Patent Application
20240239922
The present invention relates to a photocurable composition, a product of curing of the photocurable composition, and a method of forming a cured film using the photocurable composition.
Traditionally, high refractive index materials are used to form optical elements. Such high refractive index materials are produced from, for example, a composition including an organic component and particles of metal oxide, such as titanium oxide or zirconium oxide, dispersed in the organic component. Such high refractive index materials are proposed to be produced from an energy ray-curable composition including metal oxide particles (A) with a specific particle size, a (meth)acrylate (B), and a photopolymerization initiating agent (C) (see Patent Document 1).
As mentioned above, the curable composition disclosed in Patent Document 1 can be used to form high-refractive-index cured materials. However, there is a need for a material having a refractive index higher than ever.
To provide such a material with a higher refractive index, it is effective to use a method of producing a curable composition containing an increased amount of metal oxide particles. Unfortunately, the process of producing a curable composition with a high content of metal oxide particles has a problem such as difficulty in successfully dispersing metal oxide particles, and even if metal oxide particles are successfully dispersed, the resulting curable composition may have a problem such as low wettability on the application target substrate.
It is an object of the present invention, which has been made in light of the problem described above, to provide a photocurable composition containing metal oxide fine particles well dispersed even at a high concentration and having good wettability on the application target substrate, to provide a product of curing of such a photocurable composition, and to provide a method of forming a cured film using such a photocurable composition.
The inventors have created a photocurable composition including a photopolymerizable compound (A), metal oxide fine particles (B), an initiating agent (C), and solvents (S) in which the photopolymerizable compound (A) is a compound having a radically polymerizable group-containing group or a cationically polymerizable group-containing group, and the solvents (S) include two or more solvents (S1) each having a specific structure containing an oxyalkylene group and each having a Hildebrand solubility parameter of 21.0 MPa0.5 or less, and completed an aspect of the present invention based on findings that such a photocurable composition provides a solution to the problem described above. The inventors have also completed another aspect of the present invention based on findings that the problem described above can also be solved when the solvents (S) include the solvent (S1) and an additional solvent (S2) in a specific mass ratio. Specifically, the present invention provides the following aspects.
(1) A photocurable composition including: a photopolymerizable compound (A); metal oxide fine particles (B); an initiating agent (C); and solvents (S),
(2) The photocurable composition according to aspect (1), wherein the ratio of the mass of the metal oxide fine particles (B) to the mass calculated by subtracting the mass of the solvents (S) from the mass of the photocurable composition is 70 mass % or more.
(3) The photocurable composition according to aspect (1) or (2), wherein the ratio of the mass of the solvents (S1) to the mass of the solvents (S) is 20 mass % or more.
(4) The photocurable composition according to any one of aspects (1) to (3), wherein the photopolymerizable compound (A) includes a compound having: a S atom at its center; radically polymerizable group-containing groups at its two ends; and divalent linking moieties that link the center and each of the ends and each have an optionally substituted aromatic ring and a S atom.
(5) The photocurable composition according to any one of aspects (1) to (4),
(6) The photocurable composition according to any one of aspects (1) to (5), wherein the photopolymerizable compound (A) includes a compound of Formula (A1):
(7) A photocurable composition including: a photopolymerizable compound (A); metal oxide fine particles (B); an initiating agent (C); and solvents (S),
(8) A cured product including a product of curing of the photocurable composition according to any one of aspects (1) to (7).
(9) The cured product according to aspect (8), wherein the cured product has a refractive index of 1.70 or more for light at a wavelength of 520 nm.
(10) A method of forming a cured film, the method including:
(11) The method according to aspect (10), wherein applying the photocurable composition is performed by an inkjet printing method.
The present invention provides a photocurable composition containing metal oxide fine particles well dispersed even at a high concentration and having good wettability on the application target substrate, provides a product of curing of such a photocurable composition, and provides a method of forming a cured film using such a photocurable composition.
The photocurable composition includes a photopolymerizable compound (A), metal oxide fine particles (B), an initiating agent (C), and solvents (S).
The photopolymerizable compound (A) has a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
The solvents (S) include two or more solvents (S1) each having a specific structure containing an oxyalkylene group and each having a Hildebrand solubility parameter of 21.0 MPa0.5 or less. The solvents (S1) will be described in detail later.
In the photocurable composition, the solvents (S1) allow the metal oxide fine particles (B) to be well dispersed even at a high concentration, and the solvents (S1) also allow the photocurable composition to have good wettability on the application target substrate.
Hereinafter, essential and optional components for the photocurable composition will be described.
The photocurable composition contains the photopolymerizable compound (A) as a curable component. The photopolymerizable compound (A) has a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
The radically polymerizable group-containing group is typically an ethylenically unsaturated double bond-containing group. The ethylenically unsaturated double bond-containing group is preferably an alkenyl group-containing group, which contains an alkenyl group such as vinyl or allyl, and more preferably a (meth)acryloyl group-containing group.
The cationically polymerizable group-containing group is typically an epoxy group-containing group, an oxetanyl group-containing group, or a vinyloxy group-containing group. Among them, an epoxy group-containing group and a vinyloxy group-containing group are preferred. The epoxy group-containing group is preferably an alicyclic epoxy group-containing group or a glycidyl group. In this regard, the alicyclic epoxy group is an aliphatic cyclic group having two adjacent carbon atoms as ring members bonded together with an oxygen atom between them. In other words, the alicyclic epoxy group has an aliphatic ring and an epoxy group that is a three-membered ring composed of one oxygen atom and two carbon atoms on the aliphatic ring.
In the description and claims of the present application, the term “(meth)acrylic” means both “acrylic” and “methacrylic”, the term “(meth)acryloyl” means both “acryloyl” and “methacryloyl”, and the term “(meth)acrylate” means both “acrylate” and “methacrylate”.
When the photopolymerizable compound (A) has a radically polymerizable group-containing group, the photopolymerizable compound (A) may be a monofunctional compound having a single radically polymerizable group or a polyfunctional compound having two or more radically polymerizable groups, among which a polyfunctional compound is preferred.
The photopolymerizable compound (A) having a radically polymerizable group-containing group(s) is preferably a compound having one or more (meth)acryloyl groups, such as a (meth)acrylate compound or a (meth)acrylamide compound, and is more preferably a (meth)acrylate compound having one or more (meth)acryloyl groups.
Examples of the monofunctional compound having a radically polymerizable group-containing group 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-butyl acrylamide sulfonic 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, glycerol 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 phthalic acid derivative half (meth)acrylate. These monofunctional compounds may be used alone, or two or more of these monofunctional compounds may be used in combination.
Examples of the polyfunctional compound having radically polymerizable group-containing groups 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-hexane glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(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, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reaction products of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensation products of polyhydric alcohol and N-methylol(meth)acrylamide, and other polyfunctional compounds, and triacrylformal. These polyfunctional compounds may be used alone, or two or more of these polyfunctional compounds may be used in combination.
In particular, the photopolymerizable compound (A) having a radically polymerizable group-containing group(s) is preferably a trifunctional or polyfunctional compound having three or more functional groups, more preferably a tetrafunctional or polyfunctional compound having four or more functional groups, even more preferably a pentafunctional or polyfunctional compound having five or more functional groups, because such a compound tends to form a cured product with higher strength.
A photocurable composition containing metal oxide fine particles (B) might form a cured film having a metal oxide fine particle (B)-rich layer and a metal oxide fine particle (B)-poor layer, which means localization of the metal oxide fine particles (B), depending on the components of the photocurable composition.
For the prevention of such localization, the photocurable composition preferably contains a compound of Formula (A1) or (A2) below as the photopolymerizable compound (A) having a radically polymerizable group-containing group(s).
In Formulae (A1) and (A2), MAs are each independently a (meth)acryloyl group, Xs are each independently an oxygen atom, —NH—, or —N(CH3)—, Ra1s are each independently an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group, Ra2 is a hydroxyl group, an alkyl group having 1 or more and 4 or less carbon atoms, or a group represented by —X—(Ra1—O)na1-MA, where X has the same meaning as defined above, and na1 and na2 are each independently 0 or 1.
In Formula (A1), the alkyl group of Ra2 having 1 or more and 4 or less carbon atoms may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. In particular, the alkyl group is preferably methyl or ethyl.
Preferred examples of the compounds of Formulae (A1) and (A2) include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, and Compounds (1) to (32) shown below. In Compounds (1) to (32) below, MA is a (meth)acryloyl group.
To form a cured product with less localized metal oxide fine particles (B), the photocurable composition preferably has a ratio of the total mass of the compounds of Formulae (A1) and (A2) to the mass of the photopolymerizable compound(s) (A) of 20 mass % or more and 70 mass % or less, more preferably 30 mass % or more and 70 mass % or less, even more preferably 40 mass % or more and 70 mass % or less.
For ease of forming a cured product with a high refractive index, the photocurable composition preferably contains, as the photopolymerizable compound (A) having a radically polymerizable group-containing group, a compound having: a S atom at its center; radically polymerizable group-containing groups at its two ends; and divalent linking moieties that link the center to each of the ends and each have an optionally substituted aromatic ring and a S atom, more preferably contains a compound having (meth)acryloyl groups at its two ends and having a diphenyl sulfide skeleton that includes a central S atom and aromatic ring-containing divalent linking moieties, and even more preferably contains a compound of Formula (a-1) below.
In Formula (a-1), R1 and R2 are each independently a hydrogen atom or a methyl group, R3 and R4 are each independently an alkyl group having 1 or more and 5 or less carbon atoms, and p and q are each independently 0 or 1.
In the linking moiety, the aromatic ring may be an aromatic hydrocarbon ring, such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthroline ring; or an aromatic heterocyclic ring, such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, or a benzothiazole ring. In particular, the aromatic ring is preferably a benzene ring (e.g., a 1,4-phenyl group). The linking moiety may have a substituent, which may be alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylamino, dialkylamino, alkylamide, alkenyl, alkynyl, a halogen atom, cyano, nitro, alkylthiol, or N-alkylcarbamate. In particular, the substituent is preferably an alkyl group, more preferably an alkyl group having 1 or more and 5 or less carbon atoms.
R1 and R2 are each independently a hydrogen atom or a methyl group. R1 and R2 may be different from each other or may be the same. R1 and R2 are preferably the same so that the compound of Formula (a-1) can be easily synthesized or obtained commercially.
R3 and R4 are each independently an alkyl group having 1 or more and 5 or less carbon atoms. R3 and R4 may be different from each other or may be the same. R3 and R4 are preferably the same so that the compound of Formula (a-1) can be easily synthesized or obtained commercially.
The alkyl group of R3 or R4 having 1 or more and 5 or less carbon atoms may be linear or branched. The alkyl group of R3 or R4 having 1 or more and 5 or less carbon atoms may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, or tert-isopentyl.
Preferred examples of the compound of Formula (a-1) include the compounds below.
In a case where the photocurable composition contains the compound of Formula (a-1) as the photopolymerizable compound (A) having a radically polymerizable group-containing group, the photocurable composition preferably has a ratio of the mass of the compound of Formula (a-1) to the mass of the photopolymerizable compound (s) (A) of 10 mass % or more, more preferably 30 mass % or more, even more preferably 50 mass % or more, furthermore preferably 70 mass % or more, still more preferably 100 mass %.
For ease of forming a cured product with less localized metal oxide fine particles (B), the photocurable composition preferably contains a sulfur-containing (meth)acrylate of Formula (A3) below as the photopolymerizable compound (A) having a radically polymerizable group-containing group.
In Formula (A3), Ara1 is a phenyl group optionally substituted with a halogen atom, Ra21 is a single bond or an alkylene group having 1 or more and 6 or less carbon atoms, Ra22 is an alkylene group having 1 or more and 6 or less carbon atoms, and Ra23 is a hydrogen atom or a methyl group.
Ara1 is a phenyl group optionally substituted with a halogen atom. The phenyl group may be substituted with any number of halogen atoms. The phenyl group is preferably substituted with one or two halogen atoms, more preferably with one halogen atom. The phenyl group may be substituted with two or more halogen atoms the same as or different from one another. The halogen atom, with which the phenyl group may be substituted, may be fluorine, chlorine, bromine, or iodine, and is preferably fluorine, chlorine, or bromine.
Ara1 is preferably an unsubstituted phenyl group.
Ra21 is a single bond or an alkylene group having 1 or more and 6 or less carbon atoms. The alkylene group having 1 or more and 6 or less carbon atoms may be methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, or hexane-1,6-diyl.
Ra21 is preferably a single bond or a methylene group, and more preferably a single bond.
Ra22 is an alkylene group having 1 or more and 6 or less carbon atoms. The alkylene group having 1 or more and 6 or less carbon atoms may be methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, or hexane-1,6-diyl.
Ra22 is preferably methylene, ethane-1,2-diyl, or propane-1,3-diyl, and more preferably ethane-1,2-diyl or propane-1,3-diyl.
In particular, Ara1 and Ra21 in Formula (A3) are preferably a phenyl group and a single bond, respectively, for ease of obtaining the sulfur-containing (meth)acrylate or for formation of a cured product with less localized metal oxide nanoparticles (B).
Preferred examples of the sulfur-containing (meth)acrylate of Formula (A3) include 2-phenylthioethyl (meth)acrylate, 3-phenylthiopropyl (meth)acrylate, 2-benzylthioethyl (meth)acrylate, 3-benzylthiopropyl (meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate, 3-(2-chlorophenyl)propyl (meth)acrylate, 3-(3-chlorophenyl)propyl (meth)acrylate, 3-(4-chlorophenyl)propyl (meth)acrylate, 2-(2-fluorophenyl)ethyl (meth)acrylate, 2-(3-fluorophenyl)ethyl (meth)acrylate, 2-(4-fluorophenyl)ethyl (meth)acrylate, 3-(2-fluorophenyl)propyl (meth)acrylate, 3-(3-fluorophenyl)propyl (meth)acrylate, 3-(4-fluorophenyl)propyl (meth)acrylate, 2-(2-bromophenyl)ethyl (meth)acrylate, 2-(3-bromophenyl)ethyl (meth)acrylate, 2-(4-bromophenyl)ethyl (meth)acrylate, 3-(2-bromophenyl)propyl (meth)acrylate, 3-(3-bromophenyl)propyl (meth)acrylate, and 3-(4-bromophenyl)propyl (meth)acrylate.
In a case where the photocurable composition contains the sulfur-containing (meth)acrylate of Formula (A3) as the photopolymerizable compound (A) having a radically polymerizable group-containing group, the photocurable composition preferably has a ratio of the mass of the sulfur-containing (meth)acrylate of Formula (A3) to the mass of the photopolymerizable compound(s) (A) of 40 mass % or more and 100 mass % or less, more preferably 60 mass % or more and 100 mass or less, even more preferably 70 mass % or more and 100 mass % or less, furthermore preferably 80 mass % or more and 100 mass % or less.
The photopolymerizable compound (A) having a cationically polymerizable group-containing group may be a monofunctional compound having one cationically polymerizable group or a polyfunctional compound having two or more cationically polymerizable groups, among which a polyfunctional compound is preferred.
The photopolymerizable compound (A) may have a vinyloxy group-containing group as the cationically polymerizable group-containing group. In such a case, the photocurable composition may contain a vinyl ether compound as the photopolymerizable compound (A). Such a vinyl ether compound may be a monofunctional compound or a polyfunctional compound.
Preferred examples of the vinyl ether compound include vinyl phenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 1-vinyloxy-4-chlorobenzene, 1-vinyloxy-3-chlorobenzene, 1-vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethylbenzene, 1-vinyloxy-2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 2-vinyloxyfluorene, 3-vinyloxyfluorene, 4-vinyloxy-1,1′-biphenyl, 3-vinyloxy-1,1′-biphenyl, 2-vinyloxy-1,1′-biphenyl, 6-vinyloxytetralin, 5-vinyloxytetralin, and other aromatic monoviyl ether compounds; and 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2-divinyloxybenzene, 1,4-divinyloxynaphthalene, 1,3-divinyloxynaphthalene, 1,2-divinyloxynaphthalene, 1,5-divinyloxynaphthalene, 1,6-divinyloxynaphthalene, 1,7-divinyloxynaphthalene, 1,8-divinyloxynaphthalene, 2,3-divinyloxynaphthalene, 2,6-divinyloxynaphthalene, 2,7-divinyloxynaphthalene, 1,2-divinyloxyfluorene, 3,4-divinyloxyfluorene, 2,7-divinyloxyfluorene, 4,4′-divinyloxybiphenyl, 3,3′-divinyloxybiphenyl, 2,2′-divinyloxybiphenyl, 3,4′-divinyloxybiphenyl, 2,3′-divinyloxybiphenyl, 2,4′-divinyloxybiphenyl, bisphenol A divinyl ether, and other aromatic divinyl ether compounds.
Two or more of these vinyl ether compounds may be used in combination.
The photopolymerizable compound (A) may have an epoxy group-containing group as the cationically polymerizable group-containing group. In this case, the photocurable composition may contain any of various epoxy compounds as the the photopolymerizable compound (A).
Examples of the epoxy compound include difunctional epoxy resins, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, and biphenyl epoxy resin; novolac epoxy resins, such as phenol novolac epoxy resin, brominated phenol novolac epoxy resin, orthocresol novolac epoxy resin, bisphenol A novolac epoxy resin, and bisphenol AD novolac epoxy resin; alicyclic epoxy resins, such as epoxidized dicyclopentadiene phenolic resin; aromatic epoxy resins, such as epoxidized naphthalene phenolic resin; glycidyl ester epoxy resins, such as dimer acid glycidyl esters and triglycidyl esters; glycidyl amine epoxy resins, such as tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl meta-xylylene diamine, and tetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy resins, such as triglycidyl isocyanurate; trifunctional epoxy resins, such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]pheny]propane, and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; tetrafunctional epoxy resins, such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl; and a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. The 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is commercially available under the name EHPE-3150 (manufactured by Daicel Corporation).
The epoxy compound is also preferably an oligomeric or polymeric polyfunctional epoxy compound.
Typical examples of the oligomeric or polymeric polyfunctional epoxy compound include phenol novolac epoxy compounds, brominated phenol novolac epoxy compounds, orthocresol novolac epoxy compounds, xylenol novolac epoxy compounds, naphthol novolac epoxy compounds, bisphenol A novolac epoxy compounds, bisphenol AD novolac epoxy compounds, epoxidized dicyclopentadiene phenolic resins, and epoxidized naphthalene phenolic resins.
Other preferred examples of the epoxy compound include polyfunctional alicyclic epoxy compounds having an alicyclic epoxy group.
Examples of the alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4|-epoxy-6′-methyl cyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate, epoxy resins having a tricyclodecene oxide group, and compounds of Formulae (a01-1) to (a01-5) below.
Among these examples of the alicyclic epoxy compound, alicyclic epoxy compounds of Formulae (a01-1) to (a01-5) below are preferred because they can form cured products with high hardness.
In Formula (a01-1), Z01 is a single bond or a linking group (a divalent group having one or more atoms), and Ra01 to Ra018 are each independently one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
The linking group ZD1 may be, for example, a divalent group selected from the group consisting of a divalent hydrocarbon group, —O—, —O—CO—, —S—, —SO—, —SO2—, —CBr2—, —C(CBr3)2—, —C(CF3)2—, and —Ra019—O—CO—, or a group including two or more selected from the above group and bonded together.
The divalent hydrocarbon group for serving as the linking group Z01 may be, for example, a linear or branched alkylene group having 1 or more and 18 or less carbon atoms or a divalent alicyclic hydrocarbon group. The linear or branched alkylene group having 1 or more and 18 or less carbon atoms may be, for example, methylene, methylmethylene, dimethylmethylene, dimethylene, or trimethylene. The divalent alicyclic hydrocarbon group may be, for example, 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene, or any other cycloalkylene group (including any other cycloalkylidene group).
Ra019 is an alkylene group having 1 or more and 8 or less carbon atoms, and preferably methylene or ethylene.
In Formula (a1-2), Fa01 to Ra018 are each one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, Ra02 and Ra010 may be bonded to each other, Ra013 and Ra016 may be bonded to each other to form a ring, and mal is 0 or 1.
The alicyclic epoxy compound of Formula (a01-2) above is preferably a compound of Formula (a01-2-1) below, which corresponds to the compound of Formula (a01-2) in which ma1 is 0.
In Formula (a01-2-1), Ra01 to Ra012 are each one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and
In Formula (a01-3), Ra01 to Ra010 are each one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and Ra02 and Ra08 may be bonded to each other.
In Formula (a01-4), Ra01 to Ra012 are each one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group, and Ra02 and Ra010 may be bonded to each other.
In Formula (a01-5), Ra01 to Ra012 are each one selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
In Formulae (a01-1) to (a01-5), Ra01 to Ra018 may each be any organic group that does not compromise the object of the present invention, such as a hydrocarbon group, a group including carbon and halogen atoms, or a group including carbon and hydrogen atoms and a heteroatom, such as halogen, oxygen, sulfur, nitrogen, or silicon. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine.
The organic group is preferably a hydrocarbon group, a group including carbon, hydrogen, and oxygen atoms, a halogenated hydrocarbon group, a group including carbon, oxygen, and halogen atoms, or a group including carbon, hydrogen, oxygen, and halogen atoms. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group having an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms in the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, even more preferably 1 or more and 5 or less.
Examples of the hydrocarbon group include chain alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl; chain alkenyl groups, such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups, such as phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthryl, and phenanthryl; and aralkyl groups, such as benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl.
Examples of the halogenated hydrocarbon group include halogenated chain alkyl groups, such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halogenated cycloalkyl groups, such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl, and 4-bromocyclohexyl; halogenated aryl groups, such as 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, and 4-fluorophenyl; and halogenated aralkyl groups, such as 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, and 4-fluorophenylmethyl.
Examples of the group including carbon, hydrogen, and oxygen atoms include chain hydroxyalkyl groups, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, and 4-hydroxy-n-butyl; hydroxycycloalkyl groups, such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4 hydroxycyclohexyl; hydroxyaryl groups, such as 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl; hydroxyaralkyl groups, such as 2-hydroxyphenylmethyl, 3-hydroxyphenylmethyl, and 4-hydroxyphenylmethyl; chain alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, and n-icosyloxy; chain alkenyloxy groups, such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3-n-butenyloxy; aryloxy groups, such as phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, α-naphthyloxy, β-naphthyloxy, biphenyl-4-yloxy, biphenyl-3-yloxy, biphenyl-2-yloxy, anthryloxy, and phenanthryloxy; aralkyloxy groups, such as benzyloxy, phenethyloxy, α-naphthylmethyloxy, β-naphthylmethyloxy, α-naphthylethyloxy, and β-naphthylethyloxy; alkoxyalkyl groups, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; alkoxyalkoxy groups, such as methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy-n-propoxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, and 4-n-propoxy-n-butyloxy; alkoxyaryl groups, such as 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl; alkoxyaryloxy groups, such as 2-methoxyphenoxy, 3-methoxyphenoxy, and 4-methoxyphenoxy; aliphatic acyl groups, such as formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and decanoyl; aromatic acyl groups, such as benzoyl, α-naphthoyl, and β-naphthoyl; chain alkyloxycarbonyl groups, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; aryloxycarbonyl groups, such as phenoxycarbonyl, α-naphthoxycarbonyl, and β-naphthoxycarbonyl; aliphatic acyloxy groups, such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy; and aromatic acyloxy groups, such as benzoyloxy, α-naphthoyloxy, and β-naphthoyloxy.
Ra01 to Ra018 are preferably each independently one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and an alkoxy group having 1 or more and 5 or less carbon atoms. In particular, for ease of forming a cured film with excellent mechanical properties, Ra01 to Ra018 are preferably all hydrogen atoms.
In Formulae (a01-2) to (a01-5), Ra01 to Ra018 each have the same meaning as defined for Ra01 to Ra018 in Formula (a01-1). Ra02 and Ra010 in Formulae (a01-2) and (a01-4), Ra013 and Ra016 in Formula (a01-2), or Ra02 and Ra08 in Formula (a01-3) may be bonded to each other to form a divalent group, such as —CH2— or —C(CH3)2—.
Preferred examples of the alicyclic epoxy compound of Formula (a01-1) include alicyclic epoxy compounds of Formulae (a01-1a), (a01-1b), and (a01-1c) below and 2,2-bis(3,4-epoxycyclohexan-1-yl)propane (corresponding to 2,2-bis(3,4-epoxycyclohexyl)propane).
Preferred examples of the alicyclic epoxy compound of Formula (a01-2) include alicyclic epoxy compounds of Formulae (a01-2a) and (a01-2b) below.
Preferred examples of the alicyclic epoxy compound of Formula (a01-3) include S-spiro[3-oxatricyclo[3.2.1.02,4]octane-6,2′-oxirane].
Preferred examples of the alicyclic epoxy compound of Formula (a01-4) include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4-(3-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane.
Preferred examples of the alicyclic epoxy compound of Formula (a01-5) include 1,2,5,6-diepoxycyclooctane.
Moreover, the epoxy compound is preferably a compound of Formula (a1-I) below.
In Formula (a1-I), Xa1, Xa2, and Xa3 are each independently a hydrogen atom or an organic group optionally having an epoxy group, and the total number of epoxy groups in Xa1, Xa2, and Xa3 is 2 or more.
The compound of Formula (a1-I) is preferably a compound of Formula (a1-II) below.
In Formula (a1-II), Ra20 to Ra22 are each a linear, branched, or cyclic alkylene group, an arylene group, —O—, —C(═O)—, —NH—, or any combination of these groups and may be the same or different, and E1 to E3 are each a hydrogen atom or at least one substituent selected from the group consisting of an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxy group, a hydroxyl group, and a succinic anhydride group, provided that the total number of epoxy groups in E1, E2, and E3 is 2 or more.
In Formula (a1-II), for example, at least two of the Ra20-E1 group, the Ra21-E2 group, and the Ra22-E3 group are preferably groups of Formula (a1-IIa) below, and more preferably, all of the Ra20-E1 group, the Ra21-E2 group, and the Ra22-E3 group are groups of Formula (a1-IIa) below. In a single compound, two or more groups of Formula (a1-IIa) are preferably the same.
In Formula (a1-IIa), L is a linear, branched, or cyclic alkylene group, an arylene group, —O—, —C(═O)—, —NH—, or any combination of these groups, and Ca is an oxiranyl group (epoxy group). In Formula (a1-IIa), L and Ca may be bonded to form a ring structure.
In Formula (a1-IIa), the linear, branched, or cyclic alkylene group represented by L is preferably an alkylene group having 1 or more and 10 or less carbon atoms, and the arylene group represented by L is preferably an arylene group having 5 or more and 10 or less carbon atoms. In Formula (a1-IIa), L is preferably a linear alkylene group having 1 or more and 3 or less carbon atoms, a phenylene group, —O—, —C(═O)—, —NH—, or any combination of these groups, preferably at least one of a phenylene group or a linear alkylene group having 1 or more and 3 or less carbon atoms, such as methylene, or preferably a group including a combination of any of these groups and at least one of —O—, —C(═O)—, or —NH—.
In Formula (a1-IIa), L and C° may be bonded to form a ring structure. In this case, for example, a branched alkylene group and an epoxy group may be bonded to form a ring structure (a structure having an alicyclic epoxy group), examples of which include organic groups of Formulae (a1-IIb) to (a1-IId) below.
In Formula (a1-IIb), Ra23 is a hydrogen atom or a methyl group.
Examples of the compound of Formula (a1-II) include, but are not limited to, oxiranyl group- or alicyclic epoxy group-containing epoxy compounds shown below.
The epoxy compound is also preferably a siloxane compound having two or more glycidyl or alicyclic epoxy groups in the molecule (hereinafter also simply referred to as “siloxane compound”).
The siloxane compound has a siloxane skeleton including a siloxane bond (Si—O—Si) and has two or more glycidyl groups or two or more alicyclic epoxy groups in the molecule.
In the siloxane compound, the siloxane skeleton may be, for example, a cyclic siloxane skeleton or a cage or ladder polysilsesquioxane skeleton.
In particular, the siloxane compound is preferably a compound having a cyclic siloxane skeleton of Formula (a1-III) below (hereinafter also referred to as “cyclic siloxane”).
In Formula (a1-III), Ra24 and Ra25 are each an epoxy group-containing monovalent group or an alkyl group, provided that at least two of x1 Ra24s and x1 Ra25s in the compound of Formula (a1-III) are epoxy group-containing monovalent groups. In Formula (a1-III), x1 is an integer of 3 or more. In the compound of Formula (a1-III), Ra24 and Ra25 may be the same or different. Two or more Ra24s may be the same or different. Two or more Ra25s may also be the same or different. The alkyl group may be, for example, a linear or branched alkyl group having 1 or more and 18 or less carbon atoms (preferably 1 or more and 6 or less carbon atoms, more preferably 1 or more and 3 or less carbon atoms), such as methyl, ethyl, propyl, or isopropyl.
In Formula (a1-III), x1 is an integer of 3 or more. In particular, for high cross-linking reactivity for forming a cured film, x1 is preferably an integer of 3 or more and 6 or less.
The siloxane compound has two or more epoxy groups in the molecule. For high cross-linking reactivity for forming a cured film, the siloxane compound preferably has 2 or more and 6 or less epoxy groups, more preferably 2 or more and 4 or less epoxy groups.
The epoxy group-containing monovalent group is preferably an alicyclic epoxy group or a glycidyl ether group represented by -DA-O—Ra26, where DA is an alkylene group, and Ra26 is a glycidyl group, more preferably an alicyclic epoxy group, and even more preferably an alicyclic epoxy group of Formula (a1-IIIa) or (a1-IIIb) below. The DA (alkylene) group may be, for example, a linear or branched alkylene group having 1 or more and 18 or less carbon atoms, such as methylene, methylmethylene, dimethylmethylene, dimethylene, or trimethylene.
In Formulae (a1-IIIa) and (a1-IIIb), D1 and D2 are each independently an alkylene group, and ms is an integer of 0 or more and 2 or less.
In addition to the siloxane compound of Formula (a1-III), the photocurable composition may contain, as the epoxy compound, an alicyclic epoxy group-containing cyclic siloxane, an alicyclic epoxy group-containing silicone resin disclosed in Japanese Unexamined Patent Application, Publication No. 2008-248169, or a siloxane skeleton-containing compound, such as an organopolysilsesquioxane resin disclosed in Japanese Unexamined Patent Application, Publication No. 2008-19422, which has at least two epoxy functional groups per molecule.
More specifically, the siloxane compound may be any one of the cyclic siloxanes of the formulae shown below, which have two or more glycidyl groups in the molecule. The siloxane compound may also be a commercially available product, such as X-40-2670, X-40-2701, X-40-2728, X-40-2738, or X-40-2740 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).
For ease of forming a cured product with a high refractive index, the photocurable composition preferably contains a compound of Formula (A-1) below as the photopolymerizable compound (A).
In Formula (A-1), RA1, RA2, and RA3 are each independently an organic group, and at least two selected from the group consisting of an organic group of RA1, an organic group of RA2, and an organic group of RA3 each have a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
Preferred examples of the compound of Formula (A-1) include a compound of Formula (A-1a) below.
In Formula (A-1a), RA01 is an optionally substituted quinolinyl group, an optionally substituted isoquinolinyl group, or an optionally substituted 2-substituted benzothiazolyl group, the 2-substituted benzothiazolyl group has, at position 2, a group represented by —S—RA0, RA0 is a hydrogen atom, a radically polymerizable group-containing group, or a cationically polymerizable group-containing group, RA02 and RA03 are both aromatic ring-containing groups having a radically polymerizable group-containing group or both aromatic ring-containing groups having a cationically polymerizable group-containing group, and the —NH— groups bonded to the triazine ring are bonded to the aromatic rings in RA02 and RA03, respectively.
The optionally substituted quinolinyl group, the optionally substituted isoquinolinyl group, and the optionally substituted 2-substituted benzothiazolyl group all have a relatively high polarizability and all have a functional group with a relatively small volume. Therefore, the optionally substituted, quinolinyl, isoquinolinyl, or 2-substituted benzothiazolyl group of RA01 will contribute to the ability of the photocurable composition to form a cured product with a high refractive index.
The quinolinyl group of RA01 may be quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, or quinolin-8-yl. In particular, the quinolinyl group of RA01 is preferably quinolin-3-yl or quinolin-4-yl for ease of obtaining a raw material compound for the compound of Formula (A1) or for ease of synthesizing the compound of Formula (A1).
The isoquinolinyl group of RA01 may be isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, or isoquinolin-8-yl.
The quinolinyl group of RA01 and the isoquinolinyl group of RA01 may each have any substituent that does not compromise the desired effect. Examples of such a substituent include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a nitro group, and a monovalent organic group.
Examples of the substituent halogen atom include fluorine, chlorine, bromine, and iodine.
Examples of the monovalent organic group include alkyl, alkoxy, alkoxyalkyl, aliphatic acyl, aliphatic acyloxy, alkoxycarbonyl, alkylthio, and aliphatic acylthio.
The monovalent organic group is also preferably a radically polymerizable group-containing group or a cationically polymerizable group-containing group, which will be described later.
The substituent monovalent organic group may have any number of carbon atoms as long as the desired effect will not be impaired. For example, the substituent monovalent organic group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less carbon atoms, even more preferably 1 or more and 8 or less carbon atoms. The alkoxyalkyl group, the aliphatic acyl group, the aliphatic acyloxy group, the alkoxycarbonyl group, the alkoxyalkylthio group, or the aliphatic acylthio group should have at least two carbon atoms.
Preferred examples of the substituent alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.
Preferred examples of the substituent alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy.
Preferred examples of the substituent alkoxyalkyl group include methoxymethyl, ethoxymethyl, n-propyloxymethyl, n-butyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propyloxyethyl, 2-n-butyloxyethyl, 3-methoxy-n-propyloxy, 3-ethoxy-n-propyloxy, 3-n-propyloxy-n-propyloxy, 3-n-butyloxy-n-propyloxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, 4-n-propyloxy-n-butyloxy, and 4-n-butyloxy-n-butyloxy.
Preferred examples of the substituent aliphatic acyl group include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, and octanoyl.
Preferred examples of the substituent aliphatic acyloxy group include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy.
Preferred examples of the substituent alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl.
Preferred examples of the substituent alkylthio group include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, and n-octylthio.
Preferred examples of the substituent aliphatic acylthio group include acetylthio, propionylthio, butanoylthio, pentanoylthio, hexanoylthio, heptanoylthio, and octanoylthio.
The quinolinyl or isoquinolinyl group may have any number of substituents as long as the desired effect will not be impaired. The quinolinyl or isoquinolinyl group preferably has one or more and four or less substituents, more preferably one or two substituents, and even more preferably one substituent.
The quinolinyl or isoquinolinyl group may have two or more substituents different from one another.
The 2-substituted benzothiazolyl group of RA01 has, at position 2, a group represented by —S-RAO. The 2-substituted benzothiazolyl group of RA01 may have a substituent other than the group represented by —S—RA0 at a position other than position 2. RA0 is a hydrogen atom, a radically polymerizable group-containing group, or a cationically polymerizable group-containing group. The radically polymerizable group-containing group and the cationically polymerizable group-containing group will be described later.
Preferred examples of the 2-substituted benzothiazolyl group include the groups shown below.
The 2-substituted benzothiazolyl group of RA01 may have a substituent, examples of which are the same as those of the substituent that the quinolinyl or isoquinolinyl group may have.
The 2-substituted benzothiazolyl group may have any number of substituents as long as the desired effect will not be impaired. The 2-substituted benzothiazolyl group preferably has one or two substituents, more preferably one substituent.
The 2-substituted benzothiazolyl group may have two or more substituents different from one another.
RA02 and RA03 are both aromatic ring-containing groups having a radically polymerizable group-containing group or both aromatic ring-containing groups having a cationically polymerizable group-containing group.
In this regard, the —NH— groups bonded to the triazine ring are bonded to the aromatic rings in RA02 and RA3, respectively.
The aromatic ring-containing group of RA02 or RA03 may have a radically or cationically polymerizable group-containing group bonded at any position.
The aromatic ring-containing group of RA02 may have any number of radically or cationically polymerizable group-containing groups. The aromatic ring-containing group of RA03 may also have any number of radically or cationically polymerizable group-containing groups. The aromatic ring-containing group of RA02 or RA03 preferably has one, two, or three radically or cationically polymerizable group-containing groups, more preferably one or two radically or cationically polymerizable group-containing groups, even more preferably one radically or cationically polymerizable group-containing group.
The aromatic ring-containing group of RA02 or RA03 may have only one monocyclic aromatic ring or only one fused aromatic ring or may have two or more monocyclic aromatic rings and/or two or more fused aromatic rings. In a case where the aromatic ring-containing group of RA02 or RA03 has two or more monocyclic aromatic rings and/or two or more fused aromatic rings, any type of linking group may be used to link the monocyclic aromatic rings, to link the fused aromatic rings, or to link the monocyclic aromatic ring and the fused aromatic ring. The linking group may be divalent, trivalent, or polyvalent. Preferably, the linking group is divalent.
Examples of the divalent linking group include a divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group, —CONH—, —NH—, —N═N—, —CH═N—, —COO—, —O—, —CO—, —SO—, —SO2—, —S—, —S—S—, and a combination of two or more of these groups.
The divalent linking group is also preferably a group represented by —CRa001Ra002—, Ra001 and Ra002 are each independently a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a halogenated alkyl group having 1 or more and 4 or less carbon atoms. Ra001 and Ra002 may be bonded to each other to form a ring. Examples of the group represented by —CRa001Ra002— include methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, cyclopentylidene, cyclohexylidene, and cycloheptylidene.
The aromatic ring-containing group of RA02 or RA03 has a radically or cationically polymerizable group-containing group. The radically or cationically polymerizable group-containing group may be as mentioned above.
Preferred examples of the radically polymerizable group-containing group include groups of Formulae (A-I) and (A-II) below, excluding vinyloxy group-containing groups.
In Formulae (A-I) and (A-II), R01 is an alkenyl group having 2 or more and 10 or less carbon atoms, R02 is an alkylene group having 1 or more and 10 or less carbon atoms, A01 is —O—, —S—, —CO—, —CO—O—, —CO—S—, —O—CO—, —S—CO—, —CO—NH—, —NH—CO—, or —NH—, A02 is —O—, —S—, —CO—, —CO—O—, —CO—S—, —O—CO—, —S—CO—, —CO—NH—, —NH—CO—, or —NH—, and na is 0 or 1.
Preferred examples of the radically polymerizable group-containing group include the following groups:
Preferred examples of the cationically polymerizable group-containing group include a vinyloxy group and groups of Formulae (A3) to (A8) below.
In Formulae (A3) to (A8), R02 is an alkylene group having 1 or more and 10 or less carbon atoms, R04 is an epoxyalkyl group having 2 or more and 20 or less carbon atoms or an alicyclic epoxy group having 3 or more and 20 or less carbon atoms, R05 is an alicyclic epoxy group having 3 or more and 20 or less carbon atoms, R06 is a vinyl group, R07 is an alkylene group having 1 or more and 10 or less carbon atoms, A01 is —O—, —S—, —CO—, —CO—O—, —CO—S—, —O—CO—, —S—CO—, —CO—NH—, —NH—CO—, or —NH—, A03 is —O— or —NH—, and nb is 0 or 1.
Preferred examples of the cationically polymerizable group-containing group include groups represented by the following:
In a case where the aromatic ring-containing group of RA02 or RA03 has a single radically or cationically polymerizable group-containing group, preferred examples of RA02 or RA03 include groups of the formulae shown below. In the formulae below, PG is a radically or cationically polymerizable group-containing group.
Preferred examples of the compound of Formula (A1) include compounds of the formulae shown below. In the formulae below, XA is a group selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylthio group, a 3-(meth) acryloyloxy-2-hydroxy-n-propyloxycarbonyl group, and a glycidyloxy group.
The compound of Formula (A-1a) may be produced by any suitable method. Typically, the compound of Formula (A-1a) may be produced by allowing a cyanuric halide, such as cyanuric chloride, to react with aromatic amines represented by RA01—NH2, RA02—NH2, and RA03—NH2. These amines may be allowed to react simultaneously or sequentially with the cyanuric halide. Preferably, these amines are allowed to react sequentially with the cyanuric halide.
RA02 or RA03 in Formula (A1) may be formed by a process including: allowing the cyanuric halide to react with an aromatic amine having a functional group, such as hydroxyl, mercapto, carboxy, or amino; and then allowing the functional group to react with a compound for forming a radically or cationically polymerizable group-containing group. The compound for forming a radically or cationically polymerizable group-containing group may be a polymerizable group-containing compound, such as (meth)acrylic acid, (meth)acrylic acid halide, halogenated olefin, epichlorohydrin, or glycidyl (meth)acrylate.
The reaction of the functional group, such as hydroxyl, mercapto, carboxy, or amino, with the polymerizable group-containing compound may be a well-known reaction for forming an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, or a thioether bond.
The reaction for forming the radically or cationically polymerizable group-containing group may be a multi-stage reaction. For example, a radically polymerizable group-containing group of the formula below may be introduced onto an aromatic ring by a process including: allowing the cyanuric halide to react with an aromatic amine having a phenolic hydroxyl group; then allowing the phenolic hydroxyl group to react with epichlorohydrin to form a glycidyl group; and then allowing acrylic acid to react with the glycidyl group.
The above reaction is a mere example, and the radically or cationically polymerizable group-containing group may be formed by any suitable combination of various reactions.
The compound of Formula (A-1a) is usually synthesized in an organic solvent. Such an organic solvent may be any inert solvent that does not react with the cyanuric halide, the aromatic amines, the radically polymerizable group, or the cationically polymerizable group. Such a solvent may be any of organic solvent examples listed for the solvents (S).
For the production of the compound of Formula (A-1a), the cyanuric halide may be allowed to react at any suitable temperature with aromatic amines, such as the aromatic amines represented by RA01—NH2, RA02—NH2, and RA03—NH2. Typically, the reaction temperature is preferably 0° C. or more and 150° C. or less.
Other preferred examples of the compound of Formula (A-1) include compounds of Formula (A-1b) below.
In Formula (A-1b), RA11, RA12, and RA13 are each an aromatic ring-containing group, and at least one of RA2 or RA13 is a group of Formula (A-1b-1) below.
The —NH— groups bonded to the triazine ring are bonded to the aromatic rings in RA11, RA12, and RA13, respectively. In Formula (A-1b-1), Ra11 and Ra12 are each independently an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom,
As defined above, in Formula (A-1b), RA11, RA12, and RA13 are each an aromatic ring-containing group. In Formula (A-1b), the —NH— groups bonded to the triazine ring are bonded to the aromatic rings in RA11, RA12, and RA13, respectively. When the aromatic ring-containing group is a group other than the group of Formula (A-1b-1), the aromatic ring-containing group may be any type satisfying the requirements specified above.
Such an aromatic ring-containing group other than the group of Formula (A-1b-1) may have only one monocyclic aromatic ring or only one fused aromatic ring or may have two or more monocyclic aromatic rings and/or two or more fused aromatic rings. In a case where the aromatic ring-containing group has two or more monocyclic aromatic rings and/or two or more fused aromatic rings, any linking group may be used to link the monocyclic aromatic rings, to link the fused aromatic rings, or to link the monocyclic aromatic ring and the fused aromatic ring. The linking group may be divalent, trivalent, or polyvalent. Preferably, the linking group is divalent.
Examples of the divalent linking group include a divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group, —CONH—, —NH—, —N═N—, —CH═N—, —COO—, —O—, —CO—, —SO—, —SO2—, —S—, —S—S—, and any combination of two or more of these groups.
Preferred examples of the aromatic ring-containing group include an optionally substituted quinolinyl group, an optionally substituted isoquinolinyl group, and an optionally substituted 2-substituted benzothiazolyl group. Examples of these groups are the same as those of the optionally substituted quinolinyl, isoquinolinyl, and 2-substituted benzothiazolyl groups described for RA01 in Formula (A-1a).
Other preferred examples of the aromatic ring-containing group include optionally substituted phenyl, optionally substituted naphthyl, optionally substituted biphenylyl, optionally substituted phenylthiophenyl, optionally substituted phenoxyphenyl, optionally substituted phenylsulfonylphenyl, optionally substituted benzothiazolyl, optionally substituted benzoxazolyl, and optionally substituted terphenyl.
Examples of the optional substituent of these groups are the same as those of the substituent that the quinolinyl or isoquinolinyl group may have. These groups may have two or more substituents different from one another.
Preferred examples of the optionally substituted phenyl group include phenyl, 4-cyanophenyl, 3-cyanophenyl, 2-cyanophenyl, 2,3-dicyanophenyl, 2,4-dicyanophenyl, 2,5-dicyanophenyl, 2,6-dicyanophenyl, 3,4-dicyanophenyl, 3,5-dicyanophenyl, 4-nitrophenyl, 3-nitrophenyl, 2-nitrophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-iodophenyl, 3-iodophenyl, 2-iodophenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-methylphenyl, 3-methylphenyl, and 2-methylphenyl.
Preferred examples of the optionally substituted naphthyl group include naphthalen-1-yl and naphthalen-2-yl.
Preferred examples of the optionally substituted biphenylyl group include 4-phenylphenyl, 3-phenylphenyl, 2-phenylphenyl, 4-(4-nitrophenyl)phenyl, 3-(4-nitrophenyl)phenyl, 2-(4-nitrophenyl)phenyl, 4-(4-cyanophenyl)phenyl, 3-(4-cyanophenyl)phenyl, and 2-(4-cyanophenyl)phenyl.
Preferred examples of the optionally substituted phenylthiophenyl group include 4-phenylthiophenyl, 3-phenylthiophenyl, and 2-phenylthiophenyl.
Preferred examples of the optionally substituted phenoxyphenyl group include 4-phenoxyphenyl, 3-phenoxyphenyl, and 2-phenoxyphenyl.
Preferred examples of the optionally substituted phenylsulfonylphenyl group include 4-phenylsulfonylphenyl, 3-phenylsulfonylphenyl, and 2-phenylsulfonylphenyl.
Preferred examples of the optionally substituted benzothiazolyl group include benzothiazol-2-yl, benzothiazol-4-yl, benzothiazol-5-yl, benzothiazol-6-yl, and benzothiazol-7-yl.
Preferred examples of the optionally substituted benzoxazolyl group include benzoxazol-2-yl, benzoxazol-4-yl, benzoxazol-5-yl, benzoxazol-6-yl, and benzoxazol-7-yl.
Preferred examples of the optionally substituted terphenyl group include 4-(4-phenylphenyl)phenyl, 3-(4-phenylphenyl)phenyl, 2-(4-phenylphenyl)phenyl, 4-(3-phenylphenyl)phenyl, 3-(3-phenylphenyl)phenyl, 2-(3-phenylphenyl)phenyl, 4-(2-phenylphenyl)phenyl, 3-(2-phenylphenyl)phenyl, and 2-(2-phenylphenyl)phenyl.
As mentioned above, the aromatic ring-containing group other than the group of Formula (A-1b-1) may have a radically or cationically polymerizable group-containing group as a substituent.
The aromatic ring-containing group may have a radically or cationically polymerizable group-containing group bonded at any position.
The aromatic ring-containing group may have any number of radically or cationically polymerizable group-containing groups. The aromatic ring-containing group preferably has one, two, or three radically or cationically polymerizable group-containing groups, more preferably one or two radically or cationically polymerizable group-containing groups, even more preferably one radically or cationically polymerizable group-containing group.
Preferred examples of the aromatic ring-containing group having one radically or cationically polymerizable group-containing group include groups of the formulae shown below. In the formulae below, PG is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
In Formula (A-1b), at least one of RA12 or RA13 is a group of Formula (A-1b-1):
In Formula (A-1b-1), Ra11 and Ra12 are each independently an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, nA1 and nA2 are each independently an integer of 0 or more and 4 or less, Ra13 and Ra14 are each independently a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, a halogenated alkyl group having 1 or more and 4 or less carbon atoms, or a phenyl group, Ra3 and Ra4 may be bonded to each other to form a ring, Ra14 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group, and when RA12 and RA13 are both groups of Formula (A-1b-1), RA12 and RA13 both have radically polymerizable group-containing groups or cationically polymerizable group-containing groups.
The alkyl group of Ra11 or R12 having 1 or more and 4 or less carbon atoms may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.
The alkoxy group of Ra11 or Ra12 having 1 or more and 4 or less carbon atoms may be methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, or tert-butyloxy.
The halogen atom of Ra11 or Ra12 may be fluorine, chlorine, bromine, or iodine.
Examples of the alkyl group of Ra13 or Ra14 having 1 or more and 4 or less carbon atoms are the same as those of the alkyl group of Ra11 or Ra12 having 1 or more and 4 or less carbon atoms.
Examples of the halogenated alkyl group of Ra13 or Ra14 having 1 or more and 4 or less carbon atoms include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 3,3,3-trifluoroethyl, pentafluoroethyl, and heptafluoropropyl.
Preferred examples of the group of Formula (A-1b-1) include groups of the formulae shown below.
The group of Formula (A-1b-1) has a radically or cationically polymerizable group-containing group represented by RA14. The radically or cationically polymerizable group-containing group is as described above.
Preferred examples of the radically polymerizable group-containing group and preferred examples of the cationically polymerizable group-containing group are the same as those shown for the compound of Formula (A1-a).
Preferred examples of the compound of Formula (A-1b) include compounds of the formulae shown below. In the formulae below, XA is a group selected from the group consisting of (meth)acryloyloxy, (meth)acryloylthio, 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl, and glycidyloxy, and YA is a group selected from the group consisting of quinolin-3-yl, phenyl, 4-cyanophenyl, 3-cyanophenyl, 2-cyanophenyl, 3,4-dicyanophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-phenylthiophenyl, 4-phenylsulfonylphenyl, 4-iodophenyl, benzothiazol-2-yl, 2-mercaptobenzothiazol-5-yl, 4-phenylphenyl, 4-(4-nitrophenyl)phenyl, 4-(4-cyanophenyl)phenyl, naphthalen-1-yl, and 4-(4-phenylphenyl)phenyl.
The compound of Formula (A-1b) may be produced by any suitable method. Typically, the compound of Formula (A-1b) may be produced by allowing a cyanuric halide, such as cyanuric chloride, to react with aromatic amines represented by RA11—NH2, RA12—NH2, and RA13—NH2. These amines may be allowed to react simultaneously or sequentially with the cyanuric halide. Preferably, these amines are allowed to react sequentially with the cyanuric halide.
The aromatic ring-containing group bonded to the triazine ring via —NH— may have a radically or cationically polymerizable group-containing group. Such a radically or cationically polymerizable group-containing group may be formed by a process including: allowing the cyanuric halide to react with an aromatic amine having a functional group, such as hydroxyl, mercapto, carboxy, or amino; and then allowing the functional group to react with a compound for forming a radically or cationically polymerizable group-containing group. The compound for forming a radically or cationically polymerizable group-containing group may be a polymerizable group-containing compound, such as (meth)acrylic acid, (meth)acrylic acid halide, halogenated olefin, epichlorohydrin, or glycidyl (meth)acrylate.
The reaction of the functional group, such as hydroxyl, mercapto, carboxy, or amino, with the polymerizable group-containing compound may be a well-known reaction for forming an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, or a thioether bond.
The reaction for forming the radically or cationically polymerizable group-containing group may be a multi-stage reaction. For example, a radically polymerizable group-containing group of the formula below may be introduced onto an aromatic ring by a process including: allowing the cyanuric halide to react with an aromatic amine having a phenolic hydroxyl group; then allowing the phenolic hydroxyl group to react with epichlorohydrin to form a glycidyl group; and then allowing acrylic acid to react with the glycidyl group.
The above reaction is a mere example, and the radically or cationically polymerizable group-containing group may be formed by any suitable combination of various reactions.
The compound of Formula (A-1b) is usually synthesized in an organic solvent. Such an organic solvent may be any inert solvent that does not react with the cyanuric halide, the aromatic amines, the radically polymerizable group, or the cationically polymerizable group. Such a solvent may be any of organic solvent examples listed for the solvents (S).
For the production of the compound of Formula (A-1b), the cyanuric halide may be allowed to react at any suitable temperature with aromatic amines, such as the aromatic amines represented by RA-NH2, RA22—NH2, and RA13—NH2. Typically, the reaction temperature is preferably 0° C. or more and 150° C. or less.
The content of the photopolymerizable compound (A) in the photocurable composition may be any level as long as the desired effect will not be impaired. The content of the photopolymerizable compound (A) in the photocurable composition is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0.5 parts by mass or more and 40 parts by mass or less, even more preferably 1 part by mass or more and 25 parts by mass or less, based on the mass calculated by subtracting the mass of the solvents (S) described later from the mass of the photocurable composition, which corresponds to 100 parts by mass.
The photocurable composition contains metal oxide fine particles (B). The metal oxide fine particles (B) may include any type of metal oxide that does not compromise the desired effect. Preferred examples of the metal oxide fine particles (B) are at least one type of particles selected from the group consisting of zirconium oxide fine particles, titanium oxide fine particles, barium titanate fine particles, and cerium oxide fine particles. In the photocurable composition, the metal oxide fine particles (B) may include a single type of particles or a combination of two or more types of particles selected from the above group.
The photocurable composition containing the metal oxide fine particles (B) of the above type can form a cured product with a high refractive index.
To form cured products with transparency, the metal oxide fine particles (B) preferably have an average particle size of 500 nm or less or preferably has an average particle size of 2 nm or more and 100 nm or less.
The metal oxide fine particles (B) preferably have surfaces modified with an ethylenically unsaturated double bond-containing group.
When the metal oxide fine particles (B) have surfaces modified with an ethylenically unsaturated double bond-containing group, the process of forming a cured product from the photocurable composition will allow the photopolymerizable compound (A) to be polymerized together with the metal oxide fine particles (B) so that the metal oxide nanoparticles (B) can be fixed in the photopolymerizable compound (A) polymer matrix. This will make the metal oxide fine particles (B) less likely to aggregate. Thus, in particular, when the metal oxide fine particles (B) have surfaces modified with an ethylenically unsaturated double bond-containing group, the photocurable composition can easily form a cured product with less localized metal oxide fine particles (B).
For example, an ethylenically unsaturated double bond-containing capping agent may be allowed to react with the surfaces of the metal oxide fine particles (B) to form ethylenically saturated double bond-containing group-modified metal oxide fine particles (B), which have a chemical bond, such as a covalent bond, between their surfaces and the ethylenically saturated double bond-containing group.
Any suitable method may be used to bond the ethylenically unsaturated double bond-containing capping agent to the surfaces of the metal oxide fine particles (B) via a chemical bond, such as a covalent bond. In general, the surfaces of the metal oxide fine particles (B) have hydroxyl groups. The reactive group of the capping agent may be allowed to react with such hydroxyl groups so that the capping agent can be covalently bonded to the surfaces of the metal oxide fine particles (B).
Preferred examples of the reactive group of the capping agent include trialkoxysilyl groups, such as trimethoxysilyl and triethoxysilyl; dialkoxysilyl groups, such as dimethoxysilyl and diethoxysilyl; monoalkoxysilyl groups, such as monomethoxysilyl and monoethoxysilyl; trihalosilyl groups, such as trichlorosilyl; dihalosilyl groups, such as dichlorosilyl; monohalosilyl groups, such as monochlorosilyl; carboxy groups; halocarbonyl groups, such as chlorocarbonyl; a hydroxyl group; a phosphono group (—P(═O) (OH)2); and a phosphate group (—O—P(═O) (OH)2).
The trialkoxysilyl, dialkoxysilyl, monoalkoxysilyl, trihalosilyl, dihalosilyl, or monohalosilyl group will form a siloxane bond with the surfaces of the metal oxide nanoparticles (B).
The carboxy or halocarbonyl group will form a bond represented by “metal oxide-O—CO—” with the surfaces of the metal oxide nanoparticles (B).
The hydroxyl group will form a bond represented by “metal oxide-O—” with the surfaces of the metal oxide fine particles (B).
The phosphono or phosphate group will form a bond represented by “metal oxide-O—P(═O)<” with the surfaces of the metal oxide fine particles (B).
The capping agent may have a group bonded to the reactive group. Such a group may include a hydrogen atom or any organic group. Such an organic group may contain a heteroatom, such as O, N, S, P, B, Si, or halogen.
The group bonded to the reactive group may be an alkyl group that may be linear or branched and may be interrupted by an oxygen atom (—O—); an alkenyl group that may be linear or branched and may be interrupted by an oxygen atom (—O); an alkynyl group that may be linear or branched and may be interrupted by an oxygen atom (—O—); a cycloalkyl group; an aromatic hydrocarbon group; or a heterocyclic group.
These groups may be substituted with a substituent, such as a halogen atom, an epoxy-containing group, such as glycidyl, a hydroxyl group, a mercapto group, an amino group, a (meth)acryloyl, or an isocyanate group. These groups may have any number of substituents.
The group bonded to the reactive group is also preferably a group represented by —(SiRb1Rb2—O—)r—(SiRb3Rb4—O—)s—Rb5. Rb1, Rb2, Rb3, and Rb4 may be the same organic group or different organic groups. Preferred examples of the organic group include alkyl groups, such as methyl and ethyl; alkenyl groups, such as vinyl and allyl; aromatic hydrocarbon groups, such as phenyl, naphthyl, and tolyl; epoxy-containing groups, such as 3-glycidoxypropyl; and a (meth)acryloyloxy group.
In the formula, Rb5 may be, for example, —Si(CH3)3, —Si(CH3)2H, —Si(CH3)2(CH═CH2), —Si(CH3)2(CH2CH2CH2CH3), or any other terminal group.
In the formula, r and s are each independently an integer of 0 or more and 60 or less. In the formula, r and s are not simultaneously 0.
Preferred 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, and 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; and (meth)acrylic acid halides, such as (meth)acrylic acid chloride.
The capping agent may be used in any suitable amount to form a chemical bond, such as a covalent bond, on the surfaces of the metal oxide fine particles (B). Preferably, the capping agent is used in a sufficient amount to react with almost all the hydroxyl groups on the surfaces of the metal oxide fine particles (B).
The content of the metal oxide fine particles (B) in the photocurable composition may be any level as long as the object of the present invention will not be compromised. The content of the metal oxide nanoparticles (B) in the photocurable composition is preferably 5 mass % or more and 95 mass % or less, more preferably 35 mass % or more and 93 mass % or less, even more preferably 40 mass % or more and 90 masse or less, based on the mass calculated by subtracting the mass of the solvents (S) from the mass of the photocurable composition.
The photocurable composition with the content of the metal oxide fine particles (B) falling within the above range can easily form a high-refractive-index, cured product with less localized metal oxide fine particles (B).
In particular, to form high-refractive-index cured products, the photocurable composition preferably has a metal oxide fine particle (B) content of 70 mass % or more, more preferably 70 mass % or more and 95 mass % or less, even more preferably 70 mass % or more and 90 mass % or less, based on the mass calculated by subtracting the mass of the solvents (S) from the mass of the photocurable composition. In another embodiment, the content of the metal oxide fine particles (B) in the photocurable composition may have a lower limit of 65 mass % or more.
In this regard, when the surfaces of the metal oxide fine particles (B) are modified with an ethylenically unsaturated double bond-containing group, the mass of the capping agent having the ethylenically unsaturated double bond-containing group on the surfaces of the metal oxide fine particles (B) should be counted into the mass of the metal oxide fine particles (B).
The photocurable composition contains an initiating agent (C) for curing the photopolymerizable compound (A). When the photopolymerizable compound (A) has a radically polymerizable group, a radical polymerization initiating agent (C1) may be used as the initiating agent (C). When the photopolymerizable compound (A) has a cationically polymerizable group, a cationic polymerization initiating agent (C2) may be used as the initiating agent (C). The initiating agent (C) may be a photo-initiating agent, which allows regioselective curing of the photocurable composition and can be used without any concern about, for example, heat-induced degradation, volatilization, or sublimation of components of the photocurable composition.
The initiating agent (C) may be any of various conventionally-known polymerization initiating agents.
A photo-radical polymerization initiating agent is useful as the radical polymerization initiating agent (C1). Examples of such a photo-radical polymerization initiating agent include 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, 0-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 0-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 4-benzoyl-4′-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamyl benzoate, benzyl-D-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 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, benzil, 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-methoxytriazine, 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, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. These photo-radical polymerization initiating agents may be used alone, or two or more of these photo-radical polymerization initiating agents may be used in combination.
In particular, in view of the sensitivity of the photocurable composition, the photo-radical polymerization initiating agent is preferably an oxime ester compound.
Such an oxime ester compound is preferably a compound having a partial structure of Formula (c1) below.
In Formula (c1), n1 is 0 or 1, Rc2 is a monovalent organic group, Rc3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, or an optionally substituted aryl group, and * indicates a bond.
The compound having a partial structure of 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 of Formula (c1) preferably has one or two partial structures of Formula (c1).
The compound having a partial structure of Formula (c1) may be a compound of Formula (c2) below.
In Formula (c2), Rc1 is a group of Formula (c3), (c4), or (c5) below, n1 is 0 or 1, Rc2 is a monovalent organic group, and Rc3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, or an optionally substituted aryl group.
In Formula (c3), Rc4 and Rc5 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, two or more Rc5s may be the same or different and may be bonded together to form a ring, and * indicates a bond.
In Formula (c4), Rc6 and Rc7 are each independently an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic organic group, or a hydrogen atom, Rc6 and Rc7 may be bonded to each other to form a ring, Rc7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring, Rc1 is a nitro group or a monovalent organic group, n3 is an integer of 0 or more and 4 or less, and * indicates a bond.
In Formula (c5), Rc9 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, and * indicates a bond.
In Formula (c3), Rc4 is a monovalent organic group. Rc4 may be selected from various organic groups that do not compromise the object of the present invention. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of Rc4 include an optionally substituted alkyl group having 1 or more and 20 or less carbon atoms, an optionally substituted cycloalkyl group having 3 or more and 20 or less carbon atoms, an optionally substituted saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, an optionally substituted alkoxycarbonyl group having 2 or more and 20 or less carbon atoms, an optionally substituted phenyl group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 or more and 20 or less carbon atoms, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthylalkyl group having 11 or more and 20 or less carbon atoms, an optionally substituted heterocyclyl group, and an optionally substituted heterocyclylcarbonyl group.
In particular, Rc4 is preferably an alkyl group having 1 or more and 20 or less carbon atoms. The alkyl group may be linear or branched. In order for the compound of Formula (c3) to have good solubility in the photocurable composition, the alkyl group of Rc4 preferably has 2 or more carbon atoms, more preferably 5 or more carbon atoms, even more preferably 7 or more carbon atoms. In order for the compound of Formula (c3) to have good compatibility with other components in the photocurable composition, the alkyl group of Rc4 preferably has 15 or less carbon atoms, more preferably 10 or less carbon atoms.
When Rc4 has a substituent, preferred examples of the substituent include a hydroxyl group, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, an aliphatic acyl group having 2 or more and 20 or less carbon atoms, an aliphatic acyloxy group having 2 or more and 20 or less carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by —PO(OR)2 (where R is an alkyl group having 1 or more and 6 or less carbon atoms), a halogen atom, a cyano group, and a heterocyclyl group.
The heterocyclyl group of Rc4 may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The heterocyclyl group of Rc4 may also be a five- or six-membered monocyclic ring containing one or more N, S, or O atoms, or a heterocyclyl group including such monocyclic rings fused together or including such a monocyclic ring and a benzene ring fused together. When the heterocyclyl group is a fused ring, it should have up to three rings. The heterocyclic ring constituting the heterocyclyl group may be 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, or tetrahydrofuran.
The heterocyclyl group of Rc4 may have a substituent, such as a hydroxyl group, an alkoxy group having 1 or more and 6 or less carbon atoms, a halogen atom, a cyano group, or a nitro group.
Preferred examples of Rc4 described above include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl.
In order for the compound of Formula (c3) to have good solubility in the photocurable composition, Rc4 is preferably n-octyl or 2-ethylhexyl, more preferably 2-ethylhexyl.
In Formula (c3), Rc5 is a monovalent organic group. Rc5 may be selected from various organic groups that do not compromise the object of the present invention. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the monovalent organic group of Rc5 include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzoyl, optionally substituted phenoxycarbonyl, optionally substituted benzoyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthoxy, optionally substituted naphthoyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthoyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclyl, optionally substituted heterocyclylcarbonyl, amino substituted with one or two organic groups, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano, and a substituent containing a group represented by HX2C— or H2XC—, where Xs are each independently a halogen atom.
The alkyl group of Rc5 preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. The alkyl group of Rc5 may be linear or branched. Examples of the alkyl group of Rc5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. The alkyl group of Rc5 may have a carbon chain containing an ether bond (—O—). Examples of the alkyl group having an ether bond-containing carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.
The alkoxy group of Rc5 preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. The alkoxy group of Rc5 may be linear or branched. Examples of the alkoxy group of RCS include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. The alkoxy group of Rc5 may have a carbon chain containing an ether bond (—O—). Examples of the alkoxy group having an ether bond-containing carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.
The cycloalkyl or cycloalkoxy group of Rc5 preferably has 3 or more and 10 or less carbon atoms, more preferably 3 or more and 6 or less carbon atoms. Examples of the cycloalkyl group of Rc5 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the cycloalkoxy group of Rc5 include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
The saturated aliphatic acyl or acyloxy group of RCS preferably has 2 or more and 21 or less carbon atoms, more preferably 2 or more and 7 or less carbon atoms. Examples of the saturated aliphatic acyl group of Rc5 include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. Examples of the saturated aliphatic acyloxy group of Rc5 include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2,2-dimethylpropanoyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-dodecanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.
The alkoxycarbonyl group of Rc5 preferably has 2 or more and 20 or less carbon atoms, more preferably 2 or more and 7 or less carbon atoms. Examples of the alkoxycarbonyl group of Rc5 include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.
The phenylalkyl group of Rc5 preferably has 7 or more and 20 or less carbon atoms, more preferably 7 or more and 10 or less carbon atoms. The naphthylalkyl group of Rc5 preferably has 11 or more and 20 or less carbon atoms, more preferably 11 or more and 14 or less carbon atoms. Examples of the phenylalkyl group of Rc5 include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Examples of the naphthylalkyl group of Rc5 include α-naphthylmethyl, S-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(S-naphthyl)ethyl. The phenylalkyl or naphthylalkyl group of Rc5 may further have a substituent on the phenyl or naphthyl group.
The heterocyclyl group of Rc5 may further have a substituent as in the case of the heterocyclyl group of Rc4 in Formula (c3).
Examples of the heterocyclyl group in the heterocyclylcarbonyl group of Rc5 are the same as those of the heterocyclyl group of Rc5.
When Rc5 is an amino group substituted with one or two organic group, preferred examples of the organic group include alkyl having 1 or more and 20 or less carbon atoms, cycloalkyl having 3 or more and 10 or less carbon atoms, saturated aliphatic acyl having 2 or more and 21 or less carbon atoms, optionally substituted phenyl, optionally substituted benzoyl, optionally substituted phenylalkyl having 7 or more and 20 or less carbon atoms, optionally substituted naphthyl, optionally substituted naphthoyl, optionally substituted naphthylalkyl having 11 or more and 20 or less carbon atoms, and heterocyclyl. Preferred examples of the organic group are the same as those for Rc5. Examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propanoylamino, n-butanoylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α-naphthoylamino, and α-naphthoylamino.
The phenyl, naphthyl, or heterocyclyl group in Rc5 may further have a substituent. Such a substituent may be a substituent containing a group represented by HX2C— or H2XC— (e.g., a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, a halogenated alkyl group containing a group represented by HX2C— or H2XC—), alkyl having 1 or more and 6 or less carbon atoms, alkoxy having 1 or more and 6 or less carbon atoms, saturated aliphatic acyl having 2 or more and 7 or less carbon atoms, alkoxycarbonyl having 2 or more and 7 or less carbon atoms, saturated aliphatic acyloxy having 2 or more and 7 or less carbon atoms, monoalkylamino having alkyl of 1 or more and 6 or less carbon atoms, dialkylamino having alkyl of 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazin-1-yl, benzoyl, halogen, nitro, or cyano. The phenyl, naphthyl, or heterocyclyl group in Rc5 may further have any number of substituents as long as the object of the present invention will not be compromised. Preferably, the phenyl, naphthyl, or heterocyclyl group in Rc5 has one or more and four or less substituents. The phenyl, naphthyl, or heterocyclyl group in Rc5 may have two or more substituents the same as or different from one another.
The benzoyl group in Rc5 may further has a substituent. Such a substituent may be alkyl having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazin-1-yl, 2-thenoyl (thiophen-2-ylcarbonyl), furan-3-ylcarbonyl, or phenyl.
The halogen atom represented by X may be fluorine, chlorine, or bromine, and is preferably fluorine.
The substituent containing a group represented by HX2C— or H2XC— may be a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, a group having a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, a halogenated alkyl group containing a group represented by HX2C— or H2XC—, or a group having a halogenated alkyl group containing a group represented by HX2C— or H2XC—, and is more preferably a halogenated alkoxy group containing a group represented by HX2C— or H2XC— or a group having a halogenated alkoxy group containing a group represented by HX2C— or H2XC—.
The group having a halogenated alkyl group containing a group represented by HX2C— or H2XC— may be an aromatic group (e.g., phenyl, naphthyl) substituted with a halogenated alkyl group containing a group represented by HX2C— or H2XC— or a cycloalkyl group (e.g., cyclopentyl, cyclohexyl) substituted with a halogenated alkyl group containing a group represented by HX2C— or H2XC—, and is preferably an aromatic group substituted with a halogenated alkyl group containing a group represented by HX2C— or H2XC—.
The group having a halogenated alkoxy group containing a group represented by HX2C— or H2XC— may be an aromatic group (e.g., phenyl, naphthyl) substituted with a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl) substituted with a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, or a cycloalkyl group (e.g., cyclopentyl, cyclohexyl) substituted with a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, and is preferably an aromatic group substituted with a halogenated alkoxy group containing a group represented by HX2C— or H2XC—.
Rc5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The phenoxyalkyl or phenylthioalkyl group may have the same substituent as the phenyl group in Rc5 may have.
The monovalent organic group of Rc5 is preferably alkyl, cycloalkyl, optionally substituted phenyl, cycloalkylalkyl, or phenylthioalkyl optionally having a substituent on the aromatic ring. The alkyl group is preferably alkyl having 1 or more and 20 or less carbon atoms, more preferably alkyl having 1 or more and 8 or less carbon atoms, even more preferably alkyl having 1 or more and 4 or less carbon atoms, most preferably methyl. The optionally substituted phenyl group is preferably methylphenyl, more preferably 2-methylphenyl. The cycloalkyl group in the cycloalkylalkyl group preferably has 5 or more and 10 or less carbon atoms, more preferably 5 or more and 8 or less carbon atoms, even more preferably 5 or 6 carbon atoms. The alkylene group in the cycloalkylalkyl group preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more and 4 or less carbon atoms, even more preferably 2 carbon atoms. The cycloalkylalkyl group is preferably cyclopentylethyl. The alkylene group in the phenylthioalkyl group optionally having a substituent on the aromatic ring preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more and 4 or less carbon atoms, even more preferably 2 carbon atoms. The phenylthioalkyl group optionally having a substituent on the aromatic ring is preferably 2-(4-chlorophenylthio)ethyl.
The group of Formula (c3) may have two or more Rc5s that are bonded together to form a ring, such as a hydrocarbon ring or a heterocyclic ring. The heteroatom in the heterocyclic ring may be, for example, N, O, or S. In particular, the ring formed by two or more Rc5s bonded together is preferably an aromatic ring. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic ring is preferably an aromatic hydrocarbon ring. Examples of the group of Formula (c3) having two or more Rc5s bonded together to form a benzene ring are shown below.
In the group of Formula (c4), Rc8 is a nitro group or a monovalent organic group. Rc8 on the fused ring in Formula (c4) is bonded to a six-membered aromatic ring different from the aromatic ring to which the group represented by —(CO)n1— is bonded. In Formula (c4), Rc8 may be bonded at any position. When the group of Formula (c4) has one or more Rc8s, one Rc8 should preferably be bonded at position 7 of the fluorene skeleton for ease of synthesis of the compound of Formula (c2). In other words, when the group of Formula (c4) has one or more Rc8s, the group of Formula (c4) should preferably be represented by Formula (c6) below. Two or more Rc8s may be the same or different.
In Formula (c6), Rc6, Rc7, Rc8, and n3 respectively have the same meaning as Rc6, Rc7, Rc8, and n3 in Formula (c4).
Rc9 may be any monovalent organic group that does not compromise the object of the present invention. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the monovalent organic group of Rc8 may be the same as those of the monovalent organic group of Rc5 in Formula (c3).
In Formula (c4), Rc6 and Rc7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic organic group, or a hydrogen atom. Rc6 and Rc7 may be bonded to each other to form a ring. In particular, Rc6 and Rc7 are each preferably an optionally substituted chain alkyl group. The optionally substituted chain alkyl group of Rc6 or Rc7 may be linear or branched.
Rc6 and Rc7 may each be an unsubstituted chain alkyl group. In this case, the chain alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less carbon atoms, even more preferably 1 or more and 6 or less carbon atoms. Examples of the chain alkyl group of Rc6 or Rc7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. The alkyl group of Rc6 or Rc7 may have a carbon chain containing an ether bond (—O—). Examples of the alkyl group having an ether bond-containing carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.
The chain alkyl group of the substituted chain alkyl group of Rc6 or Rc7 preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less carbon atoms, even more preferably 1 or more and 6 or less carbon atoms. In this case, the number of carbon atoms in the substituent should not be counted into the number of carbon atoms in the chain alkyl group. The substituted chain alkyl group is preferably linear.
The alkyl group may have any substituent that does not compromise the object of the present invention. Preferred examples of such a substituent include alkoxy, cyano, a halogen atom, halogenated alkyl, a cyclic organic group, and alkoxycarbonyl. The halogen atom may be fluorine, chlorine, bromine, or iodine. In particular, fluorine, chlorine, or bromine is preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Examples of the cycloalkyl group are the same as those of the cycloalkyl group of Rc8. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl. Examples of the heterocyclyl group are the same as those of the heterocyclyl group of Rc8. The alkoxycarbonyl group of Rc8 may have a linear or branched alkoxy group and preferably has a linear alkoxy group. The alkoxy group in the alkoxycarbonyl group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms.
The chain alkyl group may have any number of substituents. The preferred number of substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
The chain alkoxy group of the unsubstituted chain alkoxy group of Rc6 or Rc7 preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less carbon atoms, even more preferably 1 or more and 6 or less carbon atoms. Examples of the chain alkoxy group of Rc6 or Rc8 include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. The alkoxy group of Rc6 or R may have a carbon chain containing an ether bond (—O—). Examples of the alkoxy group having an ether bond-containing carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.
The chain alkoxy group of Rc6 or Rc7 may have a substituent, examples of which are the same as those of the substituent that the chain alkyl group of Rc6 or Rc7 may have.
The cyclic organic group of Rc6 or Rc7 may be alicyclic or aromatic. The cyclic organic group may be an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclyl group. The cyclic organic group of Rc6 or Rc7 may have a substituent, examples of which are the same as those of the substituent that the chain alkyl group of Rc6 or Rc7 may have.
The aromatic hydrocarbon group of Rc6 or Rc7 is preferably a phenyl group, a group including two or more benzene rings bonded through a carbon-carbon bond, or a group including two or more benzene rings fused together. When the aromatic hydrocarbon group is a phenyl group or a group including two or more benzene rings bonded or fused together, the number of benzene rings in the aromatic hydrocarbon group is preferably, but not limited to, 3 or less, more preferably 2 or less, even more preferably 1. Preferred examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl.
The aliphatic cyclic hydrocarbon group of Rc6 or Rc7 may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is preferably, but not limited to, 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.
Examples of the heterocyclyl group of Rc6 or Rc7 may be the same as those of the heterocyclyl group of Rc5 in Formula (c3).
Rc6 and Rc8 may be bonded to each other to form a ring. The ring group formed by Rc6 and Rc8 is preferably a cycloalkylidene group. The cycloalkylidene group formed by Rc6 and Rc7 bonded together preferably has a five- or six-membered ring, more preferably a five-membered ring.
Rc7 and the benzene ring of the fluorene skeleton may form a ring, which may be an aromatic ring or an aliphatic ring.
The cycloalkylidene group formed by Rc6 and Rc7 bonded together may be fused with one or more other rings. For example, the cycloalkylidene group may be fused with 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, a pyrimidine ring, or any other ring.
In particular, the group of Rc6 or Rc7 described above is preferably, for example, a group represented by the formula -A1-A2. In the formula, A1 is a linear alkylene group, and A2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
The linear alkylene group of A1 preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. The alkoxy group of A2 may be linear or branched, and is preferably linear. The alkoxy group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. The halogen atom represented by A2 is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine, chlorine, or bromine. The halogen atom in the halogenated alkyl group of A2 is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine, chlorine, or bromine. The halogenated alkyl group may be linear or branched, and is preferably linear. Examples of the cyclic organic group of A2 are the same as those of the cyclic organic group that Rc6 or Rc7 may have as a substituent. Examples of the alkoxycarbonyl group of A2 are the same as those of the alkoxycarbonyl group that Rc6 or Rc7 may have as a substituent.
Preferred examples of Rc6 or Rc7 include alkyl groups, such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups, such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups, such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; phenylalkyl groups, such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups, such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; alkoxycarbonylalkyl groups, such as 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl; and halogenated alkyl groups, such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.
In particular, the group of Rc6 or Rc7 is preferably ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, or 3,3,4,4,5,5,5-heptafluoro-n-pentyl.
In Formula (c5), A is preferably S in particular for easy availability of a photopolymerization initiating agent with high sensitivity.
In Formula (c5), Rc9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
The monovalent organic group of Rc9 in Formula (c5) may be selected from various organic groups that do not compromise the object of the present invention. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less. Preferred examples of the organic group of Rc9 in Formula (c5) may be the same as those of the monovalent organic group of Rc5 in Formula (c3).
Rc9 is preferably benzoyl; naphthoyl; benzoyl substituted with a group selected from the group consisting of alkyl having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; nitro; or optionally substituted benzofuranylcarbonyl, and more preferably benzoyl; naphthoyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; or 4-(phenyl)phenylcarbonyl.
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, even more preferably 0 or 1. When n4 is 1, Rc9 is preferably bonded at para position with respect to the bond between the oxygen or sulfur atom and the phenyl group to which Rc9 is bonded.
In Formula (c1) or (c2), the monovalent organic group of Rc2 may be any type as long as the object of the present invention will not be compromised. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less. Preferred examples of the monovalent organic group of Rc2 may be the same as those of the monovalent organic group of Rc5 in Formula (c3). Examples of these groups are the same as those listed for Rc5 in Formula (c3).
Rc2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The phenoxyalkyl or phenylthioalkyl group may have a substituent, examples of which are the same as those of the substituent that the phenyl, naphthyl, or heterocyclyl group in RCS in Formula (c3) may further have.
In particular, the organic group of Rc2 is preferably a substituent containing a group represented by HX2C— or H2XC-shown above, an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The number of carbon atoms in the alkyl group, the optionally substituted phenyl group, or the cycloalkyl group of the cycloalkylalkyl group, the number of carbon atoms in the alkylene group of the cycloalkylalkyl group, or the number of carbon atoms in the cycloalkylalkyl group, the alkylene group of the phenylthioalkyl group optionally having a substituent on the aromatic ring, or the phenylthioalkyl group optionally having a substituent on the aromatic ring may be the same as that in RCS in Formula (c3).
Rc2 is also preferably a group represented by -A3-CO—O-A4. A3 is a divalent organic group, and preferably a divalent hydrocarbon group or an alkylene group. A4 is a monovalent organic group and preferably a monovalent hydrocarbon group.
The alkylene group of A3 may be linear or branched and is preferably linear. The alkylene group of A3 preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms, even more preferably 1 or more and 4 or less carbon atoms.
A4 is preferably, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, or an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms. Preferred examples of A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and R-naphthylmethyl.
Preferred examples of the group represented by -A3-CO—O-A4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.
Rc2 is also preferably a group of Formula (c7) or (c8) below.
In Formulae (c7) and (c8), Rc10 and Rc11 are each independently a monovalent organic group, n5 is an integer of 0 or more and 4 or less, when Rc10 and Rc11 are in adjacent positions on the benzene ring, Rc10 and Rc11 may be bonded to each other to form a ring, Rc2 is a monovalent organic group, n6 is an integer of 1 or more and 8 or less, n7 is an integer of 1 or more and 5 or less, and n8 is an integer of 0 or more and n7+3 or less.
The organic group of Rc10 or Rc11 in Formula (c7) may be the same as Rc8 in Formula (c4). Rc10 is preferably a halogenated alkoxy group containing a group represented by HX2C— or H2XC—, a halogenated alkyl group containing a group represented by HX2C— or H2XC—, an alkyl group, or a phenyl group. Rc10 and Rc11 may be bonded to each other to form a ring, which may be an aromatic ring or an aliphatic ring. The group of Formula (c7) having Rc10 and Rc11 bonded to form a ring is preferably, for example, naphthalen-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl.
In Formula (c7), n7 is an integer of 0 or more and 4 or less and preferably 0 or 1, more preferably 0.
In Formula (c8), Rc12 is an organic group. Examples of the organic group may be the same as those listed for the organic group of Rca in Formula (c4). The organic group is preferably alkyl. The alkyl group may be linear or branched. The alkyl group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms, even more preferably 1 or more and 3 or less carbon atoms. Rc2 is preferably, for example, methyl, ethyl, propyl, isopropyl, or butyl and more preferably methyl.
In 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, more preferably 1 or 2. In Formula (c8), n8 is an integer of 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, even more preferably 0.
In 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, even more preferably 1 or 2.
In Formula (c2), Rc3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, or an optionally substituted aryl group. The aliphatic hydrocarbon group of Rc3 may have a substituent, which is preferably, for example, phenyl or naphthyl.
In Formulae (c1) and (c2), Rc3 is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-cyclopentylethyl, 2-cyclobutylethyl, cyclohexylmethyl, phenyl, benzyl, methylphenyl, or naphthyl, and more preferably methyl or phenyl.
Preferred examples of the compound of Formula (c2) with Rc1 being the group of Formula (c3) include the compounds shown below.
Preferred examples of the compound of Formula (c2) with Rc1 being the group of Formula (c4) include the compounds shown below.
Preferred examples of the compound of Formula (c2) with Rc1 being the group of Formula (c5) include the compounds shown below.
The radical polymerization initiating agent (C1) is also preferably a phosphine oxide compound, which can form a photocurable composition having good curability even at depth. The phosphine oxide compound preferably has a partial substructure of Formula (c9) below.
In Formula (c9), Rc21 and Rc22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 or more and 20 or less carbon atoms, or an aromatic acyl group having 7 or more and 20 or less carbon atoms, provided that Rc21 and Rc22 are not simultaneously aliphatic acyl groups or aromatic acyl groups.
The alkyl group of Rc21 or Rc22 preferably has 1 or more and 12 or less carbon atoms, more preferably 1 or more and 8 or less carbon atoms, even more preferably 1 or more and 4 or less carbon atoms. The alkyl group of Rc21 or Rc22 may be linear or branched.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.
The cycloalkyl group of Rc21 or Rc22 preferably has 5 or more and 12 or less carbon atoms. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.
The aryl group of Rc21 or Rc22 preferably has 6 or more and 12 or less carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, and an alkoxy group having 1 or more and 4 or less carbon atoms. Examples of the aryl group include phenyl and naphthyl.
The aliphatic acyl group of Rc21 or Rc22 has 2 or more and 20 or less carbon atoms, preferably 2 or more and 12 or less carbon atoms, more preferably 2 or more and 8 or less carbon atoms, even more preferably 2 or more and 6 or less carbon atoms. The aliphatic acyl group may be linear or branched.
Examples of the aliphatic acyl group include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl.
The aromatic acyl group of Rc21 or Rc22 has 7 or more and 20 or less carbon atoms. The aromatic acyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, and an alkoxy group having 1 or more and 4 or less carbon atoms. Examples of the aromatic acyl group include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6-trimethylbenzoyl, α-naphthoyl, and β-naphthoyl.
Preferred examples of the phosphine oxide compound having a partial structure of 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.
The cationic polymerization initiating agent (C2) may be any conventionally-known one. Typical examples of the cationic polymerization initiating agent (C2) include onium salts. The cationic polymerization initiating agent (C2) may be an oxonium salt, an ammonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, and is preferably a sulfonium salt or an iodonium salt, more preferably a sulfonium salt.
The content of the initiating agent (C) in the photocurable composition may be any level. The content of the initiating agent (C) may be appropriately selected depending on the type of the radically or cationically polymerizable group or the type of the initiating agent (C).
The content of the initiating agent (C) in the photocurable composition is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, even more preferably 1 part by mass or more and 10 parts by mass or less, based on the mass calculated by subtracting the mass of the solvents (S) described later from the mass of the photocurable composition, which corresponds to 100 parts by mass.
The photocurable composition may contain a plasticizing agent (D). The plasticizing agent (D) is a component that will provide the photocurable composition with a reduced viscosity without significantly reducing the curability of the photocurable composition or the refractive index of the cured product.
The plasticizing agent (D) is preferably a compound of Formula (d-1) below.
In Formula (d-1), Rd1 and Rd2 are each independently a phenyl group optionally having 1 or more and 5 or less substituents each selected from the group consisting of an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, and a halogen atom, Rd3 and Rd4 are each independently a methylene group or an ethane-1,2-diyl group, r and s are each independently 0 or 1, and Xd is an oxygen atom or a sulfur atom.
The photocurable composition containing such a plasticizing agent (D) will have a reduced viscosity without a significant reduction in curability or without a risk of forming a cured product with a significantly reduced refractive index.
To provide the photocurable composition with a reduced viscosity, the plasticizing agent (D) preferably has a viscosity of 10 cP or less, more preferably 8 cP or less, even more preferably 6 cP or less, as measured with an E-type viscometer at 25° C.
The plasticizing agent (D) also preferably has a boiling point of 250° C. or more, more preferably 260° C. or more, under atmospheric pressure, so that it can be less volatile and easily and constantly effective in providing the photocurable composition with a reduced viscosity. The upper limit of the boiling point of the plasticizing agent (D) under atmospheric pressure is typically, but not limited to, 300° C. or less or 350° C. or less.
In Formula (d-1), Rd1 and Rd2 are each independently a phenyl group optionally having 1 or more and 5 or less substituents. The substituent that may be bonded to the phenyl group is a group selected from the group consisting of an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, and a halogen atom. The phenyl group may have any suitable number of substituents. The phenyl group may have one or more and five or less substituents and preferably has one or two substituents, more preferably one substituent. For the photocurable composition to have a reduced viscosity, Rd1 and Rd2 are each preferably an unsubstituted phenyl group.
The substituent alkyl group having 1 or more and 4 or less carbon atoms may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. The substituent alkoxy group having 1 or more and 4 or less carbon atoms may be methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, or tert-butyloxy. The substituent halogen atom may be fluorine, chlorine, bromine, or iodine.
In Formula (d-1), Rd3 and Rd4 are each independently a methylene group or an ethane-1,2-diyl group, and r and s are each independently 0 or 1.
In Formula (d-1), Xd is an oxygen atom or a sulfur atom.
Preferred examples of the compound of Formula (d-1) described above include diphenyl ether, diphenyl sulfide, dibenzyl ether, dibenzyl sulfide, diphenethyl ether, and diphenethyl sulfide. Among them, diphenyl sulfide and/or dibenzyl ether is more preferred.
For both good viscosity control and good dispersibility of the metal oxide fine particles (B), the content of the plasticizing agent (D) in the photocurable composition is preferably more than 0 mass % and 35 mass- or less, more preferably 5 mass % or more and 15 mass- or less, based on the mass of the photocurable composition.
For ease of forming a cured product with less localized metal oxide fine particles (B), the photocurable composition may contain a nitrogen-containing compound (E), such as an amine compound (E1) of Formula (e1) below and/or an imine compound (E2) of Formula (e2).
In Formula (e1), Re1, Re2, and Re3 are each independently a hydrogen atom or an organic group.
In Formula (e2), Re4, Re5, and Re6 are each independently a hydrogen atom or an organic group.
In Formulae (e1) and (e2), the organic group of Re1, Re2, Rc3, Re4, Re5, or Re6 may be selected from various organic groups that do not compromise the desired effect. The organic group is preferably a carbon atom-containing group and more preferably a group including one or more carbon atoms and at least one atom selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen. The number of carbon atoms in the carbon atom-containing group is preferably, but not limited to, 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the organic group include alkyl, cycloalkyl, optionally substituted phenyl, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthylalkyl, and optionally substituted heterocyclyl.
The organic group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 6 or less carbon atoms. The alkyl group may have a linear or branched structure. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. The alkyl group may have a carbon chain containing an ether bond (—O—). Examples of the alkyl group having an ether bond-containing carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.
The organic group is preferably a cycloalkyl group having 3 or more and 10 or less carbon atoms, more preferably a cycloalkyl group having 3 or more and 6 or less carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
The organic group is preferably a phenylalkyl group having 7 or more and 20 or less carbon atoms, more preferably a phenylalkyl group having 7 or more and 10 or less carbon atoms. The organic group is also preferably a naphthylalkyl group having 11 or more and 20 or less carbon atoms, more preferably a naphthylalkyl group having 11 or more and 14 or less carbon atoms. Examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Examples of the naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(0-naphthyl)ethyl. The phenylalkyl or naphthylalkyl group may further have a substituent on the phenyl or naphthyl group.
When the organic group is a heterocyclyl group, examples of the heterocyclyl group are the same as those of the heterocyclyl group of RA4 in Formula (c3), and the heterocyclyl group may further have a substituent.
When the organic group is a heterocyclyl group, it may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The heterocyclyl group is preferably a five- or six-membered monocyclic ring containing one or more N, S, or O atoms or preferably a heterocyclyl group including such monocyclic rings fused together or including such a monocyclic ring and a benzene ring fused together. When the heterocyclyl group is a fused ring, it should have up to three rings. The heterocyclic ring constituting the heterocyclyl group described above may be 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, or tetrahydrofuran.
The phenyl, naphthyl, or heterocyclyl group in the organic group may have a substituent, such as an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, a halogenated alkyl group having 1 or more and 6 or less carbon atoms, a halogenated alkoxy group having 1 or more and 6 or less carbon atoms, a saturated aliphatic acyl group having 2 or more and 7 or less carbon atoms, an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic acyloxy group having 2 or more and 7 or less carbon atoms, a monoalkylamino group having an alkyl group of 1 or more and 6 or less carbon atoms, a dialkylamino group having an alkyl group of 1 or more and 6 or less carbon atoms, a benzoyl group, a halogen atom, a nitro group, or a cyano group.
The phenyl, naphthyl, or heterocyclyl group in the organic group may have any suitable number of substituents and preferably has 1 or more and 4 or less substituents. The phenyl, naphthyl, or heterocyclyl group in the organic group may have two or more substituents the same as or different from one another.
In Formula (e1), Re1, Re2, and Re3 are each independently a hydrogen atom or an organic group, and at least one of Re1, Re2, or Re3 is an aromatic group-containing group.
In Formula (e2), Re4, Re5, and Re6 are each independently a hydrogen atom or an organic group, and at least one of Re4, Re5, or Re6 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. The aromatic group-containing group is preferably a hydrocarbon group. The aromatic group-containing group is preferably an aromatic hydrocarbon group (aryl group) or an aralkyl group.
The aromatic hydrocarbon group may be phenyl, naphthalen-1-yl, or naphthalen-2-yl. In particular, the aromatic hydrocarbon group is preferably phenyl.
The aralkyl group may be benzyl, 2-phenylethyl, 3-phenylpropyl, or 4-phenylbutyl.
In Formula (e1), at least one of Re1, Re2, or Re3 is preferably a group represented by Are1—CH2—. In Formula (e2), Re4 is preferably a group represented by Are1—CH2—. Are1 is an optionally substituted aromatic group.
The aromatic group of Are1 may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic group of Are1 is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group may be phenyl, naphthalen-1-yl, or naphthalen-2-yl. In particular, the aromatic hydrocarbon group is preferably phenyl.
The aromatic group of Are1 may have a substituent, examples of which are the same as those of the substituent that the organic group of Re1, Re2, Re3, Re4, Re5, or Re6 may have when it is phenyl, naphthyl, or heterocyclyl.
Preferred examples of the amine compound of 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.
Preferred examples of the imine compound of Formula (e2) include N-benzylphenylmethanimine, N-benzyldiphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropan-2-imine.
The content of the nitrogen-containing compound in the photocurable composition may be any level as long as the desired effect will not be impaired. The content of the nitrogen-containing compound (E) is preferably 5 mass % or more and 25 mass % or less, more preferably 7 mass % or more and 20 mass % or less, based on the mass of the photopolymerizable compound (A).
To form a cured product with a higher refractive index, the photocurable composition may contain a triazine compound (F), such as a compound of Formula (F1) below.
In Formula (F1), RF1, RF2, and RF3 are each independently an optionally substituted monocyclic aromatic group or an optionally substituted fused aromatic group, provided that RF1, RF2, and RF3 have no radically or cationically polymerizable group-containing group, the monocyclic aromatic group or the fused aromatic group may have a substituent containing no aromatic ring, and the three —NH— groups bonded to the triazine ring are bonded to the aromatic rings in RF, RF2, and RF3, respectively.
The monocyclic aromatic group of RF1, RF2, or RF3 may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The monocyclic aromatic group may be phenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl, thienyl, oxazolyl, or thiazolyl.
The monocyclic aromatic group may have a substituent, examples of which include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a nitro group, and a monovalent organic group, provided that the monovalent organic group has no aromatic ring.
The substituent halogen atom may be fluorine, chlorine, bromine, or iodine.
The monovalent organic group may be alkyl, alkoxy, alkoxyalkyl, aliphatic acyl, aliphatic acyloxy, alkoxycarbonyl, alkylthio, or aliphatic acylthio.
The substituent monovalent organic group may have any number of carbon atoms as long as the desired effect will not be impaired. For example, the substituent monovalent organic group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less carbon atoms, even more preferably 1 or more and 8 or less carbon atoms. The number of carbon atoms in the alkoxyalkyl, aliphatic acyl, aliphatic acyloxy, alkoxycarbonyl, alkoxyalkylthio, or aliphatic acylthio group should have a lower limit of 2.
Preferred examples of the substituent alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.
Preferred examples of the substituent alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy.
Preferred examples of the substituent alkoxyalkyl group include methoxymethyl, ethoxymethyl, n-propyloxymethyl, n-butyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propyloxyethyl, 2-n-butyloxyethyl, 3-methoxy-n-propyloxy, 3-ethoxy-n-propyloxy, 3-n-propyloxy-n-propyloxy, 3-n-butyloxy-n-propyloxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, 4-n-propyloxy-n-butyloxy, and 4-n-butyloxy-n-butyloxy.
Preferred examples of the substituent aliphatic acyl group include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, and octanoyl.
Preferred examples of the substituent aliphatic acyloxy group include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy.
Preferred examples of the substituent alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl.
Preferred examples of the substituent alkylthio group include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, and n-octylthio.
Preferred examples of the substituent aliphatic acylthio group include acetylthio, propionylthio, butanoylthio, pentanoylthio, hexanoylthio, heptanoylthio, and octanoylthio.
The monocyclic aromatic group may have any number of substituents as long as the desired effect will not be impaired. The monocyclic aromatic group preferably has one or more and four or less substituents, more preferably one or two substituents, even more preferably one substituent.
The monocyclic aromatic group may have two or more substituents different from one another.
The optionally substituted monocyclic aromatic group described above may be phenyl, 4-cyanophenyl, 3-cyanophenyl, 2-cyanophenyl, 2,3-dicyanophenyl, 2,4-dicyanophenyl, 2,5-dicyanophenyl, 2,6-dicyanophenyl, 3,4-dicyanophenyl, 3,5-dicyanophenyl, 4-nitrophenyl, 3-nitrophenyl, 2-nitrophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-iodophenyl, 3-iodophenyl, 2-iodophenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-methylphenyl, 3-methylphenyl, or 2-methylphenyl.
In particular, the optionally substituted monocyclic aromatic group is preferably phenyl, 4-cyanophenyl, 3-cyanophenyl, 2-cyanophenyl, 4-nitrophenyl, 3-nitrophenyl, or 2-nitrophenyl, more preferably phenyl or 4-cyanophenyl.
The fused aromatic group of RF1, RF2, or RF3 is a fused polycyclic group including two or more monocyclic aromatic rings fused together and lacking one hydrogen atom. The fused aromatic group may include any number of monocyclic aromatic rings fused together. The fused aromatic group preferably two or three monocyclic aromatic rings fused together, more preferably two monocyclic aromatic rings fused together. In other words, the fused aromatic group is preferably a bicyclic fused aromatic group or a tricyclic fused aromatic group, more preferably a bicyclic fused aromatic group.
The fused aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
The bicyclic fused aromatic group may be, for example, naphthalen-1-yl, naphthalen-2-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, isoquinolin-8-yl, benzoxazol-2-yl, benzoxazol-4-yl, benzoxazol-5-yl, benzoxazol-6-yl, benzoxazol-7-yl, benzothiazol-2-yl, benzothiazol-4-yl, benzothiazol-5-yl, benzothiazol-6-yl, or benzothiazol-7-yl.
The tricyclic fused aromatic group may be, for example, anthracen-1-yl, anthracen-2-yl, anthracen-9-yl, phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl, phenanthren-9-yl, acridin-1-yl, acridin-2-yl, acridin-3-yl, acridin-4-yl, or acridin-9-yl.
The polycyclic fused aromatic group, such as the bicyclic or tricyclic fused aromatic group, may have a substituent, examples of which are the same as those of the substituent that the monocyclic aromatic group may have.
The optionally substituted fused aromatic group described above is preferably naphthalen-1-yl, naphthalen-2-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, benzothiazol-2-yl, or 2-mercaptobenzothiazol-6-yl.
In particular, the optionally substituted fused aromatic group is preferably naphthalen-1-yl, quinolin-3-yl, quinolin-4-yl, or 2-mercaptobenzothiazol-6-yl, more preferably naphthalen-1-yl.
In particular, the compound of Formula (F1) described above is preferably a compound with one or two of RF1, RF2, and RF3 being optionally substituted naphthyl and with one or two of RF1, RF2, and RF3 being 4-cyanophenyl or benzothiazolyl in order to form a cured product with a good balance between refractive index, surface appearance, and heat resistance. The optionally substituted naphthyl group is preferably naphthalen-1-yl.
Preferred examples of the compound of Formula (F1) include compounds of the formulae below.
The compound of Formula (F1) may be produced by any suitable method. Typically, the compound of Formula (F1) may be produced by allowing a cyanuric halide, such as cyanuric chloride, to react with aromatic amines represented by RF1—NH2, RF2—NH2, and RF3—NH2. These amines may be allowed to react simultaneously or sequentially with the cyanuric halide. Preferably, these amines are allowed to react sequentially with the cyanuric halide.
The compound of Formula (F1) is usually synthesized in an organic solvent. Such an organic solvent may be any inert solvent that does not react with the cyanuric halide, the aromatic amines, the radically polymerizable group, or the cationically polymerizable group. Such a solvent may be any of organic solvent examples listed for the solvents (S).
For the production of the compound of Formula (F1), the cyanuric halide may be allowed to react at any suitable temperature with aromatic amines, such as the aromatic amines represented by RF1—NH2, RF2—NH2, and R3—NH2. Typically, the reaction temperature is preferably 0° C. or more and 150° C. or less.
The content of the triazine compound (F) in the photocurable composition may be any level as long as the desired effect will not be impaired. For example, the content of the triazine compound (F) in the photocurable composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.3 parts by mass or more and 20 parts by mass or less, even more preferably 0.5 parts by mass or more and 15 parts by mass or less, based on the mass calculated by subtracting the mass of the solvents (S) described later from the mass of the photocurable composition, which corresponds to 100 parts by mass.
The photocurable composition contains solvents (S) for control of the ability to be applied and other purposes. The solvents (S) should include two or more solvents (S1) of Formula (S1) below.
In Formula (S1), RS1 is an alkylene group having 2 or more and 4 or less carbon atoms, RS2 and RS3 are each a hydrogen atom, a methyl group, or an ethyl group, provided that RS2 and RS3 are not simultaneously hydrogen atoms, and ns is an integer of 1 or more and 4 or less.
The solvents (S1) each have a Hildebrand solubility parameter of 21.0 MPa0 or less.
In the photocurable composition, the solvents (S) including the solvent (S1) allow the metal oxide fine particles (B) to be well dispersed even at a high concentration, and the solvents (S) including the solvent (S1) also allow the photocurable composition to have good wettability on the application target substrate.
Moreover, the photocurable composition containing the solvents (S) including the solvent (S1) is resistant to rapid drying. In this regard, in inkjet methods, the ink needs not to be dried and thickened or solidified in inkjet heads over a long period of time. As mentioned above, the photocurable composition containing the solvents (S) including the solvent (S1) is resistant to rapid drying and thus suitable for use in inkjet methods.
The Hildebrand solubility parameter (d (MPa0.5)) may be calculated from the formula below using the dispersion term (dD (MPa0.5)), the polar term (dP (MPa0.5)), and the hydrogen-bonding term (dH (MPa0.5)) for Hansen solubility parameter.
For ease of obtaining the desired effect by using the solvent (S1), the solvent (S1) preferably has a Hildebrand solubility parameter of 17.0 MPa0.5 or more, more preferably 18.0 MPa0.5 or more, even more preferably 18.5 MPa0.5 or more.
In Formula (S1), RS1 is an alkylene group having 2 or more and 4 or less carbon atoms. The alkylene group having 2 or more and 4 or less carbon atoms is preferably ethane-1,2-diyl, (ethylene group), propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,2-diyl, or butane-1,3-diyl and more preferably ethane-1,2-diyl or propane-1,2-diyl.
Examples of the solvent of Formula (S1) having a Hildebrand solubility parameter of 21.0 MPa0.5 or less include the following: HO—(CH2CH2CH2—O)2—CH3 (dipropylene glycol monomethyl ether); HO— (C(CH3)HCH2—O) 3-CH3 (tripropylene glycol monomethyl ether); and H3C—O—(CH2CH2—O)3—CH3 (triethylene glycol dimethyl ether).
In addition to the solvent (S1), the solvents (S) may include an additional solvent (S2) other than the solvent (S1).
Examples of the additional solvent (S2) 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 (HO—CH2CH2CH2—O—CH3), propylene glycol monomethyl ether (HO—C(CH3)HCH2—O—CH3 or H3C—O—C(CH3)HCH2—OH), propylene glycol monoethyl ether (HO—CH2CH2CH2—O—CH2CH3), propylene glycol monoethyl ether (HO—C(CH3)HCH2—O—CH2CH3 or H3CH2C—O—C(CH3)HCH2—OH), propylene glycol mono-n-propyl ether (HO—CH2CH2CH2—O—CH2CH2CH3), propylene glycol mono-n-propyl ether (HO—C(CH3)HCH2—O—CH2CH2CH3 or H3CH2CH2C—O—C(CH3)HCH2—OH), propylene glycol mono-n-butyl ether (HO—CH2CH2CH2—O—CH2CH2CH2CH3), propylene glycol mono-n-butyl ether (HO—C(CH3)HCH2O—CH2CH2CH2CH3 or H3CH2CH2CH2C—O—C(CH3)HCH2—OH), dipropylene glycol monomethyl ether (HO—(C(CH3)HCH2—O)2—CH3 or H3C—O—(C(CH3)HCH2—O)2—H), dipropylene glycol monoethyl ether (HO—(CH2CH2CH2—O)2—CH2CH3), dipropylene glycol monoethyl ether (HO—(C(CH3)HCH2—O)2—CH2CH3 or H3CH2C—O—(C(CH3)HCH2—O)2—H), dipropylene glycol mono-n-propyl ether (HO—(CH2CH2CH2—O)2—CH2CH2CH3 or H3CH2CH2C—O—(CH2CH2CH2—O)2—H), dipropylene glycol mono-n-propyl ether (HO—(C(CH3)HCH2—O)2—CH2CH2CH3 or H3CH2CH2C—O—(C(CH3)HCH2—O)2—H), dipropylene glycol mono-n-butyl ether (HO—(CH2CH2CH2—O)2—CH2CH2CH2CH3 or H3CH2CH2CH2C—O—(CH2CH2CH2—O)2—H), dipropylene glycol mono-n-butyl ether (HO—C(CH3)HCH2—O)2—CH2CH2CH2CH3 or H3CH2CH2CH2C—O—(C(CH3)HCH2—O)2—H), tripropylene glycol monomethyl ether (HO—(CH2CH2CH2—O)3—CH2CH3), tripropylene glycol monomethyl ether (H3C—O—(C(CH3)HCH2—O)3—H), tripropylene glycol monoethyl ether (HO—(CH2CH2CH2—O)3—CH2CH3), and tripropylene glycol monoethyl ether (HO—(C (CH3) HCH2—O) 3-CH2CH3 or H3CH2C—O— (C (CH3) HCH2—O) 3-H); (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, and propylene glycol monoethyl ether acetate; ethers, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, and tetrahydrofuran; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters, such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; esters, such as 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-methylbutanoate, 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, and ethyl 2-oxobutanoate; aromatic hydrocarbons, such as toluene and xylene; and amides, such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, among which (poly)alkylene glycol monoalkyl ether acetates are preferred.
For ease of obtaining the desired effect by using the solvent (S1), the ratio of the mass of the solvent(s) (S1) to the mass of the solvents (S) is preferably 20 mass- or more, more preferably 30 mass % or more, even more preferably 50 mass % or more, furthermore preferably 70 mass % or more, still more preferably 90 mass % or more, most preferably 100 mass %. The ratio of the mass of the solvent(s) (S1) to the mass of solvents (S) may have any upper limit. For example, the ratio of the mass of the solvent(s) (S1) to the mass of the solvents (S) may have an upper limit of 100 mass % or less, 90 mass % or less, 70 mass % or less, 50 mass % or less, or 30 mass % or less.
The solvents (S) may include the solvent (S1) and the solvent (S2). In this case, the mass ratio (S1:S2) of the solvent (S1) to the solvent (S2) is preferably 99:1 to 25:75, more preferably 95:5 to 35:65, for the advantageous effect of the present invention described above, for the uniformity of the photocurable composition, or for the prevention of void formation during the process of forming a film on a fine trench pattern using the photocurable composition.
The solvents (S1) may include one solvent (S1-H) with a highest Hildebrand solubility parameter and the other solvent (s) (S1-L). In this case, the ratio (S1-H):(S1-L) of the mass of the solvent (S1-H) with a highest Hildebrand solubility parameter to the mass of the other solvent(s) (S1-L) is, for example, 99:1 to 1:99. For the advantageous effect of the present invention described above, for the uniformity of the photocurable composition, or for the prevention of void formation during the process of forming a film on a fine trench pattern using the photocurable composition, the mass ratio (S1-H):(S1-L) is preferably 99:1 to 30:70, more preferably 95:5 to 40:60, even more preferably 90:10 to 70:30.
The content of the solvents (S) in the photocurable composition is preferably such that the photocurable composition has a solid content of 1 mass % or more and 99 mass % or less, more preferably 5 mass % or more and 50 mass % or less, even more preferably 10 mass % or more and 30 mass % or less.
In addition to the components described above, if necessary, the photocurable composition may contain, as an additional component, any of various additives. The additive may be a sensitizing agent, a curing accelerating agent, a filling agent, a dispersing agent, an adhesion promoting agent, such as a silane coupling agent, an antioxidizing agent, an aggregation preventing agent, a thermal polymerization inhibiting agent, a defoaming agent, a surface active agent, or the like.
The content of the additive in the photocurable composition may be appropriately selected taking into account the commonly used amount of the additive.
The photocurable composition described above may be formed into a desired shape and then subjected to light exposure depending on the type of the initiating agent (C) to form a cured product.
For example, the cured product produced by this process preferably has a refractive index of 1.70 or more, more preferably 1.90 or more, at a wavelength of 520 nm. Thus, the cured product produced by this process is suitable for use in optical applications where high refractive indices are required.
For example, a cured film including a product of curing of the photocurable composition is suitable for use as a high-refractive-index film to form antireflection films or the like for various display panels, such as organic EL display panels and liquid crystal display panels.
The photocurable composition may be shaped by any suitable method selected depending on the shape of the cured product to be formed. The shaping method may be, for example, coating or casting into a mold.
Hereinafter, a method of producing a cured film will be described as a typical example of the method of producing a cured product.
First, the photocurable composition is applied to a desired substrate to form a coating film, and then, if necessary, the solvents (S) are at least partially removed from the coating film.
The photocurable composition may be applied to the substrate by any suitable method. For example, the photocurable composition may be applied to the substrate using a contact transfer-type coating device, such as a roll coater, a reverse coater, a bar coater, or a slit coater, or a non-contact coating device, such as a spinner (rotary coating device) or a curtain flow coater, to form a coating film with a desired thickness.
Alternatively, the coating film may be formed by a printing method, such as screen printing or inkjet printing. As mentioned above, the photocurable composition is resistant to rapid drying and less likely to become thick or solidify in inkjet heads. Thus, the photocurable composition can be successfully applied by inkjet printing.
After the photocurable composition is applied to the substrate, if necessary, the coating film is preferably baked so that the solvents (S) are at least partially removed from the coating film. The baking temperature may be appropriately selected taking into account the boiling point and other properties of the solvents (S). The baking may also be performed at a low temperature under reduced pressure conditions.
The baking may be performed by any suitable method, such as a method of drying the coating film using a hot plate at a temperature of 80° C. or more and 150° C. or less, preferably 85° C. or more and 120° C. or less, for a time period of 60 seconds or more and 500 seconds or less.
The coating film formed as described above may have any suitable thickness. The thickness of the coating film may be appropriately selected depending on the intended use of the cured film. Typically, the thickness of the coating film may be appropriately controlled such that a cured film can be formed preferably with a thickness of 0.1 μm or more and 10 μm or less, more preferably with a thickness of 0.2 μm or more and 5 μm or less.
The coating film formed by the method described above is then subjected to light exposure to form a cured film.
The coating film may be subjected to light exposure under any conditions that allow curing to proceed successfully. For example, the light exposure may be performed by applying active energy rays, such as ultraviolet rays or excimer laser light. The dose of the applied energy rays is typically, but not limited to, 30 mJ/cm2 or more and 5,000 mJ/cm2 or less. After the light exposure, the exposed coating film may be baked by the same method as in the heating after the application.
Hereinafter, the present invention will be described in more detail with reference to examples, which are not intended to limit the scope of the present invention.
To a 300 mL volume reaction vessel were added 3.91 g (0.027 mol) of 3-aminoquinoline and 200 mL of acetic acid. After the air in the reaction vessel was replaced with a nitrogen atmosphere, 5.00 g (0.027 mol) of cyanuric chloride was added into the reaction vessel at room temperature. Subsequently, the 3-aminoquinoline and the cyanuric chloride were allowed to react at room temperature for 2 hours. Subsequently, 6.51 g (0.060 mol) of 4-aminophenol was added into the reaction vessel, and the contents of the reaction vessel were stirred at 110° C. for 3 hours. After the stirring was completed, 200 mL of water was added to the reaction liquid to precipitate the product. The precipitate was collected by filtration and then washed with ethanol. After the washing, the precipitate was dried to give 8.80 g of an intermediate having the following structure.
A solution was obtained by mixing 8.80 g (0.018 mol) of the resulting intermediate and 100 mL of N,N-dimethylacetamide. The resulting solution was cooled in an ice bath. To the cooled solution was added dropwise 4.97 g (0.055 mol) of acrylic acid chloride while the temperature of the solution was maintained at 5° C. After the dropwise addition of acrylic acid chloride was completed, the reaction liquid was stirred at room temperature for 3 hours. Subsequently, 100 mL of water was added to the reaction liquid, and then the solid precipitate was filtered off. The resulting precipitate was purified by silica gel chromatography to give 7.2 g of Compound A-2 having the structure shown below.
1H-NMR (CDCl3): 5.74 (dd, 2H), 6.10 (dd, 2H), 6.24 (dd, 2H), 7.06-8.20 (m, 14H), 8.81 (s, 1H), 8.91 (s, 2H)
Compound A-3 having the structure shown below was obtained as in Synthesis Example 1 except that 3-aminoquinoline was replaced by 2-mercapto-6-aminobenzotriazole.
1H-INMR (CDCl3): 5.74 (dd, 2H), 6.10 (dd, 2H), 6.24 (dd, 2H), 7.06-7.52 (m, 11H), 8.91 (s, 2H), 9.43 (s, 1H), 12.28 (s, 1H)
In Examples 1 to 15 and Comparative Examples 1 to 11, Compounds A-1 to A-4 shown below were used as the photopolymerizable compound (A).
In Examples 1 to 15 and Comparative Examples 1 to 11, titanium oxide fine particles, which had a particle size of approximately 7 nm as measured with a transmission electron microscope (TEM), were used as the metal oxide fine particles (B). The titanium oxide fine particles were synthesized by a known hydrothermal method using methoxy(triethyleneoxy)propyltrimethoxysilane as a capping agent.
In Examples 1 to 15 and Comparative Examples 1 to 11, Solvents S-1 to S-3 were used as the solvent (S1) described above.
In Examples 1 to 15 and Comparative Examples 1 to 11, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, which corresponds to the radical polymerization initiating agent (C1), was used as the initiating agent (C).
Photocurable compositions of Examples 1 to 14 and Comparative Examples 1 to 10 were each obtained by dispersing 91 parts by mass of the metal oxide fine particles (B) and dissolving 8 parts by mass of the photopolymerizable compound (A) of the type shown in Table 1 or 2 and 1 part by mass of the initiating agent (C) in the solvent(s) (S) of the type shown in Table 1 or 2 such that the resulting composition had a solid content of 10 mass %.
Photocurable compositions of Example 15 and Comparative Example 11 were also each obtained by dispersing 70 parts by mass of the metal oxide fine particles (B) and dissolving 29 parts by mass of the photopolymerizable compound (A) of the type shown in Table 1 or 2 and 1 part by mass of the initiating agent (C) in the solvent(s) (S) of the type shown in Table 1 or 2 such that the resulting composition had a solid content of 10 mass %.
According to the methods described below, the resulting photocurable compositions were each subjected to the measurement of the refractive index of a cured film and each evaluated for dispersion stability, wettability, drying properties, and voids. The results of the measurement and evaluation are shown in Tables 1 and 2.
The photocurable composition was applied to a glass substrate using a spin coater. The film of the photocurable composition was then heated at 110° C. for 2 minutes to form a coating film with a thickness that allowed the formation of a 1 μm-thick cured film. The resulting coating film was exposed to light at a total dose of 100 mJ/cm2 using a high-pressure mercury lamp. The exposed coating film was heated at 110° C. for 2 minutes to form a 1 μm-thick cured film.
The refractive index of the resulting cured film was determined at a wavelength of 520 nm using a prism coupler manufactured by Metricon Inc.
After being prepared, the photocurable compositions of the examples and the comparative examples were each allowed to stand at room temperature for 1 week. After the standing for 1 week, it was visually observed how the metal oxide fine particles (B) were dispersed in the photocurable composition, and the dispersion stability of the photocurable composition was evaluated according to the criteria below.
The wettability of the photocurable composition was evaluated as the contact angle of the solvent (S) (to be contained in the photocurable composition) on the surface of a substrate with a TiO2 film deposited thereon.
The solvent (S) to be contained in each of the photocurable compositions of the examples and the comparative examples was dropped in an amount of 2.0 μL on the surface of a substrate with a TiO2 film deposited thereon, and 1,000 milliseconds after the drop, the contact angle of the solvent (S) on the substrate was measured using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle used for the evaluation was the average of the contact angles measured at three points on the substrate with a TiO2 film deposited thereon.
The drying properties of the photocurable composition were evaluated as the rate of decrease in the weight of the solvent (S) (to be contained in the photocurable composition) during heating at 100° C. under atmospheric pressure.
Specifically, first, a glass substrate was made ready for use by washing its surface with acetone. Subsequently, 0.3 g of the solvent (S) (to be contained in each of the photocurable compositions of the examples and the comparative examples) was dropped on the cleaned surface of the glass substrate.
The glass substrate with the solvent (S) dropped thereon was placed on a hot plate at 100° C., and the weight of the drop of the solvent (S) on the glass substrate was measured at intervals of 3 minutes from the time point of the drop to 30 minutes after the drop. The elapsed time (minutes) measured from the drop and the weight of the drop of the solvent (S) were plotted on a coordinate plane with the elapsed time from the drop on the horizontal axis and the weight of the drop of the solvent (S) on the vertical axis using Microsoft® Excel® to form a scatter plot.
Linear approximation was performed on the resulting scatter plot using the function of Microsoft® Excel®. The slope (g/minute) of the straight line resulting from the linear approximation was used to evaluate the drying properties according to the criteria below.
The compositions of the examples and the comparative examples with the dispersion stability evaluated as “good” (A) were subjected to the evaluation of voids. The photocurable compositions of the examples and the comparative examples were each applied to a substrate having trench patterns and then subjected to film formation under the same conditions as those for the measurement of the refractive index when a cross-sectional sample was prepared. The presence or absence of voids in the trench patterns of the cross-sectional sample was observed using a scanning electron microscope (SEM), and the result was evaluated according to the criteria below. It is preferred that no voids should be observed even in the trench pattern with a high aspect ratio.
Table 1 shows that the photocurable composition including the photopolymerizable compound (A), the metal oxide fine particles (B), the initiating agent (C), and the solvents (S) can keep the metal oxide fine particles (B) well dispersed even at a high concentration and have good wettability on the application target substrate when the solvents (S) include at least two solvents (S1) each having the specific structure of Formula (S1) above and each having a Hildebrand solubility parameter of at most 21.0 MPa0.5 or when the solvents (S) include the solvent (S1) and the additional solvent (S2) in a specific mass ratio. Table 1 also shows that the photocurable composition with such features can be formed into a uniform film with no voids even on a substrate having indented patterns, such as trench patterns.
On the other hand, Table 2 shows that the photocurable composition including the photopolymerizable compound (A), the metal oxide fine particles (B), the initiating agent (C), and the solvent (S) can hardly achieve, simultaneously, good dispersion of the metal oxide fine particles (B) and good wettability on the application target substrate when the solvent (S) does not have the specific structure of Formula (S1) above or has a Hildebrand solubility parameter of more than 21.0 MPa0.5.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-073669 | Apr 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/018485 | 4/21/2022 | WO |
