WO2022181725A1 - 硬化性樹脂組成物及び接合レンズ - Google Patents

硬化性樹脂組成物及び接合レンズ Download PDF

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Publication number
WO2022181725A1
WO2022181725A1 PCT/JP2022/007744 JP2022007744W WO2022181725A1 WO 2022181725 A1 WO2022181725 A1 WO 2022181725A1 JP 2022007744 W JP2022007744 W JP 2022007744W WO 2022181725 A1 WO2022181725 A1 WO 2022181725A1
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group
lens
carbon atoms
resin composition
structural unit
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English (en)
French (fr)
Japanese (ja)
Inventor
貴文 中山
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2023502506A priority Critical patent/JP7753334B2/ja
Priority to CN202280008602.4A priority patent/CN116802218A/zh
Publication of WO2022181725A1 publication Critical patent/WO2022181725A1/ja
Priority to US18/330,791 priority patent/US20230322985A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B13/00—Optical objectives specially designed for the purposes specified below
    • G02B13/001—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras
    • G02B13/0055—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras employing a special optical element
    • G02B13/006—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras employing a special optical element at least one element being a compound optical element, e.g. cemented elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a curable resin composition and a cemented lens.
  • a compound (monomer) containing a skeleton such as benzodithiol, benzothiazole, or phenylhydrazone is used as an absorber in the near-ultraviolet region in the cured resin.
  • These compounds are also excellent in fastness to ultraviolet irradiation, and the curable resin composition containing the above compounds can be used as an "ultraviolet cut layer" that protects resin materials that are prone to photodegradation from ultraviolet rays.
  • Patent Document 2 describes a curable resin composition containing ITO (indium tin oxide) nanoparticles and a monomer having a benzodithiol skeleton.
  • the adhesion of the obtained cured product to the glass substrate is not sufficient when a conventional curable resin composition containing a compound having a skeleton such as benzodithiol, benzothiazole or phenylhydrazone is blended.
  • a conventional curable resin composition containing a compound having a skeleton such as benzodithiol, benzothiazole or phenylhydrazone
  • further improvements are necessary for use as a lens adhesive.
  • the compatibility between the compound containing a skeleton such as benzodithiol, benzothiazole or phenylhydrazone in the composition and other resin components is not sufficient. It has also been found that further improvements are needed in terms of obtaining cured products with high transmittance.
  • the technique described in Patent Document 2 provides a resin composition that can be used as a low Abbe number resin for multilayer diffraction grating elements, and does not describe application to adhesives.
  • the present invention relates to a curable resin composition containing a monomer having a skeleton such as benzodithiol, benzothiazole, or phenylhydrazone, which provides a cured product having excellent adhesion to a glass substrate and excellent transmittance.
  • An object of the present invention is to provide a curable resin composition capable of Another object of the present invention is to provide a cemented lens containing a cured product obtained from this curable resin composition.
  • a curable resin composition comprising the following component (A) and the following component (B).
  • Component (A) A compound represented by the following general formula (1).
  • the structural unit (b1) does not have a hydrogen bonding group.
  • Ar represents an aromatic ring group represented by any one of the following general formulas (2-1) to (2-4).
  • R 101 to R 104 represent -Sp c -Pol 3 or halogen atoms.
  • Sp a and Sp b are a single bond, an optionally substituted linear alkylene group having 1 to 30 carbon atoms, or an optionally substituted linear alkylene group having 2 to 30 carbon atoms.
  • group wherein one or more —CH 2 — excluding the linking portion to L 1 or L 2 is selected from —O—, —S—, >C( O) and >NR 111 indicates a group replaced by R 111 represents -Sp d -Pol 4 or a halogen atom.
  • Sp c and Sp d represent a single bond or a divalent linking group.
  • Pol 1 and Pol 2 represent polymerizable groups
  • Pol 3 and Pol 4 represent hydrogen atoms or polymerizable groups.
  • 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 each represent 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, or 6 carbon atoms.
  • Z 1 and Z 2 may combine with each other to form an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • 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 and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • 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 and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • a x and A y may combine with each other to form a ring.
  • Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * indicates the binding position with L1 or L2.
  • the hydrogen-bonding group of the structural unit (b2) is a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an amino group, a sulfanyl group, an amide group, a urethane group, a urea group, a thiourethane group,
  • the curable resin composition according to ⁇ 1> which is at least one of a thiourea group and a sulfonamide group.
  • the component (B) has a structural unit represented by the following general formula (p1) as the structural unit (b1), and a structural unit represented by the following general formula (p2) as the structural unit (b2).
  • the curable resin composition according to ⁇ 3> which is a vinyl polymer having In the above formula, R P1 and R P2 represent a hydrogen atom or a methyl group, L P1 and L P2 represent a single bond or a divalent linking group, and Ar P is an aromatic hydrocarbon which may have a substituent. represents an aromatic heterocyclic group optionally having a group or a substituent, and R P3 represents a monovalent substituent.
  • L P2 and R P3 is a hydroxy group, carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, amino group, sulfanyl group, amide group, urethane group, urea group, thiourethane group, thiourea group and at least one group of a sulfonamide group.
  • the structural unit represented by general formula (p1) does not have a hydrogen bonding group. * indicates a binding site for incorporation into the polymer.
  • the above L 1 and L 2 are —O—, the above Sp a is a linking group having the shortest number of atoms of 11 to 30 that connects the above Pol 1 and the above L 1 , and the above Sp b is the above Pol 2
  • ⁇ 8> The cemented lens according to ⁇ 7>, wherein at least one of the lens A and the lens B is a glass lens.
  • substituents, etc. when there are a plurality of substituents or connecting groups (hereinafter referred to as substituents, etc.) indicated by a specific symbol or formula, or when a plurality of substituents, etc. are defined at the same time, there is no particular notice.
  • substituents, etc. may be the same or different from each other (regardless of the presence or absence of the expression "independently", the respective substituents, etc. may be the same or different from each other). This also applies to the number of substituents and the like.
  • substituents and the like when a plurality of substituents and the like are close to each other (especially when they are adjacent), they may be linked together to form a ring unless otherwise specified.
  • rings such as alicyclic rings, aromatic rings, and heterocyclic rings may be condensed to form condensed rings.
  • the double bond may be either E-type or Z-type, or a mixture thereof, unless otherwise specified.
  • the stereochemistry of such asymmetric carbon atoms is independently (R)-form or It can take either of the (S) forms.
  • the compounds may be mixtures of stereoisomers, such as optical isomers or diastereoisomers, or may be racemates.
  • the expression of a compound is meant to include those in which a part of the structure is changed within a range that does not impair the effects of the present invention.
  • compounds that are not specified as substituted or unsubstituted are meant to have optional substituents within a range that does not impair the effects of the present invention.
  • substituents the same applies to linking groups and rings
  • substitution or unsubstitution is not specified in the present invention
  • the meaning that the group may have any substituent as long as the desired effect is not impaired. is.
  • the term "alkyl group” is meant to include both unsubstituted alkyl groups and substituted alkyl groups.
  • this number of carbon atoms means the number of carbon atoms in the entire group unless otherwise specified in the present invention or this specification.
  • this group when this group is in the form of further having a substituent, it means the total number of carbon atoms including this substituent.
  • a numerical range represented by “to” means a range including the numerical values before and after “to” as lower and upper limits.
  • each component may be used alone or in combination of two or more.
  • the solid content in the curable resin composition of the present invention means, in addition to the compound represented by the general formula (1), the curing of the present invention. It means a component remaining in the cured product obtained from the flexible resin composition. Usually, the remainder after removing the solvent is the "solid content”.
  • (meth)acrylate represents either or both of acrylate and methacrylate
  • (meth)acryloyl represents either or both of acryloyl and methacryloyl.
  • a 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.
  • aliphatic hydrocarbon group refers to 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 groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 3-methylbutyl, hexyl, 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 group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.
  • the aliphatic hydrocarbon group (unsubstituted) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and further an alkyl group having 1 to 4 carbon atoms.
  • Preferred are methyl and ethyl groups.
  • the alkyl group means a linear or branched alkyl group.
  • the alkyl group include those described above. The same applies to alkyl groups in groups containing alkyl groups (alkoxy groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amido groups, amino groups, silyl groups substituted with alkoxy groups (alkoxysilyl groups), etc.).
  • examples of the alkylene group include groups obtained by removing one arbitrary hydrogen atom from the above alkyl group
  • examples of the straight-chain alkylene group include straight-chain among the above-mentioned alkyl groups. Examples thereof include groups obtained by removing one hydrogen atom bonded to a terminal carbon atom from an alkyl group.
  • an alicyclic hydrocarbon ring means a saturated hydrocarbon ring (cycloalkane).
  • alicyclic hydrocarbon rings 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.
  • unsaturated hydrocarbon rings include indene, indane, fluorene, and the like.
  • an alicyclic hydrocarbon group means a cycloalkyl group obtained by removing one arbitrary hydrogen atom from a cycloalkane.
  • alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl groups, and cycloalkyl groups having 3 to 12 carbon atoms. groups are preferred.
  • a cycloalkylene group represents a divalent group obtained by removing two arbitrary hydrogen atoms from a cycloalkane.
  • cycloalkylene groups include cyclohexylene groups.
  • aromatic ring means either one or both of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • an aromatic hydrocarbon ring means an aromatic ring formed only by carbon atoms.
  • the aromatic hydrocarbon ring may be monocyclic or condensed.
  • Aromatic hydrocarbon rings having 6 to 14 carbon atoms are preferred. Examples of aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like.
  • the aromatic hydrocarbon ring when the aromatic hydrocarbon ring is bonded to another ring, the aromatic hydrocarbon ring is substituted on the other ring as a monovalent or divalent aromatic hydrocarbon group. good.
  • a monovalent group when referred to as an aromatic hydrocarbon group, it means a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic hydrocarbon ring.
  • the monovalent aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, examples of which include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl and 2-anthracenyl. group, 9-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
  • a phenyl group is preferred.
  • a divalent group when referred to as an aromatic hydrocarbon group, it means a divalent group obtained by removing one arbitrary hydrogen atom from the above monovalent aromatic hydrocarbon group.
  • the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, a phenanthrylene group and the like, preferably a phenylene group, and more preferably a 1,4-phenylene group.
  • the aromatic heterocyclic ring means an aromatic ring formed by carbon atoms and heteroatoms. Heteroatoms include oxygen, nitrogen, and sulfur atoms.
  • the aromatic heterocyclic ring may be a single ring or a condensed ring, and the number of atoms constituting the ring is preferably 5-20, more preferably 5-14.
  • Each ring constituting the aromatic heterocycle is preferably a 5- or 6-membered ring.
  • the number of heteroatoms in the atoms constituting the ring is not particularly limited, it is preferably 1-3, more preferably 1-2.
  • aromatic heterocycles examples include furan ring, thiophene ring, pyrrole ring, imidazole ring, isothiazole ring, isoxazole ring, pyridine ring, pyrazine ring, quinoline ring, benzofuran ring, benzothiazole ring, benzoxazole ring, 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 means a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic heterocyclic ring.
  • monovalent aromatic heterocyclic groups include furyl, thienyl, pyrrolyl, imidazolyl, isothiazolyl, isoxazolyl, pyridyl, pyrazinyl, quinolyl, benzofuranyl (preferably 2-benzofuranyl ), benzothiazolyl group (preferably 2-benzothiazolyl group), benzoxazolyl group (preferably 2-benzoxazolyl group), and the like.
  • furyl group, thienyl group, benzofuranyl group, benzothiazolyl group and benzoxazolyl group are preferable, and 2-furyl group and 2-thienyl group are more preferable.
  • divalent aromatic heterocyclic group refers to a divalent group obtained by removing any two hydrogen atoms from an aromatic heterocyclic ring, examples of which include the above (monovalent)
  • a divalent group obtained by removing one arbitrary hydrogen atom from an aromatic heterocyclic group can be mentioned.
  • halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • the cured product obtained by the curing reaction has excellent adhesion to the glass substrate and excellent transmittance. Therefore, the cemented lens of the present invention containing this cured product as a constituent member has excellent transmittance and excellent adhesion between lenses bonded by the cured product.
  • the curable resin composition of the present invention is a curable resin composition containing the following component (A) and the following component (B).
  • Component (A) A compound represented by general formula (1) below.
  • the structural unit (b1) does not have a hydrogen bonding group.
  • the curable resin composition of the present invention contains component (A): a compound represented by general formula (1) and component (B): a specific polymer.
  • the polymer of component (B) is a structural unit (b1) having an aromatic ring that exhibits a high affinity for Ar (hereinafter abbreviated as “aromatic ring Ar”) possessed by the compound represented by general formula (1). and a structural unit (b2) having a hydrogen-bonding group, which exhibits high affinity for glass in a cemented lens or the like.
  • the curable resin composition of the present invention uses a polymer in which these structural units (b1) and (b2) are controlled to specific amounts, so that the resulting cured product is a phase of component (A) and component (B). It is thought that excellent transmittance can be achieved by improving the solubility, and excellent adhesion to optical materials such as glass (preferably glass lenses) can also be exhibited.
  • composition of the present invention contains a compound represented by the following general formula (1).
  • Ar represents an aromatic ring group represented by any one of the following general formulas (2-1) to (2-4).
  • R 101 to R 104 represent -Sp c -Pol 3 or halogen atoms.
  • Sp a and Sp b are a single bond, an optionally substituted linear alkylene group having 1 to 30 carbon atoms, or an optionally substituted linear alkylene group having 2 to 30 carbon atoms.
  • group wherein one or more —CH 2 — excluding the linking portion to L 1 or L 2 is selected from —O—, —S—, >C( O) and >NR 111 indicates a group replaced by R 111 represents -Sp d -Pol 4 or a halogen atom.
  • Sp c and Sp d represent a single bond or a divalent linking group.
  • Pol 1 and Pol 2 represent polymerizable groups
  • Pol 3 and Pol 4 represent hydrogen atoms or polymerizable groups.
  • Ar Ar above is an aromatic ring group represented by any one 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 each represent 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, or 6 carbon atoms.
  • Z 1 and Z 2 may combine with each other to form an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • 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, preferably 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 and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • 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 and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • a x and A y may combine with each other to form a ring.
  • Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * indicates the binding position with L1 or L2.
  • Y 1 regarding compound (A) described in JP-A-2012-21068 , Q 1 and Q 2 can be applied to Y 1 , Z 1 and Z 2 as they are, and A 1 and A 2 for compounds represented by general formula (I) described in JP-A-2008-107767.
  • Q 1 in general formula (2-1) is preferably -S-.
  • X in general formula (2-2) is preferably a carbon atom to which two substituents are bonded, and both A 1 and A 2 are preferably -S-.
  • the ring is preferably an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Aromatic heterocycles are more preferred.
  • the ring is preferably an unsaturated hydrocarbon ring.
  • Ar in general formula (1) is preferably an aromatic ring group represented by general formula (2-2) from the viewpoint of further improving wet heat durability and transmittance.
  • an aromatic ring group represented by general formula (2-21) below is preferable.
  • R z represents a substituent
  • Z 1 and Z 2 have the same definitions as Z 1 and Z 2 in general formula (2-2) above.
  • substituents represented by R z include substituents that may be possessed by the straight-chain alkylene groups in Sp a and Sp b described later, such as an alkyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom and a cyano groups are preferred.
  • Two Rz may be the same or different.
  • two Rz may combine to form a ring, in which case the ring to be formed is preferably a 5- or 6-membered ring, and the atoms constituting the ring are a nitrogen atom or an oxygen atom. More preferably, it contains atoms.
  • the ring formed by combining two Rz 's is more preferably a ring represented by any one of the following structures.
  • each * indicates the position of the carbon atom to which two Rz bonds in general formula (2-21).
  • the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms.
  • the aromatic ring group represented by general formula (2-21) includes 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. is preferred, and an aromatic ring group represented by the following general formula (2-21a) in which both R z are cyano groups is more preferred.
  • Z 1 and Z 2 have the same definitions as Z 1 and Z 2 in general formula (2-2) above.
  • Sp a , Sp b Sp a and Sp b are a single bond, an optionally substituted linear alkylene group having 1 to 30 carbon atoms, or an optionally substituted linear alkylene group having 2 to 30 carbon atoms.
  • group wherein one or more —CH 2 — excluding the linking portion to L 1 or L 2 is selected from —O—, —S—, >C( O) and >NR 111 indicates a group replaced by R 111 represents -Sp d -Pol 4 or a halogen atom.
  • Sp d represents a single bond or a divalent linking group
  • Pol 4 represents a hydrogen atom or a polymerizable group.
  • Sp d and Pol 4 can apply the description of Sp c and Pol 3 , respectively, which will be described later.
  • both the linking portion of Sp a to L 1 and the linking portion of Sp b to L 2 are —CH 2 —
  • the linking portion of Spa a to Pol 1 and the linking portion of Sp b to Pol 2 are —CH 2 —.
  • the definition of these connecting portions also applies to the descriptions of Spa a and Sp b below.
  • the number of carbon atoms in the above-mentioned "straight-chain alkylene group having 1 to 30 carbon atoms” and “straight-chain alkylene group having 2 to 30 carbon atoms” means the number of carbon atoms in a state without a substituent. , is synonymous with the shortest number of atoms connecting Pol 1 and L 1 , and in Sp b it is synonymous with the shortest number of atoms connecting Pol 2 and L 2 . Therefore, as the number of carbon atoms in the straight-chain alkylene group having 1 to 30 carbon atoms and the straight-chain alkylene group having 2 to 30 carbon atoms, the preferable number of carbon atoms with the shortest number of atoms described below can be applied.
  • the "straight-chain alkylene group having 1 to 30 carbon atoms" has a substituent
  • an alkyl group can also be used as the substituent. In this case, it is a branched alkylene group as a whole. It corresponds to a "straight-chain alkylene group”. This also applies to the "straight-chain alkylene group having 2 to 30 carbon atoms".
  • the shortest number of atoms connecting -O- as L 2 and the methacryloyloxy group as Pol 2 is 10.
  • the minimum number of atoms is preferably 2 to 30, more preferably 11 to 30, still more preferably 11 to 25, particularly preferably 12 to 25, especially preferably 12 to 20.
  • substituents that the straight-chain 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 amido group, an amino group, a halogen atom, a nitro group and a cyano group, preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
  • the number of substituents is not particularly limited, and may have, for example, 1 to 4 substituents.
  • Spa and Spb 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 oxirane 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 as the linking portion to Spa a or Sp b , and has a vinylidene structure, an oxirane structure and an oxetane structure. Examples thereof include polymerizable groups represented by any one of the following formulas (Pol-1) to (Pol-6).
  • a (meth)acryloyloxy group represented by the above formula (Pol-1) or formula (Pol-2) is preferable, and a 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, more preferably both are (meth)acryloyloxy groups.
  • Pol 1 and Pol 2 may be the same or different, and are preferably the same.
  • Examples of specific structures of Pol 1 -Sp a -L 1 - or Pol 2 -Sp b -L 2 - include the following structures.
  • R is a hydrogen atom or a methyl group, and * indicates the bonding position with Ar.
  • Pol 1 -Sp a -L 1 - and Pol 2 -Sp b -L 2 - may be the same or different, but are preferably the same.
  • isopropylene structures In the present invention, structures represented by the following notation indicate isopropylene structures.
  • This isopropylene structure may be either of two structural isomers in which a methyl group is bonded to one of the carbons constituting the ethylene group, or these structural isomers may be mixed.
  • the compound represented by the general formula (1) when the compound represented by the general formula (1) has a structure in which a straight-chain alkylene group is substituted with a substituent, structural isomers with different substitution positions of the substituent may exist. .
  • the compound represented by general formula (1) may be a mixture of such structural isomers.
  • R 101 to R 104 represent -Sp c -Pol 3 or halogen atoms.
  • Sp c represents a single bond or a divalent linking group
  • Pol 3 represents a hydrogen atom or a polymerizable group.
  • a linear alkylene group e.g., trans- 1,4-cyclohexylene group
  • divalent aromatic hydrocarbon group e.g
  • R 201 to R 204 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the divalent linking group represented by Sp c is preferably a single bond or a straight chain alkylene group having 1 to 10 carbon atoms, more preferably a straight chain alkylene group having 1 to 5 carbon atoms, and a straight chain alkylene group having 1 to 3 carbon atoms. Straight chain alkylene groups are more preferred.
  • the straight-chain alkylene group that can be used as Sp c is preferably an unsubstituted straight-chain alkylene group.
  • the polymerizable group that can be taken as Pol 3 is synonymous with the polymerizable group described above.
  • Pol 3 is preferably a hydrogen atom.
  • -Sp c -Pol 3 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • L 1 and L 2 may be the same or different, but are preferably the same.
  • L 1 and L 2 are —O—, and Spa has a minimum number of atoms connecting Pol 1 and L 1 of 11, from the viewpoint of further improving adhesion.
  • ⁇ 30, and Sp b is preferably a linking group with the shortest number of atoms connecting Pol 2 and L 2 of 11 to 30.
  • the compound represented by the general formula (1) is preferably a non-liquid crystal compound. That is, from the viewpoint of use as a lens material, both Spa a and Sp b described above are preferably linking groups that do not have a ring structure.
  • Me is a methyl group
  • Et is an ethyl group
  • nPr is an n-propyl group
  • iPr is an isopropyl group
  • nBu is an n-butyl group
  • tBu is a t-butyl group.
  • compounds described in [0068] to [0074] of International Publication No. 2019/131572 are also preferably mentioned as compounds represented by general formula (1) in the present invention.
  • the content of the compound represented by the general formula (1) in the curable resin composition of the present invention is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and 20 to More preferably, it is 80% by mass.
  • the curable resin composition of the present invention may contain two or more compounds represented by general formula (1).
  • the total content is preferably within the above range.
  • the curable resin composition of the present invention is a polymer containing a structural unit (b1) having an aromatic ring and a structural unit (b2) having a hydrogen-bonding group as the component (B).
  • the structural unit (b1) accounts for 10% by mass or more of the total structural units, and the structural unit (b2) accounts for 3% by mass or more.
  • structural units having a hydrogen-bonding group are always classified as structural units (b2). That is, the structural unit (b1) does not have a hydrogen-bonding group, and the structural unit having both an aromatic ring and a hydrogen-bonding group is classified as the structural unit (b2).
  • the type of the component (B) polymer is not particularly limited as long as it is a polymer containing a structural unit (b1) containing an aromatic ring and a structural unit (b2) containing a hydrogen-bonding group.
  • Vinyl polymers such as acrylic polymers, addition polymers such as polyurethanes, condensation polymers such as polyesters and polycarbonates, and ring-opening using cyclic olefin monomers, which are formed by chain polymerization of one or more monomers having a bond. Metathesis polymers and the like can be used. Among them, a vinyl polymer is preferable from the viewpoint of further improving adhesion and wet heat durability.
  • the polymer of component (B) has a structural unit (b1) having an aromatic ring.
  • the aromatic ring of the structural unit (b1) includes an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring, anthracene ring or phenanthrene ring, or a furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, Aromatic heterocycles such as benzothiazole ring and phenanthroline ring are included.
  • the aromatic ring of the structural unit (b1) is preferably a benzene ring, a naphthalene ring or a pyridine ring, and more preferably a benzene ring from the viewpoint of further improving adhesion.
  • the polymer of the component (B) preferably has a structural unit represented by the following general formula (p1) as the structural unit (b1).
  • R P1 represents a hydrogen atom or a methyl group
  • L P1 represents a single bond or a divalent linking group
  • Ar P represents an aromatic hydrocarbon group optionally having a substituent or having a substituent represents an aromatic heterocyclic group which may be
  • the structural unit represented by general formula (p1) does not have a hydrogen bonding group. That is, L P1 does not have a hydrogen bonding group and Ar 2 P does not have a hydrogen bonding group.
  • * indicates a binding site for incorporation into the polymer.
  • substituents that the aromatic hydrocarbon ring group and aromatic heterocyclic group in Ar 2 P may have include an alkyl group, an alkoxy group, an alkoxysilyl group, and an acyloxy group.
  • LP1 represents a single bond or a divalent linking group.
  • divalent linking groups that L P1 can take include an alkylene group, a divalent aromatic hydrocarbon group (eg, a 1,4-phenylene group, hereinafter referred to as an "arylene group”), and a divalent aromatic group.
  • a heterocyclic group hereinafter referred to as a “heteroarylene group”
  • Rb is an alkyl group, a monovalent aliphatic or aromatic heterocyclic group or a monovalent aromatic hydrocarbon ring group.
  • the alkylene group, arylene group and heteroarylene group that can constitute L P1 may have a substituent.
  • the substituents that the alkylene group, arylene group and heteroarylene group that may constitute L P1 may have are not particularly limited as long as they are not hydrogen bonding groups, and examples thereof include alkyl groups, cycloalkyl groups, alkoxy groups, Acyl group, acyloxy group, alkoxycarbonyl group, amino group (-N(R Y ) 2 ), amide group (-CON(R Y ) 2 or -NR Y COR Y ), sulfonamide group (-SO 2 N(R Y 1 ) 2 or —NR Y SO 2 R Y ).
  • RY is an alkyl group, a monovalent aliphatic or aromatic heterocyclic group, or a monovalent aromatic hydrocarbon ring group.
  • the number of substituents is not particularly limited, and may have, for example, 1 to 4 substituents.
  • the left side is bonded to the carbon atom to which R 1 P1 is bonded, and the right side is bonded to Ar 2 P. Also in the following, it has the same meaning.
  • Groups are also preferably mentioned.
  • Examples of structural units represented by the general formula (p1) include the following structural units. However, it is not limited to these structural units. In the following chemical structural formulas, Me represents a methyl group and t Bu represents a tert-butyl group.
  • the ratio of the structural unit (b1) containing an aromatic ring to the total structural units constituting the polymer is preferably 10 to 97% by mass, more preferably 20 to 96% by mass, and from the viewpoint of further improving the transmittance, it is 30 to 30%. 95% by weight is particularly preferred.
  • the aromatic ring-containing structural unit (b1 ) is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 75% by mass.
  • the ratio of the structural unit (b1) containing an aromatic ring and the ratio of the structural unit (b2) containing a hydrogen-bonding group to the total structural units constituting the polymer are the aromatic After determining the component corresponding to the structural unit (b1) containing the ring, determine the component corresponding to the structural unit (b2) having a hydrogen bonding group in the remaining monomer components, based on the mass ratio of these components can decide.
  • the proportion of the isocyanate compound (A1) in the monomer component is the above structural unit ( The ratio of b1) and the ratio of the diol compound (B1) in the monomer component correspond to the ratio of the structural unit (b2).
  • the polymer when the polymer is obtained by an elimination reaction during synthesis, for example, by condensation polymerization of a bifunctional acid chloride compound (A2) having an aromatic ring and a compound (B2) having two primary amino groups,
  • the structural unit (b1) has two chlorine atoms eliminated from the acid chloride compound (A2), and two hydrogen atoms from the compound (B2) (that is, two A structural unit in which one hydrogen atom is eliminated from a primary amino group corresponds to the structural unit (b2). Therefore, the content ratio of the structural units (b1) and (b2) can be determined from the mass ratio of these compounds (A2) and (B2).
  • the polymer of component (B) has a structural unit (b2) having a hydrogen bonding group.
  • the hydrogen-bonding group of the structural unit (b2) means a group having a hydrogen atom capable of forming a hydrogen bond, and includes a hydroxy group, a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an amino group, sulfanyl group, amide group, urethane group, urea group, thiourethane group, thiourea group, sulfonamide group and the like.
  • the amino group, amido group and sulfonamide group mean a monovalent group or a divalent group having a hydrogen-bonding hydrogen atom. These monovalent groups mean an amino group (--NH 2 ), an amide group (--CONH 2 ) and a sulfonamide group (--SO 2 NH 2 ), respectively.
  • R a above is a hydrogen atom, an alkyl group, a monovalent aliphatic or aromatic heterocyclic group, or a monovalent aromatic hydrocarbon ring group, preferably a hydrogen atom.
  • the hydrogen-bonding group of the structural unit (b2) includes a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an amino group, a sulfanyl group, an amide group, a urethane group, a urea group, a thiourethane group, It is preferably at least one of a thiourea group and a sulfonamide group, and more preferably at least one of a hydroxyl group, an amide group, a urethane group and a urea group from the viewpoint of further improving adhesion. .
  • the number of hydrogen-bonding groups contained in one structural unit may be one or may be two or more, and when two or more are contained, these two or more hydrogen-bonding groups are , some or all of which may be the same hydrogen-bonding groups, or may be different hydrogen-bonding groups.
  • the polymer of component (B) preferably has a structural unit represented by the following general formula (p2) as the structural unit (b2).
  • R P2 represents a hydrogen atom or a methyl group
  • L P2 represents a single bond or a divalent linking group
  • R P3 represents a monovalent substituent.
  • at least one of L P2 and R P3 is a hydroxy group, carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, amino group, sulfanyl group, amide group, urethane group, urea group, thiourethane group, thiourea group and at least one group of a sulfonamide group.
  • * indicates a binding site for incorporation into the polymer.
  • a sulfonamide group is a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an amino group, a sulfanyl group, an amide group, a urethane group, and a urea group as a hydrogen-bonding group possessed by the structural unit (b2).
  • the descriptions of groups, thiourethane groups, thiourea groups and sulfonamide groups can be applied.
  • the group represented by -L P2 -R P3 shall be interpreted based on the following rules (i) to (iii). Rule (i) shall be applied first, then rule (ii) shall be applied, and finally rule (iii) shall be applied. (i) In the group represented by -L P2 -R P3 , the structure located at the most end counted from the carbon atom to which R P2 is bonded in the longest binding chain (hereinafter referred to as "the most terminal structure"). ) corresponds to a monovalent group among the above hydrogen-bonding groups, R P3 is the monovalent group in the hydrogen-bonding group, and the remainder is interpreted as L P2 .
  • L P2 LP2 and RP3 are interpreted as an atom or an atom group that bonds to RP3 among the constituent atoms.
  • LP2 represents a single bond or a divalent linking group.
  • R a the description of R a in the description of the hydrogen-bonding group of the structural unit (b2) above can be applied.
  • the alkylene group and arylene group that can constitute L P2 may have a substituent.
  • substituents that the alkylene group and arylene group that may constitute L P2 may have include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a hydroxy group, and a carboxy group.
  • R 2 is a hydrogen atom, an alkyl group, a monovalent aliphatic or aromatic heterocyclic group, or a monovalent aromatic hydrocarbon ring group, preferably a hydrogen atom.
  • R Z is a hydroxy group, an alkyl group, a monovalent aliphatic or aromatic heterocyclic group or a monovalent aromatic hydrocarbon ring group, preferably a hydroxy group.
  • the number of substituents is not particularly limited, and may have, for example, 1 to 4 substituents.
  • the left side is attached to the carbon atom to which R 2 P2 is attached, and the right side is attached to R 2 P3 .
  • R P3 represents a monovalent substituent.
  • the monovalent substituent as R P3 includes an alkyl group, a monovalent aliphatic or aromatic heterocyclic group, an aryl group, a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a sulfanyl group, -NH 2 , -CONH 2 and -SO 2 NH 2 are preferred.
  • the alkyl group, monovalent aliphatic or aromatic heterocyclic group, and aryl group that can be used as R P3 may be substituted with a substituent.
  • Examples of the alkyl group, the monovalent aliphatic or aromatic heterocyclic group, and the substituent that the aryl group may have as R P3 include the polymerizable groups in Pol 1 and Pol 2 described above. Among them, a (meth)acryloyloxy group is preferred.
  • an alkyl group having a substituent includes an alkyl group having a polymerizable group such as a (meth)acryloyloxyalkyl group.
  • R P3 is preferably an alkyl group, an aryl group, a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a sulfanyl group, —NH 2 , —CONH 2 or —SO 2 NH 2 , an alkyl group, An aryl group, a hydroxy group or -CONH2 is more preferred, and an alkyl group, a hydroxy group or -CONH2 is even more preferred.
  • the group represented by -L P2 -R P3 is a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group,
  • a group selected from a phosphonic acid group, an amino group, a sulfanyl group, an amide group, a urethane group, a urea group, a thiourethane group, a thiourea group and a sulfonamide group it preferably contains a polymerizable group. More preferably, it contains a polymerizable group in addition to at least one of a group, a urea group and an amide group.
  • Examples of structural units represented by the general formula (p2) include the following structural units. However, it is not limited to these structural units.
  • R represents a hydrogen atom or a methyl group.
  • the ratio of the structural unit (b2) containing a hydrogen bonding group to the total structural units constituting the polymer is preferably 3 to 90% by mass, and more preferably 4 to 80% by mass from the viewpoint of further improving adhesion. From the viewpoint of further improving the transmittance, it is more preferably 5 to 70% by mass.
  • the polymer of component (B) has other structural units (other structural units) than the structural units (b1) and (b2), structural units containing hydrogen-bonding groups occupying all structural units constituting the polymer
  • the proportion of (b2) is preferably 3 to 30% by mass, more preferably 4 to 25% by mass, even more preferably 5 to 20% by mass.
  • the polymer of component (B) is preferably a vinyl polymer from the viewpoint of further improving adhesion and wet heat durability, and the structural unit (b1) is a structural unit represented by the above general formula (p1). and having a structural unit represented by the above general formula (p2) as the structural unit (b2).
  • the polymer of component (B) contains structural units other than the above-described structural units (b1) and (b2) (hereinafter also referred to as "other structural units"). good too.
  • the other structural units are not particularly limited as long as they are structural units having neither an aromatic ring nor the hydrogen bonding group described above.
  • Structural units derived from common monomers such as chemical compounds, maleic anhydride compounds and the like can be mentioned. By containing these structural units, the transmittance and wet heat durability can be adjusted to be further improved.
  • monomers selected from (meth)acrylic acid ester compounds and (meth)acrylonitrile compounds are preferred as monomers leading to other structural units, and (meth)acrylic acid ester compounds are more preferred.
  • acrylic acid ester compounds such as alkyl acrylate (preferably those having 1 to 20 carbon atoms in the alkyl group) (specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, , butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, glycidyl acrylate, methoxybenzyl acrylate, tetrahydrofurfuryl acrylate, etc.), alkyl methacrylate (the carbon atom of the alkyl group is preferably 1 to 20) and other methacrylic acid ester compounds (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl meth
  • alkyl (meth)acrylate compounds having 4 to 20 carbon atoms in the alkyl group are particularly preferred from the viewpoint of further improving the transmittance.
  • Compatibility between component (A) and component (B) in the curable resin composition of the present invention is improved by making the polymer of component (B) containing structural units derived from such monomers as other structural units.
  • component (C) which will be described later, is contained, the compatibility of the components (A) to (C) can be enhanced, and a highly transparent cured product can be obtained.
  • the polymer of component (B) preferably contains, as another structural unit, a structural unit derived from a monomer (compound) having an alkoxysilyl group.
  • the monomer having an alkoxysilyl group is not particularly limited as long as it is a compound having at least one group in which an alkoxy group is directly bonded to a silicon atom and has a polymerizable group (preferably a radically polymerizable group).
  • a monomer having a dialkoxysilyl group and/or a trialkoxysilyl group and a polymerizable group is preferable, and a monomer having a trialkoxysilyl group and a polymerizable group is more preferable.
  • ⁇ -methacryloxypropyltrialkoxysilane examples include ⁇ -methacryloxypropyltrialkoxysilane, ⁇ -methacryloxypropyldialkoxysilane, and vinyltrialkoxysilane. Of these, ⁇ -methacryloxypropyltrialkoxysilane or ⁇ -acryloxypropyltrialkoxysilane is more preferred. One type of these may be used, or two or more types may be used in combination.
  • the ratio of the other structural units to the total structural units constituting the polymer is preferably 2 to 65% by mass, more preferably 3 to 45% by mass. ⁇ 40% by mass is more preferred.
  • the weight average molecular weight (Mw) of the polymer of component (B) is preferably 1000 or more, more preferably 3000 or more, and even more preferably 5000 or more. Also, the upper limit of the weight average molecular weight is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. In the present invention, the weight average molecular weight is the weight average molecular weight in terms of polystyrene by GPC (Gel Permeation Chromatography), and the value measured under the following measurement conditions is adopted. However, an appropriate eluent can be selected and used according to the sample to be measured.
  • Measuring instrument HLC-8320GPC (trade name, manufactured by Tosoh Corporation) Columns: TOSOH TSKgel HZM-H (trade name, manufactured by Tosoh Corporation), TOSOH TSKgel HZ4000 (trade name, manufactured by Tosoh Corporation), and TOSOH TSKgel HZ2000 (trade name, manufactured by Tosoh Corporation) were connected.
  • Carrier THF Measurement temperature: 40°C
  • Carrier flow rate 0.35 ml/min
  • Sample concentration 0.1% by mass
  • Detector RI (refractive index) detector
  • the content of the polymer of component (B) in the curable resin composition of the present invention is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass or less. More preferred.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
  • the curable resin composition of the present invention may further contain other components in addition to the components (A) and (B) described above.
  • Other components include, for example, the component (C) vinyl monomer or polymerization initiator. It may also contain a silane coupling agent, for example, a monomer having an alkoxysilyl group described in the other structural units of the polymer of component (B) above.
  • the curable resin composition of the present invention also preferably contains a vinyl monomer as component (C).
  • the vinyl monomer is 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. ) acrylate monomers.
  • the number of (meth)acryloyl groups in the compound is preferably 1-4.
  • the molecular weight of the vinyl monomer is preferably 100-1000, more preferably 100-800, even more preferably 130-800.
  • the vinyl monomers may be used singly or in combination of two or more.
  • Examples of (meth)acrylate monomers that can be preferably used in the present invention include (meth)acrylate monomers described in paragraphs 0037 to 0046 of JP-A-2012-107191. Specifically, the following monomers can be used. Specific examples of (meth)acrylate monomers include, for example, monomer 1 (phenoxyethyl acrylate), monomer 2 (benzyl acrylate), monomer 3 (tricyclodecanedimethanol diacrylate), monomer 4 (dicyclopentanyl acrylate), Monomer 5 (1,6-hexanediol diacrylate), Monomer 6 (1,6-hexanediol dimethacrylate), Monomer 7 (benzyl acrylate), Monomer 8 (isobornyl methacrylate), Monomer 9 (dicyclopentanyl methacrylate) ), monomer 10 (dodecyl methacrylate), monomer 11 (dodecyl acrylate), monomer 12 (2-eth
  • dodecyl methacrylate or dodecyl acrylate can further improve wet heat durability
  • use of KAYARAD HX-620 can further improve adhesion.
  • the (meth)acrylate monomer is obtained, and it may be obtained commercially or synthesized by a conventional method.
  • the content of component (C) in the curable resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. is more preferred, and 20 to 70% by mass is even more preferred.
  • the curable resin composition of the present invention preferably contains at least one of a thermal radical polymerization initiator and a photoradical polymerization initiator as a polymerization initiator.
  • the curable resin composition of the present invention preferably contains a radical photopolymerization initiator.
  • a radical photopolymerization initiator a compound that is usually used as a radical photopolymerization initiator can be appropriately used according to the conditions of the photopolymerization (photocuring) step described later. Specifically, the following compounds can be used. can be done.
  • bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,4-trimethylpentylphosphine oxide), 6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine oxide, 1-phenyl-2-hydroxy-2-methyl propan-1-one, 1-hydroxycyclohexylphenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1,2-diphenylethanedione, methylphenylglyoxylate, 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-
  • 1-hydroxycyclohexylphenyl ketone such as Irgacure 184 (trade name) manufactured by BASF
  • BASF bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
  • the content of the photoradical polymerization initiator in the curable resin composition of the present invention is preferably 0.01 to 5.0% by mass, and 0.05 to 1 0% by mass, more preferably 0.05 to 0.5% by mass.
  • the curable resin composition of the present invention also preferably contains a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator By thermally polymerizing the curable resin composition by the action of the thermal polymerization initiator, a cured product exhibiting high heat resistance can be molded.
  • thermal radical polymerization initiator compounds commonly used as thermal radical polymerization initiators can be appropriately used according to the conditions of the thermal polymerization (thermosetting) step described below.
  • examples thereof include organic peroxides, and specifically, the following compounds can be used.
  • 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, dicumyl peroxide, di-t-butylperoxide, t-butylperoxy-2 -ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, cumene
  • the content of the thermal radical polymerization initiator in the curable resin composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0%. % by mass is more preferred, and 0.05 to 2.0% by mass is even more preferred.
  • the total content of the photoradical polymerization initiator and the thermal radical polymerization initiator is the curing of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.05 to 1.0% by mass, and 0.05 to 0.5% by mass with respect to the total mass of the resin composition. It is even more preferable to have
  • the curable resin composition of the present invention may contain components other than the above-described components (A to (C), polymerization initiators, vinyl monomers, silane coupling agents, for example, as long as it does not contradict the spirit of the present invention.
  • Polymers or monomers other than the components described above, dispersants, plasticizers, heat stabilizers, release agents, solvents, and the like may also be included.
  • the viscosity of the curable resin composition of the present invention is preferably 60 to 5,000 mPa s or less, more preferably 80 to 3,000 mPa s, and 100 to 2,000 mPa s. is more preferred. By setting the viscosity of the curable resin composition within the above range, it is possible to improve the handleability during adhesion and form a high-quality adhesive layer (cured product).
  • the cemented lens of the present invention is a cemented lens including a lens A, an adhesive layer and a lens B in this order, wherein the adhesive layer is a layer made of a cured product of the curable resin composition of the present invention.
  • the cemented lens of the present invention can be produced by bonding two or more lenses using the curable resin composition of the present invention. For example, lens A and lens B are bonded using the curable resin composition of the present invention, and lens A, a layer (adhesive layer) made of a cured product of the curable resin composition of the present invention, and lens B are bonded together.
  • Cemented lenses can be manufactured which in turn contain.
  • the cemented lens manufactured using the curable resin composition of the present invention absorbs ultraviolet light and has a structure having an adhesive layer inside that has excellent fastness to ultraviolet irradiation. Can be used as a lens.
  • a device such as an image pickup module using this cemented lens, by arranging a component containing a cured resin that is susceptible to ultraviolet rays on the opposite side of the cemented lens to the incident side of external light, there is no deterioration due to light. can be prevented.
  • the cemented lens itself has a lens made of a resin cured product, the lens is designed to be on the side opposite to the incident side of external light with respect to the adhesive layer during use, thereby achieving high durability. be able to.
  • a cemented lens can be obtained by superimposing two lenses via the curable resin composition of the present invention and then curing the adhesive to form an adhesive layer as described below. Curing is preferably carried out after removing air bubbles mixed in the adhesive after the above superimposition.
  • the adhesive layer is a layer obtained by curing the curable resin composition of the present invention.
  • the curable resin composition of the present invention is applied to the surface of one of the lenses to be cemented, the other lens is superimposed, and then cured to form an adhesive layer. be done. Curing can be performed by at least light irradiation. Moreover, after performing light irradiation, you may implement the process of further heating.
  • a light source that emits light having a wavelength with which the photoradical polymerization initiator reacts can be arbitrarily selected.
  • halogen-xenon lamps, metal halide lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, germicidal lamps, xenon lamps, LED (Light Emitting Diode) light source lamps, etc. are preferably used.
  • a laser may be used to selectively irradiate a narrow range of wavelengths of light.
  • the atmosphere during light irradiation is preferably an atmosphere replaced with air or an inert gas, and more preferably an atmosphere in which the air is replaced with nitrogen until the oxygen concentration becomes 1% or less.
  • the heating temperature when performing the heating step is 60°C or higher, preferably 70 to 200°C, more preferably 70 to 190°C, and even more preferably 80 to 180°C.
  • the thickness of the adhesive layer is preferably 10-50 ⁇ m, more preferably 20-30 ⁇ m. By setting the thickness to 10 ⁇ m or more, the effect of ultraviolet absorption can be sufficiently obtained. Further, by setting the thickness to 50 ⁇ m or less, it is possible to increase the transmittance in the short wavelength region (400 to 430 nm) of visible light 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 refractive index from the cemented lens is 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 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 (trade name) manufactured by Shimadzu Corporation).
  • the refractive index and cutoff wavelength of the adhesive layer can be adjusted within the above ranges by adjusting the amount of the compound represented by formula (1).
  • Lens A and lens B are lenses forming a cemented lens.
  • a cemented lens when a cemented lens is used, a lens closer to the external light incident side (object (object to be imaged) side) is referred to as lens A, and a lens further away is referred to as lens B.
  • the materials constituting the lens A and the lens B are not particularly limited, but at least one lens of the lens A and the lens B may be a glass lens.
  • the lens A is a glass lens
  • the lens B is more preferably a resin lens or a compound lens having a resin layer on its surface
  • the lens A is a glass lens
  • the lens B is a compound lens having a resin layer on its surface. is more preferable.
  • the resin layer is in contact with the adhesive layer in the cemented lens. This is because the structure in which the resin adhesive layer and the resin layer are in direct contact can minimize the difference in refractive index between the layers and reduce interfacial reflection within the cemented lens.
  • the adhesive layer is provided on the surface of the resin layer, which has a larger surface roughness than that of glass, the uneven surface of the resin layer is flattened, and light scattering due to the roughness of the surface of the resin layer can be prevented. Because you can.
  • lenses A, B, and C which will be described later, are not particularly limited, and examples include disc-shaped convex lenses, concave lenses, meniscus lenses, aspherical lenses, and cylindrical lenses having a cylindrical lens surface. , ball lenses, and rod lenses.
  • glass lens Any known glass lens can be used without limitation. Examples of commercially available glass lenses include BK7 manufactured by Ohara Corporation. Similar glass lenses can be used when the compound lens includes glass lenses.
  • a resin lens means a lens made of a cured resin.
  • a compound lens means a lens including a layer made of glass and a resin layer.
  • the resin layer is a layer made of a cured resin.
  • Each layer included in the compound lens may be a lens (single lens), and in this case, it is preferable that the optical axes (lines connecting the centers of curvature of both spherical surfaces) of each single lens are aligned.
  • the compound lens may have a resin layer on its surface or inside, and the compound lens used as lens B preferably has a resin layer on its surface.
  • a typical example of the compound lens used as the lens B is a compound lens in which a resin layer is formed on the surface of a glass lens.
  • the cured resin material constituting the resin layer of the resin lens or compound lens is not particularly limited, but a cured resin material with a low Abbe number is preferable.
  • a cured resin with a low Abbe number generally absorbs up to the long wavelength side (approximately 320 nm to 400 nm) of the ultraviolet light wavelength region, and thus is susceptible to photodegradation.
  • the curable resin composition of the present invention can absorb light up to the long wavelength side of the ultraviolet light region by controlling the structure of the compound contained and the film thickness when the adhesive layer is formed. This is because the photodegradation of the cured resin can be remarkably suppressed.
  • the Abbe number of the cured resin is preferably 30 or less, more preferably 25 or less.
  • the resin lens composing the lens B or the cured resin material composing the resin layer of the compound lens has a higher partial dispersion ratio ⁇ g, F.
  • the partial dispersion ratio ⁇ g,F is not particularly limited, it is preferably 0.65 or more, more preferably 0.70 or more.
  • the partial dispersion ratio ⁇ g,F is not particularly limited, it is preferably 2 or less.
  • the Abbe number ( ⁇ d) and the partial dispersion ratio ( ⁇ g, F) of the cured resin are values calculated by the following equations.
  • ⁇ d (nd-1)/(nF-nC) ⁇ g
  • F (ng-nF)/(nF-nC)
  • nd represents a refractive index at a wavelength of 587.56 nm
  • nF represents a refractive index at a wavelength of 486.13 nm
  • nC represents a refractive index at a wavelength of 656.27 nm
  • ng represents a refractive index at a wavelength of 435.83 nm.
  • the Abbe number of the cured resin can be determined using a Kalnew precision refractometer KPR-2000 (manufactured by Shimadzu Device Manufacturing Co., Ltd.) or an Abbe meter (manufactured by Atago Co., Ltd.).
  • resins that form cured resins having an Abbe number of 30 or less include resins containing structures such as 9,9'-diarylfluorene, naphthalene, biphenyl, carbazole, benzothiazole, and benzotriazole (specifically, for example, JP-A-60-38411, JP-A-10-67977, JP-A-2002-47335, JP-A-2004-83855, JP-A-2005-325331, JP-A-2007-238883, JP-A-2012-52016 2012-1498, 2016-75911, WO 2006/095610, JP-A-2-29401, etc.).
  • a cured product of a composition containing the compounds described in paragraphs 0112 to 0124 of WO 2019/131572 can also be preferably used.
  • the curable resin composition of the present invention is used in a device containing an optical lens therein, and can prevent photodegradation of the optical lens and, in turn, the device.
  • the curable resin composition of the present invention is applied in the direction in which external light is incident on the resin lens or compound lens of the housing (light-shielding property).
  • an adhesive layer formed of a material it is possible to prevent photodegradation of the above resin lens or compound lens.
  • An adhesive layer can be provided, for example, as part of the cemented lens.
  • Examples of devices that use the curable resin composition of the present invention and include an optical lens inside include an imaging module that forms an image by imaging an object with a lens optical system.
  • Examples of objects to which the imaging module is embedded include a digital camera, a PC (Personal Computer) built-in or external PC camera, an interphone with a camera, an in-vehicle camera, an endoscope, or a mobile terminal device having a photographing function.
  • An electronic device can be mentioned.
  • Mobile terminal devices include, for example, mobile phones, smart phones, PDAs (Personal Digital Assistants), and portable game machines.
  • FIG. 1 An example of the lens optical system including the adhesive layer formed from the curable resin composition of the present invention is schematically shown in FIG.
  • a lens A (3), an adhesive layer 1, a lens B (4), and a lens C (5) are arranged in this order from the object (object to be imaged) side 7 toward the image forming surface side 8.
  • Lens B(4) and Lens C(5) are compound lenses, Lens B(4) is composed of resin layer 6 and glass layer 10, and Lens C(5) is composed of resin layer 6 and glass layer 10. It is composed of a layer 11 consisting of In FIG. 1, the lens A (3), the adhesive layer 1 and the lens B (4) constitute a cemented lens 2.
  • FIG. 1 In the lens optical system shown in FIG.
  • the following lens optical systems can prevent photodegradation of the constituent lenses: (1) A lens optical system including only a cemented lens of lens A which is a glass lens and lens B which is a compound lens and no lens C; (2) a lens optical system in which lens A and lens B are glass lenses and lens C is a compound lens or a resin lens; and (3) A lens optical system including one or more additional lenses in addition to the optical system (1) or (2).
  • the lens optical system in the imaging module including the adhesive layer formed from the curable resin composition of the present invention may include the lens C.
  • lens C refers to a cemented lens in which a lens is bonded with the curable resin composition of the present invention and a lens other than the lens constituting the cemented lens, and is formed from the curable resin composition of the present invention.
  • the lens is arranged at a position farther from the external light incident side (object (object to be imaged) side) than the cemented lens including the adhesive layer.
  • the material forming the lens C is not particularly limited, but the lens C is preferably a resin lens or a compound lens. This is because, when the lens C is a resin lens or a compound lens, the cemented lens including the adhesive layer formed from the curable resin composition of the present invention is particularly effective in suppressing photodegradation due to absorption of ultraviolet rays.
  • the compound lens used as the lens C may have a resin layer on its surface or inside.
  • the preferred range and examples of the resin layer of the resin lens or compound lens forming the lens C are the same as those described above for the resin layer of the resin lens or compound lens forming the lens B.
  • EDAC 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride
  • HPMA hydroxypropyl methacrylate
  • DMAc N,N-dimethylacetamide
  • THF tetrahydrofuran
  • Ac acetyl group
  • Et ethyl group
  • the polymerization reaction was further carried out at 80° C. for 6 hours. After allowing the reaction solution to cool to room temperature and placing it in an air atmosphere, 4.3 g of Karenz AOI (trade name, 2-acryloyloxyethyl isocyanate, manufactured by Showa Denko) and Neostan U-600 (trade name, Nitto) as a catalyst were added. Kasei Co., Ltd.) 0.14 g, 2-tert-butyl-1,4-benzoquinone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.04 g as a polymerization inhibitor, and cyclohexanone 10 mL were added, then heated to 70 ° C. for 6 hours. reacted. After standing to cool, the reaction solution was added dropwise to a cooled mixed solution of 200 mL of water and 1800 mL of methanol, and the precipitated powder was collected by filtration and dried to obtain 32 g of polymer P-21.
  • Karenz AOI
  • each polymer is collectively shown below.
  • the parentheses in the following structural formulas mean structural units, and the numbers on the right side of each structural unit mean the mass content ratio of each structural unit.
  • the mass average molecular weight (Mw) of each polymer is a value measured under the above-described measurement conditions.
  • Example 1 Preparation of curable resin composition
  • Component (A), component (B) or comparative polymer, component (C) and photopolymerization initiator are mixed and stirred so that the composition shown in the table below is obtained.
  • a curable resin composition was prepared by homogenizing the mixture.
  • the evaluation results of the obtained curable resin composition are summarized in the table below.
  • T% was 90% or more.
  • each component in the table is as follows.
  • the compounding ratio of each component is based on mass.
  • Irgacure 819 product (manufactured by BASF Japan Ltd.) was blended.
  • "-" means that the component is not contained.
  • HX-620 vinyl monomer represented by the following structural formula, KAYARAD HX-620 (trade name), manufactured by Nippon Kayaku Co., Ltd.
  • Plaxel FA1DDM trade name, manufactured by Daicel, unsaturated fatty acid hydroxyalkyl ester-modified ⁇ -caprolactone (molecular weight: 230, compositional formula: CH 2 ⁇ CHCOO(CH 2 ) 2 O[CO(CH 2 ) 5 O] n H, n means the number of repetitions.)
  • Comparative Polymers 1, 3 and 4 Comparative Polymers 1, 3 and 4 described in Synthetic Examples above Comparative polymer 2: Shikou UV-3000B (trade name, manufactured by Mitsubishi Chemical Corporation, urethane acrylate containing no aromatic ring, Mw 18000)
  • Comparative curable resin composition No. c01 is not a curable resin composition defined in the present invention in that it does not contain a polymer in the first place.
  • This comparative curable resin composition No. The cured product obtained from c01 had a poor adhesion index of less than 20 N, and a non-defective rate of less than 70% in the wet heat durability test, indicating poor wet heat durability.
  • the comparative curable resin composition No. c02 is the comparative curable resin composition No. 1 in that it contains the comparative polymer 1 that does not contain a structural unit having a hydrogen-bonding group.
  • c05 is not a curable resin composition defined in the present invention in that it contains comparative polymer 4 containing less than 3% by mass of structural units having a hydrogen-bonding group as a polymer.
  • These comparative curable resin composition nos. Both of the cured products obtained from c02 or c05 have poor adhesion with an index of adhesion strength of less than 20 N, and the non-defective product rate in the wet heat durability test is less than 70%, and the wet heat durability is also poor.
  • the comparative curable resin composition No. c03 is the comparative curable resin composition No. 2 in that it contains the comparative polymer 2 that does not contain a structural unit having an aromatic ring as a polymer.
  • c04 is not a curable resin composition defined in the present invention in that it contains comparative polymer 3 containing less than 10% by mass of structural units having an aromatic ring as a polymer.
  • These comparative curable resin composition nos. In c03 and c04 the compatibility between the polymer and component (A) was low, and phase separation occurred during preparation of the composition, so evaluation could not be performed.
  • the comparative curable resin composition No. Comparative curable resin composition No. c03 was prepared by changing the type of component (A) so as not to cause phase separation.
  • the transmittance of the resulting cured product is as low as less than 88%, and the number of non-defective products in the wet heat durability test is less than 70%, and the wet heat durability is also poor. rice field.
  • the curable resin composition No. of the present invention The cured products obtained from Nos. 101 to 122 all exhibited high transmittance, high adhesion index, and were excellent in both adhesion and transmittance. Moreover, the number of non-defective products in the wet heat durability test was large, and the wet heat durability was also excellent. Moreover, the curable resin composition No. of the present invention. The cured product obtained from No. 118 and No.
  • the curable resin composition of the present invention provides a cured product obtained by a curing reaction with excellent adhesion to the glass substrate and excellent transmittance.

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JP2021143329A (ja) * 2020-03-11 2021-09-24 住友化学株式会社 重合性液晶組成物、位相差フィルム、楕円偏光板および光学ディスプレイ

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WO2025150451A1 (ja) * 2024-01-12 2025-07-17 株式会社日本触媒 共重合体、組成物及び洗剤用添加剤

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