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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—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
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—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
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets

Definitions

• the present invention relates to a photocurable liquid composition, a cured product of the photocurable liquid composition, and a method for producing a cured product using the photocurable liquid composition.
• high refractive index materials have been used to form optical members.
• Compositions in which metal oxide particles such as titanium oxide and zirconium oxide are dispersed in an organic component are used as high refractive materials.
• As a composition for forming such a high refractive material an energy ray containing a metal oxide (A) having a specific particle size, a (meth)acrylate (B), and a photopolymerization initiator (C)
• a curable composition has been proposed (see Patent Document 1).
• the present invention has been made in view of the above problems, and provides a photocurable liquid composition capable of forming a cured product in which localization of metal oxide nanoparticles is suppressed, and the photocurable liquid composition. and a method for producing a cured product using the photocurable liquid composition.
• the present inventors added a photopolymerizable monomer (A) to a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C).
• A photopolymerizable monomer
• A1 polyfunctional monomer having 3 or more ethylenically unsaturated double bonds
• a first aspect of the present invention is a photocurable liquid composition
• a photocurable liquid composition comprising a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C),
• the photopolymerizable monomer (A) has an ethylenically unsaturated double bond
• a second aspect of the present invention is a cured product of the photocurable liquid composition according to the first aspect.
• a third aspect of the present invention is to mold the photocurable liquid composition according to the first aspect; and exposing the shaped photocurable liquid composition to light.
• a photocurable liquid composition capable of forming a cured product in which localization of metal oxide nanoparticles is suppressed, a cured product of the photocurable liquid composition, and the photocurable and a method for producing a cured product using the liquid composition.
• the photocurable liquid composition contains a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C).
• a photopolymerizable monomer (A) has an ethylenically unsaturated double bond.
• the photopolymerizable monomer (A) contains a polyfunctional monomer (A1) having 3 or more ethylenically unsaturated double bonds.
• a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C) is added with 3 or more ethylene as the photopolymerizable monomer (A).
• (meth)acrylate means both acrylate and methacrylate.
• (meth)acrylic means both acrylic and methacrylic.
• (meth)acryloyl means both acryloyl and methacryloyl.
• the photocurable liquid composition may contain a solvent (S). From the viewpoint of suppressing the strength reduction of the cured product due to the solvent (S) when forming the cured product, the photocurable liquid composition contains only a small amount of the solvent (S), or the photocurable liquid composition contains only a small amount of the solvent (S). It is preferably free of solvent (S).
• the content of the solvent (S) in the photocurable liquid composition is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less. 5% by mass or less is particularly preferred, and 0.3% by mass or less is most preferred.
• the content of the solvent (S) in the photocurable liquid composition is preferably 0% by mass or more. It is particularly preferred that the photocurable liquid composition is substantially free of solvent (S).
• the fact that the photocurable liquid composition does not substantially contain the solvent (S) means that a very small amount of the solvent (S) is inevitably brought into the photocurable liquid composition accompanying the raw materials, etc. It means that the solvent (S) is not intentionally added to the liquid composition.
• the content of the solvent (S) in the photocurable liquid composition is, for example, 0.2% by mass or less, and 0.15% by mass. % or less is preferable, 0.1 mass % or less is more preferable, and 0.05 mass % or less is even more preferable.
• the viscosity of the photocurable liquid composition is preferably 70 cP or less, more preferably 60 cP or less, and even more preferably 50 cP or less, as measured at 25° C. using an E-type viscometer.
• the viscosity of the photocurable liquid composition can be adjusted, for example, by adjusting the content of the plasticizer (D), adjusting the content of the photopolymerizable monomer (A) or the metal compound particles (B), or by adjusting the content of the photocurable liquid composition. It can be adjusted by adding a small amount of solvent (S) to the liquid composition.
• the photocurable liquid composition contains a photopolymerizable monomer (A) having an ethylenically unsaturated double bond.
• Photopolymerizable monomers (A) include polyfunctional monomers (A1) having 3 or more ethylenically unsaturated double bonds. As a result, it is possible to form a cured product in which localization of the metal oxide nanoparticles (B) is suppressed.
• a bifunctional monomer (A2) and/or a monofunctional monomer (A3) can be used together with the polyfunctional monomer (A1).
• the polyfunctional monomer (A1) is an aliphatic compound that does not contain an aromatic group. is preferred.
• the number of ethylenically unsaturated double polymerization bonds possessed by the polyfunctional monomer (A1) is 3 or more and 6 or less are preferable.
• Preferred specific examples of the polyfunctional monomer (A1) include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, condensate of polyhydric alcohol and N-methylol(meth)acrylamide, and the like.
• the photocurable liquid composition preferably contains a compound represented by the following formula (A1) or the following formula (A2) as the polyfunctional monomer (A1).
• A1 and A2 MA-(O-R a1 ) na1 -X-CH 2 ) 2 -CH-X-(R a1 -O) na1 -MA (A2)
• MA is each independently a (meth)acryloyl group
• X is each independently an oxygen atom, —NH—, or —N(CH 3 )—
• each R a1 is independently an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group
• R a2 is a hydroxyl group; an alkyl group of 1 or more and 4 or less, or a group represented by -X-(R a1 -O) na1 -MA (X is as defined above), na1 and
• the alkyl group having 1 to 4 carbon atoms as R a2 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl groups.
• a methyl group and an ethyl group are preferred.
• Preferred examples of the compound represented by formula (A1) and the compound represented by formula (A2) include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth) Acrylate, glycerin tri(meth)acrylate, and compounds 1) to 32) below.
• MA is a (meth)acryloyl group.
• the mass ratio of the polyfunctional monomer (A1) to the mass of the photopolymerizable monomer (A) is 20% by mass or more and 70% by mass.
• the following is preferable, 30% by mass or more and 70% by mass or less is more preferable, and 40% by mass or more and 70% by mass or less is even more preferable.
• bifunctional monomer (A2) examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.
• the photopolymerizable monomer (A) preferably contains a compound represented by the following formula (a-1) as a bifunctional monomer (A2) in terms of easy formation of a cured product with a high refractive index.
• R 1 and R 2 are each independently a hydrogen atom or a methyl group.
• R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms.
• p and q are each independently 0 or 1;
• R 1 and R 2 are each independently a hydrogen atom or a methyl group. R 1 and R 2 may be different from each other or may be the same. R 1 and R 2 are preferably the same because the compound represented by formula (a-1) is easy to synthesize and obtain.
• R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms. R 3 and R 4 may be different from each other or may be the same. It is preferable that R 3 and R 4 are the same because the compound represented by formula (a-1) is easily synthesized and available.
• the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 may be linear or branched.
• alkyl groups having 1 to 5 carbon atoms as R 3 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and tert-pentyl group.
• Preferred specific examples of the compound represented by formula (a-1) include the following compounds.
• the ratio of the mass of the bifunctional monomer (A2) to the mass of the photopolymerizable monomer (A) is within a range that does not impair the desired effect. It is not particularly limited.
• the ratio of the mass of the bifunctional monomer (A2) to the mass of the photopolymerizable monomer (A) is preferably 0% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and 30% by mass.
• the above are particularly preferred.
• the upper limit is, for example, preferably 50% by mass or less, more preferably 45% by mass or less.
• the mass of the photopolymerizable monomer (A) is represented by the formula (a-1)
• the ratio of the mass of the compound is preferably 10% by mass or more and 30% by mass or less, more preferably 15% by mass or more and 25% by mass or less.
• Monofunctional monomers (A3) include, for example, (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide , N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid , 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate , 2-hydroxyethy
• the photopolymerizable monomer (A) is a monofunctional monomer (A3) represented by the following formula (a-2) It preferably contains the represented compound.
• R 10 is a hydrogen atom or a methyl group.
• R 11 is an alkylene group having 1 to 3 carbon atoms.
• R12 is a single bond, an oxygen atom, or a sulfur atom.
• R 13 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or a phenyl group.
• s is an integer of 0 or more and 5 or less.
• t is 0, 1 or 2;
• a plurality of R 11 may be the same or different, and are preferably the same.
• multiple R 12 may be the same or different, and are preferably the same.
• R 11 is an alkylene group having 1 to 3 carbon atoms.
• the alkylene group include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group and propane-1,2-diyl group. , and propane-2,2-diyl groups.
• methylene group, ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group, and propane-1,2-diyl group are preferred, and ethane-1,2-diyl group (ethylene group) is more preferred.
• R 12 is a single bond, an oxygen atom, or a sulfur atom, preferably a single bond.
• t is preferably 1.
• R 13 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or a phenyl group. From the viewpoint of lowering the viscosity, R 13 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.
• alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups.
• a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.
• s is an integer of 0 or more and 5 or less, preferably 0 or 1, more preferably 0;
• Preferred specific examples of the compound represented by formula (a-2) include the following compounds.
• the ratio of the mass of the monofunctional monomer (A3) to the mass of the photopolymerizable monomer (A) is within a range that does not impair the desired effect. It is not particularly limited.
• the ratio of the mass of the monofunctional monomer (A3) to the mass of the photopolymerizable monomer (A) is preferably 50% by mass or more, more preferably 55% by mass or more.
• the upper limit may be, for example, 80% by mass.
• the ratio of the mass of the photopolymerizable monomer (A) to the mass of the photocurable liquid composition excluding the mass of the solvent (S) is preferably 20% by mass or more and 90% by mass or less, and 23% by mass or more and 60% by mass. The following is more preferable, and 33% by mass or more and 50% by mass or less is even more preferable.
• the photocurable liquid composition contains metal oxide nanoparticles (B).
• the type of metal oxide that constitutes the metal oxide nanoparticles is not particularly limited as long as the desired effect is not impaired.
• Preferred examples of the metal oxide nanoparticles (B) include at least one selected from the group consisting of zirconium oxide nanoparticles, titanium oxide nanoparticles, barium titanate nanoparticles, and cerium oxide nanoparticles.
• the photocurable liquid composition may contain one of these metal oxide nanoparticles (B) alone, or may contain two or more of them in combination. When the photocurable liquid composition contains the metal oxide nanoparticles (B), it is possible to form a cured product exhibiting a high refractive index.
• the average particle size of the metal oxide nanoparticles (B) is preferably 500 nm or less, preferably 2 nm or more and 100 nm or less, from the viewpoint of the transparency of the cured product.
• the surface of the metal oxide nanoparticles (B) is preferably modified with ethylenically unsaturated double bond-containing groups.
• the photopolymerizable monomer (A) is added to the metal oxide nanoparticles (B )
• the metal oxide nanoparticles (B) are immobilized in the matrix composed of the polymer of the photopolymerizable monomer (A). This makes it difficult for the metal oxide nanoparticles (B) to aggregate. Therefore, when the surfaces of the metal oxide nanoparticles (B) are modified with ethylenically unsaturated double bond-containing groups, localization of the metal oxide nanoparticles (B) in the cured product is particularly easily suppressed.
• metal oxide nanoparticles (B) For example, by allowing a capping agent containing an ethylenically unsaturated double bond to act on the surface of the metal oxide nanoparticles (B), the surface becomes an ethylenically unsaturated double bond through a chemical bond such as a covalent bond. Metal oxide nanoparticles (B) modified with bond-containing groups are obtained.
• the method of bonding the capping agent containing an ethylenically unsaturated double bond to the surface of the metal oxide nanoparticles (B) via a chemical bond such as a covalent bond is not particularly limited. Hydroxyl groups are usually present on the surface of the metal oxide nanoparticles (B). By reacting the hydroxyl group with the reactive group of the capping agent, the capping agent is covalently bonded to the surface of the metal oxide nanoparticles (B).
• a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group
• a dialkoxysilyl group such as a dimethoxysilyl group and a diethoxysilyl group
• a trialkoxysilyl group, a dialkoxysilyl group, a monoalkoxysilyl group, a trihalosilyl group, a dihalosilyl group, and a monohalosilyl group form a siloxane bond with the surface of the metal oxide nanoparticles (B).
• a carboxy group and a halocarbonyl group form a bond represented by (metal oxide —O—CO—) with the surface of the metal oxide nanoparticles (B).
• the hydroxyl group forms a bond represented by (metal oxide —O—) with the surface of the metal oxide nanoparticles (B).
• the groups that bind to the above reactive groups include hydrogen atoms and various organic groups.
• the organic group may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
• the groups that bind to the above reactive groups include, for example, linear or branched alkyl groups that may be interrupted by oxygen atoms (—O—), linear or branched an alkenyl group optionally interrupted by an oxygen atom (--O--), may be linear or branched, and is interrupted by an oxygen atom (--O--) alkynyl groups, cycloalkyl groups, aromatic hydrocarbon groups, heterocyclic groups, etc., which may be substituted.
• substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
• substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
• the number of substituents is not particularly limited.
• R b1 , R b2 , R b3 and Rb4 are each an organic group which may be the same or different.
• organic groups include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group and tolyl group; Epoxy group-containing groups such as propyl group; (meth)acryloyloxy group and the like.
• r and s in the above formula are each independently an integer of 0 or more and 60 or less. Both r and s in the above formula cannot be zero.
• capping agents include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane. Unsaturated groups such as silane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc.
• alkoxysilane Containing alkoxysilane; unsaturated group-containing alcohols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol (meth)acrylic acid; (meth)acrylic acid halides such as (meth)acrylic acid chloride;
• the amount of the capping agent used when bonding the capping agent to the surface of the metal oxide nanoparticles (B) via a chemical bond such as a covalent bond is not particularly limited.
• a sufficient amount of capping agent is used to react with substantially all of the hydroxyl groups on the surface of the metal oxide nanoparticles (B).
• the content of the metal oxide nanoparticles (B) in the photocurable liquid composition is not particularly limited as long as the object of the present invention is not impaired.
• the content of the metal oxide nanoparticles (B) in the photocurable liquid composition is, for example, 5% by mass or more and 95% by mass with respect to the mass of the photocurable liquid composition excluding the mass of the solvent (S). %, preferably 5% by mass or more and 75% by mass or less, more preferably 35% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 65% by mass or less. In order to increase the refractive index of the cured product, it is preferably 40% by mass or more and 93% by mass or less.
• the content of the metal oxide nanoparticles (B) in the photocurable liquid composition is within the above range, localization of the metal oxide nanoparticles (B) in the cured product is suppressed, and high refractive index is achieved. It is easy to form a hardened product of a rate.
• the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group, the ethylenically unsaturated double bonds present on the surface of the metal oxide nanoparticles (B)
• the weight of the capping agent having containing groups is included in the weight of the metal oxide nanoparticles (B).
• the photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.
• photopolymerization initiator (C) examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-( 2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl
• oxime ester compounds are preferred from the viewpoint of the sensitivity of the photocurable liquid composition.
• oxime ester compound a compound having a partial structure represented by the following formula (c1) is preferable.
• n1 is 0 or 1
• R c2 is a monovalent organic group
• R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group
• * is a bond.
• the compound having the partial structure represented by formula (c1) preferably has a carbazole skeleton, fluorene skeleton, diphenyl ether skeleton, or phenyl sulfide skeleton.
• the compound having the partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).
• Compounds having a partial structure represented by formula (c1) include compounds represented by the following formula (c2).
• R c1 is a group represented by the following formula (c3), (c4), or (c5), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
• R c4 and R c5 are each independently a monovalent organic group, n2 is an integer of 0 or more and 3 or less, When n2 is 2 or 3, multiple R c5 may be the same or different, and multiple R c5 may combine with each other to form a ring. * is a bond.
• R c6 and R c7 each independently represent an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, a substituted is a cyclic organic group or a hydrogen atom, R c6 and R c7 may combine with each other to form a ring, R c7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring, R c8 is a nitro group or a monovalent organic group, n3 is an integer of 0 to 4, * is a bond.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group, A is S or O; n4 is an integer of 0 to 4, * is a bond.
• R c4 is a monovalent organic group.
• R c4 can be selected from various organic groups as long as the objects of the present invention are not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms.
• a group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• R c4 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and a carbon atom
• a saturated aliphatic acyl group optionally having 2 to 20 substituents, an alkoxycarbonyl group having 2 to 20 carbon atoms optionally having a substituent, a phenyl group optionally having a substituent , an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, having a substituent optionally substituted naphthyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, substituted a heterocyclyl group optionally having a group, a heterocyclylcarbonyl group optionally having a substituent, and the like.
• an alkyl group having 1 to 20 carbon atoms is preferable.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group as R c4 is preferably 2 or more, more preferably 5 or more, from the viewpoint of good solubility of the compound represented by formula (c3) in the photocurable liquid composition. , 7 or more are particularly preferred. Further, from the viewpoint of good compatibility between the compound represented by formula (c3) and other components in the photocurable liquid composition, the number of carbon atoms in the alkyl group as R c4 is 15 or less is preferable, and 10 or less is more preferable.
• R c4 has a substituent
• substituents include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms.
• the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, O, or such monocyclic rings are fused together or such monocyclic ring is fused with a benzene ring. is a heterocyclyl group.
• the heterocyclyl group is a condensed ring, the number of monocyclic rings constituting the condensed ring shall be up to 3.
• Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
• R c4 is a heterocyclyl group
• substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
• R c4 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups. Further, n-octyl group and 2-ethylhexyl group are preferred, and 2-ethylhexyl group is more preferred, from the viewpoint of good solubility of the compound represented by formula (c3) in the curable composition.
• R c5 is a monovalent organic group.
• R c5 can be selected from various organic groups as long as the objects of the present invention are not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms.
• a group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Examples of monovalent organic groups suitable as R c5 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents.
• optionally substituted phenyl group optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy a phenylalkyl group optionally having substituents, a naphthyl group optionally having substituents, a naphthoxy group optionally having substituents, a naphthoyl group optionally having substituents, a substituent an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, amino group substituted with one or two organic groups, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, HX 2 C- or H 2 Substituents including a group represented by XC— (where each X is
• R c5 is an alkyl group
• the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R c5 is an alkyl group, it may be linear or branched. Specific examples of when R c5 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl groups.
• R c5 is an alkyl group
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• R c5 is an alkoxy group
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• R c5 is an alkoxy group, it may be linear or branched.
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group.
• R c5 is an alkoxy group
• the alkoxy group may contain an ether bond (--O--) in the carbon chain.
• alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
• R c5 is a cycloalkyl group or a cycloalkoxy group
• the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples of R c5 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group
• the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less.
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyl group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 is an alkoxycarbonyl group
• the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less.
• Specific examples of R c5 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyl oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbony
• R c5 is a phenylalkyl group
• the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• R c5 is a naphthylalkyl group
• the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples of R c5 being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group.
• R c5 when R c5 is a naphthylalkyl group include an ⁇ -naphthylmethyl group, a ⁇ -naphthylmethyl group, a 2-( ⁇ -naphthyl)ethyl group, and a 2-( ⁇ -naphthyl)ethyl group.
• R c5 when R c5 is a phenylalkyl group or a naphthylalkyl group, R c5 may further have a substituent on the phenyl group or naphthyl group.
• R c5 is a heterocyclyl group
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• R c5 is a heterocyclylcarbonyl group
• the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c5 is a heterocyclyl group.
• R c5 is an amino group substituted with 1 or 2 organic groups
• preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms
• amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino
• the substituent includes a group represented by HX 2 C-- or H 2 XC-- (eg, HX 2 C— or H 2 XC—, a halogenated alkoxy group containing a group represented by HX 2 C— or H 2 XC—, a halogenated alkyl group containing a group represented by HX 2 C— or H 2 XC—), Alkyl group, alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated fat having 2 to 7 carbon atoms group acyloxy group, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group,
• the number of substituents is not limited as long as the object of the present invention is not impaired, and is preferably 1 to 4.
• the phenyl group, naphthyl group and heterocyclyl group contained in R c5 have multiple substituents, the multiple substituents may be the same or different.
• Substituents contained in R c5 when the benzoyl group further has a substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group. (thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group and phenyl group.
• the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, etc., and is preferably a fluorine atom.
• the substituent containing a group represented by HX 2 C-- or H 2 XC-- includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, HX 2 C-- or H 2 XC- A group having a halogenated alkoxy group including a group represented by -, a halogenated alkyl group including a group represented by HX 2 C- or H 2 XC-, represented by HX 2 C- or H 2 XC- and a group having a halogenated alkyl group containing a group, such as a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, or represented by HX 2 C-- or H 2 XC-- More preferably, it is a group having a halogenated alkoxy group containing group.
• the group having a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--.
• aromatic groups eg, phenyl group, naphthyl group, etc.
• cycloalkyl groups substituted with halogenated alkyl groups including groups represented by HX 2 C-- or H 2 XC-- eg, cyclopentyl group, cyclohexyl groups, etc.
• the group having a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--.
• aromatic groups e.g., phenyl group, naphthyl group, etc.
• alkyl groups substituted with halogenated alkoxy groups including groups represented by HX 2 C- or H 2 XC- e.g., methyl group, ethyl group , n-propyl group, i-propyl group, etc.
• a cycloalkyl group substituted with a halogenated alkoxy group including a group represented by HX 2 C- or H 2 XC- e.g., cyclopentyl group, cyclohexyl group, etc.
• Rc5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R c5 may have.
• R c5 is an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an aromatic ring which may have a substituent.
• Good phenylthioalkyl groups are preferred.
• the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. preferable.
• the optionally substituted phenyl groups a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred.
• the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6.
• the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• a cyclopentylethyl group is preferred.
• the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• a 2-(4-chlorophenylthio)ethyl group is preferred.
• the formed ring when a plurality of R c5 are present and the plurality of R c5 are bonded to each other to form a ring, the formed ring includes a hydrocarbon ring, a heterocyclic ring, and the like. be done. Heteroatoms contained in heterocycles include, for example, N, O and S. Aromatic rings are particularly preferred as the ring formed by combining a plurality of R c5 s. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferred. Specific examples of the case where a plurality of R c5 in formula (c3) are bonded to each other to form a benzene ring are shown below.
• R c8 is a nitro group or a monovalent organic group.
• R c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by —(CO) n1 — on the condensed ring in formula (c4).
• the bonding position of R c8 is not particularly limited.
• the group represented by formula (c4) has one or more R c8 , one of the one or more R c8 is fluorene, because the compound represented by formula (c4) is easy to synthesize. Attachment to the 7-position of the backbone is preferred.
• the group represented by formula (c4) when the group represented by formula (c4) has 1 or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are multiple R c8s , the multiple R c8s may be the same or different.
• R c6 , R c7 , R c8 and n3 are respectively the same as R c6 , R c7 , R c8 and n3 in formula (c4).
• R c8 is not particularly limited as long as the object of the present invention is not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the monovalent organic group for R c8 include the same preferred examples of the monovalent organic group as R c5 in formula (c3).
• R c6 and R c7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic It is an organic group or a hydrogen atom. R c6 and R c7 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as R c6 and R c7 . When R c6 and R c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
• R c6 and R c7 are unsubstituted chain alkyl groups
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less.
• Specific examples of R c6 and R c7 being chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
• n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group.
• R c6 and R c7 are alkyl groups
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• R c6 and R c7 are chain alkyl groups having a substituent
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
• the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group.
• a chain alkyl group having a substituent is preferably linear.
• the substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups.
• Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred.
• Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclyl groups. Specific examples of the cycloalkyl group are the same as the preferred examples when R c8 is a cycloalkyl group.
• aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
• heterocyclyl group are the same as the preferred examples when R c8 is a heterocyclyl group.
• R c8 is an alkoxycarbonyl group
• the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• the number of substituents is not particularly limited.
• the preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group.
• the number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
• R c6 and R c7 are chain alkoxy groups having no substituents
• the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable.
• R c6 and R c7 being chain alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert -butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
• R c6 and R c7 are alkoxy groups
• the alkoxy groups may contain an ether bond (--O--) in the carbon chain.
• alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
• R c6 and R c7 are chain alkoxy groups having substituents
• the substituents that the alkoxy groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
• R c6 and R c7 are cyclic organic groups
• the cyclic organic group may be an alicyclic group or an aromatic group.
• Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups.
• R c6 and R c7 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
• the aromatic hydrocarbon group is either a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings.
• the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings
• the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable.
• Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
• R c6 and R c7 are aliphatic cyclic hydrocarbon groups
• the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic.
• the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less.
• Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like are included.
• R c6 and R c7 are heterocyclyl groups
• the same heterocyclyl groups as R c5 in formula (c3) can be mentioned.
• R c6 and R c7 may combine with each other to form a ring.
• a group consisting of a ring formed by R c6 and R c7 is preferably a cycloalkylidene group.
• the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.
• the ring may be either an aromatic ring or an aliphatic ring.
• the cycloalkylidene group may be fused with one or more other rings.
• rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine.
• R c6 and R c7 examples include groups represented by the formula -A 1 -A 2 .
• a 1 is a linear alkylene group
• a 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
• the straight-chain alkylene group for A 1 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• A2 is an alkoxy group
• the alkoxy group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
• the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
• the halogenated alkyl group may be linear or branched, preferably linear.
• A2 is a cyclic organic group
• examples of the cyclic organic group are the same as the cyclic organic groups that Rc6 and Rc7 have as substituents.
• A2 is an alkoxycarbonyl group
• examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that Rc6 and Rc7 have as substituents.
• R c6 and R c7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl groups; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl groups; 2-
• Alkyl group 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl
• R c6 and R c7 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.
• A is S because it is easy to obtain a photopolymerization initiator with excellent sensitivity.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
• R c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups within the range that does not impede the object of the present invention.
• the organic group a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the organic group represented by Rc9 in formula ( c5 ) include the same monovalent organic groups as Rc5 in formula (c3).
• R c9 substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; benzoyl group; nitro group; optionally substituted benzofuranylcarbonyl group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group a 4-(phenyl)phenylcarbonyl group is more preferred.
• n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.
• the position to which R c9 is bonded is preferably para to the bond to which the phenyl group to which R c9 is bonded is bonded to an oxygen atom or a sulfur atom.
• the monovalent organic group as Rc2 is not particularly limited as long as it does not impair the object of the present invention.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the monovalent organic group as Rc2 include the same monovalent organic groups as Rc5 in formula (c3).
• Rc2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are those in which the phenyl group, the naphthyl group and the heterocyclyl group contained in R c5 in the formula (c3) further have a substituent. It is the same as the base.
• R c2 is a substituent containing the group represented by HX 2 C— or H 2 XC—, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or A cycloalkylalkyl group and a phenylthioalkyl group optionally having a substituent on the aromatic ring are preferred.
• Alkyl group optionally substituted phenyl group, number of carbon atoms in cycloalkyl group contained in cycloalkylalkyl group, number of carbon atoms in alkylene group contained in cycloalkylalkyl group, cycloalkylalkyl group, aromatic Regarding the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group optionally having substituents on the ring, or the phenylthioalkyl group optionally having substituents on the aromatic ring, the formula (c3 ) is the same as R c5 .
• A3 is a divalent organic group , preferably a divalent hydrocarbon group, preferably an alkylene group.
• A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
• the alkylene group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
• Preferred examples of A 4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• Preferred specific examples of A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl.
• Preferable specific examples of the group represented by -A 3 -CO-OA 4 include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n -butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-
• R c2 is also preferably a group represented by the following formula (c7) or (c8).
• R c10 and R c11 are each independently a monovalent organic group
• n5 is an integer of 0 to 4
• R c10 and R c11 may combine with each other to form a ring
• R c12 is a monovalent organic group
• n6 is an integer of 1 or less and 8 or less
• n7 is an integer of 1 or more and 5 or less
• n8 is an integer from 0 to (n7+3).
• R c10 and R c11 in formula (c7) are the same as R c8 in formula (c4).
• R c10 includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--, an alkyl group, or A phenyl group is preferred.
• the ring may be either an aromatic ring or an aliphatic ring.
• n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.
• R c12 is an organic group.
• the organic group include groups similar to the organic groups described for R c8 in formula (c4).
• alkyl groups are preferred.
• Alkyl groups may be straight or branched.
• the number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.
• R c12 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.
• n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
• n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0.
• n8 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.
• R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
• a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when R c3 is an aliphatic hydrocarbon group.
• R c3 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, A cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, a methyl group or a phenyl group is more preferable.
• Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R c1 include the following compounds.
• a phosphine oxide compound is also preferable because the deep-part curability of the photocurable liquid composition is good.
• a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.
• R c21 and R c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic group having 7 to 20 carbon atoms. group acyl groups. However, both R c21 and R c22 are not aliphatic acyl groups or aromatic acyl groups.
• the number of carbon atoms in the alkyl groups of R c21 and R c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less.
• the alkyl groups as R c21 and R c22 may be linear or branched.
• alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert- pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4,-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and An n-dodecyl group can be mentioned.
• the number of carbon atoms in the cycloalkyl groups for R c21 and R c22 is preferably 5 or more and 12 or less.
• Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.
• the number of carbon atoms in the aryl groups of R c21 and R c22 is preferably 6 or more and 12 or less.
• the aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.
• the number of carbon atoms in the aliphatic acyl groups for R c21 and R c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less.
• Aliphatic acyl groups may be straight or branched. Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, and tetradecanoyl groups. , pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl groups.
• the number of carbon atoms in the aromatic acyl groups for R c21 and R c22 is 7 or more and 20 or less.
• the aromatic acyl group may have a substituent.
• substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms.
• Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6- Examples include trimethylbenzoyl, ⁇ -naphthoyl, and ⁇ -naphthoyl groups.
• phosphine oxide compound containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, fin oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like.
• the content of the photopolymerization initiator (C) is 0.5% by mass or more and 30% by mass or less with respect to the mass (total solid content) of the photocurable liquid composition excluding the mass of the organic solvent (S) described later. is preferable, and 1% by mass or more and 20% by mass or less is more preferable.
• a photoinitiation aid may be combined with the photopolymerization initiator (C).
• Photoinitiation aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 2- ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylp-toluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto
• the photocurable liquid composition may contain a plasticizer (D).
• the plasticizer (D) is a component that reduces the viscosity of the photocurable liquid composition without significantly impairing the curability of the photocurable liquid composition or the refractive index of the cured product.
• a compound represented by the following formula (d-1) is preferable as the plasticizer (D).
• R d1 -R d3 r -X d -R d4 s -R d2 (d-1) (In formula (d-1), R d1 and R d2 are each independently a phenyl group optionally having 1 to 5 substituents, and the substituents have 1 to 4 carbon atoms.
• R d3 and R d4 are each independently a methylene group or an ethane-1,2-diyl group; , and s are each independently 0 or 1, and X d is an oxygen atom or a sulfur atom.
• the viscosity of the photocurable liquid composition is reduced without significantly impairing the curability of the photocurable liquid composition or the refractive index of the cured product. be done.
• the viscosity of the plasticizer (D) measured by an E-type viscometer at 25° C. is preferably 10 cP or less, more preferably 8 cP or less, and further preferably 6 cP or less. preferable.
• the boiling point of the plasticizer (D) under atmospheric pressure is 250° C. or higher. is preferred, and 260° C. or higher is more preferred.
• the upper limit of the boiling point of the plasticizer (D) under atmospheric pressure is not particularly limited, it may be, for example, 300° C. or lower, or 350° C. or lower.
• R d1 and R d2 in formula (d-1) are each independently a phenyl group optionally having 1 to 5 substituents.
• the substituent bonded to the phenyl group is a group selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
• the number of substituents is not particularly limited. The number of substituents is 1 or more and 5 or less, preferably 1 or 2, and preferably 1. From the viewpoint of reducing the viscosity of the photocurable liquid composition, it is preferable that each of R d1 and R d2 is an unsubstituted phenyl group.
• alkyl group having 1 to 4 carbon atoms as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. mentioned.
• alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert- A butyloxy group is mentioned.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R d3 and R d4 in formula (d-1) are each independently a methylene group or an ethane-1,2-diyl group. Moreover, r and s are 0 or 1 each independently.
• X d in formula (d-1) is an oxygen atom or a sulfur atom.
• Preferred specific examples of the compound represented by formula (d-1) described above include diphenyl ether, diphenyl sulfide, dibenzyl ether, dibenzyl sulfide, diphenethyl ether, and diphenethyl sulfide. Among these, diphenyl sulfide and/or dibenzyl ether are more preferred.
• the content of the plasticizer (D) in the photocurable liquid composition is, with respect to the mass of the entire photocurable liquid composition, in terms of both viscosity adjustment and dispersibility of the metal oxide nanoparticles (B). , more than 0% by mass and 35% by mass or less, and more preferably 5% by mass or more and 15% by mass or less.
• the photocurable liquid composition contains an amine compound (E1) represented by the following formula (e1), and/or An imine compound (E2) represented by formula (e2) may be included as the nitrogen-containing compound (E).
• NR e1 R e2 R e3 (e1) (In formula (e1), R e1 , R e2 and R e3 are each independently a hydrogen atom or an organic group.)
• R e4 ⁇ N CR e5 R e6 (e2) (In formula (e2), R e4 , R e5 and R de6 are each independently a hydrogen atom or an organic group.)
• R e1 , R e2 , R e3 , R e4 , R e5 , and R de6 are organic groups
• the organic groups are within a range that does not impair the desired effect. and can be selected from a variety of organic groups.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the organic group include an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted naphthyl group, An optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and the like can be mentioned.
• the number of carbon atoms in the alkyl group as the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• the structure of the alkyl group may be linear or branched. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl group.
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• the number of carbon atoms in the cycloalkyl group as the organic group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
• the number of carbon atoms in the phenylalkyl group as the organic group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• the number of carbon atoms in the naphthylalkyl group as the organic group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups.
• naphthylalkyl groups include ⁇ -naphthylmethyl, ⁇ -naphthylmethyl, 2-( ⁇ -naphthyl)ethyl, and 2-( ⁇ -naphthyl)ethyl groups.
• the phenylalkyl group or naphthylalkyl group may further have a substituent on the phenyl group or naphthyl group.
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• a heterocyclyl group as an organic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is preferably a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclyl group in which such monocyclic rings are condensed with each other or such monocyclic rings and a benzene ring are condensed.
• the heterocyclyl group is a condensed ring, the number of monocyclic rings constituting the condensed ring shall be up to 3.
• Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
• the substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, group, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having alkyl group having 1 to 6 carbon atoms, dialkylamino group having alkyl group having 1 to 6 carbon atoms , a benzoyl group, a halogen atom, a nitro group, a cyano group, and the like.
• the number of substituents is not particularly limited, and is preferably 1 to 4.
• the phenyl group, naphthyl group and heterocyclyl group contained in the organic group have multiple substituents, the multiple substituents may be the same or different.
• R e1 , R e2 and R e3 are each independently a hydrogen atom or an organic group, and at least one of R e1 , R e2 and R e3 is an aromatic group-containing group.
• R e4 , R e5 , and R de6 are each independently a hydrogen atom or an organic group, and at least one of R e4 , R e5 , and R de6 is an aromatic group-containing group.
• the aromatic ring in the aromatic group-containing group may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A hydrocarbon group is preferable as the aromatic group-containing group.
• Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
• Aralkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl groups.
• R e1 , R e2 and R e3 is preferably a group represented by A e1 —CH 2 —.
• R e4 is preferably a group represented by Ar e1 —CH 2 —.
• Ar e1 is an aromatic group optionally having a substituent.
• the aromatic group for Ar e1 may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
• the aromatic group for Ar e1 is preferably an aromatic hydrocarbon group.
• Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
• the substituents that the aromatic group as Ar e1 may have include the organic groups as R e1 , R e2 , R e3 , R e4 , R e5 and R de6 as phenyl group, naphthyl group and heterocyclyl group. In some cases, it is the same as the substituents these groups may have.
• amine compound represented by formula (e1) include triphenylamine, N,N-diphenylbenzylamine, N-phenyldibenzylamine, tribendialumine, N,N-dimethylphenylamine, N -methyldiphenylamine, N,N-dimethylbenzylamine, N-methyldibenzylamine, N-methyl-N-benzylphenylamine, N,N-diethylphenylamine, N-ethyldiphenylamine, N,N-diethylbenzylamine, N-ethyldibenzylamine, and N-ethyl-N-benzylphenylamine.
• imine compounds represented by formula (e2) include N-benzylphenylmethanimine, N-benzyldiphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropane-2-imine. are mentioned.
• the content of the nitrogen-containing compound in the photocurable liquid composition is not particularly limited as long as the desired effects are not impaired.
• the content of the nitrogen-containing compound (E) is preferably 5% by mass or more and 25% by mass or less, more preferably 7% by mass or more and 20% by mass or less, relative to the mass of the photopolymerizable monomer (A).
• the photocurable liquid composition may contain a solvent (S) of 5 mass % or less based on the mass of the photocurable liquid composition.
• a solvent (S) of 5 mass % or less based on the mass of the photocurable liquid composition.
• the type of solvent (S) is not particularly limited, it is typically an organic solvent.
• Organic solvents that can be blended in the photocurable liquid composition include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol
• the photocurable liquid composition may contain various additives conventionally blended in photosensitive compositions and ink compositions, as long as the objects of the present invention are not hindered. good.
• Preferable additives to be added to the photocurable liquid composition include dispersants, adhesion promoters such as silane coupling agents, antioxidants, aggregation inhibitors, antifoaming agents, surfactants and the like.
• the surfactant is not particularly limited, and known components such as fluorine-based surfactants and silicon-based surfactants can be used.
• a photocurable liquid composition is obtained by mixing predetermined amounts of the components described above and then uniformly stirring the mixture.
• the photocurable liquid composition described above is typically Molding the photocurable liquid composition according to the shape of the cured product to be formed; exposing the shaped photocurable liquid composition; A cured product is obtained by a method comprising
• the cured product produced by the above method exhibits a high refractive index of, for example, preferably 1.60 or higher, more preferably 1.61 or higher, and even more preferably 1.62 or higher, at a wavelength of 550 nm. Therefore, the cured product produced by the above method is suitably used in optical applications requiring a high refractive index.
• a film made of a cured product of the photocurable liquid composition described above is suitably used as a high refractive index film constituting an antireflection film or the like in various display panels such as an organic EL display panel and a liquid crystal display panel. be.
• the film thickness of the high refractive index film made of the cured product of the photocurable liquid composition described above is not particularly limited, and is appropriately selected according to the application.
• the film thickness of the high refractive index film is typically preferably 1 nm or more and 20 ⁇ m or less, more preferably 50 nm or more and 10 ⁇ m or less.
• the method for molding the photocurable liquid composition is not particularly limited, and is appropriately selected according to the shape of the cured product.
• the shape of the cured product includes, but is not limited to, a film shape, a lens shape, a line shape, a prism shape, and the like. Among these shapes, the membrane shape is preferred.
• the method for molding the photocurable liquid composition is not particularly limited.
• the shape of the cured product is lens-shaped, prism-shaped, or the like
• the photocurable liquid composition may be filled into a mold corresponding to the shape of the cured product using a squeegee or the like.
• the shape of the cured product is a line shape or the like, the photocurable liquid composition may be applied onto the substrate according to the shape of the cured product.
• the coating method examples include a printing method such as an inkjet method.
• a printing method such as an inkjet method.
• a method for applying the cured product in a film shape there are methods using a contact transfer type coating device such as a roll coater, a reverse coater and a bar coater, and a method using a non-contact type coating device such as a spinner (rotary coating device) and a curtain flow coater. mentioned.
• the photocurable liquid composition can be applied in a film shape by a printing method such as an inkjet method.
• the solvent (S) is removed from the molded photocurable liquid composition by a method such as heating. may be removed.
• a photocurable liquid composition molded into a desired shape such as a film shape is exposed to light to such an extent that the photocurable liquid composition is not completely cured, and then a method such as an imprint method is used.
• a method such as an imprint method is used.
• the above-mentioned photocurable liquid composition is applied to a 3D printing method, and by repeating inkjet printing and curing by exposure to laminate a thin film-like cured product, a cured product having a desired shape is formed. You may
• Exposure to the molded photocurable liquid composition is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light.
• Exposure to the shaped photocurable liquid composition may be performed regioselectively, for example, by a method such as exposure through a mask.
• a patterned cured product can be formed by developing the exposed photocurable liquid composition using an organic solvent to remove the unexposed areas.
• development processing it is preferable to sufficiently remove the developer by a method such as drying by heating after development.
• a cured product having a desired shape and a high refractive index is formed using the photocurable liquid composition containing no or only a small amount of the solvent (S).
• zirconium oxide particles B1 (average particle size 8 nm) surface-modified using 3-methacryloxypropyltrimethoxysilane as a capping agent
• ethylenically unsaturated Zirconium oxide particles B2 (average particle size 10 nm) not surface-modified with a saturated double bond-containing group capping agent
• titanium oxide particles B3 (average particle size diameter 11 nm)
• titanium oxide particles B4 average particle diameter 10 nm
• Zirconium oxide particles B2 were obtained by drying nanocrystals collected by centrifugation according to the method described in paragraph [0223] of JP-A-2018-193481.
• the mass of the capping agent is 0.8 to 1.5 times the mass of the zirconium oxide particles.
• Zirconium oxide particles B2 were obtained in the same manner as zirconium oxide particles B2, except that 3-methacryloxypropyltrimethoxysilane was further added.
• Titanium oxide particles B4 were obtained by drying nanocrystals recovered by centrifugation, following the method described in Example 8 of WO2020/106860.
• titanium oxide particles B3 surface-modified with 3-methacryloxypropyltrimethoxysilane in the step of adding a capping agent, 50% by mass of the total amount of the capping agent was replaced with 3-methacryloxypropyltrimethoxysilane. , obtained in the same manner as titanium oxide particles B4.
• a surfactant BYK-333 (manufactured by BYK-Chemie)
• Tables 2 and 3 show the viscosities of the obtained photocurable liquid compositions measured at 25° C. or 35° C. using an E-type viscometer. Note that Table 3 shows only viscosities measured at 25°C. Further, the refractive index, light transmittance, haze and yellowness index (Y.I.) of the cured film formed using the obtained photocurable liquid composition were measured according to the following recipe. These measurement results are shown in Tables 2 and 3. Furthermore, according to the following recipe, the thickness T1 of the layer rich in each metal oxide nanoparticle in the cured film formed using the photocurable liquid composition and the thickness of the layer in which each metal oxide nanoparticle is almost absent The ratio T1/T2 with respect to T2 was measured. The smaller the value of T1/T2, the more suppressed the localization of each metal oxide nanoparticle in the cured film.
• ⁇ Refractive index measurement method The photocurable liquid composition of each example and comparative example was applied onto a glass substrate using an inkjet device. Then, using a 395 nm UV-LED exposure machine, the coating film was exposed with an exposure amount of 2 J/cm 2 and cured to obtain a cured film with a thickness of 3 ⁇ m. The refractive index of the film at a light wavelength of 550 nm was determined using a Metricon prism coupler.
• ⁇ Total light transmittance, haze, and Y. I. measurement method> After applying the photocurable liquid composition of each example and comparative example by spin coating on a glass substrate, using a 385 nm UV-LED exposure machine, the coating film is exposed at an exposure amount of 2 J / cm 2 and cured. to obtain a cured film having a thickness of 10 ⁇ m.
• the membrane was purchased from Hunter Associates Laboratory, Inc.; Total light transmittance, haze, and Y.E.M. I. was measured.
• T1/T2 measurement> The refractive index of each cured film was measured by a prism coupling method using a prism coupler 2010/M manufactured by Metricon for a cured film obtained under the same conditions as the cured film to be measured for refractive index.
• each of the two layers was analyzed to obtain a thickness value for each layer.
• the thickness of each metal oxide nanoparticle-rich upper layer was defined as T1
• the thickness of each metal oxide nanoparticle-poor lower layer was defined as T2. From T1 and T2 thus obtained, the thickness ratio T1/T2 of each layer was calculated.
• the value of T1/T2 was used as an evaluation index for the degree of two-layer formation.
• a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C), It can be seen that the addition of the polyfunctional monomer (A1) that satisfies the predetermined requirements described above reduces the value of T1/T2 and suppresses the localization of the metal oxide nanoparticles (B) in the cured product. Moreover, the surface of the metal oxide nanoparticles (B) modified with an ethylenically unsaturated double bond-containing group has a better refractive index, total light transmittance, haze, or Y.O. I. It can be seen that it is excellent in various optical properties such as.

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