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WO2025164088A1 - Composition durcissable par rayonnement d'énergie active et produit durci de celle-ci - Google Patents

Composition durcissable par rayonnement d'énergie active et produit durci de celle-ci

Info

Publication number
WO2025164088A1
WO2025164088A1 PCT/JP2024/043103 JP2024043103W WO2025164088A1 WO 2025164088 A1 WO2025164088 A1 WO 2025164088A1 JP 2024043103 W JP2024043103 W JP 2024043103W WO 2025164088 A1 WO2025164088 A1 WO 2025164088A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
active energy
energy ray
curable composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/043103
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English (en)
Japanese (ja)
Inventor
和哉 前田
俊貴 児島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Chemical Industries Ltd
Original Assignee
Sanyo Chemical Industries Ltd
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Filing date
Publication date
Application filed by Sanyo Chemical Industries Ltd filed Critical Sanyo Chemical Industries Ltd
Publication of WO2025164088A1 publication Critical patent/WO2025164088A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials

Definitions

  • the present invention relates to an active energy ray-curable composition and a cured product thereof.
  • High-refractive-index particles have been widely studied as fillers for anti-reflection materials, lens materials, high-dielectric materials, and more.
  • High-refractive-index particles with an average particle size of several nanometers to several tens of nanometers are particularly popular due to their excellent transparency.
  • particles such as zirconia and titania have been used for UV-curable resins (Patent Document 1).
  • Patent Document 1 this technology does not have sufficient imprintability on glass, and a primer must be used when imprinting on a glass substrate.
  • the object of the present invention is to provide an active energy ray-curable composition that gives a cured product with a high refractive index and excellent glass adhesion and imprintability.
  • the present invention provides an active energy ray-curable composition
  • a photopolymerizable compound (A), inorganic particles (B), and a photopolymerization initiator (C) wherein the photopolymerizable compound (A) contains a monofunctional monomer (A1) and a polyfunctional monomer (A2), the inorganic particles (B) have an average particle size of 5 to 50 nm, the photopolymerizable compound (A) has a viscosity at 25°C of 300 mPa s or less, and a cured product of the photopolymerizable compound (A) has a glass transition temperature of 70°C or higher; and a cured product of the active energy ray-curable composition.
  • the photopolymerizable compound (A) contains a monofunctional monomer (A1) and a polyfunctional monomer (A2)
  • the inorganic particles (B) have an average particle size of 5 to 50 nm
  • the photopolymerizable compound (A) has a
  • the present invention makes it possible to provide an active energy ray-curable composition that gives a cured product with a high refractive index and has excellent glass adhesion and imprintability.
  • the active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a photopolymerizable compound (A), inorganic particles (B), and a photopolymerization initiator (C), wherein the photopolymerizable compound (A) contains a monofunctional monomer (A1) and a polyfunctional monomer (A2), the inorganic particles (B) have an average particle size of 5 to 50 nm, the photopolymerizable compound (A) has a viscosity at 25°C of 300 mPa s or less, and a cured product of the photopolymerizable compound (A) has a glass transition temperature of 70°C or higher.
  • the photopolymerizable compound (A) contains a monofunctional monomer (A1) and a polyfunctional monomer (A2)
  • the inorganic particles (B) have an average particle size of 5 to 50 nm
  • the photopolymerizable compound (A) has a viscosity at 25°
  • the photopolymerizable compound (A) is a compound that is cured by active energy rays, and is not particularly limited as long as it contains a monofunctional monomer (A1) and a polyfunctional monomer (A2).
  • the photopolymerizable compound (A) may be used alone or in combination of two or more kinds.
  • “(meth)acrylate” means “acrylate and/or methacrylate”
  • “(meth)acrylic” means “acrylic and/or methacrylic”.
  • Examples of the monofunctional monomer (A1) include monofunctional (meth)acrylates, monofunctional urethane (meth)acrylates, monofunctional (meth)acrylamides, and monofunctional N-vinyl compounds.
  • Monofunctional (meth)acrylates include (meth)acrylates having a chain aliphatic group having 4 to 22 carbon atoms (e.g., n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), glycidyl (meth)acrylate, hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.).
  • n-butyl (meth)acrylate e.g., isobutyl (meth)acrylate
  • alkoxyalkyl (meth)acrylate ⁇ for example, 2-methoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, etc. ⁇ , 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 4-nonylphenoxyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, alicyclic skeleton-containing (meth)acrylates [for example, C6-C12 alicyclic skeleton-containing (meth)acrylates ⁇ for example, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, acrylate, cyclohexylethyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxy
  • Examples of the monofunctional urethane (meth)acrylate include a reaction product of a monofunctional (meth)acrylate (a) having a hydroxyl group and an organic monoisocyanate compound (b).
  • Examples of the monofunctional (meth)acrylate (a) having a hydroxyl group include hydroxyalkyl (meth)acrylates (2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol monoacrylate).
  • the monofunctional (meth)acrylate (a) having a hydroxyl group may be used alone or in combination of two or more kinds.
  • the organic monoisocyanate compound (b) include an aliphatic monoisocyanate compound (b1), an alicyclic monoisocyanate compound (b2), and an aromatic monoisocyanate compound (b3).
  • Examples of the aliphatic monoisocyanate compound (b1) include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, hexyl acrylate, octyl isocyanate, lauryl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, and octadecyl isocyanate.
  • Examples of the alicyclic monoisocyanate compound (b2) include cyclohexyl isocyanate.
  • Examples of the aromatic monoisocyanate compound (b3) include phenyl isocyanate and tolylene isocyanate.
  • the organic monoisocyanate compound (b) may be used alone or in combination of two or more kinds.
  • Monofunctional urethane (meth)acrylates can be obtained by subjecting a monofunctional (meth)acrylate having a hydroxyl group (a) to a urethane reaction with an organic monoisocyanate compound (b) using a known method.
  • Commercially available products may also be used, such as Viscoat #216 (manufactured by Osaka Organic Chemical Industry Ltd.), Etermer EM2080 (manufactured by Choko Materials Industry Co., Ltd.), and Genomer 1122 (manufactured by RAHN).
  • Examples of monofunctional (meth)acrylamides include (meth)acrylamide, N-alkoxy(meth)acrylamide, N-alkyl(meth)acrylamide, N-alkoxyalkyl(meth)acrylamide, N-hydroxyalkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N-alkoxy-N-alkyl(meth)acrylamide, and cyclic amides having an N-(meth)acryloyl group (heterocyclic skeleton-containing N-(meth)acrylamide).
  • N-alkoxy(meth)acrylamides include those having an alkoxy group having 1 to 6 carbon atoms, such as N-methoxy(meth)acrylamide, N-ethoxy(meth)acrylamide, N-propoxy(meth)acrylamide, and N-butoxy(meth)acrylamide.
  • N-alkyl(meth)acrylamides include those having an alkyl group having 1 to 6 carbon atoms, such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N-butyl(meth)acrylamide.
  • N-alkoxyalkyl(meth)acrylamides include those having an alkoxyalkyl group having 1 to 6 carbon atoms, such as Nn-butoxymethylacrylamide.
  • N-hydroxyalkyl(meth)acrylamides include those having a hydroxyalkyl group having 1 to 6 carbon atoms, such as N-hydroxyethyl(meth)acrylamide.
  • the N,N-dialkyl(meth)acrylamide includes those having an alkyl group having 1 to 22 carbon atoms, and examples thereof include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N,N-diisobutyl(meth)acrylamide, N,N-di-tert-butyl(meth)acrylamide, N,N-diheptyl(meth)acrylamide, N,N-dioctyl(meth)acrylamide, N,N-di-tert-octyl(meth)acrylamide, N,N-didodecyl(meth)acrylamide, and N,N-dioctadecyl(meth)acrylamide.
  • N-alkoxy-N-alkyl(meth)acrylamides include N-n-butoxy-N-methyl(meth)acrylamide, N-methyl-N-methoxy(meth)acrylamide, N-methyl-N-ethoxy(meth)acrylamide, N-methyl-N-propoxy(meth)acrylamide, N-ethyl-N-methoxy(meth)acrylamide, N-ethyl-N-ethoxy(meth)acrylamide, N-ethyl-N-butoxy(meth)acrylamide, N-propyl-N-methoxy(meth)acrylamide, N-propyl-N-ethoxy(meth)acrylamide, N-butyl-N-methoxy(meth)acrylamide, and N-butyl-N-ethoxy(meth)acrylamide.
  • cyclic amides having an N-(meth)acryloyl group include N-(meth)acryloylmorpholine, N-(meth)acryloylthiomorpholine, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, and N-(meth)acryloylpiperidine.
  • N-vinyl compounds examples include N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, N-vinylacetamide, and N-vinyl compounds containing a heterocyclic skeleton (e.g., N-vinyl-2-pyrrolidone, 5-methyl-3-vinyl-2-oxazolidinone, N-vinylcarbazole, and N-vinylphthalimide).
  • monofunctional (meth)acrylates and monofunctional (meth)acrylamides are preferred from the standpoints of curability, refractive index, and cure shrinkage, and more preferably at least one monomer selected from the group consisting of alicyclic skeleton-containing (meth)acrylates, aromatic ring skeleton-containing (meth)acrylates, and heterocyclic skeleton-containing N-(meth)acrylamides.
  • alicyclic skeleton-containing (meth)acrylate isobornyl acrylate is preferred
  • aromatic ring skeleton-containing (meth)acrylate phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, o-phenoxyphenylethyl acrylate, m-phenoxybenzyl acrylate, (naphthyl)methyl acrylate, benzyl acrylate, etc.
  • heterocyclic skeleton-containing N-(meth)acrylamides N-(meth)acryloylmorpholine, etc. are preferred.
  • (meth)acrylates containing an aromatic ring skeleton specifically phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, o-phenoxyphenylethyl acrylate, m-phenoxybenzyl acrylate, (naphthyl)methyl acrylate, and benzyl acrylate.
  • polyfunctional monomer (A2) examples include polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds.
  • polyfunctional (meth)acrylate compounds include difunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, pentafunctional (meth)acrylates, and hexafunctional or higher (meth)acrylates.
  • bifunctional (meth)acrylate examples include di(meth)acrylates containing an aromatic ring skeleton ⁇ for example, di(meth)acrylates of alkylene oxide (hereinafter, alkylene oxide may be abbreviated as "AO") adducts of dihydric phenol compounds [monocyclic phenols (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, bisphenol F, bisphenol S, etc.)] (for example, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, etc.), acrylic-modified bisphenoxyethanol fluorene, binaphthol derivatives, naphthothiol derivatives, etc. ⁇ , monomers containing a fluorene skeleton (fluorene acrylate derivatives), monomers containing a biphenyl skeleton (4-bipheny
  • di(meth)acrylate of an AO adduct of a dihydric phenol compound examples include a di(meth)acrylate of an adduct of 4 moles of ethylene oxide (hereinafter, ethylene oxide may be abbreviated as "EO”) to resorcinol, a di(meth)acrylate of an adduct of 4 moles of propylene oxide (hereinafter, propylene oxide may be abbreviated as "PO”) to dihydroxynaphthalene, a di(meth)acrylate of an adduct of 4 moles of EO to bisphenol A, a di(meth)acrylate of an adduct of 10 moles of EO to bisphenol A, and a di(meth)acrylate of an adduct of 20 moles of EO to bisphenol A.
  • EO ethylene oxide
  • propylene oxide propylene oxide
  • trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, tri(meth)acrylates of AO adducts of trimethylolpropane [trimethylolpropane with 6 moles of EO, 9 moles of EO, 15 moles of EO, 20 moles of EO, and 9 moles of PO, etc.], pentaerythritol tri(meth)acrylate, tri(meth)acrylates of AO adducts of pentaerythritol [pentaerythritol with 6 moles of EO, etc.], and tri(meth)acrylates of AO adducts of glycerin [glycerin with 6 moles of EO and 3 moles of PO, etc.].
  • tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate, tetra(meth)acrylates of AO adducts of pentaerythritol [pentaerythritol with 2 mol of EO, 4 mol of EO, 10 mol of EO, 15 mol of EO, and 35 mol of EO, etc.], and tetra(meth)acrylates of AO adducts of ditrimethylolpropane [ditrimethylolpropane with 10 mol of EO, etc.].
  • pentafunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate and penta(meth)acrylates of AO adducts of dipentaerythritol (e.g., dipentaerythritol with 2 moles of EO, 4 moles of EO, 10 moles of EO, and 15 moles of EO).
  • hexa- or higher functional (meth)acrylates examples include dipentaerythritol hexa(meth)acrylate, hexa(meth)acrylate of an AO adduct of dipentaerythritol [such as an EO 2-mol adduct, EO 4-mol adduct, EO 10-mol adduct, and EO 15-mol adduct of dipentaerythritol], and hexa(meth)acrylate of a lactone ( ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone) adduct of dipentaerythritol [such as an ⁇ -caprolactone 3-mol adduct, ⁇ -caprolactone 6-mol adduct, and ⁇ -caprolactone 12-mol adduct of dipentaerythritol].
  • AO adduct of dipentaerythritol such as an EO 2-
  • polyfunctional urethane (meth)acrylate compounds include difunctional urethane (meth)acrylates, trifunctional urethane (meth)acrylates, tetrafunctional urethane (meth)acrylates, pentafunctional urethane (meth)acrylates, and hexafunctional or higher urethane (meth)acrylates.
  • the polyfunctional urethane (meth)acrylate may be a commercially available product, such as Ebecryl 230, Ebecryl 8807, Ebecryl 9270, Ebecryl 8800, Ebecryl 4513, Ebecryl 680, Ebecryl 5129, KRM 8296, or KRM 8904 (all manufactured by Daicel Allnex Corporation).
  • polyfunctional (meth)acrylate compounds are preferred from the standpoints of curability, refractive index, and cure shrinkage, and di- to hexafunctional (meth)acrylates are more preferred.
  • difunctional (meth)acrylates at least one monomer selected from the group consisting of alicyclic skeleton-containing di(meth)acrylates, aromatic ring skeleton-containing di(meth)acrylates, and heterocyclic skeleton-containing di(meth)acrylates is even more preferred, and alicyclic skeleton-containing di(meth)acrylates and aromatic ring skeleton-containing di(meth)acrylates are particularly preferred.
  • the alicyclic skeleton-containing di(meth)acrylate is preferably dimethylol-tricyclodecane diacrylate or dimethylol-tricyclodecane dimethacrylate
  • the aromatic ring skeleton-containing di(meth)acrylate is preferably ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, acrylic-modified bisphenoxyethanol fluorene, 4,4'-bisacryloxymethyl biphenyl, or the like
  • the tri- to hexafunctional (meth)acrylate is preferably trimethylolpropane tri(meth)acrylate or trimethylolpropane dimethacrylate.
  • the weight ratio of the monofunctional monomer (A1) to the polyfunctional monomer (A2) [(A1)/(A2)] is preferably 0.1 to 9, and more preferably 0.2 to 9.
  • the photopolymerizable compound (A) preferably contains a small amount of monomers with a chemical formula weight of 230 or less, and more preferably contains a small amount of monomers with a chemical formula weight of 200 or less.
  • the content of monomers with a chemical formula weight of 200 or less is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 25% by weight or less, based on the weight of the photopolymerizable compound (A).
  • the monomers constituting the photopolymerizable compound (A) preferably contain a monomer having at least one aromatic ring, and more preferably contain a monomer having two or more aromatic rings. Furthermore, to reduce cure shrinkage, it is preferable to contain a monomer having an alicyclic skeleton.
  • the content of at least one monomer selected from the group consisting of alicyclic skeleton-containing (meth)acrylates, aromatic ring skeleton-containing (meth)acrylates, and heterocyclic skeleton-containing N-(meth)acrylamides in the photopolymerizable compound (A) is preferably 1 to 99 wt %, and more preferably 10 to 80 wt %, based on the weight of the photopolymerizable compound (A).
  • the viscosity of the photopolymerizable compound (A) at 25°C is 300 mPa s or less, preferably 1 to 200 mPa s, and more preferably 50 to 150 mPa s, from the viewpoint of imprintability.
  • the viscosity of the photopolymerizable compound (A) at 25°C can be adjusted by the types and constituent ratios of the monomers constituting the photopolymerizable compound (A).
  • the viscosity of the photopolymerizable compound (A) at 25° C. was measured as follows.
  • the viscosity of the photopolymerizable compound (A) at 25°C is measured based only on the composition of the photopolymerizable compound (A) constituting the active energy ray-curable composition, and does not depend on the inorganic particles (B), the photopolymerization initiator (C), and other components.
  • the glass transition temperature of the cured product of the photopolymerizable compound (A) is 70°C or higher, preferably 90°C or higher, more preferably 90 to 300°C, and even more preferably 90 to 250°C, from the viewpoints of heat resistance and adhesion.
  • the glass transition temperature of the cured product of the photopolymerizable compound (A) can be adjusted by the types and composition ratio of the monomers constituting the photopolymerizable compound (A).
  • the glass transition temperature is the temperature at which the loss tangent (tan ⁇ ) of the dynamic viscoelasticity of a polymer obtained by polymerizing the photopolymerizable compound (A) by the method described below is measured by the method described below.
  • the glass transition temperature of the cured product of the photopolymerizable compound (A) is measured by the following method.
  • the glass transition temperature of the cured product of the photopolymerizable compound (A) is measured based only on the composition of the photopolymerizable compound (A) constituting the active energy ray-curable composition, and does not depend on the inorganic particles (B), the photopolymerization initiator (C), and other components.
  • (3) (2) is irradiated with 1000 mJ/ cm2 of UV-A light at an illuminance of 1500 mW/ cm2 using an ultraviolet irradiation device (e.g., VPS/I600 manufactured by Fusion UV Systems Japan, lamp: D bulb) in an environment of 25°C, and then (2) is turned over and cured from the other side at 1000 mJ/ cm2 .
  • an ultraviolet irradiation device e.g., VPS/I600 manufactured by Fusion UV Systems Japan, lamp: D bulb
  • the cured sample of (3) is cut into a length of 40 mm, a width of 5 mm, and a thickness of 1 mm to prepare a test piece.
  • ⁇ Dynamic viscoelasticity measurement method> Using this test piece, measurements are made under the following conditions using a dynamic viscoelasticity measuring device (for example, Rheogel-E4000, manufactured by UBM). Measurement mode: temperature dependence, measurement temperature range: -80°C to 350°C, frequency: 10 Hz, heating rate: 4°C/min, strain waveform: sine wave, measurement jig: tensile.
  • the temperature at which the ratio of the loss modulus E" to the storage modulus E' in the obtained spectrum (loss tangent tan ⁇ ) shows a maximum value is defined as the glass transition temperature (Tg).
  • Methods for adjusting the glass transition temperature include, for example, using a photopolymerizable compound (A) whose homopolymer has a high glass transition temperature, or increasing the number of functional groups, in order to increase the glass transition temperature.
  • the refractive index of the photopolymerizable compound (A) is preferably 1.50 or more, more preferably 1.55 or more, and particularly preferably 1.60 or more.
  • a photopolymerizable compound having a refractive index of less than 1.50 may be used in combination as long as it does not affect the decrease in the refractive index.
  • the refractive index of the photopolymerizable compound (A) is a value measured at 25°C in an uncured state using the D line of the sodium spectrum with an Abbe refractometer (DR-M2 manufactured by Atago Co., Ltd., etc.) in accordance with JIS-K0062:1992.
  • the refractive index of the photopolymerizable compound (A) is measured based only on the composition of the photopolymerizable compound (A) constituting the active energy ray-curable composition, and does not depend on the inorganic particles (B), the photopolymerization initiator (C), and other components.
  • the inorganic particles (B) will be described below.
  • the inorganic particles (B) are not particularly limited as long as they are particles of an inorganic compound with an average particle size of 5 to 50 nm. Examples include compounds of metal elements and compounds of nonmetal elements, and examples of such compounds include hydrogen compounds, oxides, oxoacids, hydroxides, halides, sulfates, nitrates, carbonates, acetates, and metal complexes. Among the above inorganic compounds, oxides of metal elements, oxides of nonmetal elements, and oxides containing metal elements and nonmetal elements are preferred from the viewpoint of refractive index.
  • the inorganic particles (B) may be used alone or in combination of two or more kinds.
  • the oxide particles as inorganic particles (B) are preferably at least one type of particles selected from the group consisting of TiO2 , SiO2 , BaTiO3 , ZnO , MgO , SnO2 , Al2O3 , ZrO2 , CeO2 , Fe2O3 , Fe3O4 , WO3 , Y2O3 , SrTiO3 , FeTiO3 , MnTiO3 , Nb2O5 , and KTaO3 .
  • the average particle diameter of the inorganic particles (B) is 5 to 50 nm, because this provides excellent dispersion stability and a cured product with high light transmittance and refractive index.
  • the average particle diameter of the inorganic particles (B) is the average primary particle diameter measured from approximately 300 particles in a photograph (25k) observed with a transmission electron microscope [JEOL Ltd., JEM-F200].
  • the average primary particle diameter is the particle diameter obtained by averaging the diameter (circle-equivalent diameter) of a circle having an area equivalent to the area determined for each particle from the photograph for all particles measured.
  • the inorganic particles (B) preferably have an average particle size of 5 to 40 nm.
  • the shape of the inorganic particles (B) is not particularly limited, and may be, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous. Among these, spherical shapes are preferred because they provide excellent dispersion stability and allow the production of cured products with high light transmittance and refractive index.
  • the crystalline structure of the inorganic particles (B) is not particularly limited, but a monoclinic system is preferred because it provides excellent dispersion stability and a cured product with high light transmittance and refractive index.
  • the photopolymerization initiator (C) may be any of a photoradical polymerization initiator, a photoanionic polymerization initiator, and a photocationic polymerization initiator.
  • Examples of the photopolymerization initiator (C) include benzoin compounds (C1), alkylphenone compounds (C2), anthraquinone compounds (C3), thioxanthone compounds (C4), ketal compounds (C5), benzophenone compounds (C6), phosphine oxides (C7), and oxime ester compounds (C8).
  • Examples of the benzoin compound (C1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.
  • Examples of the alkylphenone compound (C2) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.
  • Examples of the anthraquinone compound (C3) include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone.
  • Examples of the thioxanthone compound (C4) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone.
  • Examples of the ketal compound (C5) include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • Examples of the benzophenone compound (C6) include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone.
  • Examples of the phosphine oxide (C7) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • Examples of the oxime ester compound (C8) include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime).
  • photopolymerization initiators (C) 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred from the viewpoint of curability.
  • the photopolymerization initiator (C) may be used alone or in combination of two or more kinds.
  • the active energy ray-curable composition of the present invention preferably contains a dispersant (D).
  • the dispersant (D) is a surfactant containing at least one functional group selected from the group consisting of a carboxyl group, a phosphate group, a thiol group, a hydroxyl group, and an amino group, and it adsorbs to the surfaces of inorganic particles, thereby dispersing the inorganic particles uniformly in the cured product.
  • surfactants containing a carboxyl group include saturated fatty acids having 12 to 36 carbon atoms (lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, etc.) and/or salts thereof, monocarboxylic acids of alkylene oxide adducts (polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, etc.) and/or salts thereof, compounds having a (meth)acryloyloxy group or a vinyl group and a carboxyl group (carboxyethyl (meth)acrylate, ⁇ -carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-methacrylo
  • surfactants containing a phosphate group include alkyl phosphate esters having 4 to 36 carbon atoms (2-ethylhexyl acid phosphate, oleyl acid phosphate, etc.) and/or salts thereof, phosphate esters of alkylene oxide adducts (butoxyethyl acid phosphate, etc.) and salts thereof, and compounds having a (meth)acryloyloxy group or a vinyl group and a phosphate group (2-methacryloyloxyethyl caproate acid phosphate, acid phosphooxypropylene glycol monomethacrylate, and 2-methacryloyloxyethyl acid phosphate (2-hydroxyethyl methacrylate acid phosphate), etc.) and salts thereof.
  • surfactants containing a thiol group include alkylthiols having 8 to 36 carbon atoms (such as 1-dodecanethiol) and aromatic thiols (such as 2-mercaptobenzothiazole).
  • examples of surfactants containing a hydroxyl group include saturated alcohols having 8 to 36 carbon atoms (octanol, decanol, octadecanol, docosanol, triacontanol, etc.), alkylene oxide adducts of saturated alcohols having 8 to 36 carbon atoms (polyethylene glycol monolaurate, etc.), sorbitan fatty acid esters (sorbitan monostearate, sorbitan monolaurate, etc.), and compounds having a (meth)acryloyloxy group or a vinyl group and a hydroxyl group (hydroxyethyl (meth)acrylate, 4-hydroxybutyl acrylate, N-(2-hydroxyethyl)acryl
  • surfactants containing an amino group include amine compounds having 8 to 36 carbon atoms (such as N,N-dimethyldodecylamine), and compounds having a (meth)acryloyloxy group or a vinyl group and an amino group (such as 2-(dimethylamino)ethyl methacrylate and N-[3-(dimethylamino)propyl]acrylamide).
  • surfactants containing a carboxyl group surfactants containing a phosphate group, or surfactants containing a hydroxyl group are preferred from the viewpoint of dispersion stability, and more preferred are compounds having a (meth)acryloyloxy group or a vinyl group and a carboxyl group, compounds having a (meth)acryloyloxy group or a vinyl group and a phosphate group, and compounds having a (meth)acryloyloxy group or a vinyl group and a hydroxyl group, and particularly preferred are carboxyethyl (meth)acrylate, ⁇ -carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate, methyl (meth)acrylate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate and 2-methacryloyloxye
  • the active energy ray-curable composition of the present invention can be diluted with a solvent (E) as needed within a range that does not impair the effects of the present invention.
  • the solvent (E) is preferably an organic solvent from the viewpoints of compatibility with other components and dispersibility.
  • organic solvents examples include alcohols (e.g., methanol, ethanol, isopropanol, butanol, 3-methoxybutanol, and octanol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone), esters (e.g., ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, methoxybutyl acetate (3-methoxybutyl acetate), propylene glycol monomethyl ether acetate (2-methoxy-1-methylethyl acetate), and propylene glycol monoethyl ether acetate), ethers (e.g., ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene
  • methanol, isopropanol, butanol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, methoxybutyl acetate, toluene, and xylene are preferred from the viewpoint of compatibility with the active energy ray-curable composition of the present invention.
  • the solvent (E) may be used alone or in combination of two or more kinds.
  • the active energy ray-curable composition of the present invention may contain other additives as needed within the range that does not impair the effects of the present invention.
  • the additives include mold release agents, antioxidants, hindered amine light stabilizers, ultraviolet absorbers, antistatic agents, colorants, polymerization inhibitors, chain transfer agents, fillers, surfactants, plasticizers, dispersants, and thixotropy-imparting agents (thickeners).
  • Examples of the mold release agent (F) include fluorine additives, acrylic leveling agents, and silicone leveling agents.
  • fluorine additives include BM-1000 and BM-1100 (all manufactured by BM CHEMIE), Megafac F-142D, F-172, F-173, F-183, F-178, F-471, F-477, F-444, F-552, and F-554 (all manufactured by DIC Corporation), and Surflon S-242, S-420, S-431, S-386, S-611, S-651, S-656, S-658, and S-693 (all manufactured by AGC Seimi Chemical Co., Ltd.).
  • acrylic leveling agents examples include Disparlon UVX-36 (manufactured by Kusumoto Chemicals Co., Ltd.).
  • silicone leveling agents examples include KP-423 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow KL-401 (manufactured by Kyoeisha Co., Ltd.).
  • the mold release agent (F) may be used alone or in combination of two or more kinds.
  • the refractive index of the active energy ray-curable composition of the present invention is preferably 1.60 to 1.80 from the viewpoint of improving the brightness of optical lenses.
  • the viscosity of the active energy ray-curable composition of the present invention at 25° C. is preferably 300 mPa ⁇ s or less from the viewpoints of the coatability of the active energy ray-curable composition and the imprintability of the cured product.
  • the viscosity of the active energy ray-curable composition of the present invention at 25° C. can be measured under the following conditions using an E-type viscosity measuring device ("VISCOMETER TV-25L" manufactured by Toki Sangyo Co., Ltd.) or the like. [Measurement conditions] Cone rotor: Standard cone rotor (1°34' x R24) Measurement temperature: 25°C Measurement range: M Rotation speed: 50 rpm
  • the weight proportion of the photopolymerizable compound (A) in the present invention is preferably 3 to 50% by weight, more preferably 4 to 30% by weight, based on the total weight of the photopolymerizable compound (A), the inorganic particles (B), and the photopolymerization initiator (C). If the weight ratio of the photopolymerizable compound (A) is less than 3% by weight, the imprinting properties may be insufficient, and if it exceeds 50% by weight, the refractive index of the cured product may be insufficient.
  • the weight proportion of the inorganic particles (B) in the present invention is preferably 49% by weight to 96% by weight, more preferably 69% by weight to 95% by weight, based on the total weight of the photopolymerizable compound (A), the inorganic particles (B), and the photopolymerization initiator (C). If the weight ratio of the inorganic particles (B) is less than 49% by weight, the refractive index of the cured product may be insufficient, and if it exceeds 96% by weight, the imprintability may be insufficient.
  • the weight proportion of the photopolymerization initiator (C) is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, and particularly preferably 1 to 3% by weight, based on the total weight of the photopolymerizable compound (A), inorganic particles (B), and photopolymerization initiator (C).
  • the weight proportion of the dispersant (D) is preferably 1 to 20% by weight, and more preferably 1 to 10% by weight, based on the total weight of the photopolymerizable compound (A) and inorganic particles (B).
  • the weight proportion of the solvent (E) is preferably 0 to 800% by weight, more preferably 0.1 to 700% by weight, and particularly preferably 1 to 500% by weight, based on the total weight of the photopolymerizable compound (A), inorganic particles (B), and photopolymerization initiator (C).
  • the weight proportion of other additives is preferably 0.01 to 10% by weight based on the total weight of the photopolymerizable compound (A), inorganic particles (B), and photopolymerization initiator (C), from the perspective of the refractive index of the cured product.
  • the active energy ray-curable composition of the present invention can be produced, for example, by uniformly mixing the photopolymerizable compound (A), inorganic particles (B), photopolymerization initiator (C), dispersant (D), solvent (E) and other additives using a known mechanical mixing method (a method using a mechanical stirrer, a magnetic stirrer, or the like).
  • the inorganic particles (B) may be dispersed in an organic solvent (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, etc.), in which case a mixture of the active energy ray-curable composition of the present invention and the organic solvent is obtained.
  • the organic solvent may be distilled off under reduced pressure.
  • the cured product of the present invention is obtained by curing the active energy ray-curable composition of the present invention, and can be obtained, for example, by irradiating a coating film obtained by molding the active energy ray-curable composition of the present invention with active energy rays to cure it.
  • active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, electron beams, etc.
  • Ultraviolet rays refer to rays with a wavelength of 200 nm to 410 nm.
  • the wavelength of the active energy ray is not particularly limited as long as it can cure the composition, but is preferably 350 nm to 410 nm, and more preferably 385 nm to 405 nm.
  • a typical example of the active energy ray is light with a wavelength of 395 nm.
  • the irradiation intensity of the active energy rays is not particularly limited as long as it can cure the composition, but it is preferably 20 mW/cm 2 to 20,000 mW/cm 2 .
  • the cumulative exposure dose of the active energy rays is preferably 100 mJ/cm 2 to 30,000 mJ/cm 2.
  • the irradiation time may be determined depending on the irradiation intensity.
  • light sources that can be used include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, etc. (Latest Trends in UV/EB Curing Technology, edited by RadTech Research Group, CMC Publishing, p. 138, 2006), and LEDs. Compared to other light sources, LEDs consume less power and generate less ozone, resulting in lower running costs and a lower environmental impact.
  • an LED light source ultraviolet irradiation device for example, LED light source ultraviolet irradiation device "FJ100" 150 x 20 365, manufactured by Phoseon Technology Co., Ltd.] can be used.
  • the shape of the portion irradiated with active energy rays can be an area type with a certain surface area, or a line type.
  • a line type the entire coating film can be irradiated with light by moving the coating film relative to the light source, or by moving the light source relative to the coating film.
  • a line type it is easy to adjust the irradiation time, and therefore the cumulative exposure amount.
  • Irradiation with active energy rays may be carried out in the atmosphere. Because the composition of the present invention has good reactivity, the reaction of the composition can be allowed to proceed and harden even in the atmosphere. It is particularly preferable to irradiate the composition with active energy rays in a dry atmosphere to harden it. In this case, moisture absorption by the cured composition can be suppressed.
  • the cured product may be further heated. Heating further accelerates curing and reduces the linear expansion coefficient of the cured product. If further heating is performed, the heating temperature is preferably 90°C or higher.
  • the refractive index of the cured product of the present invention is preferably 1.60 or higher, and more preferably 1.60 to 1.80, from the perspective of improving the brightness of optical lenses.
  • the active energy ray-curable composition of the present invention can be cured to produce molded articles that can be suitably used as optical components (optical lenses, optical lens sheets, films, coating materials for decorative films, coating materials for optical fibers, hard coat films, anti-reflection films, etc.).
  • the method for producing the optical component using the active energy ray-curable composition of the present invention is not particularly limited, and for example, coating and molding can be performed by the following method: That is, the composition of the present invention is coated onto a transparent substrate (including a transparent film) using a bar coater or the like so as to give a thickness of 50 nm to 150 ⁇ m after curing, a mold is pressed onto the coated film, and the coated film is cured by irradiating the transparent substrate with active energy rays described below, and then the coated film is released from the mold to obtain an optical component.
  • the transparent substrate includes those made from glass, methyl methacrylate (co)polymers, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polycycloolefin, and other resins.
  • An active energy ray-curable composition comprising a photopolymerizable compound (A), inorganic particles (B), and a photopolymerization initiator (C), wherein the photopolymerizable compound (A) contains a monofunctional monomer (A1) and a polyfunctional monomer (A2), the inorganic particles (B) have an average particle size of 5 to 50 nm, the photopolymerizable compound (A) has a viscosity at 25°C of 300 mPa s or less, and a cured product of the photopolymerizable compound (A) has a glass transition temperature of 70°C or higher.
  • the active energy ray -curable composition according to ⁇ 1> wherein the inorganic particles (B) are at least one type of particles selected from the group consisting of TiO2, SiO2, BaTiO3, ZnO, MgO, SnO2, Al2O3 , ZrO2 , CeO2 , Fe2O3 , Fe3O4 , WO3 , Y2O3 , SrTiO3 , FeTiO3 , MnTiO3, Nb2O5 , and KTaO3.
  • the inorganic particles (B) are at least one type of particles selected from the group consisting of TiO2, SiO2, BaTiO3, ZnO, MgO, SnO2, Al2O3 , ZrO2 , CeO2 , Fe2O3 , Fe3O4 , WO3 , Y2O3 , SrTiO3 , FeTiO3 , MnTiO3, Nb2O5 ,
  • ⁇ 4> The active energy ray-curable composition according to any one of ⁇ 1> to ⁇ 3>, wherein the monofunctional monomer (A1) is at least one monomer selected from the group consisting of alicyclic skeleton-containing (meth)acrylates, aromatic ring skeleton-containing (meth)acrylates, and heterocyclic skeleton-containing N-(meth)acrylamides.
  • the monofunctional monomer (A1) is at least one monomer selected from the group consisting of alicyclic skeleton-containing (meth)acrylates, aromatic ring skeleton-containing (meth)acrylates, and heterocyclic skeleton-containing N-(meth)acrylamides.
  • ⁇ 5> The active energy ray-curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polyfunctional monomer (A2) is at least one monomer selected from the group consisting of alicyclic skeleton-containing di(meth)acrylates, aromatic ring skeleton-containing di(meth)acrylates, and heterocyclic skeleton-containing di(meth)acrylates.
  • the polyfunctional monomer (A2) is at least one monomer selected from the group consisting of alicyclic skeleton-containing di(meth)acrylates, aromatic ring skeleton-containing di(meth)acrylates, and heterocyclic skeleton-containing di(meth)acrylates.
  • ⁇ 6> The active energy ray-curable composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a dispersant (D), wherein the dispersant (D) is a surfactant containing at least one functional group selected from the group consisting of a carboxyl group, a phosphate group, a thiol group, a hydroxyl group, and an amino group.
  • D a dispersant
  • the dispersant (D) is a surfactant containing at least one functional group selected from the group consisting of a carboxyl group, a phosphate group, a thiol group, a hydroxyl group, and an amino group.
  • D is a surfactant containing at least one functional group selected from the group consisting of a carboxyl group, a phosphate group, a thiol group, a hydroxyl group, and an amino group.
  • ⁇ 7> A cured product of the active energy ray-curable composition according to any one
  • A-1) Phenoxydiethylene glycol acrylate [P2H-A: manufactured by Kyoeisha Chemical Co., Ltd., refractive index (25°C): 1.51]
  • A-2) o-phenoxyphenylethyl acrylate [A-LEN-10: manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index (25°C): 1.58]
  • A-3) m-phenoxybenzyl acrylate [POB-A: manufactured by Kyoeisha Chemical Co., Ltd., refractive index (25°C): 1.57]
  • B-1 A solution of zirconium oxide (ZrO 2 ) particles dispersed in methyl ethyl ketone [trade name “Zircostar AX-ZP-158-A, solid content: 70% by weight, average particle size of zirconia particles: 17 nm", manufactured by Nippon Shokubai Co., Ltd.]
  • B-2) Titanium oxide (TiO 2 ) particles [trade name "TTO-51(C), average particle size of titanium oxide particles: 10-30 nm", manufactured by Ishihara Sangyo Kaisha, Ltd.]
  • B-3) A solution in which barium titanate (BaTiO 3 ) particles are dispersed in propylene glycol monomethyl ether [product name "9714BT, solid content: 15% by weight, average particle diameter of barium titanate particles: approximately 40 nm", manufactured by Tokushiki Co., Ltd.]
  • C-1 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name "IRGACURE TPO", manufactured by BASF)
  • C-2) Omnirad TPO-L [2,4,6-trimethylbenzoylethylphenylphosphine oxide, manufactured by IGM Resins B.V.]
  • C-3) 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184", manufactured by BASF)
  • D-1 2-acryloyloxyethyl hexahydrophthalic acid [HOA-HH: Kyoeisha Chemical Co., Ltd., HLB: 11.4]
  • D-2 2-acryloyloxyethyl succinate
  • HA-MS Kyoeisha Chemical Co., Ltd., HLB: 15.2]
  • D-3 Acrylic oligomer [(ACA)Z200M: manufactured by Daicel Allnex Co., Ltd.]
  • D-4) 2-methacryloyloxyethyl caproate acid phosphate [KAYAMER PM-21: manufactured by Nippon Kayaku Co., Ltd., HLB: 5.3]
  • D-5 Acid phosphoxypropylene glycol monomethacrylate [Hosmer PP: manufactured by Unichemical Co., Ltd., HLB: 5.1]
  • D-6) 2-mercaptobenzothiazole [Suncerer M: manufactured by Sanshin Chemical Industry Co., Ltd., HLB: 2.0]
  • E-1 PGMEA [2-methoxy-1-methylethyl acetate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
  • E-2 MEK [methyl ethyl ketone: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
  • E-3) Cyclohexanone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
  • E-4) MBA [3-methoxybutyl acetate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
  • the active energy ray-curable compositions prepared in each example and comparative example were evaluated using the following methods for the viscosity of the photopolymerizable compound (A), the glass transition temperature (Tg) of the cured product of the photopolymerizable compound (A), the refractive index and adhesion of the cured product of the active energy ray-curable composition, and the imprintability and dispersion stability of the active energy ray-curable composition.
  • (3) (2) was irradiated with 1000 mJ/ cm2 of UV-A light at an illuminance of 1500 mW/cm2 using an ultraviolet irradiation device (VPS/I600 manufactured by Fusion UV Systems Japan, lamp: D bulb) in an environment of 25°C, and then (2) was turned over and cured from the other side at 1000 mJ/ cm2 .
  • the cured sample of (3) was cut into a length of 40 mm, a width of 5 mm, and a thickness of 1 mm to prepare a test piece.
  • (5) Using the above test piece, measurements were made under the following conditions using a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM).
  • Measurement mode temperature dependence, measurement temperature range: -80°C to 350°C, frequency: 10 Hz, heating rate: 4°C/min, strain waveform: sine wave, measurement jig: tensile.
  • the temperature at which the ratio of the loss modulus E" to the storage modulus E' in the obtained spectrum (loss tangent tan ⁇ ) showed a maximum value was defined as the glass transition temperature (Tg).
  • the active energy ray-curable composition was dropped onto a glass substrate [Eagle XG, manufactured by Corning Corporation] and applied by spin coating at 3000 rpm for 30 seconds, and then dried at 100°C for 3 minutes. After that, the composition was cured by irradiating it with ultraviolet light at 1000 mJ/ cm2 using an ultraviolet irradiation device [VPS/I600, manufactured by Fusion UV Systems Co., Ltd.] in a nitrogen atmosphere, to obtain a cured product with a film thickness of 100 nm for refractive index evaluation.
  • an ultraviolet irradiation device [VPS/I600, manufactured by Fusion UV Systems Co., Ltd.] in a nitrogen atmosphere
  • ⁇ Refractive index> The refractive index of the cured product prepared as described above at 589 nm was measured using a reflection spectroscopic film thickness meter [FE-3000, manufactured by Otsuka Electronics Co., Ltd.]. In this case, a refractive index of 1.60 or higher is considered to be satisfactory.
  • ⁇ Method for evaluating adhesion> For the cured product for evaluation, cellophane adhesive tape was applied to the surface of the cured product and peeled off at an angle of 90 degrees. The state of peeling of the cured product from the glass was visually observed and evaluated according to the following criteria. ⁇ : 90% or more of the cured product remains on the glass substrate. ⁇ : 50% to less than 90% of the cured product remains on the glass substrate. ⁇ : Less than 50% of the cured product remains on the glass substrate.
  • the active energy ray-curable composition was stored at 25°C for one week, one month, or three months. Whether the dispersion state of the particles was maintained after storage was evaluated. If there was no visible change and the particles did not settle for one week but settled or gelled within one month, the evaluation was marked "Good.” If the particles did not settle for one month but settled or gelled within three months, the evaluation was marked "Excellent.” If the particles did not settle for three months, the evaluation was marked "Excellent.” If the coated particles settled within one week or if there was a clear increase in viscosity and gelled, the evaluation was marked "Poor.”
  • Comparative Examples 1 and 3 in which active energy ray-curable compositions were used in which the glass transition temperature of the photopolymerizable compound (A) was outside the range specified by the present invention, exhibited low adhesion and poor imprintability. Furthermore, Comparative Example 2, in which an active energy ray-curable composition in which the viscosity of the photopolymerizable compound (A) was outside the range specified by the present invention was used, exhibited poor imprintability. In contrast, each of the Examples produced cured products that showed good results in all categories.
  • the cured product of the active energy ray-curable composition of the present invention has a high refractive index and is therefore useful as an optical component.
  • it is useful as an optical component such as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle improving lenses, etc.), optical compensation films, retardation films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and photosensitive optical waveguides.

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Abstract

La composition durcissable par rayonnement d'énergie active selon l'invention comprend un composé photopolymérisable (A), des particules inorganiques (B) et un photo-initiateur (C). La composition durcissable par rayonnement d'énergie active est caractérisée en ce que le composé photopolymérisable (A) comprend un monomère monofonctionnel (A1) et un monomère polyfonctionnel (A2), le diamètre moyen des particules inorganiques (B) est compris entre 5 et 50 nm, la viscosité du composé photopolymérisable (A) est égale ou inférieure à 300 mPa·s à 25 °C et la température de transition vitreuse d'un produit durci du composé photopolymérisable (A) est égale ou supérieure à 70 °C.
PCT/JP2024/043103 2024-02-01 2024-12-05 Composition durcissable par rayonnement d'énergie active et produit durci de celle-ci Pending WO2025164088A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010064534A1 (fr) * 2008-12-01 2010-06-10 昭和電工株式会社 Procédé de formage
JP2013018827A (ja) * 2011-07-08 2013-01-31 Showa Denko Kk 硬化性組成物およびその硬化物
WO2022203081A1 (fr) * 2021-03-26 2022-09-29 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, composant optique, procédé de production de composant optique et dispositif électroluminescent
WO2024117094A1 (fr) * 2022-11-28 2024-06-06 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, composant optique, procédé de production de composant optique, dispositif émetteur de lumière, et procédé de production de dispositif émetteur de lumière

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010064534A1 (fr) * 2008-12-01 2010-06-10 昭和電工株式会社 Procédé de formage
JP2013018827A (ja) * 2011-07-08 2013-01-31 Showa Denko Kk 硬化性組成物およびその硬化物
WO2022203081A1 (fr) * 2021-03-26 2022-09-29 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, composant optique, procédé de production de composant optique et dispositif électroluminescent
WO2024117094A1 (fr) * 2022-11-28 2024-06-06 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, composant optique, procédé de production de composant optique, dispositif émetteur de lumière, et procédé de production de dispositif émetteur de lumière

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