Photosensitive composition, cured product and method for manufacturing cured product

Abstract

The object of the present invention is to provide a photosensitive composition capable of forming a cured product with high transparency, a cured product of the photosensitive composition, and a method for manufacturing the cured product using the aforementioned photosensitive composition. In the photosensitive composition comprising a substrate component (A) having photopolymerizability and a photopolymerization initiator (B), a phosphine oxide compound (B1) and an oxime ester compound (B2) serving as the photopolymerization initiator (B) are combined in such a way that the mass ratio of the oxime ester compound (B2) to the total mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35% by mass or more.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition, a cured product of the photosensitive composition, and a method for manufacturing a cured product using the aforementioned photosensitive composition. Background Technology

[0002] For a long time, photosensitive compositions containing photopolymerizable compounds with unsaturated double bonds and photopolymerization initiators have been used as coating materials for hard coatings, light-transmitting materials constituting display panels such as liquid crystal display panels and organic EL display panels, and materials used to form protective films and insulating films in touch panels. These compositions can provide transparent cured products.

[0003] As such photosensitive compositions, for example, photosensitive compositions for forming protective films, insulating films, etc. in touch panels have been proposed, which contain photopolymerizable monomers, a transparent resin as a mixture of resins with a specific structure, a photopolymerization initiator, and a solvent (see Patent Document 1). In Patent Document 1, an oxime ester compound is described as a photopolymerization initiator that can provide a photosensitive composition with excellent sensitivity.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2013-064973 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, for photosensitive compositions containing oxime ester compounds as photopolymerization initiators that can provide transparent cured products, there is often room for improvement in the transparency of the resulting cured product.

[0009] The present invention was made in view of the above-mentioned problems, and aims to provide a photosensitive composition capable of forming a cured material with high transparency, a cured material of the photosensitive composition, and a method for manufacturing the cured material using the aforementioned photosensitive composition.

[0010] Methods for solving problems

[0011] The inventors of this application discovered that by using a combination of a phosphine oxide compound (B1) and an oxime ester compound (B2) in a specific ratio as the photopolymerization initiator (B) in a photosensitive composition comprising a photopolymerizable substrate component (A) and a photopolymerization initiator (B), the aforementioned problems can be solved, thus completing the present invention. More specifically, the present invention provides the following methods.

[0012] The first aspect of the present invention is a photosensitive composition comprising a substrate component (A) and a photopolymerization initiator (B).

[0013] The substrate component (A) includes at least one of a resin (A1) and a photopolymerizable monomer (A2).

[0014] When the substrate component (A) does not contain a photopolymerizable monomer (A2), the resin (A1) contains a photopolymerizable resin (A1-1) having olefinic unsaturated double bonds.

[0015] The photopolymerization initiator (B) combination comprises a phosphine oxide compound (B1) and an oxime ester compound (B2).

[0016] The mass ratio of the oxime ester compound (B2) to the total mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35% by mass or more.

[0017] The second aspect of the present invention is a cured product of the photosensitive composition involved in the first aspect.

[0018] The third aspect of the present invention is a method for manufacturing a cured product, comprising:

[0019] The photosensitive composition involved in the first method is shaped according to the desired shape of the cured product; and

[0020] The shaped photosensitive composition is exposed.

[0021] Invention Effects

[0022] According to the present invention, a photosensitive composition capable of forming a cured material with high transparency, a cured material of the photosensitive composition, and a method for manufacturing the cured material using the aforementioned photosensitive composition can be provided. Detailed Implementation

[0023] Photosensitive Compositions

[0024] The photosensitive composition comprises a substrate component (A) and a photopolymerization initiator (B). The substrate component (A) comprises at least one of a resin (A1) and a photopolymerizable monomer (A2).

[0025] In the case where the substrate component (A) does not contain a photopolymerizable monomer (A2), the resin (A1) contains a photopolymerizable resin (A1-1) having olefinic unsaturated double bonds.

[0026] The photopolymerization initiator (B) combination comprises a phosphine oxide compound (B1) and an oxime ester compound (B2).

[0027] The mass ratio of the oxime ester compound (B2) to the total mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35% by mass or more.

[0028] The photosensitive composition having the above-described structure is well cured by exposure, providing a cured product with high transparency.

[0029] The following describes the essential or optional components contained in the photosensitizing composition.

[0030] <Substrate Composition (A)>

[0031] The photosensitive composition includes a substrate component (A) that imparts shape-enhancing properties to the photosensitive composition. The substrate component (A) includes at least one of a resin (A1) and a photopolymerizable monomer (A2).

[0032] In the case where the substrate component (A) does not contain a photopolymerizable monomer (A2), the resin (A1) contains a photopolymerizable resin (A1-1) having olefinic unsaturated double bonds.

[0033] [Resin (A1)]

[0034] The resin (A1) is not particularly limited as long as it is transparent and imparts film-forming and other shaping properties to the photosensitive composition. Specific examples of such resin materials include polyacetal resins, polyamide resins, polycarbonate resins, polyester resins (polybutylene terephthalate, polyethylene terephthalate, polyarylate, etc.), FR-AS resins, FR-ABS resins, AS resins, ABS resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, fluorinated resins, polyimide resins, polyamide-imide resins, polyamide-bismaleimide resins, polyetherimide resins, polybenzoxazole resins, polybenzothiazole resins, polybenzimidazole resins, silicone resins, BT resins, polymethylpentene, ultra-high molecular weight polyethylene, FR-polypropylene, (meth)acrylic resins (polymethyl methacrylate, etc.), and polystyrene, etc.

[0035] The structure of these resins (A1) is not particularly limited without hindering the purpose of this invention. They can be linear, branched, or network-like. Furthermore, when the resin (A1) is an organosilicon resin, it can also be a so-called silsesquioxane resin. The structure of the silsesquioxane resin is not particularly limited and can be any structure known previously, such as cage-like, incomplete cage-like, ladder-like, or random.

[0036] These resin materials can be used in combination of two or more types.

[0037] The resin material described above is preferably dissolved in the photosensitive composition. Without hindering the objectives of the present invention, the resin material may be a suspension, such as latex.

[0038] From the viewpoint of easily forming cured products with excellent mechanical properties, the resin (A1) preferably contains a photopolymerizable resin (A1-1) having olefinic unsaturated double bonds.

[0039] From the viewpoint that it is easy to pattern the cured material using photolithography when using the photosensitive composition, the resin (A1) preferably includes an alkali-soluble resin (A1-2).

[0040] It should be noted that the resin material (A1) sometimes belongs to both photopolymerizable resin (A1-1) and alkali-soluble resin (A1-2).

[0041] In this specification, the term "alkali-soluble resin (A1-2)" refers to a resin that possesses functional groups (e.g., phenolic hydroxyl groups, carboxyl groups, sulfonic acid groups, etc.) within its molecule that make it alkali-soluble.

[0042] Regarding resins preferred as alkali-soluble resins (A1-2), examples include resins (a-1) having a Cardo structure (hereinafter also referred to as "Cardo resin (a-1)").

[0043] When using a resin with a Cardo structure (a-1) as the alkali-soluble resin (A1-2), it is easy to obtain a photosensitive composition with excellent resolution, and it is easy to use the photosensitive composition to form a cured product that does not easily flow excessively due to heating. Therefore, it is easy to form a cured product with the desired shape.

[0044] [Resin with Cardo structure (a-1)]

[0045] As a resin with a Cardo structure (a-1), a resin that has a Cardo structure in its structure and has specified alkali solubility can be used. A Cardo structure refers to a structure in which a second and a third ring structure are bonded to one carbon atom constituting the first ring structure. It should be noted that the second and third ring structures can be the same structure or different structures.

[0046] As a representative example of the Cardo structure, a structure in which two aromatic rings (such as a benzene ring) are bonded to the 9th carbon atom of the fluorene ring can be cited.

[0047] There are no particular limitations on the Cardo resin (a-1), and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferred. The Cardo resin (a-1) represented by the following formula (a-1) has (meth)acryloyl groups, and therefore also belongs to the category of photopolymerizable resins (A1-1).

[0048] It should be noted that in the specification and claims of this application, "(meth)acrylate" refers to both acrylate and methacrylate. In the specification and claims of this application, "(meth)propylene" refers to both "propylene" and "methpropylene". In the specification and claims of this application, "(meth)acryloyl" refers to both acryloyl and methacryloyl.

[0049] [Chemical Formula 1]

[0050]

[0051] In equation (a-1), X a This represents the group indicated by the following formula (a-2). t1 represents an integer greater than 0 and less than 20.

[0052] [Chemical Formula 2]

[0053]

[0054] In the above equation (a-2), R a1 Each can independently represent a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms, or a halogen atom. R a2 Each can independently represent a hydrogen atom or a methyl group, R a3 Each independently represents a straight-chain or branched alkylene group, t2 represents 0 or 1, W a This represents the group represented by the following formula (a-3).

[0055] [Chemical Formula 3]

[0056]

[0057] In equation (a-2), R is... a3 Preferably, it is an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, and most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl.

[0058] In formula (a-3), ring A represents an aliphatic ring that can fused with aromatic rings and may have substituents. The aliphatic ring can be an aliphatic hydrocarbon ring or an aliphatic heterocycle.

[0059] Examples of aliphatic rings include monocyclic alkanes, bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes.

[0060] Specifically, examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, as well as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0061] The aromatic ring that can fused with the aliphatic ring can be an aromatic hydrocarbon ring or an aromatic heterocycle, preferably an aromatic hydrocarbon ring. Specifically, benzene rings and naphthalene rings are preferred.

[0062] As a preferred example of a divalent group represented by formula (a-3), the following groups can be cited.

[0063] [Chemical Formula 4]

[0064]

[0065] The divalent group X in formula (a-1) a Residue Z can be provided by enabling a The tetracarboxylic acid dianhydride reacts with a diol compound represented by formula (a-2a) and is thus introduced into Cardo resin (a-1).

[0066] [Chemical Formula 5]

[0067]

[0068] In equation (a-2a), R a1 R a2 R a3 And t2 is as explained with respect to equation (a-2). Regarding ring A in equation (a-2a), it is as explained with respect to equation (a-3).

[0069] The diol compound represented by formula (a-2a) can be manufactured, for example, by the following methods.

[0070] First, as needed, following conventional methods, replace the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formulas (a-2b) with -R. a3 The -OH group is then subjected to glycidylation using epichlorohydrin or the like to obtain the epoxy compound represented by the following formula (a-2c).

[0071] Next, the diol compound represented by formula (a-2c) is obtained by reacting the epoxy compound with acrylic acid or methacrylic acid.

[0072] In equations (a-2b) and (a-2c), R a1 R a3And t2 is as explained with respect to equation (a-2). Regarding ring A in equations (a-2b) and (a-2c), it is as explained with respect to equation (a-3).

[0073] It should be noted that the method for manufacturing the diol compound represented by formula (a-2a) is not limited to the method described above.

[0074] [Chemical Formula 6]

[0075]

[0076] As preferred examples of diol compounds represented by formula (a-2b), the following diol compounds can be cited.

[0077] [Chemical Formula 7]

[0078]

[0079] In the above formula (a-1), R a0 It is a hydrogen atom or -CO-Y a -COOH represents a group. Here, Y a This refers to the residue obtained by removing the anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride.

[0080] In the above formula (a-1), Z a This refers to the residue obtained by removing two anhydride groups from a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include those represented by the following formula (a-4), such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride. Among these, pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride is preferred, and from the perspective of a wide development process tolerance, pyromellitic dianhydride is preferred.

[0081] In the above formula (a-1), t1 represents an integer greater than 0 and less than 20.

[0082] [Chemical Formula 8]

[0083]

[0084] (In equation (a-4), R) a4 R a5 and R a6 Each of these groups independently represents one of the following: hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, and fluorine atoms. t3 represents an integer between 0 and 12.

[0085] R can be selected as the equation (a-4) a4 The alkyl group is an alkyl group with 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. a4 In the case of alkyl groups, from the viewpoint of easily obtaining Cardo resin with excellent heat resistance, the number of carbon atoms is preferably 1 to 6 or less, more preferably 1 to 5 or less, even more preferably 1 to 4 or less, and particularly preferably 1 to 3 or less.

[0086] R a4 When the alkyl group is alkyl, it can be either straight-chain or branched.

[0087] As R in equation (a-4) a4 From the perspective of easily obtaining Cardo resins with excellent heat resistance, each of the following is more preferably an alkyl group having 1 to 10 carbon atoms: R in formula (a-4) a4 More preferably, it is a hydrogen atom, methyl, ethyl, n-propyl or isopropyl, and particularly preferably a hydrogen atom or methyl.

[0088] From the perspective of easily preparing high-purity tetracarboxylic acid dianhydrides, the multiple R values ​​in formula (a-4) a4 Preferably, they are the same group.

[0089] In equation (a-4), t3 represents an integer greater than 0 and less than 12. By making the value of t3 less than 12, the purification of tetracarboxylic dianhydride can be facilitated.

[0090] From the perspective of ease of purification of tetracarboxylic dianhydride, the upper limit of t3 is preferably 5, and more preferably 3.

[0091] From the perspective of the chemical stability of tetracarboxylic acid dianhydride, the lower limit of t3 is preferably 1, and more preferably 2.

[0092] In equation (a-4), t3 is particularly preferably 2 or 3.

[0093] R can be selected as the equation (a-4) a5 and R a6 Alkyl groups with 1 to 10 carbon atoms and which can be selected as R a4 The same applies to alkyl groups with 1 to 10 carbon atoms.

[0094] Considering the ease of purification of tetracarboxylic dianhydride, R a5 and R a6Preferably, it is an alkyl group with 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, further preferably 1 to 4, and especially preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

[0095] Examples of tetracarboxylic acid dianhydrides represented by formula (a-4) include, for example, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid dianhydride (also known as “norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid dianhydride”), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-(methylnorbornane)-5,5”,6,6”-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid dianhydride (also known as “norbornane-2-spiro-2”-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid dianhydride”). -Cyclohexanone-6'-spiro-2"-norbornane-5,5"-,6,6"-tetracarboxylic dianhydride", methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-(methylnorbornane)-5,5"-,6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2"-norbornane-5,5"-,6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2"-norbornane-5,5"-,6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptan ... -α-Cyclooctanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro- α-Cyclotridecane-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecane-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, etc.

[0096] The weight-average molecular weight of Cardo resin (a-1) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 10,000. By setting it within the above range, good developability can be obtained, as well as sufficient heat resistance and mechanical strength for the cured product.

[0097] [Novolac resin (a-2)]

[0098] From the viewpoint of suppressing excessive heat flow in the cured product caused by heating, it is also preferable that the alkali-soluble resin (A1-2) includes Novolac resin (a-2).

[0099] As the Novolac resin (a-2), various Novolac resins conventionally incorporated into photosensitive compositions can be used. Preferably, the Novolac resin (a-2) is a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol") with an aldehyde under an acid catalyst.

[0100] (Phenols)

[0101] Phenols that can be used in the production of Novolac resin (a-2) include, for example, phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenephenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; and 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, and p-butylphenol. Phenols, including alkylphenols such as p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and resorcinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A, etc. These phenols can be used alone or in combination of two or more.

[0102] Among these phenols, m-cresol and p-cresol are preferred, and a combination of m-cresol and p-cresol is more preferred. In this case, various properties such as heat resistance of the cured product formed using the photosensitive composition can be adjusted by changing the ratio of the two.

[0103] The mixing ratio of m-cresol to p-cresol is not particularly limited, but is preferably 3 / 7 to 8 / 2 or less in terms of the molar ratio of m-cresol to p-cresol. By using m-cresol and p-cresol in the ratios within the aforementioned range, it is easy to obtain a photosensitive composition that can form a cured product with excellent heat resistance.

[0104] In addition, Novolac resins manufactured using m-cresol and 2,3,5-trimethylphenol are also preferred. When using such Novolac resins, it is particularly easy to obtain photosensitive compositions that can form cured products that do not flow excessively due to heating during post-baking.

[0105] The mixing ratio of m-cresol to 2,3,5-trimethylphenol is not particularly limited, but it is preferably 70 / 30 or more and 95 / 5 or less, based on the molar ratio of m-cresol to 2,3,5-trimethylphenol.

[0106] (Aldehydes)

[0107] Aldehydes that can be used in the production of Novolac resin (a-2) include, for example, formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

[0108] (Acid catalyst)

[0109] Examples of acid catalysts that can be used in the production of Novolac resin (a-2) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts can be used alone or in combination of two or more.

[0110] (molecular weight)

[0111] For the weight-average molecular weight (Mw; hereinafter also simply referred to as "weight-average molecular weight") of Novolac resin (a-2) converted to polystyrene, from the viewpoint of the resistance of the cured product formed using the photosensitive composition to flow caused by heating, the lower limit is preferably 2000, more preferably 5000, particularly preferably 10000, further preferably 15000, and most preferably 20000. The upper limit is preferably 50000, more preferably 45000, further preferably 40000, and most preferably 35000.

[0112] As Novolac resin (a-2), at least two resins with different weight-average molecular weights converted from polystyrene can be used in combination. By using resins with different weight-average molecular weights in combination, a balance can be achieved between the developability of the photosensitive composition and the heat resistance of the cured product formed using the photosensitive composition.

[0113] [Modified epoxy resin (a-3)]

[0114] As an alkali-soluble resin (A1-2), considering the ease of forming a cured product that is not easily deformed by heating and has high water resistance, it can be included as an adduct obtained by adding a polybasic anhydride (a-3c) to the reactant of an epoxy compound (a-3a) and a carboxylic acid containing an unsaturated group (a-3b). Such an adduct is also described as "modified epoxy resin (a-3)".

[0115] It should be noted that, in the specification and claims of this application, compounds that meet the above definition but do not belong to the aforementioned Cardo structure resin (a-1) are referred to as modified epoxy resins (a-3).

[0116] Modified epoxy resin (a-3) has unsaturated groups derived from carboxylic acid (a-3b) containing unsaturated groups, and therefore also belongs to photopolymerizable resins (A1-1).

[0117] The following describes epoxy compounds (a-3a), carboxylic acids containing unsaturated groups (a-3b), and polybasic anhydrides (a-3c).

[0118] <Epoxy Compounds (a-3a)>

[0119] The epoxy compound (a-3a) is not particularly limited as long as it has an epoxy group. It can be an aromatic epoxy compound with an aromatic group or an aliphatic epoxy compound without an aromatic group. It is preferred to be an aromatic epoxy compound with an aromatic group.

[0120] The epoxy compound (a-3a) can be a monofunctional epoxy compound or a polyfunctional epoxy compound with two or more functions, preferably a polyfunctional epoxy compound.

[0121] Specific examples of epoxy compounds (a-3a) include difunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidylp-aminophenol, tetraglycidylm-phenylenediamine, and tetraglycidyldiaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; and phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, and trihydroxybiphenyl triglycidyl ether. Trifunctional epoxy resins include methyl phenylmethane triglycidyl ether, glyceryl triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]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; and tetrafunctional epoxy resins include tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraepoxypropoxybiphenyl.

[0122] Furthermore, as the epoxy compound (a-3a), an epoxy compound having a biphenyl skeleton is preferred.

[0123] The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in the main chain.

[0124] The epoxy compound with a biphenyl skeleton is preferably a polyfunctional epoxy compound with two or more epoxy groups.

[0125] By using epoxy compounds with a biphenyl backbone, it is easy to obtain photosensitive compositions that exhibit excellent balance between sensitivity and developability and can form cured products with excellent adhesion to the substrate.

[0126] [Chemical Formula 9]

[0127]

[0128] (In formula (a-3a-1), R) a7 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group that may have substituents, where j is an integer from 1 to 4.

[0129] R a7When the alkyl group has 1 to 12 carbon atoms, specific examples of alkyl groups 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, isonyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

[0130] R a7 In the case of halogen atoms, specific examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0131] R a7 When the phenyl group can have substituents, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 to 5, preferably 0 or 1.

[0132] Examples of substituents include alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, aliphatic acyl groups with 2 to 4 carbon atoms, halogen groups, cyano groups, and nitro groups.

[0133] There is no particular limitation on the epoxy compound (a-3a) having the biphenyl skeleton represented by the above formula (a-3a-1). For example, epoxy compounds represented by the following formula (a-3a-2) can be cited.

[0134] [Chemical Formula 10]

[0135]

[0136] (In formula (a-3a-2), R) a7 And j is the same as in equation (a-3a-1), where k is the average number of repetitions of the structural units within the parentheses, which is between 0 and 10.

[0137] Among the epoxy compounds represented by formula (a-3a-2), the compound represented by formula (a-3a-3) is preferred from the viewpoint that it is particularly easy to obtain a photosensitive composition with excellent balance between sensitivity and developability.

[0138] [Chemical Formula 11]

[0139]

[0140] (In equation (a-3a-3), k is the same as in equation (a-3a-2).)

[0141] (Carboxylic acids containing unsaturated groups (a-3b))

[0142] In preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with a carboxylic acid (a-3b) containing an unsaturated group.

[0143] As the carboxylic acid containing unsaturated groups (a-3b), monocarboxylic acids containing reactive unsaturated double bonds such as acrylic acid groups or methacrylic acid groups in the molecule are preferred. Examples of such carboxylic acids containing unsaturated groups include acrylic acid, methacrylic acid, β-styrylic acid, β-furfurylic acid, α-cyanocinonic acid, and cinnamic acid. In addition, carboxylic acids containing unsaturated groups (a-3b) can be used alone or in combination of two or more.

[0144] Epoxides (a-3a) can be reacted with carboxylic acids (a-3b) containing unsaturated groups using known methods. Preferred reaction methods include, for example, reacting epoxides (a-3a) with carboxylic acids (a-3b) containing unsaturated groups in an organic solvent at a reaction temperature between 50°C and 150°C for several hours to tens of hours, using tertiary amines such as triethylamine and benzylethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride, pyridine, or triphenylphosphine as catalysts.

[0145] The ratio of the amounts of the epoxy compound (a-3a) and the carboxylic acid containing unsaturated groups (a-3b) used in the reaction is generally preferred to be 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and particularly preferably 1:0.9 to 1:1.1, based on the ratio of the epoxy equivalent of the epoxy compound (a-3a) to the carboxylic acid equivalent of the carboxylic acid containing unsaturated groups (a-3b).

[0146] If the ratio of the amount of epoxy compound (a-3a) used to the amount of carboxylic acid containing unsaturated groups (a-3b) used is 1:0.5 to 1:2 in terms of the aforementioned equivalent ratio, there is a tendency to improve the crosslinking efficiency, which is preferred.

[0147] (polyacid anhydrides (a-3c))

[0148] Polybasic anhydrides (a-3c) are anhydrides of carboxylic acids having two or more carboxyl groups.

[0149] As a polyacid anhydride (a-3c), there is no particular limitation. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, compounds represented by the following formula (a-3c-1), and compounds represented by the following formula (a-3c-2) can be cited. In addition, polyacid anhydrides (a-3c) can be used alone or in combination of two or more.

[0150] [Chemical Formula 12]

[0151]

[0152] (In formula (a-3c-2), R) a8 This refers to alkylene groups with 1 to 10 carbon atoms that may have substituents.

[0153] From the viewpoint of easily obtaining a photosensitive composition with excellent balance between sensitivity and developability, a compound having two or more benzene rings is preferred as the polybasic acid anhydride (a-3c). Furthermore, the polybasic acid anhydride (a-3c) is more preferably a compound represented by formula (a-3c-1) and at least one of the compounds represented by formula (a-3c-2).

[0154] The method for reacting an epoxy compound (a-3a) with a carboxylic acid containing an unsaturated group (a-3b) and then reacting the polybasic anhydride (a-3c) can be appropriately selected from known methods.

[0155] Furthermore, regarding the usage ratio, based on the molar number of OH groups in the component after the reaction of the epoxy compound (a-3a) and the carboxylic acid containing unsaturated groups (a-3b), and the equivalent ratio of the anhydride groups of the polybasic acid anhydride (a-3c), it is typically 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it within the above range, a photosensitive composition with good developability can be easily obtained.

[0156] The acid value of the modified epoxy resin (a-3), based on the solid component of the resin, is preferably 10 mg KOH / g or more and 150 mg KOH / g or less, more preferably 70 mg KOH / g or more and 110 mg KOH / g or less. By setting the acid value of the resin to 10 mg KOH / g or more, sufficient solubility in the developer can be obtained. In addition, by setting the acid value to 150 mg KOH / g or less, sufficient curability can be obtained, and good surface properties of the cured product can be achieved.

[0157] The weight-average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 to 40,000, more preferably 2,000 to 30,000. By setting the weight-average molecular weight to 1,000 or more, it is easy to form a cured product with excellent heat resistance and strength. In addition, by setting the weight-average molecular weight to 40,000 or less, it is easy to obtain a photosensitive composition that exhibits sufficient solubility in a developer.

[0158] [Acrylic resin (a-4)]

[0159] Acrylic resin (a-4) is also preferred as a component of alkali-soluble resin (A1-2).

[0160] As an acrylic resin (a-4), a resin comprising structural units from (meth)acrylic acid and / or structural units from other monomers such as (meth)acrylates can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. (Meth)acrylates are compounds represented by the following formula (a-4-1), and are not particularly limited, as long as they do not impede the purpose of the present invention.

[0161] [Chemical Formula 13]

[0162]

[0163] In the above formula (a-4-1), R a9 R is a hydrogen atom or a methyl group. a10 It is a monovalent organic group. This organic group may contain heteroatoms or other bonds and substituents besides hydrocarbon groups. Furthermore, this organic group can be in any form, including straight-chain, branched-chain, and cyclic.

[0164] As R a10Substituents in the organic groups other than hydrocarbon groups are not particularly limited, as long as they do not impair the effects of the invention. Examples include halogen atoms, hydroxyl groups, mercapto groups, thioether groups, cyano groups, isocyano groups, cyanate groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, thiocarbamoyl groups, nitro groups, nitroso groups, carboxylate groups, acyl groups, acyloxy groups, sulfinyl groups, sulfonate groups, phosphino groups, phosphinyl groups, phosphono acid groups, hydroxyimino groups, alkyl ether groups, alkyl thioether groups, aryl ether groups, aryl thioether groups, and amino groups (-NH2, -NHR, -NRR': R and R' each independently represent a hydrocarbon group). The hydrogen atoms in the above substituents can be replaced by hydrocarbon groups. In addition, the hydrocarbon groups included in the above substituents can be any of the following forms: straight-chain, branched, or cyclic.

[0165] Additionally, as R a10 The organic groups can have reactive functional groups such as acryloyloxy, methacryloyloxy, epoxy, and oxetyl.

[0166] Acryloyloxy, methacryloyloxy, and other acyl groups having unsaturated double bonds can be manufactured, for example, by reacting unsaturated carboxylic acids such as acrylic acid and methacrylic acid with at least a portion of the epoxy groups in an acrylic resin (a-4) containing a structural unit having an epoxy group.

[0167] By reacting an unsaturated carboxylic acid with at least a portion of its epoxy groups, a polybasic acid anhydride can be reacted with the groups generated through the reaction.

[0168] Specific examples of polybasic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.

[0169] As a specific example, when acrylic acid is reacted with a structural unit derived from glycidyl methacrylate, a hydroxyl-containing structural unit as shown in the following reaction formula is generated. By reacting a polyacid anhydride such as tetrahydrophthalic acid with such a hydroxyl-containing structural unit, a structural unit having a carboxyl group and an unsaturated double bond that imparts alkali solubility to the resin is generated.

[0170] [Chemical Formula 14]

[0171]

[0172] Acrylic resins (a-4) contain organic groups derived from formula (a-4-1) and having unsaturated double bonds as R. a10 In the case of the structural unit of the compound, this acrylic resin also belongs to the category of photopolymerizable resins (A1-1).

[0173] As R a10 Preferably, the groups are alkyl, aryl, aralkyl, or heterocyclic, and these groups can be substituted with halogen atoms, hydroxyl groups, alkyl groups, or heterocyclic groups. Additionally, if these groups include an alkylene moiety, the alkylene moiety can be interrupted by an ether bond, a thioether bond, or an ester bond.

[0174] When the alkyl group is straight-chain or branched, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of preferred alkyl groups 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.

[0175] When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferred alicyclic groups included in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclic nonyl, tricyclic decyl and tetracyclic dodecyl.

[0176] The compound represented by formula (a-4-1) contains a chain group with an epoxy group as R. a10 Specific examples of compounds represented by formula (a-4-1) in the case of (meth)acrylate include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and other alkyl methacrylates.

[0177] Furthermore, the compound represented by formula (a-4-1) can be a (meth)acrylate containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

[0178] Specific examples of compounds represented by formula (a-4-1) being (meth)acrylates containing alicyclic epoxy groups include compounds represented by formulas (a-4-1a) to (a-4-1o). Among these, compounds represented by formulas (a-4-1a) to (a-4-1e) are preferred in order to keep the developability within a suitable range, and compounds represented by formulas (a-4-1a) to (a-4-1c) are more preferred.

[0179] [Chemical Formula 15]

[0180]

[0181] [Chemical Formula 16]

[0182]

[0183] [Chemical Formula 17]

[0184]

[0185] In the above formula, R a20 R represents a hydrogen atom or a methyl group. a21 R represents a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms. a22 This represents a divalent hydrocarbon group with 1 to 10 carbon atoms, and t represents an integer between 0 and 10. As R a21 Preferably, it is a straight-chain or branched alkylene group, such as methylene, ethylene, propylene, 1,4-butylene, ethyl ethylene, 1,5-pentane, or 1,6-hexane. As R a22 For example, methylene, ethylene, propylene, 1,4-butylene, ethyl ethylene, 1,5-pentene, 1,6-hexene, phenylene, cyclohexene, -CH2-Ph-CH2- (Ph represents phenylene).

[0186] Furthermore, acrylic resins (a-4) can be copolymers obtained by further polymerizing monomers other than (meth)acrylates. Examples of monomers other than (meth)acrylates include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrene compounds. These monomers can be used alone or in combination of two or more.

[0187] Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl (meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, and N-hydroxyethyl-N-methyl (meth)acrylamide.

[0188] Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, medoconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and so on.

[0189] Examples of allyl compounds include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and other allyl esters; allyl oxyethanol; and so on.

[0190] Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and other alkyl vinyl ethers; vinylphenyl ether, vinyltolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinylnaphthyl ether, vinylanthryl ether, and other vinyl aryl ethers; and so on.

[0191] Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthate.

[0192] Examples of styrene derivatives include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, and other alkylstyrene; methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, and other alkoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and other halogenated styrene; and so on.

[0193] The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (a-4) are not particularly limited to the extent that they do not impair the purpose of the present invention. The amount of structural units derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less, relative to the mass of the acrylic resin (a-4).

[0194] When the acrylic resin (a-4) contains structural units with unsaturated double bonds, the amount of structural units with unsaturated double bonds in the acrylic resin (a-4) is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less.

[0195] By including the acrylic resin (a-4) with structural units having unsaturated double bonds in the amount within the above range, the acrylic resin can be introduced into the crosslinking reaction within the resist film and homogenized. Therefore, it is effective in improving the heat resistance and mechanical properties of the cured film.

[0196] The weight-average molecular weight of the acrylic resin (a-4) is preferably 2,000 to 50,000, more preferably 3,000 to 30,000. By setting it to the above range, there is a tendency to easily obtain a uniformity in the film-forming ability and post-exposure developability of the photosensitive composition.

[0197] In addition to the resins mentioned above, resins belonging to both photopolymerizable resins (A1-1) and alkali-soluble resins (A1-2) include: polyester prepolymers obtained by condensing polyols with monobasic or polybasic acids; polyester (meth)acrylates obtained by reacting polyols with (meth)acrylic acid; polyurethane (meth)acrylates obtained by reacting polyols with compounds having two isocyanate groups and then with (meth)acrylic acid; and epoxy (meth)acrylate resins obtained by reacting bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol Novolac type epoxy resin, Resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc., with (meth)acrylic acid.

[0198] The above has described resins that are alkali-soluble (A1-2) and resins that belong to both photopolymerizable resins (A1-1) and alkali-soluble resins (A1-2). However, resins that do not belong to alkali-soluble resins (A1-2) but belong to photopolymerizable resins (A1-1) include polyacetal resins, polyamide resins, polycarbonate resins, polyester resins (polybutylene terephthalate, polyethylene terephthalate, polyarylates, etc.), FR-AS resins, FR-ABS resins, AS resins, ABS resins, polyphenylene ether resins, and polyphenylene sulfide resins. Unsaturated group modified resins are obtained by introducing unsaturated groups such as (meth)acryloyl, vinyl, and allyl groups into resins such as polysulfone resin, polyethersulfone resin, polyetheretherketone resin, fluorinated resin, polyimide resin, polyamide-imide resin, polyamide-bismaleimide resin, polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzimidazole resin, silicone resin, BT resin, polymethylpentene, ultra-high molecular weight polyethylene, FR-polypropylene, (meth)acrylic resin (polymethyl methacrylate, etc.), and polystyrene.

[0199] There are no particular limitations on the methods for modifying unsaturated groups. For example, resins can be modified by copolymerizing monomers with unsaturated groups. In the case of resins having hydroxyl, amino, etc., groups with unsaturated double bonds such as (meth)acryloyl, vinyl, allyl, etc., can be introduced onto such functional groups.

[0200] [Photopolymerizable monomer (A2)]

[0201] The photosensitive composition may contain a photopolymerizable monomer (A2) alone or in combination with the aforementioned resin (A1). As the photopolymerizable monomer (A2), compounds that have traditionally been incorporated into the photosensitive composition may be used without particular limitation.

[0202] Examples of monofunctional photopolymerizable monomers include (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-phenoxy-2-hydroxypropyl methacrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glyceryl mono(meth)acrylate, tetrahydrofurfuryl methacrylate, dimethylamino methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and half-methacrylates of phthalic acid derivatives, etc. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

[0203] Examples of multifunctional photopolymerizable monomers 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, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 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)acryloyloxydiethoxyphenyl)propane, 2,2- Bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glyceryl triacrylate, glyceryl polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., toluene diisocyanate), reactants of trimethyl-1,6-hexanediisocyanate and 1,6-hexanediisocyanate with 2-hydroxyethyl methacrylate, methylene bis(meth)acrylamide, (meth)acrylamidomethyl methylene ether, condensates of polyols and N-hydroxymethyl(meth)acrylamide, and other multifunctional monomers, 1,3,5-triacryloylhexahydro-1,3,5-triazine (triacrylformal), etc. These multifunctional photopolymerizable monomers can be used alone or in combination of two or more.

[0204] Furthermore, considering the ease with which a high-refractive-index cured product can be formed, the compound represented by the following formula (a-01) is also preferred as a photopolymerizable monomer (A2).

[0205] It is also preferred to include compounds represented by the following formula.

[0206] [Chemical Formula 18]

[0207]

[0208] (In formula (a-01), W) 01 and W 02 Each of the groups is independently represented by the following formula (a-02).

[0209] [Chemical Formula 19]

[0210]

[0211] In equation (a-02), ring Z 01 X represents an aromatic hydrocarbon ring. 01 R represents a single bond or a group indicated by -S-. 01 The term "alkylene group" indicates a single bond, an alkylene group with 1 to 4 carbon atoms, or an alkylene group with 1 to 4 carbon atoms that can be substituted by a hydroxyl group, in R... 01 In the case of alkylene oxide, the oxygen atom in the alkylene oxide reacts with the ring Z. 01 Bonding, R 02 Indicates monovalent hydrocarbon group, hydroxyl group, -OR 4A The group shown, -SR 4B The indicated groups include acyl, alkoxycarbonyl, halogen, nitro, cyano, mercapto, carboxyl, amino, carbamoyl, and -NHR. 4C The shown groups, -N(R) 4D The groups shown in )2, sulfonyl groups, or monovalent hydrocarbon groups, -OR 4A The group shown, -SR 4B The groups shown are acyl, alkoxycarbonyl, and -NHR. 4C The indicated group or -N(R) 4D At least a portion of the hydrogen atoms bonded to the carbon atoms in the group shown in )2 are converted by a monovalent hydrocarbon group, hydroxyl group, or -OR group. 4a The group shown, -SR 4B The indicated groups include acyl, alkoxycarbonyl, halogen, nitro, cyano, mercapto, carboxyl, amino, carbamoyl, and -NHR. 4C The shown groups, -N(R) 4D The group shown in )2, the group formed by substitution of methanesulfonyloxy or sulfonyl, R 4A ~R 4D Independently representing a monovalent hydrocarbon group, M represents an integer greater than 0, R 03 It consists of a hydrogen atom, a vinyl group, or a (meth)acryloyl group, with two R atoms. 03 At least one of them is vinyl or (meth)acryloyl.

[0212] Excluding W 01 and W 02 Both of these have hydrogen atoms as R. 03 In this situation,

[0213] Y-shaped ring 01 and ring Y 02 R represents the same or different aromatic hydrocarbon rings. 00 Represents a single bond, a methylene group that may have substituents, an ethylene group that may have substituents and may contain heteroatoms between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, R 3A and R3B (These can be used to independently represent cyano, halogen, or monovalent hydrocarbon groups; N1 and N2 can independently represent integers from 0 to 4.)

[0214] In the above equation (a-02), ring Z is used as the ring. 01 Examples include benzene rings, fused polycyclic aromatic hydrocarbon rings [e.g., fused bicyclic hydrocarbon rings (e.g., naphthalene rings, etc. C]]. 8-20 Fused bicyclic hydrocarbon rings, preferably C 10-16 Fused bicyclic hydrocarbon rings, fused tricyclic aromatic hydrocarbon rings (e.g., anthracene rings, phenanthrene rings, etc.), and fused 2- to 4-cyclic aromatic hydrocarbon rings, etc. 01 Preferably, it is a benzene ring or a naphthalene ring, more preferably a naphthalene ring. It should be noted that W in formula (a-01) 01 and W 02 Each is an independent group represented by the above formula (a-02), therefore, W 01 and W 02 Each contains a ring Z 01 W 01 The ring Z included 01 With W 02 The ring Z included 01 They can be the same or different. For example, one ring can be a benzene ring and the other ring can be a naphthalene ring, but it is particularly preferred that both rings are naphthalene rings.

[0215] Additionally, through X 01 And with W 01 and W 02 The carbon atoms directly bonded to these two are in the Z-ring. 01 The substitution position is not particularly limited. For example, ring Z 01 In the case of a naphthalene ring, the ring Z bonded to the aforementioned carbon atom 01 The corresponding groups can be 1-naphthyl, 2-naphthyl, etc.

[0216] In the above formula (a-02), X 01 Independently represents a single bond or a group indicated by -S-, typically a single bond.

[0217] In the above formula (a-02), R is used as 01 Preferred examples include single bonds; alkylene groups with 1 to 4 carbon atoms, such as methylene, ethylene, 1,3-propylene, 1,2-propylene, and butane-1,2-diyl; and alkylene groups with 1 to 4 carbon atoms that can be substituted by hydroxyl groups, such as -CH2-O-(methyleneoxy), -CH2CH2-O-(ethyleneoxy), -CH2CH2CH2-O-(propyleneoxy), and -CH2CH(OH)CH2-O-. It should be noted that R... 01In the case of alkylene oxide, the oxygen atom in the alkylene oxide reacts with the ring Z. 01 Bonding. Additionally, W in equation (a-01) 01 and W 02 Each is independently represented by a group according to the following formula (a-02), therefore, W 01 and W 02 Each contains R as a divalent group 01 W 01 Includes R 01 With W 02 The R included 01 They can be the same or different.

[0218] In the above formula (a-02), R is used as 02 Examples include alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, etc.). 1-12 Alkyl, preferably C 1-8 Alkyl, more preferably C 1-6 Alkyl groups, etc.), cycloalkyl groups (cyclohexyl groups, etc., C1656), etc. 5-10 Cycloalkyl, preferably C 5-8 cycloalkyl, more preferably C 5-6 cycloalkyl, etc.), aryl (e.g., phenyl, tolyl, xylyl, naphthyl, etc. C 6-14 Aryl, preferably C 6-10 Aryl, more preferably C 6-8 Aryl (e.g., aryl), aralkyl (benzyl, phenethyl, etc. C 6-10 Aryl-C 1-4 Alkyl groups (e.g., alkyl groups); hydroxyl groups; alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc. C60) 1-12 Alkoxy, preferably C 1-8 Alkoxy, more preferably C 1-6 Alkoxy, etc.), cycloalkoxy (cyclohexyloxy, etc. C 5-10 Cycloalkoxy, etc.), aryloxy (phenoxy, etc. C 6-10 Aryloxy, arylalkyloxy (e.g., benzyloxy, etc. C 6-10 Aryl-C 1-4 Alkyloxy groups, etc. -OR 4A The shown group [where R is a group of groups] 4A Indicates a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above). ; Alkyl thio groups (methyl thio, ethyl thio, propyl thio, butyl thio, etc. C 1-12 Alkyl thio group, preferably C 1-8 Alkyl thio group, more preferably C 1-6 alkyl thiols, etc.), cycloalkyl thiols (cyclohexyl thiols, etc. C 5-10 cycloalkyl thiols, etc.), aryl thiols (phenyl thiols, etc. C 6-10 Arylthio), aralkylthio (e.g., benzylthio, etc. C6-10 Aryl-C 1-4 alkyl thioyl) etc. -SR 4B The shown group [where R is a group of groups] 4B Indicates a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above). ; Acyl group (acetyl group, etc. C 1-6 Acyl groups, etc.); Alkoxycarbonyl groups (methoxycarbonyl groups, etc., C 1-4 Alkoxy-carbonyl groups, etc.; halogen atoms (fluorine, chlorine, bromine, iodine, etc.); nitro groups; cyano groups; mercapto groups; carboxyl groups; amino groups; carbamoyl groups; alkylamino groups (methylamino, ethylamino, propylamino, butylamino, etc. C 1-12 Alkylamino, preferably C 1-8 Alkylamino, more preferably C 1-6 Alkylamino, etc.), cycloalkylamino (cyclohexylamino, etc. C 5-10 Cycloalkylamino (e.g.), arylamino (e.g., phenylamino) C 6-10 Arylamino), aralkylamino (e.g., benzylamino, etc. C 6-10 Aryl-C 1-4 Alkylamino) etc. -NHR 4C The shown group [where R is a group of groups] 4C [Indicates a monovalent hydrocarbon group (e.g., the monovalent hydrocarbon group exemplified above).]; Dialkylamino (dimethylamino, diethylamino, dipropylamino, dibutylamino, etc., di(C 1-12 alkyl)amino, preferably di(C) 1-8 alkyl)amino, more preferably di(C) 1-6 Alkyl)amino, etc.), dicycloalkylamino (dicyclohexylamino, etc., di(C 5-10 Cycloalkyl amino (e.g.), diarylamino (e.g., diphenylamino) and di(C) 6-10 Arylamino), diarylalkylamino (e.g., dibenzylamino, etc., di(C) 6-10 Aryl-C 1-4 alkyl)amino) etc.-N(R 4D The group shown in )2 [where R is in the formula] 4D Independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above). ]; (meth)acryloyloxy; sulfonyl; the above-mentioned monovalent hydrocarbon groups, -OR 4A The group shown, -SR 4B The groups shown are acyl, alkoxycarbonyl, and -NHR. 4C The indicated group or -N(R) 4D At least a portion of the hydrogen atoms bonded to the carbon atoms in the group shown in )2 are represented by the aforementioned monovalent hydrocarbon group, hydroxyl group, or -OR group. 4A The group shown, -SR 4B The indicated groups include acyl, alkoxycarbonyl, halogen, nitro, cyano, mercapto, carboxyl, amino, carbamoyl, and -NHR.4C The shown groups, -N(R) 4D Groups shown in )2, (meth)acryloyloxy, methanesulfonyloxy, or sulfonyl-substituted groups [e.g., alkoxyaryl (e.g., methoxyphenyl, etc. C 1-4 Alkoxy C 6-10 aryl), alkoxycarbonylaryl (e.g., methoxycarbonylphenyl, ethoxycarbonylphenyl, etc. C 1-4 Alkoxy-carbonyl C 6-10 Aryl groups, etc.

[0219] Among them, R is representative. 02 It can be a monovalent hydrocarbon group, -OR 4A The group shown, -SR 4B The indicated groups include acyl, alkoxycarbonyl, halogen, nitro, cyano, and -NHR. 4C The shown groups, -N(R) 4D Groups shown in )2, etc.

[0220] As the preferred R 02 Examples of monovalent hydrocarbon groups include [e.g., alkyl groups (e.g., C145-C ... 1-6 Alkyl), cycloalkyl (e.g., C10) 5-8 cycloalkyl), aryl (e.g., C12) 6-10 Aryl), aralkyl (e.g., C40) 6-8 Aryl-C 1-2 [alkyl) etc., alkoxy (C 1-4 Alkyl groups, etc. R is particularly preferred. 02 alkyl [C 1-4 Alkyl (especially methyl) etc.], aryl [e.g., C 6-10 Aryl (especially phenyl) and other monovalent hydrocarbon groups (especially alkyl).

[0221] It should be noted that when M is an integer greater than 2, multiple R... 02 They can be different or the same. Additionally, W 01 The R included 02 With W 2 The R included 02 They can be the same or different.

[0222] In the above formula (a-02), R 02 The number M can be determined based on the ring Z. 01 The type can be selected, for example, it can be 0 to 4, preferably 0 to 3, and more preferably 0 to 2. It should be noted that W 01 M and W in 02 The M in the equation can be the same or different.

[0223] In the above formula (a-02), R 03 It can be a hydrogen atom, a vinyl group, or a (meth)acryloyl group. Two Rs 03 At least one of them is vinyl or (meth)acryloyl. That is, it does not include W. 01 and W 02 Both of these have hydrogen atoms as R. 03 The situation.

[0224] W 01 The R included 03 With W 02 The R included 03 They can be the same or different, as long as they are not both hydrogen atoms. W is preferred. 01 The R included 03 and W 02 The R included 03 Both of these are (meth)acryloyl groups.

[0225] As R 03 From the perspective of ease of synthesis and acquisition of the compound represented by formula (a-01), vinyl or (meth)acryloyl is preferred.

[0226] In the above equation (a-01), Y is used as the ring. 01 and ring Y 02 Examples include benzene rings, fused polycyclic aromatic hydrocarbon rings [e.g., fused bicyclic hydrocarbon rings (e.g., naphthalene rings, etc. C]]. 8-20 Fused bicyclic hydrocarbon rings, preferably C 10-16 Fused bicyclic hydrocarbon rings, fused tricyclic aromatic hydrocarbon rings (e.g., anthracene rings, phenanthrene rings, etc.), and fused 2- to 4-cyclic aromatic hydrocarbon rings, etc. (Y ring) 01 and ring Y 02 Preferably, it is a benzene ring or a naphthalene ring, more preferably a benzene ring. It should be noted that ring Y... 01 and ring Y 02 They can be the same or different; for example, one ring can be a benzene ring and the other ring can be a naphthalene ring.

[0227] In the above formula (a-01), R 00 The terms "-O-", "-NH-", or "-S-" represent single bonds, and can include a single bond. Examples of substituents include cyano groups, halogen atoms (fluorine, chlorine, bromine, etc.), and monovalent hydrocarbon groups (e.g., alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, etc.). 1-6 alkyl), aryl (phenyl, etc. C 6-10Aryl groups, etc., are heteroatoms; for example, oxygen, nitrogen, sulfur, silicon, etc.

[0228] In the above formula (a-01), R is... 3A and R 3B Examples of non-reactive substituents include cyano groups, halogen atoms (fluorine, chlorine, bromine, etc.), and monovalent hydrocarbon groups (e.g., alkyl, aryl (phenyl, etc.)). 6-10 Aryl (e.g.), preferably cyano or alkyl, particularly preferably alkyl. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, etc. 1-6 Alkyl (e.g., C10) 1-4 Alkyl groups, especially methyl groups, etc. It should be noted that when N1 is an integer of 2 or more, R... 3A They can be different or the same. Additionally, when N² is an integer greater than 2, R... 3B They can be different or the same. Furthermore, R 3A With R 3B They can be the same or different. Also, R... 3A and R 3B Relative to ring Y 01 and ring Y 02 The bonding positions (substitution positions) are not particularly limited. Preferred substitution numbers N1 and N2 are 0 or 1, especially 0. It should be noted that N1 and N2 can be the same or different from each other.

[0229] The compound represented by formula (a-01) exhibits high reactivity while maintaining excellent optical and thermal properties. This is especially true for compounds with cyclic Y... 01 and ring Y 02 It is a benzene ring, R 00 In the case of single bonds, the compound represented by the above formula (a-01) has a fluorene skeleton and has superior optical and thermal properties.

[0230] Furthermore, the compound represented by the above formula (a-01) can provide a cured product with high hardness.

[0231] Among the compounds represented by the above formula (a-01), the following compounds are particularly preferred examples.

[0232] [Chemical Formula 20]

[0233]

[0234] [Chemical Formula 21]

[0235]

[0236] [Chemical Formula 22]

[0237]

[0238] [Chemical Formula 23]

[0239]

[0240] [Chemical Formula 24]

[0241]

[0242] [Chemical Formula 25]

[0243]

[0244] [Chemical Formula 26]

[0245]

[0246] [Chemical Formula 27]

[0247]

[0248] [Chemical Formula 28]

[0249]

[0250] [Chemical Formula 29]

[0251]

[0252] [Chemical Formula 30]

[0253]

[0254] [Chemical Formula 31]

[0255]

[0256] In the case of forming a cured product with a high refractive index, it is also preferable that the photosensitive composition comprises a sulfide compound (A2-1) with the following structure and a (meth)acrylate compound (A2-2) with the following structure as a photopolymerizable monomer (A2). In this case, the photosensitive composition contains a solvent (S), or, even without containing a solvent (S), a low-viscosity photosensitive composition applicable to inkjet printing and the like can be prepared.

[0257] (Thioether compound (A2-1))

[0258] The thioether compound (A2-1) is a compound represented by the following formula (a2-1).

[0259] [Chemical Formula 32]

[0260]

[0261] In equation (a2-1), R a01 and R a02 Each can be independently a hydrogen atom or a methyl group. R a03 and R a04 Each is an alkyl group with 1 to 5 carbon atoms. p and q are each 0 or 1.

[0262] R a01 and R a02 Each can be independently a hydrogen atom or a methyl group. R a01 and R a02 They can be different or the same. Considering the ease of synthesis and acquisition of the thioether compound (A2-1), R is preferred. a01 and R a02 same.

[0263] R a03 and R a04 Each is an alkyl group having 1 to 5 carbon atoms. R a03 and R a04 They can be different or the same. Considering the ease of synthesis and acquisition of the thioether compound (A2-1), R is preferred. a03 and R a04 same.

[0264] As R a03 and R a04 Alkyl groups with 1 to 5 carbon atoms can be either straight-chain or branched. Regarding R... a03 and R a04 Examples of alkyl groups with 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl.

[0265] The following compounds are preferred examples of thioether compounds (A2-1).

[0266] [Chemical Formula 33]

[0267]

[0268] ((Meth)acrylate compound (A2-2))

[0269] (Meth)acrylate compound (A2-2) is a compound represented by the following formula (a2-2).

[0270] [Chemical Formula 34]

[0271]

[0272] In equation (a2-2), R a010 It can be a hydrogen atom or a methyl group. R a011 It is an alkylene group with 1 to 3 carbon atoms. R a012 It can be a single bond, an oxygen atom, or a sulfur atom. R a013 It is an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms. m1 is an integer with 0 to 5. m2 is 1 or 2.

[0273] In equation (a2-2), when m2 is 2, multiple R a011 They can be the same or different, but the same is preferred. When m² is 2, multiple R... a012 They can be the same or different, but the same is preferred.

[0274] R a011 It is an alkylene group having 1 to 3 carbon atoms. Specific examples of alkylene groups include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, and propane-2,2-diyl. Among these, methylene, ethane-1,2-diyl (ethylene), propane-1,3-diyl, and propane-1,2-diyl are preferred, and ethane-1,2-diyl (ethylene) is more preferred.

[0275] R a012 It is a single bond, an oxygen atom, or a sulfur atom, preferably a single bond. R a012 In the case of a single bond, m2 is preferably 1.

[0276] R a013 It is an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these, methyl and ethyl are preferred, and methyl is more preferred.

[0277] Specific examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these, methoxy and ethoxy are preferred, and methoxy is more preferred.

[0278] m1 is an integer greater than or equal to 0 and less than or equal to 5, preferably 0 or 1, and more preferably 0.

[0279] The following compounds are preferred examples of (meth)acrylate compounds (A2-2).

[0280] [Chemical Formula 35]

[0281]

[0282] When the photosensitive composition comprises a thioether compound (A2-1) and a (meth)acrylate compound (A2-2) as photopolymerizable monomers (A2), the total ratio of the mass of the thioether compound (A2-1) to the mass of the (meth)acrylate compound (A2-2) relative to the mass of the substrate component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and most preferably 100% by mass.

[0283] When the photosensitive composition comprises a thioether compound (A2-1) and a (meth)acrylate compound (A2-2) as photopolymerizable monomers (A2), the mass ratio of the thioether compound (A1) relative to the mass of the photosensitive composition excluding the mass of the solvent (S) is preferably 5% by mass or more and 30% by mass or less, more preferably 7% by mass or more and 25% by mass or less, and even more preferably 9% by mass or more and 20% by mass or less.

[0284] When the photosensitive composition comprises a thioether compound (A2-1) and a (meth)acrylate compound (A2-2) as a photopolymerizable monomer (A2), the mass ratio of the (meth)acrylate compound (A2) relative to the mass of the photosensitive composition excluding the mass of the solvent (S) is preferably 10% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and even more preferably 30% by mass or more and 40% by mass or less.

[0285] When the photosensitive composition contains a sulfide compound (A2-1) and a (meth)acrylate compound (A2-2) as photopolymerizable monomers (A2), by including the sulfide compound (A2-1) and the (meth)acrylate compound (A2-2) in amounts within the above-mentioned range in the photosensitive composition, the photosensitive composition exhibits excellent photocurability and low viscosity, and can be used to form cured products with high refractive index.

[0286] It should be noted that when the photosensitive composition contains a sulfide compound (A2-1) and a (meth)acrylate compound (A2-2) as photopolymerizable monomers (A2), it is preferable that the mass of the (meth)acrylate compound (A2-2) is greater than the mass of the sulfide compound (A2-1) from the viewpoint of easily using the photosensitive composition to form a cured product with a high refractive index.

[0287] The content of substrate component (A) in the photosensitive composition is not particularly limited to the extent that it does not impair the purpose of the present invention. The content of substrate component (A) in the photosensitive composition is preferably 10% by mass or more and 99.5% by mass or less, more preferably 30% by mass or more and 99% by mass or less, relative to the mass of the photosensitive composition excluding the mass of the solvent (S).

[0288] The content of resin (Al) in the photosensitive composition is preferably 99.5% by mass or less, more preferably 20% by mass or more than 85% by mass or less, and even more preferably 25% by mass or more than 75% by mass or less, relative to the mass of the photosensitive composition excluding the mass of solvent (S).

[0289] The content of photopolymerizable monomer (A2) in the photosensitive composition is preferably 99.5% by mass or less, more preferably 1% by mass or more than 50% by mass, and more preferably 5% by mass or more than 40% by mass, relative to the mass of the photosensitive composition excluding the solvent (S). By setting it to the above range, there is a tendency to easily obtain a balance of sensitivity, developability, and resolution.

[0290] <Photopolymerization Initiator (B)>

[0291] In the photosensitive composition, as a photopolymerization initiator (B), the composition comprises a phosphine oxide compound (B1) and an oxime ester compound (B2). The mass ratio of the oxime ester compound (B2) to the total mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35% by mass or more.

[0292] By using such a photopolymerization initiator (B), it is possible to form cured products with both high refractive index and high transparency using photosensitive compositions. The photopolymerization initiator (B) containing a phosphine oxide compound (B1) and an oxime ester compound (B2) is particularly helpful in improving the transparency of the cured product.

[0293] Without prejudice to the purpose of the invention, the photosensitive composition may contain other photopolymerization initiators (B3) besides phosphine oxide compound (B1) and oxime ester compound (B2).

[0294] From the perspective of easily obtaining the desired effect, the total ratio of the mass of the phosphine oxide compound (B1) to the mass of the oxime ester compound (B2) relative to the mass of the photopolymerization initiator (B) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.

[0295] [phosphine oxide compound (B1)]

[0296] Phosphorus oxide compound (B1) is a pentavalent phosphorus compound with P=O bonds. As phosphorus oxide compound (B1), pentavalent phosphorus compounds with P=O bonds that have been used as photopolymerization initiators can be used without particular restriction.

[0297] Examples of phosphine oxide compounds include compounds having a partial structure represented by the following formula (bI).

[0298] [Chemical Formula 36]

[0299]

[0300] In formula (bI), R b01 and R b02 Each group is independently an alkyl, cycloalkyl, aryl, aliphatic acyl group with 2 to 20 carbon atoms, or an aromatic acyl group with 7 to 20 carbon atoms. Among them, R... b01 and R b02 These two are not both aliphatic acyl groups or aromatic acyl groups.

[0301] As R b01 and R b02 The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. As R b01 and R b02 The alkyl group can be either straight-chain or branched.

[0302] Specific examples of alkyl groups 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.

[0303] As R b01 and R b02 The cycloalkyl group preferably has 5 or more and 12 or fewer carbon atoms. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.

[0304] As R b01 and R b02 The aryl group preferably has 6 to 12 carbon atoms. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups with 1 to 4 carbon atoms, and alkoxy groups with 1 to 4 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.

[0305] As R b01 and R b02The aliphatic acyl group has 2 to 20 carbon atoms, preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 6. The aliphatic acyl group can be linear or branched.

[0306] Specific examples of aliphatic acyl groups include acetyl, propionyl, butyryl, valeryl, hexanoyl, heptayl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanyl, octadecanoyl, nonadecanyl, and eicosanoyl.

[0307] As R b01 and R b02 The aromatic acyl group has 7 to 20 carbon atoms. The aromatic acyl group may have substituents. Examples of substituents include halogen atoms, alkyl groups with 1 to 4 carbon atoms, and alkoxy groups with 1 to 4 carbon atoms. Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6-trimethylbenzoyl, α-naphthoyl, and β-naphthoyl.

[0308] Preferred examples of phosphine oxide compounds (B1) that include the structural portion represented by formula (bI) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphine ester, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0309] [Oxime ester compound (B2)]

[0310] Oxime esters (B2) are compounds having bonds represented by >C=NO-CO-. As oxime esters (B2), compounds having bonds represented by >C=NO-CO- that have traditionally been used as photopolymerization initiators can be used without particular restriction.

[0311] When using only oxime ester compound (B2) as photopolymerization initiator (B), it is sometimes difficult to form a cured product with sufficiently high transparency. On the other hand, when oxime ester compound (B2) is used in combination with phosphine oxide compound (B1) as photopolymerization initiator (B), it is easy to form a cured product with excellent transparency.

[0312] The oxime ester compound (B2) is preferably a compound that does not include compounds having peaks in the wavelength region above 320 nm and below 400 nm in the absorption spectrum, and exhibiting an absorption coefficient of 10 or more at any wavelength in the wavelength region above 400 nm. In this case, a cured product with particularly excellent transparency is easily formed.

[0313] As an oxime ester compound (B2), for example, an oxime ester compound represented by the following formula (b1) is preferred.

[0314] [Chemical Formula 37]

[0315]

[0316] In the above formula (b1), R b11 This indicates an alkyl group with 1 to 10 carbon atoms that may have substituents, a phenyl group that may have substituents, or a carbazole group that may have substituents. a is 0 or 1. R b12 R represents an alkyl group having 1 to 10 carbon atoms, a phenyl group having a substituent, or a carbazole group having a substituent. b13 It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group that may have substituents.

[0317] R b11 When the alkyl group having 1 to 10 carbon atoms is a substituent, the type of substituents in the alkyl group is not particularly limited to the extent that it does not impair the purpose of the present invention.

[0318] Examples of preferred substituents that may be present in alkyl groups having 1 to 10 carbon atoms include alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkoxy groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxy carbonyl groups having 2 to 20 carbon atoms, saturated aliphatic acyloxy groups having 2 to 20 carbon atoms, phenyl groups that may have substituents, phenoxy groups that may have substituents, phenyl thio groups that may have substituents, benzoyl groups that may have substituents, and phenoxy groups that may have substituents. Carbonyl group, benzoyloxy group which may have substituents, phenylalkyl group which may have substituents with 7 to 20 carbon atoms, naphthyl group which may have substituents, naphthoxy group which may have substituents, naphthyl group which may have substituents, naphthoxycarbonyl group which may have substituents, naphthyloxycarbonyl group which may have substituents, naphthylalkyl group which may have 11 to 20 carbon atoms, heterocyclic group which may have substituents, heterocyclic carbonyl group which may have substituents, amino group, amino group substituted with one or two organic groups, morpholino-1-yl group, piperazine-1-yl group, halogen, nitro group, and cyano group, etc.

[0319] Alkyl groups having 1 to 10 carbon atoms can be straight-chain or branched. In this case, the alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0320] R b11 In the case of a phenyl group that may have substituents, the type of substituent is not particularly limited to the extent that it does not impair the purpose of the present invention. Preferred examples of substituents that may be present in the phenyl group include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl group that may have substituents, phenoxy group that may have substituents, benzoyl group that may have substituents, phenoxycarbonyl group that may have substituents, benzoyloxy group that may have substituents, phenylalkyl group that may have substituents, naphthyl group that may have substituents, naphthyloxy group that may have substituents, naphthyloxycarbonyl group that may have substituents, naphthylalkyl group that may have substituents, heterocyclic group that may have substituents, amino group, amino group substituted with one or two organic groups, morpholino-1-yl, piperazine-1-yl, halogen, nitro, and cyano, etc. In R b11 When the phenyl group is a phenyl group that can have substituents, and the phenyl group has multiple substituents, the multiple substituents can be the same or different.

[0321] When the substituent of the phenyl group is an alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1. Furthermore, the alkyl group can be straight-chain or branched. Specific examples of the substituent of the phenyl group being an 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, isonyl, n-decyl, and isodecyl. Additionally, the alkyl group may contain an ether bond (-O-) in the carbon chain. In this case, examples of substituents for the phenyl group include alkoxyalkyl and alkoxyalkoxyalkyl groups. When the substituent of the phenyl group is an alkoxyalkyl group, -R is preferred. b14 -OR b15 The group indicated by R. b14 It is an alkylene group with 1 to 10 carbon atoms, which can be straight-chain or branched. R b15 It is an alkyl group with 1 to 10 carbon atoms, which can be straight-chain or branched. R b14 The number of carbon atoms is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. b15The number of carbon atoms is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0322] When the phenyl group has an alkoxy group as a substituent, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6 or less. Furthermore, the alkoxy group can be straight-chain or branched. Specific examples of phenyl groups having an alkoxy group 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. Additionally, the alkoxy group can contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, 2-methoxy-1-methylethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.

[0323] When the substituent of the phenyl group is a cycloalkyl or cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6 or less. Specific examples of phenyl groups with cycloalkyl substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of phenyl groups with cycloalkoxy substituents include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

[0324] When the substituent of the phenyl group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of phenyl groups having a saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecananoyl, and n-hexadecanoyl. Specific examples of phenyl groups having saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonanoyloxy, n-decyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, and n-hexadecanoyloxy.

[0325] When the phenyl group has an alkoxycarbonyl substituent, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. Specific examples of phenyl groups having an alkoxycarbonyl substituent 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.

[0326] When the substituent of the phenyl group is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10. Furthermore, when the substituent of the phenyl group is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, more preferably 11 to 14. Specific examples of the phenyl group having a phenylalkyl substituent include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of the phenyl group having a naphthylalkyl substituent include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. When the phenyl group has a phenylalkyl or naphthylalkyl substituent, the substituent may further have substituents on the phenyl or naphthyl group.

[0327] When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a heterocyclic group formed by the fusion of the monocyclic rings with each other or with a benzene ring. When the heterocyclic group is a fused ring, the number of monocyclic rings constituting the fused ring is set to 3 or less. Examples of heterocyclic rings constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnabar, and quinoxaline. When the substituent of the phenyl group is a heterocyclic group, the heterocyclic group may further have substituents.

[0328] When the substituent of the phenyl group is an amino group substituted by one or two organic groups, preferred examples of the organic groups include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, saturated aliphatic acyloxy groups with 2 to 20 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenylalkyl groups with 7 to 20 carbon atoms that may have substituents, naphthyl groups that may have substituents, naphthoyl groups that may have substituents, naphthylalkyl groups with 11 to 20 carbon atoms that may have substituents, and heterocyclic groups, etc. Specific examples of these preferred organic groups include groups that are the same as those described above for the substituents of the phenyl group. Specific examples of amino groups 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, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α-naphthoylamino, β-naphthoylamino, and N-acetyl-N-acetyloxyamino, etc.

[0329] Examples of substituents that further substituent the phenyl, naphthyl, and heterocyclic groups included in the phenyl group include alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxy carbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, monoalkylamino groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, halogens, nitro groups, and cyano groups. When the phenyl, naphthyl, and heterocyclic groups included in the phenyl group have further substituents, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4 or less. When the phenyl, naphthyl, and heterocyclic groups included in the phenyl group have multiple substituents, the multiple substituents may be the same or different.

[0330] The above is about R b11 Substituents are described for phenyl groups that may have substituents, and among these substituents, alkyl or alkoxyalkyl groups are preferred.

[0331] R b11 When the phenyl group is a substituted phenyl group, the number of substituents and their bonding positions are not particularly limited without affecting the purpose of the invention. b11 In the case of a phenyl group that can have substituents, from the perspective of excellent base production efficiency, the phenyl group that can have substituents is preferably o-tolyl.

[0332] R b11In the case of a carbazolyl group that may have substituents, the type of substituent is not particularly limited to the extent that it does not impair the purpose of the present invention. Examples of preferred substituents that may be present on the carbon atom of the carbazolyl group include alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, cycloalkoxy groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, saturated aliphatic acyloxy groups with 2 to 20 carbon atoms, phenyl groups that may have substituents, phenoxy groups that may have substituents, phenylthio groups that may have substituents, phenyl carbonyl groups that may have substituents, benzoyl groups that may have substituents, and other substituents. The group may include phenoxycarbonyl, benzoyloxy, phenylalkyl with 7 to 20 carbon atoms, naphthyl, naphthoxy, naphthylcarbonyl, naphthyloxy, naphthyloxycarbonyl, naphthyloxy, naphthyloxy, naphthylalkyl with 11 to 20 carbon atoms, heterocyclic, heterocyclic carbonyl, amino, amino substituted with one or two organic groups, morpholino-1-yl, piperazine-1-yl, halogen, nitro, and cyano.

[0333] R b11 In the case of a carbazolyl group that may have substituents, examples of preferred substituents that may be present on the nitrogen atom of the carbazolyl group include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenoxycarbonyl groups that may have substituents, phenylalkyl groups with 7 to 20 carbon atoms that may have substituents, naphthyl groups that may have substituents, naphthoyl groups that may have substituents, naphthoxycarbonyl groups that may have substituents, naphthylalkyl groups with 11 to 20 carbon atoms that may have substituents, heterocyclic groups that may have substituents, and heterocyclic carbonyl groups that may have substituents. Among these substituents, alkyl groups with 1 to 20 carbon atoms are preferred, alkyl groups with 1 to 6 carbon atoms are more preferred, and ethyl groups are particularly preferred.

[0334] Regarding specific examples of substituents that the carbazoyl group may have, the following are examples: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenylalkyl that may have substituents, naphthylalkyl that may have substituents, heterocyclic groups that may have substituents, and amino groups substituted with one or two organic groups, and R b11 The same applies to examples of substituents present in a phenyl group that may have substituents.

[0335] R b11 Examples of substituents in the case where the phenyl, naphthyl, or heterocyclic group included in the carbazolyl group has further substituents include alkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic acyl groups having 2 to 7 carbon atoms; alkoxy carbonyl groups having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; phenyl; naphthyl; benzoyl; naphthyl; benzoyl group substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, and phenyl; monoalkylamino groups having 1 to 6 carbon atoms; dialkylamino groups having 1 to 6 carbon atoms; morpholino-1-yl; piperazine-1-yl; halogen; nitro; cyano. When the carbazoyl group has substituents including phenyl, naphthyl, and heterocyclic groups, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4 or less. When the phenyl, naphthyl, and heterocyclic groups have multiple substituents, the multiple substituents may be the same or different.

[0336] R b12 It can be an alkyl group with 1 to 10 carbon atoms that may have a substituent, or a phenyl group that may have a substituent, or a carbazolyl group that may have a substituent.

[0337] R b12 When the alkyl group having a substituent has 1 to 10 carbon atoms, the alkyl group can be straight-chain or branched. In this case, the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

[0338] R b12 In this invention, the substituents of alkyl or phenyl groups are not particularly limited to the extent that they do not impair the purpose of the invention.

[0339] Examples of preferred substituents that alkyl groups may have on carbon atoms include alkoxy groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, cycloalkoxy groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, alkoxy carbonyl groups with 2 to 20 carbon atoms, saturated aliphatic acyloxy groups with 2 to 20 carbon atoms, phenyl groups that may have substituents, phenoxy groups that may have substituents, phenyl thio groups that may have substituents, benzoyl groups that may have substituents, and phenoxy carbonyl groups that may have substituents. Benzoyloxy group may have substituents; phenylalkyl group may have substituents with 7 to 20 carbon atoms; naphthyl group may have substituents; naphthoxy group may have substituents; naphthyl group may have substituents; naphthoxycarbonyl group may have substituents; naphthyloxy group may have substituents; naphthylalkyl group may have substituents with 11 to 20 carbon atoms; heterocyclic group may have substituents; heterocyclic carbonyl group may have substituents; amino group; amino group substituted with one or two organic groups; morpholino-1-yl group; piperazine-1-yl group; halogen group; nitro group; and cyano group, etc.

[0340] Examples of preferred substituents that a phenyl group may have on a carbon atom include, in addition to the groups exemplified above as preferred substituents that an alkyl group may have on a carbon atom, alkyl groups having 1 to 20 carbon atoms.

[0341] For specific examples of substituents that alkyl or phenyl groups may have, the following are examples: alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenylalkyl that may have substituents, naphthylalkyl that may have substituents, heterocyclic groups that may have substituents, and amino groups substituted with one or two organic groups, and R b11 The same applies to examples of substituents present in a phenyl group that may have substituents.

[0342] R b12Examples of substituents in the case where the alkyl or phenyl substituent includes phenyl, naphthyl, or heterocyclic group further having substituents include alkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic acyl groups having 2 to 7 carbon atoms; alkoxy carbonyl groups having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; phenyl; naphthyl; benzoyl; naphthyl; benzoyl group substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, and phenyl; monoalkylamino groups having 1 to 6 carbon atoms; dialkylamino groups having 1 to 6 carbon atoms; morpholino-1-yl; piperazine-1-yl; halogen; nitro; cyano. When the alkyl or phenyl group has substituents including phenyl, naphthyl, and heterocyclic groups, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4 or less. When the phenyl, naphthyl, and heterocyclic group has multiple substituents, the multiple substituents may be the same or different.

[0343] R b12 In the case where the carbazolyl group can have substituents, the types of substituents that the carbazolyl group may have are not particularly limited to the extent that they do not impair the purpose of the present invention. As a preferred example of substituents that the carbazolyl group may have, [the following is a list of substituents related to R]. b11 The same applies to examples of substituents in the case of carbazole groups that may have substituents.

[0344] Considering the reactivity of the compound represented by formula (b1), as R b12 Preferably, it is a group represented by formula (b2) or formula (b3) below.

[0345] [Chemical Formula 38]

[0346]

[0347] [Chemical Formula 39]

[0348]

[0349] In equation (b2), R b16 and R b17 Each is a monovalent organic group, and b is 0 or 1. In formula (b3), R b18 The group is selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups, and cyano groups, where A is S or O, and c is an integer between 0 and 4.

[0350] R in equation (b2) b16 Various organic groups can be selected from within the scope of the invention without prejudice to its objectives. As R b16Preferred examples include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenoxycarbonyl groups that may have substituents, phenylalkyl groups that may have 7 to 20 carbon atoms that may have substituents, naphthyl groups that may have substituents, naphthylcarbamoyl groups that may have substituents, naphthoxycarbonyl groups that may have substituents, naphthylalkyl groups that may have 11 to 20 carbon atoms that may have substituents, heterocyclic groups that may have substituents, and heterocyclic carbonyl groups that may have substituents.

[0351] R b16 In this context, alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and ethyl groups are particularly preferred.

[0352] R in equation (b2) b17 Without particularly limiting the scope of the invention, various organic groups may be selected. Regarding R... b17 Specific examples of preferred functional groups include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, phenyl groups that may have substituents, naphthyl groups that may have substituents, and heterocyclic groups that may have substituents. Among these functional groups, R is used as... b17 More preferably, it is a phenyl group that may have a substituent, or a naphthyl group that may have a substituent, and particularly preferably 2-methylphenyl and naphthyl.

[0353] As R b16 Or R b17 Examples of substituents, such as alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxy carbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, monoalkylamino groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, halogens, nitro groups, and cyano groups, etc. b16 Or R b17 When the phenyl, naphthyl, and heterocyclic groups contained therein are further substituents, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4. b16 Or R b17 When the phenyl, naphthyl, and heterocyclic groups contained therein have multiple substituents, the multiple substituents can be the same or different.

[0354] R in equation (b3) b18In the case of an organic group, R b18 Various organic groups can be selected from within the scope of the present invention without prejudice to the purpose of the invention. As R in formula (b3) b18 Preferred examples of organic groups include alkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic acyl groups having 2 to 7 carbon atoms; alkoxy carbonyl groups having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; phenyl groups; naphthyl groups; benzoyl groups; naphthyl groups; benzoyl groups substituted with groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholino-1-yl groups, piperazine-1-yl groups, and phenyl groups; monoalkylamino groups having alkyl groups having 1 to 6 carbon atoms; dialkylamino groups having alkyl groups having 1 to 6 carbon atoms; morpholino-1-yl groups; piperazine-1-yl groups; halogen groups; nitro groups; cyano groups; 2-methylphenylcarbonyl groups; 4-(piperazine-1-yl)phenylcarbonyl groups; 4-(phenyl)phenylcarbonyl groups.

[0355] R b18 In the presence of benzoyl, naphthoyl, benzoyl group substituted with a group selected from the group consisting of alkyl, morpholino-1-yl, piperazine-1-yl, and phenyl groups having 1 to 6 carbon atoms, nitro group, more preferably benzoyl, naphthoyl, 2-methylphenylcarbonyl, 4-(piperazine-1-yl)phenylcarbonyl, or 4-(phenyl)phenylcarbonyl.

[0356] Furthermore, in formula (b3), c is preferably an integer between 0 and 3, more preferably an integer between 0 and 2, and particularly preferably 0 or 1. When c is 1, R b18 The bonding position is preferably relative to R b18 The chemical bond between the phenyl group and the sulfur atom is para-position.

[0357] R b13 It is a phenyl group with 1 to 6 carbon atoms, or a phenyl group that may have substituents. In the case of a phenyl group that may have substituents, the substituents that the phenyl group may have are related to R. b11 The same applies when the phenyl group can have substituents. As R b13 Preferably, it is methyl, ethyl, or phenyl, more preferably methyl or phenyl.

[0358] As a preferred compound among the compounds represented by the above formula (b1), the compound represented by the following formula (b4) can be cited as an example.

[0359] [Chemical Formula 40]

[0360]

[0361] In the above equation (b4), a and R b12and R b13 As described above. R b19 The group is selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups, and cyano groups, where d is an integer between 0 and 4.

[0362] In equation (b4) above, R b19 Without being particularly limited to the scope of the invention, when the organic group is selected, it may be suitably chosen from various organic groups. As R b19 Preferred examples include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl with substituents, phenoxy with substituents, benzoyl with substituents, phenoxycarbonyl with substituents, benzoyloxy with substituents, phenylalkyl with substituents, naphthyl with substituents, naphthyloxy with substituents, naphthyl with substituents, naphthyloxycarbonyl with substituents, naphthylalkyl with substituents, heterocyclic with substituents, amino, amino substituted with one or two organic groups, morpholino-1-yl, piperazine-1-yl, halogen, nitro, and cyano. When s is an integer of 2 to 4, R... b19 They can be the same or different. Furthermore, the number of carbon atoms in a substituent does not include the number of carbon atoms in any further substituents that the substituent may possess.

[0363] R b19 When the carbon atom is alkyl, it is preferable to have 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Additionally, R... b19 In the case of an alkyl group, it can be either straight-chain or branched. As R... b19 Specific examples of alkyl groups 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, isonyl, n-decyl, and isodel. Additionally, R... b19 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0364] R b19 In the case of an alkoxy group, it is preferable to have 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Additionally, R... b19 In the case of an alkoxy group, it can be either straight-chain or branched. As R... b19Specific examples of alkoxy groups 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. Additionally, R... b19 In the case of an alkoxy group, the alkoxy group can contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.

[0365] R b19 When the carbon atom is cycloalkyl or cycloalkoxy, it is preferable to have 3 or more but less than 10 carbon atoms, and more preferably 3 or more but less than 6 carbon atoms. As R b19 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R b19 Specific examples of cycloalkoxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

[0366] R b19 When the group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, it is preferable to have 2 or more carbon atoms and 20 or less, and more preferably 2 or more carbon atoms and 7 or less. As R b19 Specific examples of saturated aliphatic acyl groups include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecananoyl, and n-hexadecanoyl. As R b19 Specific examples of saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonanoyloxy, n-decyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, and n-hexadecanoyloxy.

[0367] R b19 In the case of an alkoxycarbonyl group, it is preferable to have 2 or more but less than 20 carbon atoms, and more preferably 2 or more but less than 7 carbon atoms. As R b19Specific examples of alkoxycarbonyl groups 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.

[0368] R b19 When the carbon atom is phenylalkyl, it is preferable to have 7 or more and 20 or less carbon atoms, and more preferably 7 or more and 10 or less carbon atoms. Additionally, R... b19 When the carbon atom is naphthylalkyl, it is preferable to have 11 to 20 carbon atoms, and more preferably 11 to 14 carbon atoms. As R b19 Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R b19 Specific examples of naphthylalkyl groups include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. b19 In the case of phenylalkyl or naphthylalkyl, R b19 It may further have substituents on the phenyl or naphthyl group.

[0369] R b19 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a heterocyclic group formed by the fusion of said monocyclic rings with each other or with a benzene ring. In the case of a fused ring heterocyclic group, the number of monocyclic rings constituting the fused ring is set to 3 or less. Examples of heterocyclic rings constituting said heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnamic acid, and quinoxaline, etc. b19 In the case of a heterocyclic group, the heterocyclic group may further have substituents.

[0370] R b19When the amino group is substituted by one or two organic groups, preferred examples of the organic groups include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 20 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenylalkyl groups with 7 to 20 carbon atoms that may have substituents, naphthyl groups that may have substituents, naphthylalkyl groups that may have substituents, naphthylalkyl groups with 11 to 20 carbon atoms that may have substituents, and heterocyclic groups, etc. Specific examples of these preferred organic groups are related to R. b19 Similarly, specific examples of amino groups 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, propionylamino, n-butyrylamino, n-valerylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzoylamino, α-naphthoylamino, and β-naphthoylamino.

[0371] As R b19 Examples of substituents, such as alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxy carbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, monoalkylamino groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, halogens, nitro groups, and cyano groups, etc. b19 When the phenyl, naphthyl, and heterocyclic groups contained therein are further substituents, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4. b19 When the phenyl, naphthyl, and heterocyclic groups contained therein have multiple substituents, the multiple substituents can be the same or different.

[0372] R b19 In view of factors such as chemical stability, low steric hindrance, and ease of synthesis of oxime ester compounds, the preferred group is selected from the group consisting of alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, and saturated aliphatic acyl groups with 2 to 7 carbon atoms. More preferably, it is an alkyl group with 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0373] For R b19When the bonded phenyl group is considered to have the position of the chemical bond between the phenyl group and the main skeleton of the oxime ester compound as position 1 and the position of the methyl group as position 2, R b19 The bonding position on the phenyl group is preferably at position 4 or 5, more preferably at position 5. Furthermore, d is preferably an integer between 0 and 3, more preferably an integer between 0 and 2, and particularly preferably 0 or 1.

[0374] R in equation (b4) above b13 R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group that may have substituents. b13 For example, as explained above with respect to equation (b1). R in equation (b4) b13 Preferably, it is methyl, ethyl, or phenyl, and more preferably methyl or phenyl.

[0375] Among oxime ester compounds, the following compounds are preferred examples of compounds included in formula (b1) but not in formula (b4).

[0376] [Chemical Formula 41]

[0377]

[0378] Furthermore, among the oxime ester compounds represented by formula (b4) that are particularly suitable as oxime ester compounds, compounds with the following formula can be cited as examples.

[0379] [Chemical Formula 42]

[0380]

[0381] [Chemical Formula 43]

[0382]

[0383] [Chemical Formula 44]

[0384]

[0385] [Chemical Formula 45]

[0386]

[0387] [Chemical Formula 46]

[0388]

[0389] [Chemical Formula 47]

[0390]

[0391] [Chemical Formula 48]

[0392]

[0393] Furthermore, considering the sensitivity of the photosensitive composition and the transparency of the cured product, the oxime ester compound represented by the following formula (1) is particularly preferred as oxime ester compound (B2).

[0394] [Chemical Formula 49]

[0395]

[0396] (In equation (1), R) b1 R is a hydrogen atom, a nitro group, or a monovalent organic group. b2 and R b3 Each can be a chain alkyl group that may have substituents, a cyclic organic group that may have substituents, or a hydrogen atom, R b2 With R b3 They can bond together to form a ring, R b4 R is a monovalent organic group. b5 (The atom is a hydrogen atom, an alkyl group with 1 to 11 carbon atoms that may have substituents, or an aryl group that may have substituents; n1 is an integer from 0 to 4, and n2 is 0 or 1.)

[0397] In equation (1), R b1 It can be a hydrogen atom, a nitro group, or a monovalent organic group. R b1 In equation (1), the fluorene ring is bonded to -(CO). n2 - indicates that the group is bonded to a different 6-membered aromatic ring. In formula (1), R b1 There are no particular restrictions on the bonding position relative to the fluorene ring. The compound represented by formula (1) has more than one R b1 In the case of the ease of synthesis of the compound represented by formula (1), it is preferable to have one or more R. b1 One of the bonds in R is attached to two positions in the fluorene ring. b1 In the case of multiple Rs, multiple Rs b1 They can be the same or different.

[0398] R b1 In the case of an organic group, R b1 Without particularly limiting the scope of the invention, various organic groups may be appropriately selected without prejudice to the purpose of the invention. As R b1Preferred examples of organic groups include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, saturated aliphatic acyloxy, alkoxy carbonyl, phenyl with substituents, phenoxy with substituents, benzoyl with substituents, phenoxy carbonyl with substituents, benzoyloxy with substituents, phenylalkyl with substituents, naphthyl with substituents, naphthoxy with substituents, naphthyl with substituents, naphthyloxy carbonyl with substituents, naphthyloxy with substituents, naphthylalkyl with substituents, heterocyclic with substituents, heterocyclic carbonyl with substituents, amino groups substituted with one or two organic groups, morpholino-1-yl, and piperazine-1-yl, etc.

[0399] R b1 When the alkyl group is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20 or less, more preferably 1 to 6 or less. Additionally, R... b1 In the case of an alkyl group, it can be either straight-chain or branched. As R... b1 Specific examples of alkyl groups 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, isonyl, n-decyl, and isodel. Additionally, R... b1 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0400] R b1 When the alkoxy group is alkoxy, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 6. Additionally, R... b1 In the case of an alkoxy group, it can be either straight-chain or branched. As R... b1 Specific examples of alkoxy groups 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. Additionally, R... b1In the case of an alkoxy group, the alkoxy group can contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.

[0401] R b1 When the cycloalkyl or cycloalkoxy group is used, the number of carbon atoms in the cycloalkyl or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. As R b1 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R b1 Specific examples of cycloalkoxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

[0402] R b1 When the acyl group or acyloxy group is a saturated aliphatic acyl group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. As R b1 Specific examples of saturated aliphatic acyl groups include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2,2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecananoyl, and n-hexadecanoyl. As R b1 Specific examples of saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonanoyloxy, n-decyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, and n-hexadecanoyloxy.

[0403] R b1 In the case of an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R b1Specific examples of alkoxycarbonyl groups 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.

[0404] R b1 When the alkyl group is phenyl, the number of carbon atoms in the phenyl alkyl group is preferably 7 to 20, more preferably 7 to 10. Additionally, R... b1 When the alkyl group is naphthylalkyl, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R b1 Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R b1 Specific examples of naphthylalkyl groups include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. b1 In the case of phenylalkyl or naphthylalkyl, R b1 It may further have substituents on the phenyl or naphthyl group.

[0405] R b1 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a heterocyclic group formed by the fusion of said monocyclic rings with each other or with a benzene ring. In the case of a fused ring, the number of rings in the monocyclic ring constituting the fused ring is set to 3 or less. The heterocyclic group can be an aromatic group (heteroaryl) or a non-aromatic group. Examples of heterocycles constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnamon, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. b1 In the case of a heterocyclic group, the heterocyclic group may further have substituents.

[0406] R b1 In the case of a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R b1 The same applies to heterocyclic groups.

[0407] Rb1 When the amino group is substituted by one or two organic groups, preferred examples of the organic groups include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic acyl groups with 2 to 21 carbon atoms, phenyl groups that may have substituents, benzoyl groups that may have substituents, phenylalkyl groups with 7 to 20 carbon atoms that may have substituents, naphthyl groups that may have substituents, naphthylalkyl groups that may have substituents, naphthylalkyl groups with 11 to 20 carbon atoms that may have substituents, and heterocyclic groups, etc. Specific examples of these preferred organic groups are related to R. b1 Similarly, specific examples of amino groups 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, propionylamino, n-butyrylamino, n-valerylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzoylamino, α-naphthoylamino, and β-naphthoylamino.

[0408] As R b1 Examples of substituents, such as alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, saturated aliphatic acyl groups with 2 to 7 carbon atoms, alkoxy carbonyl groups with 2 to 7 carbon atoms, saturated aliphatic acyloxy groups with 2 to 7 carbon atoms, monoalkylamino groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, morpholino-1-yl, piperazine-1-yl, halogens, nitro groups, and cyano groups, etc. b1 When the phenyl, naphthyl, and heterocyclic groups contained therein are further substituents, the number of such substituents is not limited to the extent that it does not impair the purpose of the present invention, but is preferably 1 to 4. b1 When the phenyl, naphthyl, and heterocyclic groups contained therein have multiple substituents, the multiple substituents can be the same or different.

[0409] Among the groups described above, R is used as... b1 , is nitro, or R b10 When the group represented by -CO- is present, there is a tendency for increased sensitivity, which is preferred. R b10 Without particularly limiting the scope of the invention, various organic groups may be selected. Regarding R... b10Examples of preferred functional groups include alkyl groups having 1 to 20 carbon atoms, phenyl groups that may have substituents, naphthyl groups that may have substituents, and heterocyclic groups that may have substituents. Among these groups, R... b10 The preferred forms are 2-methylphenyl, thiophene-2-yl, and α-naphthyl.

[0410] Additionally, R b1 When the atom is hydrogen, there is a tendency for improved transparency, which is preferred. It should be noted that R... b1 It is a hydrogen atom and R b4 When the group is represented by formula (1a) or (1b) as described later, there is a tendency for the transparency to become better.

[0411] In equation (1), R b2 and R b3 Each can be a chain alkyl group that may have substituents, a cyclic organic group that may have substituents, or a hydrogen atom. R b2 With R b3 These groups can bond together to form rings. Among these groups, R... b2 and R b3 Preferably, it is a chain alkyl group that may have substituents. R b2 and R b3 In the case of a chain alkyl group that may have substituents, the chain alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

[0412] R b2 and R b3 When the alkyl group is a chain without substituents, the number of carbon atoms in the chain alkyl group is preferably 1 to 20 or less, more preferably 1 to 10 or less, and particularly preferably 1 to 6 or less. As R b2 and R b3 Specific examples of alkyl groups that are chains 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, isonyl, n-decyl, and isodel. Additionally, R... b2 and R b3 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

[0413] R b2 and R b3When the alkyl group is a substituent, the number of carbon atoms in the alkyl group is preferably 1 to 20 or less, more preferably 1 to 10 or less, and particularly preferably 1 to 6 or less. In this case, the number of carbon atoms in the alkyl group does not include the number of carbon atoms in the substituent. The alkyl group with substituent is preferably linear.

[0414] The substituents that the alkyl group may have are not particularly limited to the extent that they do not impair the purpose of the invention. Preferred examples of substituents include cyano groups, halogen atoms, cyclic organic groups, and alkoxycarbonyl groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, fluorine atoms, chlorine atoms, and bromine atoms are preferred. Examples of cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclic groups. Specific examples of cycloalkyl groups include R... b1 The preferred examples are the same for cycloalkyl groups. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthraceneyl, and phenanthrene. Specific examples of heterocyclic groups include R... b1 The preferred example is the case where it is a heterocyclic group. R b1 In the case of an alkoxycarbonyl group, the alkoxy group may contain a straight-chain or a branched-chain alkoxy group, preferably a straight-chain alkoxy group. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.

[0415] When the chain alkyl group has substituents, the number of substituents is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. Typically, the number of substituents is 1 to 20 or less, preferably 1 to 10 or less, and more preferably 1 to 6 or less.

[0416] R b2 and R b3 In the case of a cyclic organic group, the cyclic organic group can be an alicyclic group or an aromatic group. Examples of cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. R b2 and R b3 In the case of a cyclic organic group, the cyclic organic group may have substituents and R b2 and R b3 The same applies to the case of chain alkyl groups.

[0417] R b2 and R b3When the aromatic hydrocarbon group is an aromatic hydrocarbon group, it is preferably a phenyl group, or a group formed by multiple benzene rings bonded together by carbon-carbon bonds, or a group formed by multiple benzene rings fused together. When the aromatic hydrocarbon group is a phenyl group, or a group formed by multiple benzene rings bonded together or fused together, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Specific examples of preferred aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthraceneyl, and phenanthrene.

[0418] R b2 and R b3 When the aliphatic cyclic hydrocarbon group is used, it can be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

[0419] R b2 and R b3 In the case of a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O atoms, or a heterocyclic group formed by the fusion of said monocyclic rings with each other or with a benzene ring. In the case of a fused ring, the number of rings in the monocyclic ring constituting the fused ring is set to 3 or less. The heterocyclic group can be an aromatic group (heteroaryl) or a non-aromatic group. Examples of heterocycles constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, zoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

[0420] R b2 With R b3 They can bond together to form a ring. Contains R b2 With R b3 The group forming the ring is preferably a cycloalkane group. R b2 With R b3 When a cycloalkane group is formed by bonding, the ring constituting the cycloalkane group is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

[0421] R b2 With R b3When the bonded group is a cycloalkane-ide group, the cycloalkane-ide group can fused with one or more other rings. Examples of rings that can fused with cycloalkane-ide groups include benzene rings, naphthalene rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, furan rings, thiophene rings, pyrrole rings, pyridine rings, pyrazine rings, and pyrimidine rings.

[0422] The above explanation of R b2 and R b3 As an example of a preferred functional group, formula -A can be cited. 1 -A 2 The group represented by A1 can be a straight-chain alkylene group, and A2 can be an alkoxy group, cyano group, halogen atom, haloalkyl group, cyclic organic group, or alkoxycarbonyl group.

[0423] A 1 The linear alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6. A 2 When the alkoxy group is an alkoxy group, it can be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6. 2 When the atom is a halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, and fluorine, chlorine, or bromine atoms are more preferred. A 2 In the case of a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group can be linear or branched, preferably linear. A 2 In the case of a cyclic organic group, examples of cyclic organic groups are similar to R. b2 and R b3 The same applies to cyclic organic groups that function as substituents. A 2 In the case of alkoxycarbonyl, examples of alkoxycarbonyl are similar to R. b2 and R b3 The same applies to alkoxycarbonyl groups, which are substituents.

[0424] As R b2 and R b3Preferred specific examples include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxyn-propyl, 4-methoxyn-butyl, 5-methoxyn-pentyl, 6-methoxyn-hexyl, 7-methoxyn-heptyl, 8-methoxyn-octyl, 2-ethoxyethyl, 3-ethoxyn-propyl, 4-ethoxyn-butyl, 5-ethoxyn-pentyl, 6-ethoxyn-hexyl, 7-ethoxyn-heptyl, and 8-ethoxyn-octyl; and 2-cyanoethyl, 3-cyanoethyl, 2-methoxyn-propyl, 3-ethoxyn-propyl, 4-ethoxyn-butyl, 5-ethoxyn-pentyl, 6-ethoxyn-hexyl, 7-ethoxyn-heptyl, and 8-ethoxyn-octyl. Cyanoalkyl groups including 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 including 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; 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, and 2-cyclopentyl. Cycloalkyl alkyl groups including ethyl, 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; 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, and 5-ethoxycarbonyl. Alkoxycarbonyl alkyl groups such as n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl; 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, etc.

[0425] As R b2 and R b3 The preferred groups mentioned above are 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, and 3,3,4,4,5,5,5-heptafluoron-pentyl.

[0426] As R b4 Examples of preferred organic groups, with R b1Similarly, examples include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl with substituents, phenoxy with substituents, benzoyl with substituents, phenoxycarbonyl with substituents, benzoyloxy with substituents, phenylalkyl with substituents, naphthyl with substituents, naphthoxy with substituents, naphthyl with substituents, naphthyloxycarbonyl with substituents, naphthylalkyl with substituents, heterocyclic with substituents, heterocyclic carbonyl with substituents, amino groups substituted with one or two organic groups, morpholino-1-yl, and piperazine-1-yl, etc. Specific examples of these groups are related to R. b1 The specific examples of these groups described are the same. Furthermore, as R... b4 Cycloalkyl alkyl groups, phenoxyalkyl groups having substituents on the aromatic ring, and phenylthioalkyl groups having substituents on the aromatic ring are also preferred. The substituents that phenoxyalkyl and phenylthioalkyl groups may have with respect to R... b1 The phenyl group contained therein may have the same substituents.

[0427] In organic groups, as R b4 The preferred alkyl group is an alkyl group, a cycloalkyl group, a phenyl group that may have substituents, or a cycloalkylalkyl group, or a phenylthioalkyl group that may have substituents on an aromatic ring. As an alkyl group, it is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 8 carbon atoms, particularly preferably an alkyl group with 1 to 4 carbon atoms, and most preferably methyl. Among the phenyl groups that may have substituents, methylphenyl is preferred, more preferably 2-methylphenyl. The cycloalkyl group containing the cycloalkyl group preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and particularly preferably 5 or 6 carbon atoms. The alkylene group containing the cycloalkylalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The alkylene group containing the phenylthioalkyl group that may have substituents on an aromatic ring preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 2 carbon atoms. Among the phenylthioalkyl groups that may have substituents on an aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

[0428] Additionally, as R b4 -A 3 -CO-OA 4 The indicated functional group is also preferred. A 3 It is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0429] A 3When the alkylene group is alkylene, it can be linear or branched, preferably linear. A 3 When the alkylene group is alkylene, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0430] As A 4 Preferred examples include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. As A 4 Preferred specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

[0431] As -A 3 -CO-OA 4 Preferred examples of the indicated group 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.

[0432] The above is about R b4 This has been explained, as R b4 Preferably, it is a group represented by formula (1a) or formula (1b) below.

[0433] [Chemical Formula 50]

[0434]

[0435] (In equations (1a) and (1b), R) b7 and R b8 Each is an organic group, n3 is an integer between 0 and 4, R b7 and R b8 When R is present at an adjacent position on the benzene ring b7 With R b8 They can bond together to form a ring, where n4 is an integer greater than or equal to 1 and less than or equal to 8, n5 is an integer greater than or equal to 1 and less than or equal to 5, n6 is an integer greater than or equal to 0 and less than or equal to (n5+3), and R b9 (It is an organic group.)

[0436] R in equation (1a)b7 and R b8 Examples of the organic groups involved are related to R. b1 Similarly. As R b7 Preferably, it is an alkyl or phenyl group. b7 When it is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R b7 The preferred methyl group. R b7 With R b8 When a ring is formed by bonding, the ring can be either an aromatic ring or an aliphatic ring. As R b7 With R b8 Preferred examples of groups forming a ring, represented by formula (1a), include naphth-1-yl, 1,2,3,4-tetrahydronaphth-5-yl, etc. In the above formula (1a), n3 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0437] In equation (1b) above, R b9 It is an organic group. Examples of organic groups include those related to R. b1 The organic group described herein is the same as the organic group. Among the organic groups, alkyl groups are preferred. Alkyl groups can be straight-chain or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R b9 Examples of preferred compounds include methyl, ethyl, propyl, isopropyl, and butyl, with methyl being more preferred.

[0438] In formula (1b) above, n5 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In formula (1b) above, n6 is 0 or more and (n5+3) or less, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In formula (1b) above, n4 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

[0439] In equation (1), R b5 It is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms that may have substituents, or an aryl group that may have substituents. As R b5 In the case of an alkyl group, the substituents that can be present are preferably phenyl, naphthyl, etc. Additionally, as R... b1 In the case of an aryl group, the substituents that may be present are preferably alkyl groups, alkoxy groups, halogen atoms, etc., having 1 to 5 carbon atoms.

[0440] In equation (1), R is used as b5Examples of the preferred atoms include hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, etc., with methyl or phenyl being more preferred.

[0441] Specific examples of preferred compounds represented by formula (1) include PI-43 to PI-83.

[0442] [Chemical Formula 51]

[0443]

[0444] [Chemical Formula 52]

[0445]

[0446] [Other photopolymerization initiators (B3)]

[0447] Other photopolymerization initiators (B3) include, specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one. 4-Ketoketone, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzoyladium dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthracene Quinone, 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'-bis(dimethylaminobenzophenone), 4,4'-bis(diethylaminobenzophenone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxybenzene Ethyl ketone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, 4-dimethylaminobenzoate, 9-phenylacridinium, 1,7-bis(9-acridyl)heptane, 1,5-bis(9-acridyl)pentane, 1,3-bis(9-acridyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)triazine, 2-methyl-4,6-bis(trichloromethyl)triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-Bis(trichloromethyl)triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxystyryl)-4,6 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyltriazine, etc.

[0448] Other photopolymerization initiators (B3) can be used alone or in combination of two or more.

[0449] The content of photopolymerization initiator (B) is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, relative to the mass of the photosensitive composition (excluding the mass of the solvent (S) described later). By keeping the content of photopolymerization initiator (B) within the above-mentioned range, a photosensitive composition with good curability can be obtained.

[0450] The mass ratio of the oxime ester compound (B2) to the total mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is preferably 35% by mass or more, more preferably 40% by mass or more and 95% by mass or less, and even more preferably 50% by mass or more and 90% by mass or less.

[0451] Photoinitiating aids can be combined with photopolymerization initiator (B). Examples of photoinitiating agents include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionic acid, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, and other thiol compounds. These photoinitiators can be used alone or in combination of two or more.

[0452] <Solvent (S)>

[0453] The photosensitive composition may contain a solvent (S) for purposes such as adjusting coatability. The type of solvent (S) is not particularly limited, but typically an organic solvent.

[0454] Examples of organic solvents that can be incorporated into photosensitive compositions include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ... Alcohol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and other ethers. Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, ethyl hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and 3-methyl-3-methoxypropionate. Other esters include methyl ethyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0455] The content of solvent (S) in the photosensitive composition is not particularly limited to the extent that it does not impair the purpose of the present invention. For example, the content of solvent (S) in the photosensitive composition may be 95% by mass or less, 80% by mass or less, 50% by mass or less, 30% by mass or less, or 20% by mass or less, relative to the mass of the photosensitive composition.

[0456] In addition, when the photosensitive composition contains a solvent (S), the content of the solvent (S) in the photosensitive composition may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more.

[0457] When the cured product of a photosensitive composition is a cured film, such cured films are often used to form high refractive index films in display panels such as organic EL panels.

[0458] In this case, in order to avoid damaging the various components that make up the display panel, it is desirable to minimize the evaporation of solvent (S) during the formation of the high refractive index film and the generation of gas escaping from the solvent (S) remaining in the high refractive index film.

[0459] The problem of solvent (S) evaporation and gas escape can be eliminated by reducing the solvent (S) content in the photosensitive composition. However, generally, when the solvent content in the photosensitive composition is reduced, the coatability of the composition is significantly impaired, especially making it difficult to apply to coating methods such as inkjet printing.

[0460] However, photosensitive compositions comprising the aforementioned sulfide compound (A2-1) and (meth)acrylate compound (A2-2) can sometimes achieve a low viscosity suitable for inkjet printing, even without solvent (S) or with only a small amount of solvent (S).

[0461] Regarding the viscosity of the photosensitive composition, the viscosity measured at 25°C using an E-type viscometer is preferably 40 cP or less, more preferably 30 cP or less, even more preferably 28 cP or less, and particularly preferably 25 cP or less.

[0462] The viscosity of the photosensitive composition can be adjusted, for example, by adjusting the content of the substrate component (A) and the solvent (S).

[0463] Considering the issues of solvent (S) evaporation and gas escape, the solvent (S) content of the photosensitive composition should preferably be 5% by mass or less. Furthermore, the solvent (S) content of the photosensitive composition is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0464] Considering the issues of solvent (S) evaporation and gas escape, the optimal photosensitive composition is one that substantially does not contain solvent (S). "Substantially does not contain solvent (S)" means that, apart from a very small amount of solvent (S) inevitably being carried into the photosensitive composition along with the raw materials, no solvent (S) is intentionally added to the photosensitive composition.

[0465] In the case where the photosensitive composition substantially does not contain solvent (S), the content of solvent (S) in the photosensitive composition is, for example, 0.2% by mass or less, preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less.

[0466] [Other ingredients]

[0467] Without hindering the objectives of the present invention, the photosensitive composition may include, in addition to the components described above, various additives conventionally incorporated into photosensitive compositions. Preferred additives for inclusion in the photosensitive composition include dispersants, adhesion promoters such as silane coupling agents, antioxidants, antiflocculation agents, defoamers, and surfactants. As for surfactants, there are no particular limitations; known components such as fluorinated surfactants and silicone surfactants may be used.

[0468] In addition, when a high refractive index cured material is formed, the photosensitive composition may contain metal compound particles, said metal compound particles being at least one selected from the group consisting of titanium oxide particles, barium titanate particles, cerium oxide particles, and zinc sulfide particles.

[0469] When the photosensitive composition contains the aforementioned metal compound particles, it is particularly easy to form a cured product exhibiting a high refractive index.

[0470] From the perspective of the transparency of the cured product, the average particle size of the metal compound particles is preferably less than 500 nm, and more preferably more than 2 nm and less than 100 nm.

[0471] The content of metal compound particles in the photosensitive composition is not particularly limited to a extent that does not impair the purpose of the present invention. The content of metal compound particles in the photosensitive composition is preferably 5% by mass or more and 70% by mass or less, more preferably 35% by mass or more and 70% by mass or less, and even more preferably 45% by mass or more and 60% by mass or less, relative to the mass of the photosensitive composition excluding the solvent (S).

[0472] By keeping the content of metal compound particles in the photosensitive composition within the above-mentioned range, it is easy to obtain a low-viscosity photosensitive composition and to easily form a cured product with a high refractive index.

[0473] <Method for manufacturing photosensitive composition>

[0474] After mixing the above-described components in the specified amounts, stir the mixture thoroughly to obtain a photosensitive composition.

[0475] Methods for manufacturing solidified products

[0476] Typically, the photosensitive composition described above can be cured by a method comprising:

[0477] The photosensitive composition is molded according to the desired shape of the cured product; and

[0478] The shaped photosensitive composition is exposed.

[0479] The method for molding the photosensitive composition is not particularly limited and can be appropriately selected according to the shape of the cured product. Examples of cured product shapes include film shapes, lens shapes, line shapes, prism shapes, etc., but are not limited to these. Among these shapes, film shapes are preferred.

[0480] When the cured material is in the shape of a lens, prism, or similar object, the photosensitive composition can be filled into a mold corresponding to the shape of the cured material using a scraper or similar tool.

[0481] When the cured material has a linear or similar shape, the photosensitive composition can be coated onto the substrate according to the shape of the cured material. Examples of coating methods include, for instance, inkjet printing.

[0482] In addition, when the photosensitive composition contains an alkali-soluble resin (A1-2) as a substrate component (A), a cured material patterned in any shape, such as a line or dot, can be formed by photolithography using an alkaline developer or an organic solvent as the developer.

[0483] Methods for coating cured materials into film shapes include using contact transfer coating apparatus such as roller coaters, reverse coaters, and bar coaters, as well as non-contact coating apparatus such as spin coaters and curtain flow coaters. Alternatively, photosensitive compositions can also be coated into film shapes using printing methods such as inkjet printing.

[0484] When the photosensitive composition contains a solvent (S), the solvent (S) can be removed from the molded photosensitive composition by means of heating or the like after the photosensitive composition is molded into the desired shape.

[0485] It should be noted that, for example, for photosensitive compositions already formed into a desired shape such as a film, the semi-cured photosensitive composition can be shaped by methods such as imprinting after exposure to a degree of incomplete curing. In this case, the shaped semi-cured photosensitive composition can be further exposed to fully cure it to the desired degree.

[0486] Alternatively, the aforementioned photosensitive composition can be applied to 3D printing, repeatedly performing inkjet printing and exposure-based curing to stack thin film-like cured materials, thereby forming a cured material of the desired shape.

[0487] As an exposure method for curing the photosensitive composition formed by the above method, various methods known as curing methods for photosensitive compositions can be appropriately applied.

[0488] Exposure of the molded photosensitive composition can be performed by irradiation with active energy rays such as ultraviolet light or excimer laser.

[0489] Exposure of the molded photosensitive composition can be performed in a position-selective manner, for example, by exposure through a mask. In the case of position-selective exposure, the exposed photosensitive composition can be developed using an organic solvent to remove the unexposed areas, thereby forming a patterned cured product.

[0490] Examples of developing solutions include organic developing solutions such as monoethanolamine, diethanolamine, and triethanolamine, as well as aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

[0491] In the case of developing, it is preferable to remove the developer thoroughly after developing by methods such as drying based on heating.

[0492] The methods described above can be used to form a cured material with the desired shape and high transparency.

[0493] Furthermore, the cured product obtained using the aforementioned photosensitive composition exhibits excellent flexural resistance and is not easily broken even when bent, thus making it suitable for use in flexible devices. For example, no cracking occurs when a 50 nm thick film formed from the aforementioned cured product is wound around a cylindrical stainless steel rod with a radius of 6 mm, preferably 2 mm.

[0494] [Example]

[0495] The present invention is illustrated below with examples, but the scope of the invention is not limited to these examples.

[0496] [Examples 1-5 and Comparative Examples 1-3]

[0497] In Examples 1-5 and Comparative Examples 1-3, the following compound with the structure was used as the sulfide compound (A2-1) as the base component (A).

[0498] [Chemical Formula 53]

[0499]

[0500] In Examples 1-5 and Comparative Examples 1-3, the (meth)acrylate compound (A2-2) used as the base material component (A) was a compound with the following structure.

[0501] [Chemical Formula 54]

[0502]

[0503] In Examples 1-5 and Comparative Examples 1-3, zirconium oxide particles (average particle size 10 nm) and titanium oxide particles (average particle size 100 nm) were used as metal compound particles.

[0504] In Examples 1-5, the following compound was used as the phosphine oxide compound (B1).

[0505] (B1-1): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0506] (B1-2): 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide

[0507] (B1-3): Ethyl (2,4,6-trimethylbenzoyl)phenylphosphine ester

[0508] In Examples 1-5 and Comparative Examples 1-3, compounds OE1, OE2, and OE3 with the following structures were used as oxime ester compounds (B2). Compounds OE1, OE2, and OE3 all exhibit peaks in the absorption spectrum in the wavelength region above 320 nm and below 400 nm, and show an absorptivity of 10 or more at any wavelength in the wavelength region above 400 nm.

[0509] [Chemical Formula 55]

[0510]

[0511] In Examples 1-5 and Comparative Examples 1-3, propylene glycol monomethyl ether was used as solvent (S).

[0512] The components described above were mixed evenly at the ratios recorded in Table 1 to obtain the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3.

[0513] The viscosity of the obtained photosensitive composition, measured at 25°C using an E-type viscometer, is recorded in Table 1. Furthermore, the refractive index and light transmittance of the cured film formed using the obtained photosensitive composition were measured according to the following processing method. The results of the refractive index measurement are recorded in Table 1.

[0514] <Methods for Determining Refractive Index>

[0515] The photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 were coated onto a glass substrate using an inkjet printer. The coated films were then cured by exposure to a 395 nm UV-LED exposure machine at an exposure dose of 2 J / cm², resulting in a cured film with a thickness of 3 μm. The refractive index of this film at a wavelength of 550 nm was evaluated using a prism coupler manufactured by Metricon.

[0516] <Method for measuring transmittance>

[0517] The light transmittance of the films obtained during refractive index measurement was measured using an Otsuka Electronics MCPD transmittance meter. Based on the measured transmittance, the transmittance of the cured products formed using the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 was evaluated according to the following criteria.

[0518] ◎: Light transmittance is over 96%.

[0519] 〇: Light transmittance is above 95% and below 96%.

[0520] △: Light transmittance is above 93% and below 95%.

[0521] ×: Light transmittance is less than 93%.

[0522] [Table 1]

[0523]

[0524] As can be seen from Examples 1 to 5, the photosensitive composition comprising a sulfide compound (A2-1) and a (meth)acrylate compound (A2-2) with specified structures as substrate component (A) and a photopolymerization initiator composition comprising a phosphine oxide compound (B1) and an oxime ester compound (B2) as photopolymerization initiator (B) has low viscosity and can provide a cured product with excellent transparency.

[0525] According to Comparative Examples 1 to 3, when using a photosensitive composition containing only an oxime ester compound (B2) as a photopolymerization initiator (B), a cured product with excellent transparency cannot be formed.

[0526] [Example 6, Comparative Example 4 and Comparative Example 5]

[0527] In Examples 6, 4, and 5, compounds with the following structures were used as photopolymerizable monomers (A) as substrate component (A).

[0528] [Chemical Formula 56]

[0529]

[0530] In Example 6, Comparative Example 4 and Comparative Example 5, titanium oxide particles (average particle size 100 nm) were used as metal compound particles.

[0531] In Example 6 and Comparative Example 4, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was used as the phosphine oxide compound (B1).

[0532] In Example 6 and Comparative Example 5, compounds OE1 and OE2 with the aforementioned structures were used as oxime ester compounds (B2).

[0533] In Example 6, Comparative Example 4 and Comparative Example 5, propylene glycol monomethyl ether was used as solvent (S).

[0534] The components described above were mixed evenly at the ratios recorded in Table 2 to obtain the photosensitive compositions of Example 6, Comparative Example 4, and Comparative Example 5.

[0535] The viscosity of the obtained photosensitive composition, measured at 25°C using an E-type viscometer, is recorded in Table 2. Furthermore, the refractive index and light transmittance of the cured film formed using the obtained photosensitive composition were measured according to the aforementioned processing method. The results of the refractive index measurement are recorded in Table 2.

[0536] [Table 2]

[0537]

[0538] As can be seen from Example 6, a photosensitive composition comprising a substrate component (A) and a photopolymerization initiator (B), and comprising a phosphine oxide compound (B1) and an oxime ester compound (B2) as photopolymerization initiators (B), can provide a cured product with excellent transparency.

[0539] According to Comparative Examples 4 and 5, when using photosensitive compositions containing only phosphine oxide compound (B1) or only oxime ester compound (B2) as photopolymerization initiators (B), it is impossible to form a cured product with excellent transparency.

[0540] [Examples 7-12-10 and Comparative Examples 6-10]

[0541] In Examples 7-12 and Comparative Examples 6-10, resins R1, R2, and R3 were used as resin (A1). Resin R1 was the Cardo resin obtained in Preparation Example 1 below. Resin R2 was an acrylic resin containing structural units I-IV, with the amount of each structural unit being the value (mass %) indicated in the lower right corner of the brackets for each unit. Resin R3 was a methacryloyl-modified silicone resin having a methacryloyl group (a sesquioxane resin whose monomer composition included 2-(3-(triethoxysilylpropyl)carbamoyl)cyclohexanecarboxylic acid (40 mol%), 3-(trimethoxysilyl)propyl methacrylate (40 mol%), and phenyltrimethoxysilane (20 mol%)). Resins R1 and R2 were alkali-soluble.

[0542] [Chemical Formula 57]

[0543]

[0544] [Preparation Example 1]

[0545] First, 235 g of bisphenol fluorene-type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were added to a 500 mL four-necked flask. Air was blown into the flask at a rate of 25 mL / min while heating to dissolve the resin at 90–100 °C. Next, the solution was slowly heated to 120 °C until completely dissolved, while still cloudy. The solution gradually became transparent and viscous, and stirring continued under these conditions. The acid value was measured during this process, and heating and stirring were continued until the acid value fell below 1.0 mg KOH / g. The target acid value was reached after 12 hours. The solution was then cooled to room temperature to obtain a colorless, transparent, solid bisphenol fluorene-type epoxy acrylate represented by the following formula.

[0546] [Chemical Formula 58]

[0547]

[0548] Next, 600g of 3-methoxybutyl acetate was added to 307.0g of the bisphenol fluorene-type epoxy acrylate obtained in this manner. After dissolution, 80.5g of biphenyl dianhydride and 1g of tetraethylammonium bromide were mixed in, and the mixture was slowly heated to 110–115°C for 4 hours. After confirming the disappearance of the anhydride groups, 38.0g of 1,2,3,6-tetrahydrophthalic anhydride was mixed in, and the mixture was reacted at 90°C for 6 hours to obtain Cardo resin. The disappearance of the anhydride groups could be confirmed using IR spectroscopy.

[0549] In Examples 7-12 and Comparative Examples 6-10, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (A2).

[0550] In Examples 7-12, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was used as the phosphine oxide compound (B1).

[0551] In Examples 7-12 and Comparative Examples 6-10, the aforementioned compounds OE1, OE2 and OE3 were used as oxime ester compounds (B2).

[0552] In Examples 7-12 and Comparative Examples 6-10, propylene glycol monomethyl ether was used as solvent (S).

[0553] The components described above were mixed evenly at the ratios recorded in Table 2 to obtain the photosensitive compositions of Examples 7-12 and Comparative Examples 6-10.

[0554] The sensitivity of the obtained photosensitive composition and the light transmittance of the cured film formed using the obtained photosensitive composition were measured according to the following processing method. The measurement results are recorded in Table 2.

[0555] <Sensitivity Measurement Method>

[0556] The photosensitive compositions of the examples and comparative examples were spin-coated onto a glass substrate and dried at 100°C for 2 minutes. Subsequently, the coating was exposed using a 395nm UV-LED exposure machine to obtain a film. The obtained film was immersed in a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide), and the glass substrate was removed after 2 minutes. After rinsing with pure water and drying, the film thickness was measured. The film thickness after TMAH immersion was at least 90% of the film thickness before TMAH immersion, and the exposure dose was 200 mJ / cm. 2 The following situations are classified as ◎, indicating that the exposure amount is greater than 200mJ / cm. 2 And it is 1J / cm 2 The following situation is judged as ○. Additionally, at an exposure of 1 J / cm²... 2 If the material does not solidify under the specified conditions, it is considered as ×.

[0557] <Method for measuring transmittance>

[0558] The photosensitive compositions of Examples 7-12 and Comparative Examples 6-10 were spin-coated onto a glass substrate and dried at 100°C for 2 minutes. Subsequently, they were exposed using a 395nm UV-LED exposure machine at 2J / cm². 2 The coating film is exposed to a certain amount of exposure to cure it, resulting in a cured film with a thickness of 3μm.

[0559] The light transmittance of the obtained cured film was measured using an Otsuka Electronics MCPD transmittance meter. Based on the measured transmittance, the transmittance of the cured products formed using the photosensitive compositions of Examples 5-10 and Comparative Examples 6-10 was evaluated according to the following criteria.

[0560] ◎: Light transmittance is over 95%.

[0561] 〇: Light transmittance is above 93% and below 95%.

[0562] ×: Light transmittance is less than 93%.

[0563] [Table 3]

[0564]

[0565] As can be seen from Examples 5 to 10, a photosensitive composition comprising a substrate component (A) and a photopolymerization initiator (B), and combining a phosphine oxide compound (B1) and an oxime ester compound (B2) as photopolymerization initiators (B), can provide a cured product with excellent transparency.

[0566] According to Comparative Examples 6 to 10, when using photosensitive compositions containing only phosphine oxide compound (B1) or only oxime ester compound (B2) as photopolymerization initiators (B), it is impossible to form a cured product with excellent transparency.

Claims

1. A photosensitive composition which is a photosensitive composition comprising a base material component (A) and a photopolymerization initiator (B), the base material component (A) comprises a photopolymerizable monomer (A2), the photopolymerization initiator (B) is a combination of a phosphine oxide compound (B1) and an oxime ester compound (B2), the photopolymerizable monomer (A2) is a thioether compound (A2-1) represented by the following formula (a2-1) and a (meth)acrylate compound (A2-2) represented by the following formula (a2-2), a mass ratio of a mass W2 of the oxime ester compound (B2) with respect to a total of a mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35 mass% or more, [Chemical Formula 1] In formula (a2-1), R a01 and R a02 each independently is a hydrogen atom or a methyl group, R a03 and R a04 each independently is an alkyl group having 1 to 5 carbon atoms, p and q each independently are 0 or 1, [Chemical Formula 2] In formula (a2-2), R a010 is a hydrogen atom or a methyl group, R a011 is an alkylene group having 1 to 3 carbon atoms, R a012 is a single bond, an oxygen atom, or a sulfur atom, R a013 is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, m1 is an integer of 0 to 5, and m2 is 1 or 2. 2.A photosensitive composition which is a photosensitive composition comprising a base material component (A) and a photopolymerization initiator (B), the base material component (A) is a photopolymerizable monomer (A2) having an ethylenic unsaturated double bond represented by the following formula, [Chemical Formula 3] the photopolymerization initiator (B) is a combination of a phosphine oxide compound (B1) and an oxime ester compound (B2), the oxime ester compound (B2) is a compound represented by the following formula OE1, [Chemical Formula 4] a mass ratio of a mass W2 of the oxime ester compound (B2) with respect to a total of a mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35 mass% or more. 3.A photosensitive composition which is a photosensitive composition comprising a base material component (A) and a photopolymerization initiator (B), the base material component (A) comprises a resin (A1) and a photopolymerizable monomer (A2), the photopolymerization initiator (B) is a combination of a phosphine oxide compound (B1) and an oxime ester compound (B2), the resin (A1) is any of a Cardo resin, an acrylic resin comprising structural units I to IV represented by the following formula, and a methacryl-modified silicone resin having a methacryl group, [Chemical Formula 5] the oxime ester compound (B2) is a compound represented by the following formula OE1, [Chemical Formula 6] a mass ratio of a mass W2 of the oxime ester compound (B2) with respect to a total of a mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2) is 35 mass% or more.

4. The photosensitive composition of claim 1, wherein The oxime ester compound (B2) comprises a compound having a peak in a wavelength region of 320 nm or more and less than 400 nm in an absorption spectrum and showing a light absorption coefficient of 10 or more at any wavelength in a wavelength region of 400 nm or more.

5. The photosensitive composition of claim 1, wherein The oxime ester compound (B2) is a compound represented by the following formula (1), [Chemical Formula 7] In formula (1), R b1 is a hydrogen atom, a nitro group, or a monovalent organic group, R b2 and R b3 each is a chain alkyl group which can have a substituent, a cyclic organic group which can have a substituent, or a hydrogen atom, R b2 and R b3 may be bonded to each other to form a ring, R b4 is a monovalent organic group, R b5 is a hydrogen atom, an alkyl group having 1 or more and 11 or less carbon atoms which can have a substituent, or an aryl group which can have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1. 6.A cured product of the photosensitive composition according to any one of claims 1 to 5. 7.A method for producing a cured product, comprising: molding the photosensitive composition according to any one of claims 1 to 5 according to a shape of a cured product to be formed; and exposing the molded photosensitive composition.

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