Photocurable liquid composition, cured product, and method for producing cured product

Abstract

Provided are: a photocurable liquid composition capable of forming cured objects containing metal oxide nanoparticles inhibited from localizing; a cured object formed from the photocurable liquid composition; and a method for producing a cured object from said photocurable liquid composition.　The photocurable liquid composition comprises one or more photopolymerizable monomers (A), metal oxide nanoparticles (B), and a photopolymerization initiator (C), wherein the photopolymerizable monomers (A) include a polyfunctional monomer (A1) having three or more, ethylenically unsaturated double bonds.

Description

Technical Field

[0001] 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 aforementioned photocurable liquid composition.

Background Art

[0002] Conventionally, high refractive index materials have been used for forming optical members. As high refractive materials, for example, compositions in which metal oxide particles such as titanium oxide and zirconium oxide are dispersed in an organic component have been used. As a composition for forming such a high refractive material, an energy ray-curable composition containing metal oxide (A) having a specific particle diameter, (meth)acrylate (B), and a photopolymerization initiator (C) has been proposed (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when a composition containing metal oxide (A) and a polymerizable monomer having an ethylenically unsaturated double bond such as (meth)acrylate (B) as described in Patent Document 1 is cured to form a high refractive material, in the cured product, there is a problem that a portion rich in metal oxide (A) and a portion containing almost no metal oxide (A) are separated, making it difficult to form a homogeneous cured product. More specifically, when the composition described in Patent Document 1 is cured to form a cured film, inside the cured film, it is likely to phase-separate into a layer rich in metal oxide (A) and a layer containing almost no metal oxide (A).

[0005] The present invention has been made in view of the above problems, and an object thereof is to provide a photocurable liquid composition capable of forming a cured product in which the localization of metal oxide nanoparticles is suppressed, a cured product of the photocurable liquid composition, and a method for producing a cured product using the above-described photocurable liquid composition.

Means for Solving the Problems

[0006] The present inventors have found that the above problems can be solved by including a polyfunctional monomer (A1) having three or more ethylenically unsaturated double bonds as the photopolymerizable monomer (A) in a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C), and have completed the present invention. More specifically, the present invention provides the following.

[0007] A first aspect of the present invention is a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C), wherein the photopolymerizable monomer (A) has an ethylenically unsaturated double bond, and the photopolymerizable monomer (A) contains a polyfunctional monomer (A1) having three or more ethylenically unsaturated double bonds, and is a photocurable liquid composition.

[0008] A second aspect of the present invention is a cured product of the photocurable liquid composition according to the first aspect.

[0009] A third aspect of the present invention is a method for producing a cured product, including molding the photocurable liquid composition according to the first aspect and exposing the molded photocurable liquid composition.

Effects of the Invention

[0010] According to the present invention, it is possible to provide a photocurable liquid composition capable of forming a cured product in which the localization of metal oxide nanoparticles is suppressed, a cured product of the photocurable liquid composition, and a method for producing a cured product using the above-described photocurable liquid composition.

Modes for Carrying Out the Invention

[0011] ≪Photocurable Liquid Composition≫ The photocurable liquid composition contains a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C). The 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. By incorporating a polyfunctional monomer (A1) having 3 or more ethylenically unsaturated double bonds as the photopolymerizable monomer (A) into the photocurable liquid composition containing the photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C), the localization of the metal oxide nanoparticles (B) in the cured product of the photocurable liquid composition is suppressed.

[0012] In the specification and claims of the present application, “(meth)acrylate” means both acrylate and methacrylate. In the specification and claims of the present application, “(meth)acrylic” means both acrylic and methacrylic. In the specification and claims of the present application, “(meth)acryloyl” means both acryloyl and methacryloyl.

[0013] The photocurable liquid composition may contain a solvent (S). From the viewpoint of suppressing the decrease in the strength of the cured product due to the solvent (S) when forming the cured product, etc., it is preferable that the photocurable liquid composition contains only a small amount of the solvent (S) or that the photocurable liquid composition does not contain the 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, still more preferably 2% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less. There is no particular lower limit for the content of the solvent (S) in the photocurable liquid composition, and it is preferably 0% by mass or more. The photocurable liquid composition preferably substantially does not contain a solvent (S). That the photocurable liquid composition substantially does not contain a solvent (S) means that in addition to an extremely small amount of the solvent (S) being inevitably brought into the photocurable liquid composition due to being attached to raw materials or the like, the solvent (S) is not intentionally added to the photocurable liquid composition. When the photocurable liquid composition substantially does not contain a solvent (S), the content of the solvent (S) in the photocurable liquid composition is, for example, 0.2% by mass or less, preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less.

[0014] 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 the viscosity measured using an E-type viscometer at 25°C. The viscosity of the photocurable liquid composition can be adjusted, for example, by adjusting the content of the plasticizer (D), or by adjusting the content of the photopolymerizable monomer (A) or the metal Oxide nano particles (B), or by adding a small amount of the solvent (S) to the photocurable liquid composition.

[0015] Hereinafter, the essential or optional components contained in the photocurable liquid composition will be described.

[0016] <Photopolymerizable monomer (A)> The photocurable liquid composition contains a photopolymerizable monomer (A) having an ethylenically unsaturated double bond. The photopolymerizable monomer (A) contains a polyfunctional monomer (A1) having 3 or more ethylenically unsaturated double bonds. As a result, a cured product with suppressed localization of the metal oxide nanoparticles (B) can be formed. Also, as the photopolymerizable monomer (A), a bifunctional monomer (A2) and / or a monofunctional monomer (A3) can be used together with the polyfunctional monomer (A1).

[0017] In terms of easily obtaining a cured product with high transparency and easily suppressing the localization of metal oxide nanoparticles (B) in the cured product, the polyfunctional monomer (A1) is preferably an aliphatic compound not containing an aromatic group.

[0018] In terms of the curability of the photocurable liquid composition and the suppression of the localization of metal oxide nanoparticles (B) in the cured product, the number of ethylenically unsaturated double bonds possessed by the polyfunctional monomer (A1) is preferably 3 or more and 6 or less.

[0019] Preferable specific examples of the polyfunctional monomer (A1) include, for example, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, condensates of polyhydric alcohols and N-methylol(meth)acrylamide, and the like.

[0020] Further, the photocurable liquid composition preferably contains, as the polyfunctional monomer (A1), a compound represented by the following formula (A1) or the following formula (A2).

Chemical formula

[0021] In formula (A1), examples of the alkyl group having 1 to 4 carbon atoms as R a2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred.

[0022] 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 the following compounds 1) to 32). In the following compounds 1) to 32), MA is a (meth)acryloyl group. 1) (MA-NH-CH 2 ) 4 -C 2) (MA-N(CH 3 )-CH 2 ) 4 -C 3) (MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 4 -C 4) (MA-O-CH 2 CH 2 -O-CH 2 ) 4 -C 5) (MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 4 -C 6) (MA-O-CH 2 CH 2-NH-CH 2 ) 4 -C 7)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 4 -C 8)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 4 -C 9)(MA-NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-MA) 3 10)(MA-N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-MA) 3 11)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -O-CH 2 CH 2 CH 2 -O-MA) 3 12)(MA-O-CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -O-CH 2 CH 2 -O-MA) 3 13)(MA-O-CH 2 CH 2CH 2 -NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-CH 2 CH 2 CH 2 -O-MA) 3 14)(MA-O-CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-CH 2 CH 2 -O-MA) 3 15)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-CH 2 CH 2 CH 2 -O-MA) 3 16)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-CH 2 CH 2 -O-MA) 3 17)(MA-NH-CH 2 ) 2 -CH-NH-MA 18)(MA-N(CH 3 )-CH 2 ) 2 -CH-N(CH 3 )-MA 19)(MA - O - CH 2 CH 2 CH 2 - O - CH 2 ) 2 - CH - O - CH 2 CH 2 CH 2 - O - MA 20)(MA - O - CH 2 CH 2 - O - CH 2 ) 2 - CH - C - O - CH 2 CH 2 - O - MA 21)(MA - O - CH 2 CH 2 CH 2 - NH - CH 2 ) 2 - CH - NH - CH 2 CH 2 CH 2 - O - MA 22)(MA - O - CH 2 CH 2 - NH - CH 2 ) 2 - CH 2 - NH - CH 2 CH 2 - O - MA 23)(MA - O - CH 2 CH 2 CH 2 - N(CH 3 ) - CH 2 ) 2 - CH 2 - N(CH 3 ) - CH 2 CH 2 CH 2 - O - MA 24)(MA - O - CH 2 CH 2 - N(CH 3 ) - CH 2 ) 2 - CH 2 - N(CH 3 ) - CH 2 CH 2 - O - MA 25)(MA - NH - CH 2 ) 3-C-CH 2 CH 3 26)(MA-N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3 27)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 CH 3 28)(MA-O-CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 CH 3 29)(MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 CH 3 30)(MA-O-CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 CH 3 31)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3 32)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3

[0023] In terms of suppressing the localization of the metal oxide nanoparticles (B) in the cured product, the ratio of the mass of the polyfunctional monomer (A1) to the mass of the photopolymerizable monomer (A) is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 70% by mass or less.

[0024] Examples of the bifunctional monomer (A2) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, urethane (meth)acrylate (i.e., the reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and the like.

[0025] From the viewpoint of easily forming a cured product having a high refractive index, the photopolymerizable monomer (A) preferably contains a compound represented by the following formula (a-1) as the bifunctional monomer (A2). [Chemical formula] In formula (a-1), R 1 , and R 2 are each independently a hydrogen atom or a methyl group. R3 and R 4 is each independently an alkyl group having 1 to 5 carbon atoms. p and q are each independently 0 or 1.

[0026] R 1 and R 2 is 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. Since the compound represented by the formula (a-1) is easy to synthesize and obtain, it is preferable that R 1 and R 2 are the same.

[0027] R 3 and R 4 is 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. Since the compound represented by the formula (a-1) is easy to synthesize and obtain, it is preferable that R 3 and R 4 are the same.

[0028] R 3 and R 4 The alkyl group having 1 to 5 carbon atoms as may be linear or branched. Examples of the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a tert-pentyl group.

[0029] Preferable specific examples of the compound represented by the formula (a-1) include the following compounds.

Chemical formula

[0030] When the photocurable liquid composition contains a bifunctional monomer (A2), the ratio of the mass of the bifunctional monomer (A2) to the mass of the photopolymerizable monomer (A) is not particularly limited as long as the desired effect is not impaired. 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, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit is preferably, for example, 50% by mass or less, and more preferably 45% by mass or less. When the photopolymerizable monomer (A) contains a compound represented by the formula (a-1) as the bifunctional monomer (A2), the ratio of the mass of the compound represented by the formula (a-1) to the mass of the photopolymerizable monomer (A) is preferably 10% by mass or more and 30% by mass or less, and more preferably 15% by mass or more and 25% by mass or less.

[0031] Examples of the monofunctional monomer (A3) include (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-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives. These monofunctional monomers (A3) can be used alone or in combination of two or more.

[0032] From the viewpoint of reducing the viscosity of the photocurable liquid composition and easily forming a cured product with a high refractive index, the photopolymerizable monomer (A) preferably contains, as the monofunctional monomer (A3), a compound represented by the following formula (a-2).

Chemical formula

[0033] In formula (a-2), when t is 2, a plurality of R 11 may be the same or different, and are preferably the same. When t is 2, a plurality of R 12 may be the same or different, and are preferably the same.

[0034] R 11 is an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a propane-2,2-diyl group. Among these, a methylene group, an ethane-1,2-diyl group (ethylene group), a propane-1,3-diyl group, and a propane-1,2-diyl group are preferred, and an ethane-1,2-diyl group (ethylene group) is more preferred.

[0035] R 12 is a single bond, an oxygen atom, or a sulfur atom, and a single bond is preferred. When R 12 is a single bond, t is preferably 1.

[0036] 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 reducing 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 the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Among these, 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.

[0037] Preferable specific examples of the compound represented by the formula (a-2) include the following compounds.

Chemical formula

[0038] When the photopolymerizable monomer (A) contains a monofunctional monomer (A3), the ratio of the mass of the monofunctional monomer (A3) to the mass of the photopolymerizable monomer (A) is not particularly limited as long as the desired effect is not impaired. 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.

[0039] The ratio of the mass of the photopolymerizable monomer (A) to the mass excluding the mass of the solvent (S) of the photocurable liquid composition is preferably 20% by mass or more and 90% by mass or less, more preferably 23% by mass or more and 60% by mass or less, and further preferably 33% by mass or more and 50% by mass or less.

[0040] 〔Metal oxide nanoparticles (B)〕 The photocurable liquid composition contains metal oxide nanoparticles (B). The type of the metal oxide constituting the metal oxide nanoparticles is not particularly limited as long as the desired effects are 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 a combination of two or more thereof. By containing the above metal oxide nanoparticles (B), the photocurable liquid composition can form a cured product exhibiting a high refractive index.

[0041] From the viewpoint of the transparency of the cured product, the average particle diameter of the metal oxide nanoparticles (B) is preferably 500 nm or less, and more preferably 2 nm or more and 100 nm or less.

[0042] Preferably, the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group. When the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group, when forming a cured product, the photopolymerizable monomer (A) polymerizes together with the metal oxide nanoparticles (B), and the metal oxide nanoparticles (B) are fixed in a matrix composed of a polymer of the photopolymerizable monomer (A). This makes it difficult for the metal oxide nanoparticles (B) to aggregate. Therefore, when the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group, it is particularly easy to suppress the localization of the metal oxide nanoparticles (B) in the cured product.

[0043] For example, by allowing a capping agent containing an ethylenically unsaturated double bond to act on the surface of the metal oxide nanoparticles (B), metal oxide nanoparticles (B) whose surface is modified with an ethylenically unsaturated double bond-containing group via a chemical bond such as a covalent bond can be obtained.

[0044] The method of bonding a 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. Usually, hydroxyl groups are present on the surface of the metal oxide nanoparticles (B). By reacting such hydroxyl groups with the reactive groups possessed by the capping agent, the capping agent covalently bonds to the surface of the metal oxide nanoparticles (B). Preferable examples of the reactive groups possessed by the capping agent include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group; dialkoxysilyl groups such as dimethoxysilyl group and diethoxysilyl group; monoalkoxysilyl groups such as monomethoxysilyl group and monoethoxysilyl group; trihalosilyl groups such as trichlorosilyl group; dihalosilyl groups such as dichlorosilyl group; monohalosilyl groups such as monochlorosilyl group; carboxy group; halocarbonyl groups such as chlorocarbonyl group; hydroxyl group; phosphono group (-P(=O)(OH) 2 ); phosphate group (-O-P(=O)(OH) 2 ).

[0045] The trialkoxysilyl group, dialkoxysilyl group, monoalkoxysilyl group, trihalosilyl group, dihalosilyl group, and monohalosilyl group form a siloxane bond with the surface of the metal oxide nanoparticles (B). The carboxy group and the 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 phosphono group and the phosphate group form a bond represented by (metal oxide - O - P(=O)<) with the surface of the metal oxide nanoparticles (B).

[0046] In the capping agent, examples of the groups bonded to the above reactive groups include a hydrogen atom and various organic groups. The organic group may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms. Examples of the group bonded to the above reactive group include linear or branched alkyl groups which may be interrupted by an oxygen atom (-O-), linear or branched alkenyl groups which may be interrupted by an oxygen atom (-O-), linear or branched alkynyl groups which may be interrupted by an oxygen atom (-O-), cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. These groups may be substituted with 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.

[0047] In addition, examples of the group bonded to the above reactive group include a group represented by -(SiR b1 R b2 -O-) r -(SiR b3 R b4 -O-) s -R b5 . R b1 , R b2 , R b3 , and Rb4 are each an organic group which may be the same or different. Preferable examples of the organic group 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 3-glycidoxypropyl group; and (meth)acryloyloxy group. In the above formula, examples of R b5 include terminal groups such as -Si(CH 3 ) 3 , -Si(CH 3 ) 2 H, -Si(CH 3 ) 2 (CH=CH 2 ), and -Si(CH 3 ) 2 (CH 2 CH 2 CH 2 CH 3 ). In the above formula, r and s are each independently an integer of 0 or more and 60 or less. It is not the case that both r and s in the above formula are 0.

[0048] Preferable specific examples of the capping agent include unsaturated group-containing alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane; 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.

[0049] When the capping agent is bonded to the surface of the metal oxide nanoparticles (B) via a chemical bond such as a covalent bond, the amount of the capping agent used is not particularly limited. Preferably, an amount of the capping agent sufficient to react with substantially all of the hydroxyl groups on the surface of the metal oxide nanoparticles (B) is used.

[0050] The content of the metal oxide nanoparticles (B) in the photocurable liquid composition is not particularly limited as long as it does not inhibit the object of the present invention. 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 or less, 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, based on the mass excluding the mass of the solvent (S) of the photocurable liquid composition. In order to make the cured product have a higher refractive index, 40% by mass or more and 93% by mass or less is preferable. When the content of the metal oxide nanoparticles (B) in the photocurable liquid composition is within the above range, it is easy to form a cured product with a high refractive index while suppressing the localization of the metal oxide nanoparticles (B) in the cured product. In addition, when the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group, the mass of the capping agent having the ethylenically unsaturated double bond-containing group present on the surface of the metal oxide nanoparticles (B) is included in the mass of the metal oxide nanoparticles (B).

[0051] <Photopolymerization initiator (C)> The photopolymerization initiator (C) is not particularly limited, and a conventionally known photopolymerization initiator can be used.

[0052] As the photoinitiator (C), specifically, 1-hydroxycyclohexyl phenyl 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]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetoxyoxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamyl benzoate, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine and the like. These photoinitiators (C) can be used alone or in combination of two or more kinds.,

[0053] Among the photoinitiators (C), oxime ester compounds are preferred in terms of the sensitivity of the photocurable liquid composition., As the oxime ester compound, a compound having a partial structure represented by the following formula (c1) is preferred.,

[0054] [Chemical formula] (In formula (c1), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, * is a bond.)

[0055] The compound having a partial structure represented by formula (c1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenyl sulfide skeleton., The compound having a partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).

[0056] Examples of the compound having the partial structure represented by the formula (c1) include the compound represented by the following formula (c2).

[0057] [Chemical formula] (In the 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 aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.)

[0058] [Chemical formula] (In the formula (c3), 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, a plurality of R c5 may be the same or different, and a plurality of R c5 may be bonded to each other to form a ring.) * represents a bond.)

[0059] [Chemical formula] (In the formula (c4), R c6 and R c7 are each independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R c6 and R c7 may be bonded to 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 c8is a nitro group or a monovalent organic group, n3 is an integer of 0 or more and 4 or less, * is a bond.)

[0060] [Chemical formula] (In formula (c5), 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 or more and 4 or less, * is a bond.)

[0061] In formula (c3), R c4 is a monovalent organic group. R c4 can be selected from various organic groups as long as it does not inhibit the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and a halogen atom is more preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less is preferable, and 1 or more and 20 or less is more preferable. R c4 Preferable examples of include an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, a saturated aliphatic acyl group which may have a substituent having 2 to 20 carbon atoms, an alkoxycarbonyl group which may have a substituent having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent, etc.

[0062] R c4Among them, an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. From the viewpoint of good solubility in the photocurable liquid composition of the compound represented by the formula (c3), R c4 The number of carbon atoms of the alkyl group as is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. Further, from the viewpoint of good compatibility between the compound represented by the formula (c3) and other components in the photocurable liquid composition, R c4 The number of carbon atoms of the alkyl group as is preferably 15 or less, more preferably 10 or less.

[0063] R c4 When having a substituent, preferred examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aliphatic acyloxy group having 2 to 20 carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by -PO(OR) 2 (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclyl group, and the like.

[0064] R c4 When is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. R c4When it is a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclic group formed by condensation of such monocyclic rings with each other or such monocyclic rings and a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is up to 3. Examples of the heterocyclic ring constituting such a heterocyclic group 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, etc. R c4 When it is a heterocyclic group, examples of the substituent that the heterocyclic 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, etc.

[0065] R described above c4 Preferable specific examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a pentan-3-yl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. Also, Light Curability Liquid From the viewpoint of good solubility of the compound represented by the formula (c3) in the composition, an n-octyl group and a 2-ethylhexyl group are preferable, and a 2-ethylhexyl group is more preferable.

[0066] In the formula (c3), R c5 is a monovalent organic group. R c5It can be selected from various organic groups as long as the object of the present invention is not inhibited. As the organic group, a carbon atom-containing group is preferable, and a group composed of 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 preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less. R c5 Examples of the monovalent organic group suitable as 2 C- or H 2 include substituents containing a group represented by XC- (wherein X is each independently a halogen atom), etc.

[0067] R c5 When is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Also, R c5 When is an alkyl group, it may be linear or branched. R c5Specific examples of the case where R is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group. Also, when R c5 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

[0068] R c5 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Also, when R c5 is an alkoxy group, it may be linear or branched. When R c5 is an alkoxy group, specific examples include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. Also, when R c5 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

[0069] R c5 When R 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. R c5 Specific examples of the case where R is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, etc. R c5 Specific examples of the case where R is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group, etc.

[0070] R c5 When R is a saturated aliphatic acyl group or a 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 Specific examples of the case where R is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, an n-nonanoyl group, an n-decanoyl group, an n-undecanoyl group, an n-dodecanoyl group, an n-tridecanoyl group, an n-tetradecanoyl group, an n-pentadecanoyl group, and an n-hexadecanoyl group, etc. R c5 Specific examples of the case where R is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group, etc.

[0071] R c5 When R 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. R c5 Specific examples of the case where R is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

[0072] R c5 When R 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. Also, R c5 When R 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. R c5 Specific examples of the case where R is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. R c5 Specific examples of the case where R is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. c5 When R is a phenylalkyl group or a naphthylalkyl group, R c5 may further have a substituent on the phenyl group or the naphthyl group.

[0073] R c5 When R is a heterocyclic group, the heterocyclic group is the same as R in formula (c3), and the heterocyclic group may further have a substituent. c4 When R is a heterocyclic group, the heterocyclic group is the same as that in the case where R is a heterocyclic group, and the heterocyclic group may further have a substituent. R c5 When R is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where R is a heterocyclic group. c5 When R is a heterocyclic group, it is the same as the case where R is a heterocyclic group.

[0074] R c5 When R is an amino group substituted by one or two 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, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group, etc. Specific examples of these preferred organic groups are the same as those of R. Specific examples of the amino group substituted by 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 group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. c5 are the same as those of R. Specific examples of the amino group substituted by 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 group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc.

[0075] R c5When the phenyl group, naphthyl group, and heterocyclyl group contained therein further have a substituent, examples of the substituent include HX 2 C- or H 2 Substituents containing a group represented by XC- (for example, HX 2 C- or H 2 Halogenated alkoxy group containing a group represented by XC-, HX 2 C- or H 2 Halogenated alkyl group containing a group represented by XC-), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen, a nitro group, and a cyano group, etc. are mentioned. R c5 When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have a substituent, the number of the substituents is not limited as long as it does not inhibit the object of the present invention, and 1 to 4 are preferable. R c5 When the phenyl group, naphthyl group, and heterocyclyl group contained in R have a plurality of substituents, the plurality of substituents may be the same or different.

[0076] R c5 When the benzoyl group contained in R further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a 2-tenoyl group (thiophen-2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group, etc.

[0077] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, etc., and a fluorine atom is preferable.

[0078] HX 2 C- or H 2 Examples of the substituent containing a group represented by XC- include HX2 C- or H 2 A halogenated alkoxy group containing a group represented by XC-, HX 2 C- or H 2 A group having a halogenated alkoxy group containing a group represented by XC-, HX 2 C- or H 2 A halogenated alkyl group containing a group represented by XC-, HX 2 C- or H 2 Examples include a group having a halogenated alkyl group containing a group represented by XC-, etc., HX 2 C- or H 2 A halogenated alkoxy group containing a group represented by XC-, or HX 2 C- or H 2 It is more preferable that it is a group having a halogenated alkoxy group containing a group represented by XC-.

[0079] HX 2 C- or H 2 Examples of the group having a halogenated alkyl group containing a group represented by XC- include HX 2 C- or H 2 An aromatic group (e.g., phenyl group, naphthyl group, etc.) substituted with a halogenated alkyl group containing a group represented by XC-, HX 2 C- or H 2 A cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.) substituted with a halogenated alkyl group containing a group represented by XC- etc., HX 2 C- or H 2 It is preferable that it is an aromatic group substituted with a halogenated alkyl group containing a group represented by XC-.

[0080] HX 2 C- or H 2 Examples of the group having a halogenated alkoxy group containing a group represented by XC- include HX 2 C- or H 2 An aromatic group (e.g., phenyl group, naphthyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by XC-, HX 2 C- or H 2An alkyl group (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by XC-, HX 2 C- or H 2 A cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.) substituted with a halogenated alkoxy group containing a group represented by XC-, etc., HX 2 C- or H 2 It is preferably an aromatic group substituted with a halogenated alkoxy group containing a group represented by XC-.

[0081] Also, R c5 As, a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. 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.

[0082] Among the monovalent organic groups, R c5Examples thereof include an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The cycloalkyl group contained in the cycloalkylalkyl group preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and particularly preferably 5 or 6 carbon atoms. The alkylene group contained in the cycloalkylalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

[0083] In the group represented by the formula (c3), R c5 When there are a plurality of them and the plurality of R c5 are bonded to each other to form a ring, examples of the formed ring include a hydrocarbon ring and a heterocyclic ring. Examples of the hetero atom contained in the heterocyclic ring include N, O, and S. As the ring formed by bonding a plurality of R c5 to each other, an aromatic ring is particularly preferable. 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 preferable. In the formula (c3), specific examples of the case where a plurality of R c5 are bonded to each other to form a benzene ring are shown below.

[0084]

Chemical formula

[0085] In the group represented by formula (c4), 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). In formula (c4), the bonding position of R c8 is not particularly limited. When the group represented by formula (c4) has one or more R c8 , since the synthesis of the compound represented by formula (c4) is easy, etc., it is preferable that one of the one or more R c8 is bonded to the 7-position of the fluorene skeleton. That is, when the group represented by formula (c4) has one or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are a plurality of R c8 , the plurality of R c8 may be the same or different.

[0086]

Chemical formula

[0087] When R c8 is a monovalent organic group, R c8 is not particularly limited as long as it does not inhibit the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group composed of 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 preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less. R c8 When is a monovalent organic group, preferable examples thereof include the same groups as the preferable examples of the monovalent organic group as R c5 in formula (c3).

[0088] In formula (c4), R c6 and R c7 are each independently a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R c6 and R c7 may be bonded to each other to form a ring. Among these groups, R c6 and R c7 are preferably a chain alkyl group which may have a substituent. 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.

[0089] R c6 and R c7 are a chain alkyl group having no substituent, the number of carbon atoms of 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. Specific examples of R c6 and R c7 when they are a chain alkyl group 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, 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. Further, when R c6 and R c7 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

[0090] R c6 and R c7When it is a chain alkyl group having a substituent, the number of carbon atoms of 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. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.

[0091] The substituent that the alkyl group may have is not particularly limited as long as it does not inhibit the object of the present invention. Preferable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferable examples when R c8 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferable examples when R c8 is a heterocyclyl group. R c8 When it is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

[0092] When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The preferable number of substituents varies depending on the number of carbon atoms of 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.

[0093] R c6 and R c7When it is a chain alkoxy group having no substituent, the number of carbon atoms of the chain alkoxy 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. R c6 and R c7 When R and R are chain alkoxy groups, specific examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, 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, and isodecyloxy group. Also, when R c6 and R c7 are alkoxy groups, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.

[0094] R c6 and R c7 When they are chain alkoxy groups having substituents, the substituents that the alkoxy group may have are the same as those when R c6 and R c7 are chain alkyl groups.

[0095] R c6 and R c7 When R and R are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon group, aromatic hydrocarbon group, and heterocyclyl group. R c6 and R c7 When they are cyclic organic groups, the substituents that the cyclic organic group may have are the same as those when R c6 and R c7 are chain alkyl groups.

[0096] R c6 and R c7 When R and R are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by a plurality of benzene rings bonded through carbon-carbon bonds, or a group formed by a plurality of benzene rings condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by a plurality of benzene rings bonded or condensed, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

[0097] R c6 and R c7 When R and R are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0098] R c6 and R c7 When R and R are heterocyclyl groups, the same groups as the heterocyclyl group as R in formula (c3) can be mentioned. c5

[0099] R c6 and R c7 may be bonded to each other to form a ring. The group consisting of the ring formed by R and R is preferably a cycloalkylidene group. c6 and R c7 R c6 and R c7 ​When combined to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

[0100] R c7 When forming a ring with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

[0101] R c6 and R c7 When the group formed by the combination is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring, etc.

[0102] Among the R c6 and R c7 described above, examples of preferred groups include the group represented by formula -A 1 -A 2 In the formula, A 1 is a linear alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

[0103] A 1 The number of carbon atoms of the linear alkylene group of A 2 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A 2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A 2When it is a halogenated alkyl group, 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, with a linear structure being preferred. A 2 When it is a cyclic organic group, examples of the cyclic organic group are R c6 and R c7 and are the same as the cyclic organic groups that R 2 has as substituents. A c6 When it is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are R c7 and R

[0104] R c6 and R c7Preferable specific examples thereof include alkyl groups such as an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; alkoxyalkyl groups such as a 2-methoxyethyl group, a 3-methoxy-n-propyl group, a 4-methoxy-n-butyl group, a 5-methoxy-n-pentyl group, a 6-methoxy-n-hexyl group, a 7-methoxy-n-heptyl group, an 8-methoxy-n-octyl group, a 2-ethoxyethyl group, a 3-ethoxy-n-propyl group, a 4-ethoxy-n-butyl group, a 5-ethoxy-n-pentyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; cyanoalkyl groups such as a 2-cyanoethyl group, a 3-cyano-n-propyl group, a 4-cyano-n-butyl group, a 5-cyano-n-pentyl group, a 6-cyano-n-hexyl group, a 7-cyano-n-heptyl group, and an 8-cyano-n-octyl group; phenylalkyl groups such as a 2-phenylethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, and an 8-phenyl-n-octyl group; cycloalkylalkyl groups such as a 2-cyclohexylethyl group, a 3-cyclohexyl-n-propyl group, a 4-cyclohexyl-n-butyl group, a 5-cyclohexyl-n-pentyl group, a 6-cyclohexyl-n-hexyl group, a 7-cyclohexyl-n-heptyl group, an 8-cyclohexyl-n-octyl group, a 2-cyclopentylethyl group, a 3-cyclopentyl-n-propyl group, a 4-cyclopentyl-n-butyl group, a 5-cyclopentyl-n-pentyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group;2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and alkoxycarbonylalkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

[0105] R c6 and R c7 As, among the above, preferred groups 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-heptafluoro-n-pentyl group.

[0106] In formula (c5), from the viewpoint of easily obtaining a photopolymerization initiator with excellent sensitivity, A is particularly preferably S.

[0107] In formula (c5), R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group. R in formula (c5) c9When it is a monovalent organic group, it can be selected from various organic groups as long as the object of the present invention is not inhibited. As the organic group, a carbon atom-containing group is preferable, and a group composed of 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 preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less. In formula (c5), R c9 When it is an organic group, preferred examples include R in formula (c3) c5 The same groups as the monovalent organic group as

[0108] R c9 Among them, benzoyl group; naphthoyl group; benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group; nitro group; benzofuranylcarbonyl group which may have a substituent is preferable, and benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group are more preferable.

[0109] In formula (c5), 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. When n4 is 1, the bonding position of R c9 is preferably the para position with respect to the bond to which the phenyl group to which R c9 is bonded is bonded to an oxygen atom or a sulfur atom.

[0110] In formulas (c1) and (c2), the monovalent organic group as R c2 is not particularly limited as long as the object of the present invention is not inhibited. As the organic group, a carbon atom-containing group is preferable, and a group composed of 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 preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less. Rc2 Preferable examples of the monovalent organic group as R in formula (c3) c5 include the same groups as the monovalent organic group as R. Specific examples of these groups are the same as the groups described for R in formula (c3) c5 . Also, as R c2 , cycloalkylalkyl groups, phenoxyalkyl groups which may have substituents on the aromatic ring, phenylthioalkyl groups which may have substituents on the aromatic ring are also preferable. The substituents which the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R in formula (c3) c5 further have substituents.

[0111] Among the organic groups, as R c2 , substituents containing groups represented by the above HX 2 C- or H 2 XC-, alkyl groups, cycloalkyl groups, phenyl groups which may have substituents, cycloalkylalkyl groups, or phenylthioalkyl groups which may have substituents on the aromatic ring are preferable. The number of carbon atoms of the cycloalkyl group contained in the alkyl group, the phenyl group which may have substituents, the cycloalkylalkyl group, the number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group, the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have substituents on the aromatic ring, or the phenylthioalkyl group which may have substituents on the aromatic ring is the same as that of R in formula (c3) c5 .

[0112] Also, as R c2 , groups represented by -A 3 -CO-O-A 4 are also preferable. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A 4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0113] A 3 When A is an alkylene group, the alkylene group may be linear or branched, with a linear structure being preferred. A 3 When A is an alkylene group, 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.

[0114] A 4 Suitable examples of A 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. A 4 Specific suitable examples of A include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group, etc.

[0115] -A 3 -CO-O-A 4 Specific suitable examples of the group represented by -CO-O-A include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n-butyloxycarbonylethyl group, a 2-n-pentyloxycarbonylethyl group, a 2-n-hexyloxycarbonylethyl group, a 2-benzyloxycarbonylethyl group, a 2-phenoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 3-ethoxycarbonyl-n-propyl group, a 3-n-propyloxycarbonyl-n-propyl group, a 3-n-butyloxycarbonyl-n-propyl group, a 3-n-pentyloxycarbonyl-n-propyl group, a 3-n-hexyloxycarbonyl-n-propyl group, a 3-benzyloxycarbonyl-n-propyl group, and a 3-phenoxycarbonyl-n-propyl group, etc.

[0116] Also, R c2 is preferably a group represented by the following formula (c7) or (c8).

Chemical formula

[0117] The organic groups as R c10 and R c11 in formula (c7) are the same as R c8 in formula (c4). As R c10 , 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 preferable. When R c10 and R c11 are bonded to each other to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by formula (c7) in which R c10 and R c11 form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like.) In the above formula (c7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.)

[0118] In the above formula (c8), R c12 is an organic group. Examples of the organic group include R c8Groups similar to the organic group described above can be mentioned. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of 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 Examples of R preferably include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

[0119] In the above formula (c8), 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. In the above formula (c8), n8 is 0 or more and (n7 + 3) or less, 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. In the above formula (c8), 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.

[0120] In formula (c2), R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent. R c3 Examples of the substituent that may be present when R is an aliphatic hydrocarbon group preferably include a phenyl group, a naphthyl group, etc.

[0121] In formulas (c1) and (c2), R c3 Examples of R preferably include 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, etc. Among these, a methyl group or a phenyl group is more preferable.

[0122] Suitable specific examples of the compound represented by formula (c2) and having a group represented by formula (c3) as R c1 include the following compounds.

Chemical formula

[0123]

Chem.

[0124]

Chem.

[0125]

Chem.

[0126] represented by formula (c2) and having a group represented by formula (c4) as R c1 Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c4) as R include the following compounds.

Chem.

[0127]

Chem.

[0128]

Chem.

[0129]

Chem.

[0130]

Chem.

[0131] represented by formula (c2) and having a group represented by formula (c5) as R c1 Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R include the following compounds.

Chem.

[0132] As the photopolymerization initiator (C), a phosphine oxide compound is also preferable from the viewpoint of good deep curability of the photocurable liquid composition. As the phosphine oxide compound, a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.

Chemical formula

[0133] R c21 and R c22 as the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. R c21 and R c22 as the alkyl group may be linear or branched. Specific examples of the alkyl group 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, 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 n-dodecyl group.

[0134] R c21 and R c22The number of carbon atoms of the cycloalkyl group as [specified] is preferably 5 or more and 12 or less. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.

[0135] R c21 and R c22 The number of carbon atoms of the aryl group as [specified] is preferably 6 or more and 12 or less. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like. Specific examples of the aryl group include a phenyl group and a naphthyl group.

[0136] R c21 and R c22 The number of carbon atoms of the aliphatic acyl group as [specified] 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. The aliphatic acyl group may be linear or branched. Specific examples of the aliphatic acyl group include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a heptadecanoyl group, an octadecanoyl group, a nonadecanoyl group, and an icosanoyl group.

[0137] R c21 and R c22The number of carbon atoms of the aromatic acyl group as such is 7 or more and 20 or less. The aromatic acyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like. Specific examples of the aromatic acyl group include a benzoyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,6-dimethylbenzoyl group, a 2,6-dimethoxybenzoyl group, a 2,4,6-trimethylbenzoyl group, an α-naphthoyl group, and a β-naphthoyl group.

[0138] Preferable specific examples of the phosphine oxide compound containing the structural moiety represented by the formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0139] The content of the photopolymerization initiator (C) is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, based on the mass of the photocurable liquid composition (total solid content) excluding the mass of the organic solvent (S) described later. By setting the content of the photopolymerization initiator (C) within the above range, a photocurable liquid composition having good curability can be obtained.

[0140] A photoinitiator may be combined with the photoinitiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 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-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and thiol compounds such as 3-mercaptopropionate. These photoinitiators can be used alone or in combination of two or more.

[0141] 〔Plasticizer (D)〕 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.

[0142] As the plasticizer (D), a compound represented by the following formula (d-1) is preferred. 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 which may have 1 to 5 substituents, and the substituents are selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, R d3 , and Rd4 is each independently a methylene group or an ethane-1,2-diyl group, r and s are each independently 0 or 1, and X d is an oxygen atom or a sulfur atom.)

[0143] By including such a plasticizer (D) in the photocurable liquid composition, the photocurable liquid composition is reduced in viscosity without significantly impairing the curability of the photocurable liquid composition and the refractive index of the cured product. From the viewpoint of reducing the viscosity of the photocurable liquid composition, 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 even more preferably 6 cP or less. Also, from the viewpoint that the plasticizer (D) is less volatile and it is easy to maintain the effect of reducing the viscosity of the photocurable liquid composition, the boiling point of the plasticizer (D) under atmospheric pressure is preferably 250°C or higher, more preferably 260°C or higher. The upper limit of the boiling point of the plasticizer (D) under atmospheric pressure is not particularly limited, and for example, it may be 300°C or lower, or 350°C or lower.

[0144] R in formula (d-1) d1 , and R d2 are each independently a phenyl group which may have 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. When the phenyl group has a substituent, the number of substituents is not particularly limited. The number of substituents is 1 to 5, preferably 1 or 2, and preferably 1. From the viewpoint of reducing the viscosity of the photocurable liquid composition, it is preferable that R d1 , and R d2 are each an unsubstituted phenyl group.

[0145] Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0146] R in formula (d-1) d3 , and R d4 are each independently a methylene group or an ethane-1,2-diyl group. Also, r and s are each independently 0 or 1. X in formula (d-1) d is an oxygen atom or a sulfur atom.

[0147] 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.

[0148] The content of the plasticizer (D) in the photocurable liquid composition is preferably 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, from the viewpoint of achieving both viscosity adjustment and dispersibility of the metal oxide nanoparticles (B) with respect to the total mass of the photocurable liquid composition.

[0149] [Nitrogen-containing compound (E)] For the purpose of further facilitating the suppression of the localization of the metal oxide nanoparticles (B) in the cured product, the photocurable liquid composition may contain an amine compound (E1) represented by the following formula (e1) and / or an imine compound (E2) represented by the following formula (e2) as the nitrogen-containing compound (E). NR e1R 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.)

[0150] In formula (e1) and formula (e2), when R e1 , R e2 , R e3 , R e4 , R e5 , and R de6 are organic groups, the organic groups can be selected from various organic groups as long as the desired effects are not impaired. As the organic group, a carbon atom-containing group is preferable, and a group composed of 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 preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.) Preferable examples of the organic group include an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group which may have a substituent, and a heterocyclyl group which may have a substituent, etc.)

[0151] The number of carbon atoms of the alkyl group as the organic group is preferably from 1 to 20, more preferably from 1 to 6. The structure of the alkyl group may be linear or branched. Specific examples of the case where it is an alkyl group 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, 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. Further, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

[0152] The number of carbon atoms of the cycloalkyl group as the organic group is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

[0153] The number of carbon atoms of the phenylalkyl group as the organic group is preferably from 7 to 20, more preferably from 7 to 10. Further, the number of carbon atoms of the naphthylalkyl group as the organic group is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. Specific examples of the naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. The phenylalkyl group or the naphthylalkyl group may further have a substituent on the phenyl group or the naphthyl group.

[0154] When the heterocyclic group is an organic group, the heterocyclic group is the same as the case where R in the formula (c3) c4 is a heterocyclic group, and the heterocyclic group may further have a substituent.

[0155] The heterocyclic group as an organic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclic group formed by condensation of such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is up to 3. Examples of the heterocyclic ring constituting such a heterocyclic group 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, etc.

[0156] Examples of the substituents when the phenyl group, naphthyl group, and heterocyclic group contained in the above organic groups have substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, halogenated alkoxy groups having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms, dialkylamino groups having an alkyl group having 1 to 6 carbon atoms, benzoyl groups, halogen atoms, nitro groups, and cyano groups, etc. When the phenyl group, naphthyl group, and heterocyclyl group contained in the organic group have substituents, the number of the substituents is not particularly limited, and is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in the organic group have a plurality of substituents, the plurality of substituents may be the same or different.

[0157] In formula (e1), 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. Also, in formula (e2), 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 an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As the aromatic group-containing group, a hydrocarbon group is preferable. As the aromatic group-containing group, an aromatic hydrocarbon group (aryl group) and an aralkyl group are preferable. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group. Among these aromatic hydrocarbon groups, a phenyl group is preferable. Examples of the aralkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.

[0158] In formula (e1), it is preferable that at least one of R e1 , R e2 , and R e3 is a group represented by Ar e1 -CH 2 -. Also, in formula (d2), it is preferable that R e4 is a group represented by Ar e1 -CH 2 -. Ar e1is an aromatic group which may have a substituent. Ar e1 The aromatic group as Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Ar e1 As the aromatic group as Ar, an aromatic hydrocarbon group is preferred. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group. Among these aromatic hydrocarbon groups, a phenyl group is preferred. Ar e1 The substituent which the aromatic group as Ar may have is R e1 、R e2 、R e3 、R e4 、R e5 、and R de6 When the organic groups as R are a phenyl group, a naphthyl group, and a heterocyclyl group, they are the same as the substituents which these groups may have.

[0159] Preferable specific examples of the amine compound represented by the formula (e1) include triphenylamine, N,N-diphenylbenzylamine, N-phenyldibenzylamine, tribenzylamine, 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.

[0160] Preferable specific examples of the imine compound represented by the formula (e2) include N-benzylphenylmethanimine, N-benzyl-diphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropan-2-imine.

[0161] The content of the nitrogen-containing compound in the photocurable liquid composition is not particularly limited as long as the desired effect is 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, based on the mass of the photopolymerizable monomer (A).

[0162] 〔Solvent (S)〕 The photocurable liquid composition may contain a solvent (S) of 5% by mass or less based on the mass of the photocurable liquid composition. The type of the solvent (S) is not particularly limited, but is typically an organic solvent.

[0163] Examples of organic solvents that can be incorporated into the photocurable liquid composition include (poly)alkylene glycol monoalkyl ethers such as 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 monoethyl 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 monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2 - heptanone, 3 - heptanone; alkyl lactates such as methyl 2 - hydroxypropionate, ethyl 2 - hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide, etc. can be mentioned.;

[0164] [Other components] The photocurable liquid composition may contain various additives conventionally incorporated in photosensitive compositions and ink compositions, in addition to the components described above, as long as the object of the present invention is not impaired. Preferred additives incorporated in the photocurable liquid composition include dispersants, adhesion promoters such as silane coupling agents, antioxidants, anti-aggregation agents, defoaming 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.

[0165] [Method for producing photocurable liquid composition] The photocurable liquid composition can be obtained by mixing the components described above in predetermined amounts and then stirring the mixture uniformly.

[0166] ≪Method for producing cured product≫ The photocurable liquid composition described above is typically shaping the photocurable liquid composition according to the shape of the cured product to be formed, and Exposing the formed photocurable liquid composition, it is made into a cured product by a method including.

[0167] The cured product produced by the above method exhibits a high refractive index, for example, as the refractive index at a wavelength of 550 nm, preferably 1.60 or more, more preferably 1.61 or more, and even more preferably 1.62 or more. Therefore, the cured product produced by the above method is suitably used in optical applications where a high refractive index is required. For example, a film made of the cured product of the aforementioned photocurable liquid composition 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.

[0168] The film thickness of the high refractive index film made of the cured product of the aforementioned photocurable liquid composition 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 μm or less, and more preferably 50 nm or more and 10 μm or less.

[0169] The method for forming the photocurable liquid composition is not particularly limited and is appropriately selected according to the shape of the cured product. Examples of the shape of the cured product include, but are not limited to, a film shape, a lens shape, a line shape, a prism shape, etc. Among these shapes, a film shape is preferred. The method for forming the photocurable liquid composition is not particularly limited. When the shape of the cured product is a lens shape, a prism shape, etc., the photocurable liquid composition may be filled into a mold corresponding to the shape of the cured product using a squeegee or the like. When the shape of the cured product is a line shape or the like, the photocurable liquid composition may be applied onto a substrate according to the shape of the cured product. Examples of the application method include printing methods such as an inkjet method. Light Curing Photonic liquid compositionAs a method of applying a substance in a film shape, methods using contact transfer type coating devices such as roll coaters, reverse coaters, bar coaters, etc., and non-contact type coating devices such as spin coaters (rotary coating devices), curtain flow coaters, etc. can be mentioned. Further, the photocurable liquid composition can also be applied in a film shape by a printing method such as an inkjet method.

[0170] When the photocurable liquid composition contains a solvent (S), after shaping the photocurable liquid composition into a desired shape, the solvent (S) may be removed from the shaped photocurable liquid composition by a method such as heating.

[0171] In addition, for example, after performing exposure to such an extent that the photocurable liquid composition does not completely cure on the photocurable liquid composition shaped into a desired shape such as a film shape, it may be shaped with respect to the semi-cured photocurable liquid composition by a method such as an imprint method. In this case, further exposure is performed on the shaped semi-cured photocurable liquid composition to sufficiently cure the photocurable liquid composition to a desired degree. Further, the above-mentioned photocurable liquid composition may be applied to a 3D printing method, and a cured product having a desired shape may be formed by repeating inkjet printing and curing by exposure to laminate a thin film-like cured product.

[0172] As an exposure method for curing the photocurable liquid composition formed by the above method, various methods known as curing methods for photosensitive compositions can be appropriately applied. Exposure of the formed photocurable liquid composition is performed, for example, by irradiating active energy rays such as ultraviolet rays and excimer laser light.

[0173] Exposure of the formed photocurable liquid composition may be performed selectively by position, for example, by a method such as exposure through a mask. When performing exposure selectively by position, a patterned cured product can be formed by developing the exposed photocurable liquid composition using an organic solvent to remove the unexposed portion. When performing development processing, it is preferable to sufficiently remove the developer by a method such as drying by heating after development.

[0174] By the method described above, a cured product having a desired shape and a high refractive index is formed using the above-described photocurable liquid composition containing no or only a small amount of the solvent (S).

Examples

[0175] Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these examples.

[0176] 〔Examples 1 to 10 and Comparative Example 1〕 In the examples and the comparative example, the following compounds were used as the photopolymerizable monomer (A). <Polyfunctional monomer (A1)> A1-a: Dipentaerythritol hexaacrylate A1-b: Compound of the following formula CH=CH 2 -CO-O-CH 2 CH 2 CH 2 -O-CH 2 ) 2 -CH-O-CH 2 CH 2 CH 2 -O-CO-CH=CH 2 A1-c: Trimethylolpropane triacrylate <Bifunctional monomer (A2)> A2-a: Compound having the following structure

Chemical formula

[0177] In the examples and comparative examples, as the metal oxide nanoparticles (B), zirconium oxide particles B1 (average particle size: 8 nm) surface-modified using 3-methacryloxypropyltrimethoxysilane as a capping agent, zirconium oxide particles B2 (average particle size: 10 nm) not surface-modified with an ethylenically unsaturated double bond-containing group capping agent, titanium oxide particles B3 (average particle size: 11 nm) surface-modified using 3-methacryloxypropyltrimethoxysilane as a capping agent, and titanium oxide particles B4 (average particle size: 10 nm) not surface-modified with an ethylenically unsaturated double bond-containing group capping agent were used. For the zirconium oxide particles B2, they were obtained by drying the nanocrystals recovered by centrifugation in accordance with the method described in paragraph

[0223] of JP-A-2018-193481. For the zirconium oxide particles B1 surface-modified with 3-methacryloylpropyltrimethoxysilane, in the step of adding the capping agent, 3-methacryloxypropyltrimethoxysilane as a capping agent in an amount 0.8 to 1.5 times the mass of the zirconium oxide particles was further added, and otherwise they were obtained in the same manner as the zirconium oxide particles B2. For the titanium oxide particles B4, they were obtained by drying the nanocrystals recovered by centrifugation in accordance with the method described in Example 8 of WO 2020 / 106860. For the titanium oxide particles B3 surface-modified with 3-methacryloylpropyltrimethoxysilane, in the step of adding the capping agent, 50% by mass of the total amount of the capping agent was replaced with 3-methacryloxypropyltrimethoxysilane, and otherwise they were obtained in the same manner as the titanium oxide particles B4.

[0178] In the examples and comparative examples, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was used as the photopolymerization initiator (C).

[0179] The photopolymerizable monomer (A) of the type and amount (parts by mass) described in Table 1, the metal oxide nanoparticles (B) of the type and amount (parts by mass) described in Table 1, 6.0 parts by mass of a photopolymerization initiator (C), and 1.0 part by mass of a surfactant (BYK-333 (manufactured by BYK Chemie)) were uniformly mixed to obtain the photocurable liquid compositions of Examples 1 to 10 and Comparative Example 1. The photopolymerizable monomer (A) of the type and amount (parts by mass) described in Table 3, the metal oxide nanoparticles (B) of the type and amount (parts by mass) described in Table 3, 1.0 part by mass of a photopolymerization initiator (C), and PGMEA (propylene glycol monomethyl ether acetate) as a solvent (S) were uniformly mixed so that the concentration of components other than the solvent (S) was 10% by mass to obtain the photocurable liquid compositions of Example 10 and Example 11.

[0180] The viscosities of the obtained photocurable liquid compositions measured at 25 °C or 35 °C using an E-type viscometer are shown in Tables 2 and 3. Note that Table 3 shows only the 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 formulation. These measurement results are shown in Tables 2 and 3. Furthermore, according to the following formulation, the ratio T1 / T2 of the thickness T1 of the layer rich in each metal oxide nanoparticle to the thickness T2 of the layer in which each metal oxide nanoparticle hardly exists in the cured film formed using the photocurable liquid composition was measured. The smaller the value of T1 / T2, the more the localization of each metal oxide nanoparticle in the cured film is suppressed.

[0181] <Refractive Index Measurement Method> Using an inkjet apparatus, the photocurable liquid compositions of each example and comparative example were applied onto a glass substrate. Then, using a 395 nm UV-LED exposure machine, the coating film was exposed and cured with an exposure amount of 2 J / cm 2 to obtain a cured film with a thickness of 3 μm. The refractive index of the film at a light wavelength of 550 nm was determined using a prism coupler manufactured by Metricon.

[0182] <Measurement Method of Total Light Transmittance, Haze, and Y.I.> After applying the photocurable liquid compositions of the examples and comparative examples by spin coating on a glass substrate, using a 385 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 10 μm. For the film, the total light transmittance, haze, and Y.I. were measured using a desktop spectrocolorimeter manufactured by Hunter Associates Laboratory, Inc.

[0183] <T1 / T2 Measurement> For the cured film obtained under the same conditions as the cured film to be measured for refractive index, using a prism coupler 2010 / M manufactured by Metricon, the refractive index of each cured film was measured by the prism coupling method. When two layers with different refractive indices were detected in the cured film, each of the two layers was analyzed to obtain the value of the thickness of each layer. The thickness of the upper layer rich in each metal oxide nanoparticle was designated as T1, and the thickness of the lower layer with fewer metal oxide nanoparticles was designated as T2. It was calculated as the ratio T1 / T2 of the thicknesses of each layer from T1 and T2 thus obtained. The value of T1 / T2 was used as an evaluation index for the degree of bilayer formation.

[0184]

Table 1

[0185]

Table 2

[0186]

Table 3

[0187] According to Table 1, Table 2, and Table 3, by blending a polyfunctional monomer (A1) that satisfies the aforementioned predetermined requirements into a photocurable liquid composition containing a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C), it can be seen that the value of T1 / T2 decreases and the localization of the metal oxide nanoparticles (B) in the cured product is suppressed. Further, it can be seen that when the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group, it is excellent in various optical properties such as refractive index, total light transmittance, haze, or Y.I.

Claims

1. A photocurable liquid composition comprising a photopolymerizable monomer (A), metal oxide nanoparticles (B), and a photoinitiator (C), wherein the photopolymerizable monomer (A) has an ethylenically unsaturated double bond, the photopolymerizable monomer (A) contains a polyfunctional monomer (A1) having three or more of the ethylenically unsaturated double bonds, the ratio of the mass of the polyfunctional monomer (A1) to the mass of the photopolymerizable monomer (A) is 15% by mass or more and 70% by mass or less, the polyfunctional monomer (A1) is a compound represented by the following formula (A1): 【Chemical 1】 or a compound represented by the following formula (A2): (MA-(O-R ａ１ ) ｎａ１ -X-CH ２ ) ２ -CH-X-(R ａ１ -O) ｎａ１ -MA...(A2) (In formula (A1) and formula (A2), MA is, independently of each other, a (meth)acryloyl group, and X is, independently of each other, an oxygen atom, -NH-, or -N(CH ３ )-, R ａ１ is, independently of each other, an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group, and R ａ２ is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or a group represented by -X-(R ａ１ -O) ｎａ１ -MA (X is as defined above), and na1 and na2 are, independently of each other, 0 or 1.) and is a compound represented by the photopolymerizable monomer (A) contains, as a bifunctional monomer (A2), a compound represented by the following formula (a-1): [Chemical 2] (In formula (a-1), 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, and p and q are each independently 0 or 1.) and is a compound represented by the photopolymerizable monomer (A) contains a monofunctional monomer (A3), the monofunctional monomer (A3) is a compound represented by the following formula (a-2): 【Chemical Formula 3】 (In formula (a-2), R １０ is a hydrogen atom or a methyl group. R １１ is an alkylene group having 1 to 3 carbon atoms. R １２ 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.) and is a compound represented by a photocurable liquid composition in which the surface of the metal oxide nanoparticles (B) is modified with an ethylenically unsaturated double bond-containing group.

2. The photocurable liquid composition according to claim 1, wherein the polyfunctional monomer (A1) is an aliphatic compound containing no aromatic group.

3. The photocurable liquid composition according to claim 1 or 2, wherein the number of the ethylenically unsaturated double bonds of the polyfunctional monomer (A1) is 3 or more and 6 or less.

4. The photocurable liquid composition according to any one of claims 1 to 3, wherein the ratio of the mass of the polyfunctional monomer (A1) to the mass of the photopolymerizable monomer (A) is 20% by mass or more and 70% by mass or less.

5. The photocurable liquid composition according to any one of claims 1 to 4, wherein the photoinitiator (C) contains a phosphine oxide-based compound.

6. A cured product of the photocurable liquid composition according to any one of claims 1 to 5.

7. The cured product according to claim 6, having a refractive index of 1.60 or more measured at a light wavelength of 550 nm.

8. A method for producing a cured product, comprising molding the photocurable liquid composition according to any one of claims 1 to 5 and exposing the molded photocurable liquid composition.

9. The method for producing a cured product according to claim 8, wherein the method of molding the photocurable liquid composition is coating. ​

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