SuperHZ2000 (trade name, manufactured by Tosoh).
  • Carrier THF Measurement temperature: 40 ° C
  • Carrier flow rate 0.35 mL / min
  • Sample concentration 0.1%
  • Detector RI (refractive index) detector
  • curable resin composition B 150 g of zirconium oxide dispersion (trade name: SZR-K, manufactured by Sakai Chemical Co., Ltd.), 45.6 g of FA-512AS (trade name, manufactured by Hitachi Kayaku Co., Ltd.) and KAYARAD HX -620 (trade name, manufactured by Nippon Kayaku Co., Ltd.) was added and stirred until uniform. Methanol and MEK (methyl ethyl ketone) were distilled off by suction under reduced pressure while heating in a water bath at about 70 ° C. To the mixture obtained after distillation, 1.0 g of IRGACURE 651 (trade name, manufactured by BASF) was added and dissolved to prepare a curable resin composition B.
  • IRGACURE 651 (trade name, manufactured by BASF) was added and dissolved to prepare a curable resin composition B.
  • the curable resin composition A is supplied to a mold processed into the shape of the diffraction grating shown in FIG. BK7 (borosilicate crown glass) was placed on the resin, and the resin was pressed to extend the resin to the outermost periphery of the mold.
  • a cured product was obtained by irradiating 1.0 J / cm 2 of ultraviolet rays using an EXECURE 3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere having an oxygen concentration of 1% or less.
  • a diffractive optical element was manufactured by removing the cured product integrated with the flat glass from the mold.
  • the curable resin composition B is supplied to the surface side of the cured product of the diffractive optical element, and the flat glass (BK7 (borosilicate crown glass)) is placed in contact with the supplied curable resin composition B.
  • the resin was pressed and stretched to a desired range.
  • the curable resin composition B was cured by irradiating with ultraviolet rays of 2.0 J / cm 2 using EXECURE3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere having an oxygen concentration of 1% or less.
  • EXECURE3000 trade name, manufactured by HOYA Corporation
  • the produced multilayer diffractive optical element 5 is formed by sandwiching the cured product 2 of the curable resin composition A and the cured product 3 of the curable resin composition B between two flat glass plates 1.
  • the multilayer diffractive optical element has a diameter of 20 mm, a thickness of the cured product of the curable resin composition A of 5 ⁇ m (excluding the diffraction grating portion), and a thickness of the cured product of the curable resin composition B of 150 ⁇ m (excluding the diffraction grating portion).
  • the diffraction grating has a disk-like structure with a lattice thickness of 10.2 ⁇ m and a total thickness of 165.2 ⁇ m.
  • An EXECURE 3000 (trade name, manufactured by HOYA Corporation) was used as a UV irradiation device in an atmosphere having an oxygen concentration of 1% or less, and after irradiating with 2 J / cm 2 ultraviolet rays, the glass plate was peeled off to prepare a cured product. The refractive index was measured for the cured product on the SUS plate.
  • ⁇ Preparation of cured product of curable resin composition B> The curable resin composition B prepared above was sandwiched between two borosilicate glasses whose surfaces were hydrophobized with dichlorodimethylsilane, and the thickness was adjusted to 150 ⁇ m.
  • EXECURE3000 (trade name, manufactured by HOYA Corporation) as a UV irradiation device in an atmosphere with an oxygen concentration of 1% or less, after irradiating with 2 J / cm 2 ultraviolet rays, the two glass plates are peeled off to prepare a cured product. bottom.

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PCT/JP2021/007485 2020-02-28 2021-02-26 硬化物、硬化性樹脂組成物、光学部材、レンズ、回折光学素子及び多層型回折光学素子、並びに、化合物 Ceased WO2021172552A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022181725A1 (ja) * 2021-02-25 2022-09-01 富士フイルム株式会社 硬化性樹脂組成物及び接合レンズ
JP2023058288A (ja) * 2021-10-13 2023-04-25 キヤノン株式会社 光学素子、光学機器、撮像装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11926113B2 (en) * 2022-08-03 2024-03-12 Himax Technologies Limited Optical element and method for manufacturing optical element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077057A (ja) * 2010-10-06 2012-04-19 Sumitomo Chemical Co Ltd ジヒドロキシベンゼン化合物の製造方法
WO2017098988A1 (ja) * 2015-12-08 2017-06-15 Dic株式会社 重合性化合物及び光学異方体
WO2019044863A1 (ja) * 2017-08-30 2019-03-07 富士フイルム株式会社 硬化物、光学部材、レンズ、化合物、及び硬化性組成物
WO2020171197A1 (ja) * 2019-02-22 2020-08-27 富士フイルム株式会社 樹脂組成物、硬化物、回折光学素子、多層型回折光学素子

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014045818A1 (ja) 2012-09-20 2014-03-27 富士フイルム株式会社 光重合方法、インクセット、画像形成方法、インク組成物並びにこれらに用いる光重合開始剤および水溶性ビイミダゾール
KR102487304B1 (ko) * 2015-01-16 2023-01-11 디아이씨 가부시끼가이샤 중합성 조성물 및 그것을 사용한 광학 이방체
JP6237934B2 (ja) * 2015-01-16 2017-11-29 Dic株式会社 重合性組成物及びそれを用いた光学異方体
WO2017145484A1 (ja) 2016-02-25 2017-08-31 富士フイルム株式会社 水性硬化性組成物、及び、水溶性光重合開始剤
CN110476480B (zh) * 2017-03-30 2022-03-15 富士胶片株式会社 有机el图像显示装置
WO2019131572A1 (ja) * 2017-12-26 2019-07-04 富士フイルム株式会社 レンズ用接着剤、接合レンズ、および撮像モジュール
JP6923744B2 (ja) * 2018-03-14 2021-08-25 富士フイルム株式会社 硬化物、光学部材、レンズ、及び化合物
JP7281881B2 (ja) * 2018-07-31 2023-05-26 住友化学株式会社 水平配向液晶硬化膜およびこれを含む積層体
JP7311958B2 (ja) * 2018-11-09 2023-07-20 住友化学株式会社 垂直配向液晶硬化膜およびそれを含む積層体
EP3990569B1 (en) * 2019-06-28 2024-12-04 Rolic Technologies AG New polymerizable liquid crystal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077057A (ja) * 2010-10-06 2012-04-19 Sumitomo Chemical Co Ltd ジヒドロキシベンゼン化合物の製造方法
WO2017098988A1 (ja) * 2015-12-08 2017-06-15 Dic株式会社 重合性化合物及び光学異方体
WO2019044863A1 (ja) * 2017-08-30 2019-03-07 富士フイルム株式会社 硬化物、光学部材、レンズ、化合物、及び硬化性組成物
WO2020171197A1 (ja) * 2019-02-22 2020-08-27 富士フイルム株式会社 樹脂組成物、硬化物、回折光学素子、多層型回折光学素子

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022181725A1 (ja) * 2021-02-25 2022-09-01 富士フイルム株式会社 硬化性樹脂組成物及び接合レンズ
JP2023058288A (ja) * 2021-10-13 2023-04-25 キヤノン株式会社 光学素子、光学機器、撮像装置
US12601864B2 (en) 2021-10-13 2026-04-14 Canon Kabushiki Kaisha Optical element, optical equipment, and imaging apparatus

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