TW201607935A - Composition, film, optical device, and compound - Google Patents

Abstract

The invention provides a composition, a film, an optical device, and a compound that can form a film having a high refractive index and exhibits excellent developability and curability. The composition of the invention includes a compound represented by the following general formula (1). In the general formula (1), Ar1-Ar4 each represent an aromatic ring group independently. At least one of Ar1-Ar4 is a polycyclic aromatic group and satisfies the following requirement 1 or requirement 2. Requirement 1: At least one of Ar1-Ar4 has a substituent containing an acid group and a polymerizable group. Requirement 2: At least one of Ar1-Ar4 has a substituent containing an acid group and at least one of Ar1-Ar4 has a substituent containing a polymerizable group.

Description

Composition, film, optical device, compound

The present invention relates to a composition comprising a compound having a specific structure, a film obtained from the composition, an optical device comprising the film, and a compound contained in the composition.

In the past, a film formed of a composition (a composition containing a resin or a polymerizable compound) used in an optical material or the like is required to have a high refractive index. Further, when it is applied to various members, a pattern is required. Therefore, the composition is also required to have excellent developability and hardenability. Under the circumstances, for example, Patent Document 1 discloses an alkali-soluble photosensitive resin composition in which a component having a polymerizable group and an anthracene skeleton is disclosed.

[Chemical 1] [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-161315

[Problems to be solved by the invention]

In recent years, as optical devices (solid-state imaging devices, display devices, and the like) are highly functionalized or miniaturized, a refractive index, developability, and hardenability are further required for a composition used as an optical material. The present inventors have studied the composition described in Patent Document 1, and as a result, it has been confirmed that the above three properties cannot be simultaneously achieved and further improvement is required. The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition which can form a film exhibiting a high refractive index and which exhibits excellent developability and hardenability. Another object of the present invention is to provide a film formed of the above composition, an optical device including the film, and a compound. [Means for solving the problem]

The present inventors have made an effort to solve the above problems, and as a result, have found that a desired effect can be obtained by using a compound having a specific structure, and the present invention has been completed. That is, the inventors of the present invention have found that the above problems can be solved by the following configuration.

(1) A composition comprising a compound represented by the following formula (1). (2) The composition according to (1), wherein, in the formula (1), Ar ³ is bonded to Ar ⁴ . (3) The composition according to (1) or (2), wherein the compound is a compound represented by the following formula (2). (4) The composition according to (3), wherein in the formula (2), at least one of Ar ⁵ and Ar ⁶ is a polycyclic aromatic group. (5) The composition according to any one of (1) to (4) wherein the acid group is a carboxylic acid group. (6) The composition according to any one of (1) to (5) further comprising a polymerizable compound other than the compound represented by the formula (1). (7) The composition according to any one of (1) to (6) further comprising a polymer having an acid group and a polymerizable group. (8) The composition according to (7), wherein the polymer further has an aromatic ring group. (9) The composition according to any one of (1) to (8), wherein the substituent comprising an acid group and a polymerizable group is a group represented by the formula (X-1). (10) A film formed from the composition according to any one of (1) to (9). (11) An optical device comprising the film of (10). (12) A compound represented by the following formula (1). (13) The compound according to (12), wherein, in the formula (1), Ar ³ is bonded to Ar ⁴ . (14) A compound according to (12) or (13), wherein the formula (1) is represented by the formula (2). (15) The compound according to (14), wherein in the formula (2), at least one of Ar ⁵ and Ar ⁶ is a polycyclic aromatic group. The compound according to any one of (12) to (15), wherein the acid group is a carboxylic acid group. (17) The compound according to any one of (12) to (16), wherein the substituent comprising an acid group and a polymerizable group is a group represented by the formula (X-1). [Effects of the Invention]

According to the present invention, it is possible to provide a composition which can form a film exhibiting a high refractive index and which also exhibits excellent developability and hardenability. Further, according to the present invention, a film formed of the composition, an optical device including the film, and a compound can be provided.

Hereinafter, the composition and the like of the present invention will be described. Further, in the present specification, the (meth) acrylate means acrylate or methacrylate, and the (meth) propylene oxime means propylene methoxy or methacryloxy group. Further, in the present specification, the numerical range indicated by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

<Composition> The composition of the present invention contains the compound represented by the formula (1).

[Chemical 2] General formula (1)

In the formula (1), Ar ¹ to Ar ⁴ each independently represent an aromatic ring group. The aromatic ring group may have a substituent as described below. Further, Ar ¹ to Ar ⁴ may be bonded to each other by a single bond or a divalent linking group. The type of the aromatic ring group is not particularly limited, and examples thereof include an aromatic hydrocarbon group (aryl group), an aromatic heterocyclic group (heteroaryl group), and a group in which these are combined. Specific examples of the ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a triphenylene ring, an anthracene ring, a condensed tetraphenyl ring, and a biphenyl ring (two phenyl groups may be used arbitrarily The connection style is linked, and the triphenyl ring (three phenyl groups can be linked in any connection mode). Examples of the aromatic heterocyclic group include an aromatic heterocyclic group containing a five-membered ring, a six-membered ring or a seven-membered ring or a fused ring thereof. Examples of the hetero atom contained in the aromatic heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, and an imidazole. Ring, pyrazole ring, triazole ring, furazan ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring , benzothiophene ring, anthracene ring, porphyrin ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, anthracene Cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, indazole ring, acridine ring, pyridine ring, morpholine Phenanthroline) ring, phenazine ring, naphthyridine ring, anthracene ring, acridine ring and the like.

In addition, at least one of Ar ¹ to Ar ⁴ is a polycyclic aromatic group, and at least one of the refractive index of the formed film is more excellent, the developability is excellent, and the curability is excellent (hereinafter, also referred to as " More preferably, the effect of the present invention is that the two to four of Ar ¹ to Ar ⁴ are polycyclic aromatic groups. The polycyclic aromatic group is a group formed by condensing a plurality of aromatic ring groups, and specific examples thereof include a polycyclic aromatic hydrocarbon group (polycyclic aromatic hydrocarbon ring group) or a polycyclic aromatic heterocyclic group. Here, the polycyclic aromatic hydrocarbon group means a group containing an aromatic hydrocarbon ring having two or more rings, and more specifically, a condensed ring having two or more monocyclic aromatic hydrocarbon rings (benzene rings). Base. Among them, a group containing a ring in which two or more monocyclic aromatic hydrocarbon rings are condensed with each other is preferred. Specific examples of the ring constituting the polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a 1,2-benzophene ring, and a 1,2-benzo compound. Fluoranene ring, anthracene ring, triphenylene ring, tetracene ring, benzofluorene ring, picene ring, anthracene ring, pentacene ring, hexacene Ring, heptacene ring, coronene ring, and the like. Among them, a naphthalene ring is preferred. In addition, the polycyclic aromatic heterocyclic group is a group containing an aromatic heterocyclic ring having two or more rings, and more specifically, has two or more rings and has one or more monocyclic aromatic impurities. The base of the condensed ring of the ring. Among them, a ring containing one or more monocyclic aromatic hydrocarbon rings and one or more monocyclic heterocyclic ring-condensed rings or a ring containing two or more monocyclic heterocyclic rings is preferable. Base. Specific examples of the ring constituting the polycyclic aromatic heterocyclic group include an acridine ring, a benzoquinoline ring, an oxazole ring, a phenazine ring, a phenazin ring, a phenanthroline ring, a carboline ring, and a ring. a cyclazine ring, a quindoline ring, a benzo[lmn]phenanthridine, thebenidine ring, a quinindoline ring, a triphenyldithiazine ring, Triphenyl dioxin ring, phenanthrazine ring, anthrazine ring, naphthalene diazabenzene ring, diazacarbazole ring (representing any carbon atom constituting a porphyrin ring) a ring substituted with a nitrogen atom), a phenoline ring, a dibenzofuran ring, a dibenzothiophene ring, a naphthopyrene ring, a naphthothiophene ring, a benzodifuran ring, a benzodithiophene ring, a naphtho Difuran ring, naphthacene dithiophene ring, indenofuran ring, indenodifuran ring, indenothiophene ring, indenodithiophene ring, thioindole ring, phenoxathiin ring, naphtho[2,3 -b] thiophanthrene ring (naphthothiophene ring) and the like. The monocyclic heterocyclic ring constituting the polycyclic aromatic heterocyclic group is not particularly limited, and specific examples thereof include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, and a thiazole ring. , isothiazole ring, thiadiazole ring, imidazole ring, pyrazole ring, triazole ring, furazan ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring Wait.

The following substituents may be contained in Ar ¹ to Ar ⁴ . Examples of the type of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), an alkynyl group, an aryl group, and a heteroaryl group. Base, cyano, hydroxy, nitro, carboxy, alkoxy, aryloxy, nonyloxy, heteroaryloxy, decyloxy, amine methoxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyl Oxyl, amine (including anilino), ammonium, mercaptoamine, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkyl or aromatic Alkylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkyl or arylsulfinyl, alkyl or arylsulfonyl, hydrazine Alkyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, aryl or heterocyclic azo, fluorenylene, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, Phosphoninyl, decyl, decyl, ureido, boronic acid (-B(OH) ₂ ), phosphate (-OPO(OH) ₂ ), sulfate (-OSO ₃ H), or a combination of these groups The basis of the formation.

Further, the compound satisfies the following requirement 1 or requirement 2. Requirement 1: At least one of Ar ¹ to Ar ⁴ has a substituent including an acid group and a polymerizable group. Requirement 2: At least one of Ar ¹ to Ar ⁴ has a substituent including an acid group, and at least one of Ar ¹ to Ar ⁴ has a substituent containing a polymerizable group. Hereinafter, each requirement will be described in detail.

(Requirement 1) The requirement 1 is that at least one of Ar ¹ to Ar ⁴ has a substituent including an acid group and a polymerizable group (hereinafter, simply referred to as "substituent X"). Further, the substituent X is a so-called monovalent substituent. In a requirement, as long as at least one of Ar ¹ ~ Ar ⁴ has a substituent X can be, also two or more Ar ¹ ~ Ar ⁴ comprises a substituent group X. Further, a plurality of substituents X may be substituted with any one of Ar ¹ to Ar ⁴ . Further, Ar ¹ to Ar ⁴ may further contain a substituent other than the substituent X. Examples of the "acid group" contained in the substituent X include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boronic acid group. More preferably, it is a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and further preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphine group. An acid group or a phosphinic acid group is particularly preferably a carboxylic acid group.

The "polymerizable group" contained in the substituent X may, for example, be a radical polymerizable group or a cationic polymerizable group. As the radical polymerizable group, a generally known radical polymerizable group can be used, and a preferred radical polymerizable group is a polymerizable group having an ethylenically unsaturated bond capable of undergoing radical polymerization, and specific examples thereof include a polymerizable group. Vinyl, (meth) propylene decyloxy, and the like. Among them, a (meth) propylene fluorenyloxy group is preferred, and an acryloxy group is more preferred. As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specific examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spiro ortho acid. Spiroorthoester, ethyleneoxy, and the like. Among them, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group or a vinyloxy group is particularly preferred.

The substituent X may contain two or more acid groups, and in this case, the types of the acid groups may be the same or different. Two or more polymerizable groups may be contained in the substituent X. In this case, the types of the polymerizable groups may be the same or different. The form in which the acid group and the polymerizable group are contained in the substituent X may be a chain-like saturated hydrocarbon group (which may be linear or branched, preferably having a carbon number of 1 to 10) or a cyclic saturated hydrocarbon group. A linking group such as a carbon number of 3 to 10) or an aromatic group (preferably, a carbon number of 5 to 10, for example, a phenylene group) is bonded to an acid group and a polymerizable group to form a monovalent substituent. A preferred embodiment of the substituent X is a group represented by the formula (X-1). Further, in the following formula, "*" indicates the bonding position.

[Chemical 3] General formula (X-1)

In the general formula (X-1), L _X1 , L _X2 and L _X3 each independently represent a single bond or a divalent linking group. The divalent linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It may be unsubstituted and may further have a substituent. More specifically, the divalent linking group may, for example, be a divalent chain saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 20 carbon atoms) or a divalent cyclic saturated hydrocarbon group (more preferably Preferably, the carbon number is 3 to 20), the divalent aromatic group (preferably having a carbon number of 5 to 20, such as a phenyl group), -O-, -S-, -SO ₂ -, -NR _L -, -CO -, -NH-, -COO-, -CONR _L -, -O-CO-O-, -SO ₃ -, -NHCOO-, -SO ₂ NR _L -, -NH-CO-NH-, or A group in which two or more kinds are combined (for example, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, etc.). Here, R _L represents a hydrogen atom or an alkyl group (preferably, a carbon number of 1 to 10).

The divalent linking group may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, and a hydroxyl group and an amino group. a carboxyl group having 1 to 6 carbon atoms such as a carboxyl group, a sulfonylamino group, an N-sulfonylguanamine group or an ethoxycarbonyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; A halogen atom such as chlorine or bromine; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a carbonate group such as a cyano group or a t-butyl carbonate; and the like.

In the formula (X-1), W represents a trivalent linking group. The trivalent linking group is preferably a group obtained by removing one arbitrary hydrogen atom from the specific example of the divalent linking group represented by the above L _X1 to L _X3 . More specifically, -CH<, -N<, etc. are mentioned.

In the formula (X-1), V _a represents an acid group. The definition of the acid group is as described above. In the formula (X-1), V _b represents a polymerizable group. The definition of the polymerizable group is as described above.

(Requirement 2) at least one of the elements 2 are intended to Ar ¹ ~ Ar ⁴ has a substituent group containing an acid group (hereinafter, also simply referred to as "substituent Y"), and Ar ¹ ~ Ar ^4, at least one having a polymerizable The substituent of the group (hereinafter, also referred to simply as "substituent Z"). Further, the substituent Y and the substituent Z are so-called monovalent substituents. In elements 2, as long as at least one of Ar ¹ ~ Ar ⁴ has a substituent Y can be, also two or more Ar ¹ ~ Ar ⁴ comprises a substituent group Y. Further, a plurality of substituents Y may be substituted with any one of Ar ¹ to Ar ⁴ . In elements 2, as long as at least one of Ar ¹ ~ Ar ⁴ has a substituent Z can, also two or more Ar ¹ ~ Ar ⁴ comprises a substituent group Z. Further, a plurality of substituents Z may be substituted with any one of Ar ¹ to Ar ⁴ . Further, the substituent Y and the substituent Z may be simultaneously substituted on any of Ar ¹ to Ar ⁴ . Further, Ar ¹ to Ar ⁴ may further contain a substituent other than the substituent Y and the substituent Z. The definition of the acid group contained in the substituent Y is as described above. The substituent Y contains at least one acid group, and may contain two or more acid groups. When two or more acid groups are contained, the types of acid groups may be the same or different. The definition of the polymerizable group contained in the substituent Z is as described above. The substituent Z contains at least one polymerizable group, and may contain two or more polymerizable groups. When two or more polymerizable groups are contained, the types of the polymerizable groups may be the same or different.

A preferred embodiment of the substituent Y is a group represented by the formula (Y-1). Further, in the following formula, "*" indicates the bonding position. General formula (Y-1) *-L _Y1 - V _{a In} the above formula (Y-1), L _Y1 represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as those of the divalent linking group represented by the above L _X1 to L _X3 . Further, the substituent may further L _Y1 V _a. In the formula (Y-1), V _a represents an acid group.

A preferred embodiment of the substituent Z is a group represented by the formula (Z-1). Further, in the following formula, "*" indicates the bonding position. General formula (Z-1) *-L _Z1 - V _{b In} the above formula (Z-1), L _Z1 represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as those of the divalent linking group represented by the above L _X1 to L _X3 . In addition, L _Z1 may further replace V _b . In the formula (Z-1), V _b represents a polymerizable group.

(Preferred embodiment) As one of the preferable embodiments of the compound represented by the above formula (1), Ar ³ is bonded to Ar ⁴ in terms of the effect of the present invention being more excellent. Here, "Ar ³ and Ar ^{4 are} linked" means that Ar ³ and Ar ^{4 are} linked via a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as those of the divalent linking group represented by the above L _X1 to L _X3 .

The best form of the compound represented by the above formula (1) is a compound represented by the formula (2), and the effect of the present invention is more excellent.

[Chemical 4] General formula (2)

In the formula (2), Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ each independently represent an aromatic ring group. The definition of the aromatic ring group is as described above. Further, the aromatic ring group may have a substituent. Further, Ar ⁵ to Ar ⁶ each constitute an aromatic ring group in the form of two carbon atoms in the formula (2). Further, at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ is a polycyclic aromatic group, and more preferably Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ in terms of the effect of the present invention. Two to four of them are polycyclic aromatic groups. Among them, in terms of the effect of the present invention being more excellent, at least one of Ar ⁵ to Ar ⁶ is preferably a polycyclic aromatic group. Further, when at least one of Ar ⁵ to Ar ⁶ is a polycyclic aromatic group, each of Ar ⁵ to Ar ⁶ constitutes a polycyclic aromatic ring group in the form of two carbon atoms in the formula (2).

Further, the compound satisfies the following requirement 3 or requirement 4. Requirement 3: At least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group and a polymerizable group (the substituent X). Requirement 4: At least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group (the substituent Y), and at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has A substituent containing a polymerizable group (the substituent Z).

In the element 3, at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may have a substituent X, and two or more of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may include a substituent X. Further, a plurality of substituents X may be substituted with any one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ . Further, Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may further include a substituent other than the substituent X. Further, the definition and preferred form of the substituent X are as described above.

In the element 4, at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may have a substituent Y (or a substituent Z), and ^{two of} Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may be used. The above includes a substituent Y (or a substituent Z). Further, a plurality of substituents Y (or a plurality of substituents Z) may be substituted with any one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ . Further, Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ may further include a substituent other than the substituent Y (or the substituent Z). Further, the substituent Y and the substituent Z may be simultaneously substituted in any one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ . Further, the definitions and preferred forms of the substituent Y and the substituent Z are as described above.

The method for synthesizing the compound represented by the formula (1) is not particularly limited, and a known method can be used for the synthesis.

<Composition> The composition of the present invention contains the compound represented by the above formula (1). In addition, the compound represented by the formula (1) may be used alone or in combination of two or more. In the case where the film of the composition of the present invention is used as the high-refractive-index film, the content of the compound represented by the formula (1) contained in the composition is more excellent in terms of the effects of the present invention. With respect to all the solid components in the composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 30% by mass or more. The upper limit is not particularly limited, and may be, for example, 100% by mass, and in the case of including any of the other optional components described below, it is usually 80% by mass or less, and in many cases, it is 60% by mass or less. Further, the solid content means a component which forms the following film, and does not contain a solvent.

<Other optional components> The composition may contain other compounds than the compound represented by the above formula (1), and may contain, for example, a polymerizable compound, a polymer, a polymerization initiator, a surfactant, and a decane coupling agent. (silane coupling agent), inorganic particles, solvent, polymerization inhibitor, and the like. Hereinafter, a representative example of any component which can be contained in the composition will be described in detail.

(Polymerizable Compound) The polymerizable compound different from the compound represented by the formula (1) may be contained in the composition. The strength of the formed film is improved by using a polymerizable compound and performing a hardening treatment. The type of the polymerizable compound is not particularly limited, and a known polymerizable compound can be used. The type of the polymerizable group contained in the polymerizable compound is not particularly limited, and examples thereof include a polymerizable group included in the substituent X. The number of the polymerizable groups in the polymerizable compound is not particularly limited, and it is preferable to contain two or more polymerizable groups from the viewpoint that the strength of the formed film is more excellent. In other words, a polyfunctional polymerizable compound is preferred. Further, the composition may contain only one polymerizable compound, and may contain two or more kinds of polymerizable compounds.

The polymerizable compound is not particularly limited, and examples thereof include a compound containing an ethylenically unsaturated bond. An example of a compound containing an ethylenically unsaturated bond can be referred to the description of paragraphs 0033 to 0034 of JP-A-2013-253224, the contents of which are incorporated herein. The compound containing an ethylenically unsaturated bond is preferably a vinyloxy-modified pentaerythritol tetraacrylate (commercially available as NK ESTER ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available as KAYARAD D). -330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available) KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and (meth) acrylonitrile The structure of the ethylene glycol and propylene glycol residues. In addition, such an oligomer type can also be used. In addition, paragraphs [0107] to [0118] of Japanese Patent Laid-Open Publication No. 2012-251125 (corresponding International Publication No. 2012/153826) or Japanese Patent Laid-Open No. 2012-255148 (corresponding International Publication No.) The polymerizable compound described in paragraphs [0114] to [0128] of [2012-157784], and the contents thereof are incorporated in the specification of the present application.

Other preferred embodiments of the polymerizable compound include a polymerizable compound represented by the following formula (M1).

[Chemical 5] General formula (M1)

In the above formula (M1), Ar ¹¹ to Ar ¹⁴ each independently represent an aromatic ring group which may have a substituent, and one or more of Ar ¹¹ to Ar ¹⁴ include a substituent having a polymerizable group. Further, Ar ¹¹ to Ar ¹⁴ may be bonded to each other, and it is preferable that Ar ¹³ and Ar ¹⁴ are bonded to each other. The definition of the aromatic ring group represented by Ar ¹¹ to Ar ¹⁴ is synonymous with the definition of the aromatic ring group represented by Ar ¹ to Ar ⁴ in the formula (1), and the preferred embodiment is also the same. Further, the polymerizable group of the substituent contained in Ar ¹¹ to Ar ¹⁴ is preferably a radical polymerizable group.

One or more of Ar ¹¹ to Ar ¹⁴ include a substituent having a polymerizable group. In particular, in terms of the strength of the formed film being more excellent, it is preferred that two to four of Ar ¹¹ to Ar ¹⁴ include a substituent having a polymerizable group, and more preferably Ar ¹¹ to Ar ¹⁴ Two or three substituents having a polymerizable group are contained, and it is particularly preferable that two of Ar ¹¹ to Ar ¹⁴ include a substituent having a polymerizable group. In addition, the structure of the substituent having a polymerizable group is not particularly limited, and a group represented by the following formula (M2) is preferred because the effect of the present invention is more excellent. The general formula (M2) *-L _B -V _b L _B represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as those of the divalent linking group represented by the above L _X1 to L _X3 . V _b represents a polymerizable group. The definition of the polymerizable group is as described above.

In the above formula (M1), Ar ¹¹ to Ar ¹⁴ may be bonded to each other. The ring formed when Ar ¹¹ to Ar ¹⁴ are bonded to each other is preferably an alicyclic ring. Examples of the linking group when Ar ¹¹ to Ar ¹⁴ are bonded to each other include a single bond, -O-, and the like, and a single bond is preferred. Ring Ar Ar ¹¹ ~ ¹⁴ are connected to each other are formed by (Ar ¹¹ ~ Ar comprises means connected to the time base ¹⁴ are coupled to each other in a ring not condensed ring Ar Ar ¹¹ ~ ¹⁴ are interconnected results to be formed The number of rings of the whole is preferably 5 or 6, more preferably 5. When Ar ¹¹ to Ar ¹⁴ are respectively connected to each other, it is preferable that two of Ar ¹¹ to Ar ¹⁴ are adjacent to each other, and more preferably Ar ¹³ and Ar ^{14 are} bonded, and particularly preferably Ar ¹¹ to Ar ¹⁴ are Ar only. ¹³ and Ar ¹⁴ links.

When the polymerizable compound is contained in the composition, the content of the polymerizable compound contained in the composition is preferably excellent in the effect of the present invention with respect to all the solid components in the composition. 20% by mass to 95% by mass, more preferably 30% by mass to 80% by mass, still more preferably 35% by mass to 60% by mass. In addition, the mass ratio of the compound represented by the formula (1) to the polymerizable compound is not particularly limited, and the effect of the present invention is more excellent, and 100 parts by mass of the compound represented by the formula (1). The content of the polymerizable compound is preferably from 10 parts by mass to 120 parts by mass, more preferably from 30 parts by mass to 90 parts by mass. Further, in the composition, the polymerizable compound may be used alone or in combination of two or more.

The (polymer) composition may also contain a polymer, and in terms of the effect of the present invention being more excellent, a polymer having an acid group and a polymerizable group is preferred. Specific examples and preferred embodiments of the acid group and the polymerizable group are the same as those of the acid group and the polymerizable group in the compound represented by the formula (1). The position of the acid group and the polymerizable group in the polymer is not particularly limited, and examples thereof include a side chain or a terminal. Further, the polymer preferably contains a repeating unit having an acid group and a repeating unit having a polymerizable group. Further, in terms of the more excellent refractive index of the formed film, the polymer preferably contains an aromatic ring group. Specific examples and preferred embodiments of the aromatic ring group are the same as those of the compound represented by the formula (1). Further, it is preferred that the polymer contain a repeating unit having an aromatic ring group. The main skeleton of the polymer is not particularly limited, and is preferably, for example, an acrylic polymer, a polyether, a acrylamide, a polyamide, a polyimide, an acrylic polymer, a polyester, etc., more preferably an acrylic polymerization. Things. The weight average molecular weight of the polymer is not particularly limited, and is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, still more preferably from 5,000 to 30,000, still more preferably from 7,000 to 20,000. Further, in the present specification, the weight average molecular weight is a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the following conditions (solvent: tetrahydrofuran (THF)). · Body: HLC-8220 GPC (manufactured by Tosoh) · Column: guard column (HZ-L), TSK gel Super (HZM-M), TSK gel Super (HZ4000) ), TSK gel Super (HZ3000), TSK gel Super (HZ2000) linked column column / dissolving solution: tetrahydrofuran · feeding conditions: sample pump 0.35 mL / min, reference pump (reference pump) 0.2 mL /min · Column temperature adjustment: 40 ° C · Measurement sample: 0.1 wt% concentration (implemented by 0.5 μm membrane filter) · Injection volume: 10 μm · Measurement time: 26 minutes

In a preferred embodiment of the polymer, the effect of the present invention is more excellent, and the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the formula (including C) The polymer of the repeating unit represented.

[Chemical 6]

In the general formulae (A) to (C), R _1A , R _1B and R _1C each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms). In the general formulae (A) to (C), L _1A , L _1B and L _1C each independently represent a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as those of the divalent linking group represented by the above L _X1 to L _X3 . In the formula (A), R _2A represents an acid group. In the formula (B), R _2B represents a polymerizable group. In the formula (C), R _2C represents an aromatic ring group.

When the polymer is contained in the composition, the content of the polymer contained in the composition is preferably 10% with respect to the total solid content of the composition in terms of the effect of the present invention being more excellent. % to 95% by mass, more preferably 20% by mass to 80% by mass. In addition, the mass ratio of the compound represented by the formula (1) to the polymer is not particularly limited, and in terms of the effect of the present invention, the polymerization is carried out with respect to 100 parts by mass of the compound represented by the formula (1). The content of the substance is preferably from 10 parts by mass to 200 parts by mass, more preferably from 20 parts by mass to 150 parts by mass. Further, in the composition, the polymer may be used alone or in combination of two or more.

(Polymerization Initiator) The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound by either light or heat, and is preferably a photopolymerization initiator. . In the case where polymerization is started by light, a polymerization initiator which is photosensitive to an ultraviolet ray region to visible light is preferred. Further, in the case where polymerization is started by heat, a polymerization initiator which decomposes at 150 ° C to 250 ° C is preferred. The polymerization initiator is preferably a compound having at least an aromatic group, and examples thereof include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, and a ketal derivative. Compound, thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, hydrazine compound, hydrazine compound, oxazine oxime compound, metallocene An onium salt compound such as a compound, an organic boron salt compound, a diterpene compound, a thiol compound, or the like. The polymerization initiator can be referred to the description of paragraphs 0217 to 0228 of JP-A-2013-253224, and the contents thereof are incorporated in the specification. As the ruthenium compound, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used as a commercial product. As the acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Co., Ltd.) are commercially available. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Japan) can be used as a commercial product. In addition, paragraphs [0119] to [0215] of Japanese Patent Laid-Open Publication No. 2012-251125 (corresponding International Publication No. 2012/153826) or Japanese Patent Laid-Open No. 2012-255148 (corresponding international publications) The polymerization initiator described in paragraphs [0129] to [0226] of 2012-157784, and the contents thereof are incorporated in the specification of the present application. In the case where the polymerization initiator is contained in the composition, the content of the polymerization initiator contained in the composition is more excellent in the effect of the present invention than the total solid content in the composition. It is preferably from 0.1% by mass to 10% by mass, more preferably from 0.5% by mass to 5% by mass.

(Interacting Agent) The surfactant is not particularly limited, and various interface activities such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used. Agent. Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, and Megafac F482. , Megafac F554, Megafac F780, Megafac F781 (above manufactured by Dainippon Ink & Chemical (DIC) Co., Ltd.), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M Co., Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above is Asahi Glass Co., Ltd.) Manufactured by the company, PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA). The surfactant may be referred to in paragraphs [0256] to [0264] of Japanese Patent Laid-Open Publication No. 2012-251125 (corresponding International Publication No. 2012/153826) or Japanese Patent Laid-Open No. 2012-255148 (corresponding international publication) The surfactants described in paragraphs [0295] to [0303] of the Japanese Patent Publication No. 2012-157784, and the contents thereof are hereby incorporated by reference. When the surfactant is contained in the composition, the content of the surfactant contained in the composition is preferably excellent in terms of the effect of the present invention with respect to all the solid components in the composition. From 0.01% by mass to 10% by mass, more preferably from 0.01% by mass to 5% by mass.

(decane coupling agent) The decane coupling agent is not particularly limited, and examples thereof include N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM) -602), N-β-aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-amine Propyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ- Aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) )Wait. When the decane coupling agent is contained in the composition, the content of the decane coupling agent contained in the composition is preferably excellent in terms of the effect of the present invention with respect to all the solid components in the composition. From 0.01% by mass to 10% by mass, more preferably from 0.01% by mass to 5% by mass.

(Polymerization Inhibitor) In order to suppress unnecessary polymerization of the polymerizable compound during production or storage of the composition of the present invention, a polymerization inhibitor may be contained in the composition. Examples of the polymerization inhibitor include a phenolic hydroxyl group-containing compound, an N-oxide compound, a piperidine 1-oxyl radical compound, a pyrrolidine 1-oxy radical compound, and an N-nitrosophenylhydroxylamine. And diazonium compounds, cationic dyes, sulfur-containing compounds, nitro-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ . When the polymerization inhibitor is contained in the composition, the content of the polymerization inhibitor contained in the composition is preferably excellent in terms of the effect of the present invention with respect to all the solid components in the composition. 0.001% by mass to 1% by mass, more preferably 0.001% by mass to 0.5% by mass.

(Inorganic Particles) The inorganic particles are preferably inorganic particles having a high refractive index and being colorless, white or transparent, and examples thereof include titanium (Ti), zirconium (Zr), aluminum (Al), cerium (Si), zinc (Zn) or magnesium. The oxide particles of (Mg) are more preferably titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles or cerium oxide (SiO ₂ ) particles. The primary particle diameter of the inorganic particles is not particularly limited, but is preferably 1 nm to 100 nm, more preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. When the primary particle diameter of the inorganic particles is within the above range, the dispersibility is excellent, and the refractive index and the transmittance are improved. The refractive index of the inorganic particles is not particularly limited, and from the viewpoint of obtaining a high refractive index, it is preferably 1.75 to 2.70, more preferably 1.90 to 2.70. The specific surface area of the inorganic particles is not particularly limited, but is preferably from 10 m ² /g to 400 m ² /g, more preferably from 20 m ² /g to 200 m ² /g, still more preferably 30 m ² /g - 150 m ² /g. Further, the shape of the inorganic particles is not particularly limited, and examples thereof include a rice grain shape, a spherical shape, a cubic shape, a spindle shape, and an indefinite shape. The inorganic particles may also be inorganic particles surface-treated with an organic compound. Examples of the organic compound used in the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, or a titanate coupling agent. Among them, a stearic acid or a decane coupling agent is preferred. Further, in terms of further improvement in weather resistance, the surface of the inorganic particles is preferably covered with an oxide such as aluminum, lanthanum or zirconia. As the inorganic particles, commercially available inorganic particles can be preferably used. The inorganic particles may be used singly or in combination of two or more.

For the purpose of removing foreign matter or reducing defects, the composition of the present invention is preferably filtered by a filter. The filter is not particularly limited as long as it is a filter that has been used for filtration purposes and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon, or a polyolefin resin such as polyethylene or polypropylene (polypropylene) may be used (including high density and high density). A filter composed of a molecular weight or the like. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably from about 0.1 μm to about 7.0 μm, preferably from about 0.2 μm to about 2.5 μm, more preferably from about 0.2 μm to about 1.5 μm, still more preferably from 0.3 μm to 0.7 μm. By setting it as the range, it is possible to suppress the clogging of the filter, and it is possible to reliably remove fine foreign matter such as impurities or aggregates contained in the composition. Different filters can also be combined when using filters. In this case, the filtration by the first filter may be performed only once or twice or more. In the case where two or more filters are combined in combination with different filters, it is preferable that the pore diameters of the second time or later are equal or larger than those of the first filter. Further, the first filter having a different pore diameter may be combined within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Nihon Pall Co., Ltd., Advantec Toyo Co., Ltd., and Nihon Entegris Co., Ltd. (formerly Nihon, Japan) Mykrolis), or KITZ Micro Filter Co., Ltd., and other filters are available. As the second filter, a filter formed of the same material as the first filter or the like can be used. The pore diameter of the second filter is preferably from about 0.2 μm to about 10.0 μm, preferably from about 0.2 μm to about 7.0 μm, more preferably from about 0.3 μm to about 6.0 μm. By setting it as the range, the foreign matter mixed in the composition can be removed in a state in which the component particles contained in the composition remain. For example, the filtration by the first filter may be carried out only with a dispersion, and after mixing other components, the second filtration may be performed.

<Application> The use of the compound and the composition of the present invention is not particularly limited, and for example, a high refractive member (micro lens, a color filter) or a contiguous layer of a display device or a solid-state imaging element Transparent film such as layer, white pixel of color filter, lens (glass lens, lens for digital camera, Fresnel lens, prism lens, etc.) ), an over coat agent for optical use, a hard coat agent, an antireflection film, a light fiber, an optical waveguide, a sealing material for a light emitting diode (LED), LEDs are useful for planarizing materials and coating materials for solar cells.

<Film> The film of the present invention is a film obtained from the composition of the present invention. The cured film can be obtained by subjecting the composition to a hardening treatment. The refractive index of the film of the present invention is not particularly limited, but is preferably 1.55 or more, and more preferably 1.6 to 2.0. The light transmittance of the film of the present invention is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and still more preferably 100% in the entire wavelength region of 400 nm to 700 nm. The thickness of the film of the present invention is not particularly limited, but is preferably 0.1 μm to 20 μm, more preferably 0.1 μm to 10 μm, still more preferably 0.5 μm to 4 μm. The method for curing the composition of the present invention is not particularly limited, and examples thereof include heating or exposure. The apparatus used for heating is not particularly limited, and a blower dryer, an oven, an infrared dryer, a heating drum, or the like can be used. The device to be used for the exposure is not particularly limited, and a mercury lamp, a metal halide lamp, a xenon (Xe) lamp, a chemical lamp, a carbon arc lamp, or the like can be used. The film can be applied to various uses, for example, to an optical device such as a solid-state imaging element or a display device.

<Solid Photographic Element> The film of the present invention can be preferably applied to a solid-state imaging element. For example, the configuration may be such as to include a solid-state imaging device (Charge Coupled Device (CCD) image sensor, complementary MOS image sensor, etc.) on the substrate. A plurality of light-receiving elements such as photodiodes and polysilicon in the light-receiving region, and an undercoat film as a film of the present invention are provided below the color filter.

<Display Device> The film of the present invention can be preferably applied to a display device. The display device of the present invention is preferably a small-sized high-definition used in a view finder or a head-mount display of a digital single-lens reflex camera. An electroluminescence (EL) display device (for example, an Organic Light Emitting Diode (OLED)), for example, preferably arranged on a substrate such as glass as a matrix (matrix) A display device for a display area. Hereinafter, an embodiment of a display device of the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a display device using a composition of the present invention as a base agent for a color filter. In the display device 100, each pixel generates three primary colors (red, green, and blue) by, for example, a combination of a plurality of organic EL elements 20 that generate white light and color filters 50 (50R, 50 G, 50B). a kind of light. The pitch (center-to-center distance) p of the plurality of organic EL elements 20 is, for example, 30 μm or less, and specifically, for example, about 2 μm to 3 μm. In other words, the display device 100 is a display device called a microdisplay having an extremely small size of the organic EL element 20. Further, an eyepiece (not shown) is provided on the display device 100, and the user can view the image displayed on the display device 100 in an enlarged manner via the eyepiece. Therefore, what the user can observe is only the portion of the range of the angle of the entrance of the eyepiece displayed in the image of the display device 100. The organic EL elements 20 are arranged in a matrix on the substrate 10 and covered by the protective film 30. A sealing substrate (not shown) including glass or the like is bonded to the entire surface of the protective film 30 via an adhesive layer (not shown). A color filter 50 is provided on the surface of the substrate 10 on the sealing substrate. The color filter 50 has a red-transmissive region (not shown) that faces the plurality of organic EL elements 20. A semi-transmissive region (not shown) is provided in a portion of the transmission color region. As a result, in the display device 100, even when the size of the organic EL element 20 is small, color mixing due to diffraction of light passing through the adjacent transmission color regions can be suppressed. A base layer 40 as a film of the present invention is provided below the color filter 50. [Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, with respect to the present example, after the preparation of the composition, all were filtered using DFA4201 NXEY (0.45 μm nylon filter) manufactured by Pall Japan.

<Synthesis of Compound> The following A-1 to A-3 were synthesized by a known method. Further, the identification of each compound was carried out by nuclear magnetic resonance (NMR). The ¹ H-NMR chart (chart) of A-2 is shown in Fig. 2 .

<Synthesis Example 1: Synthesis of A-1> A solution of 50 g of 5-bromo-1-indanone (manufactured by Wako Pure Chemical Industries, Ltd.) and benzene phthalate (32 g) in 1500 mL of methanol was heated to 40 ° C to make it completely dissolved. To 100 g of methanol of 40 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) while being kept at 30 ° C or lower, the solution was added dropwise to the solution. After the dropwise addition, the mixture was heated at 55 ° C for 2 hours and then cooled to 0 ° C. The target anthrone 37 g was obtained by filtration. Add a solution of 35 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) in a solution of 30 g of fluorenone obtained and 20 g of 2-naphthalene boronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in a 500 mL solution of THF. 65 ° C. To this was added tetrakis(triphenylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.). After heating and stirring for 5 hours, the organic layer was obtained by liquid separation, and 500 mL of methanol was added to the obtained organic layer. The precipitated target Y (31 g, 90%) was obtained by filtration.

2-(4-bromophenyl)-benzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 189.0 was added dropwise while stirring 1.5 mL of tetrahydrofuran containing 15.8 g (0.2171 mol) of diced magnesium (manufactured by Wako Pure Chemical Industries, Ltd.). A solution of g (0.6514 mol) in tetrahydrofuran (2000 mL) was used to prepare a Grignard reagent. Thereafter, it was cooled to 0 ° C, and while adding heat, a Grignard reagent was added to the target Y80 g. After the dropwise addition, the mixture was stirred for 30 minutes, and then a saturated aqueous solution of ammonium chloride was added dropwise to terminate the reaction. The oil was separated and concentrated to obtain an oil, and the obtained oil was purified by column chromatography (hexane/ethyl acetate = 3/1) to obtain the objective tertiary alcohol 98 g. (Yield: 77.2%).

The obtained tertiary alcohol 98 g (0.1730 mol) and dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) 33.3 g (0.2076 mol), 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.8 g (0.02595 mol) The 600 mL solution of toluene was heated to 60 °C. To the solution, methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 249.9 g (2.595 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour, and then water and ethyl acetate were added thereto, and liquid separation was carried out to obtain an oil. The obtained oil was purified by column chromatography (hexane/ethyl acetate = 2/1). The target dihydroxyl group 113 g was obtained (yield: 91.9%).

[Chemistry 7]

A solution of 2.6 g of methyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.7 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) in 20 mL of dimethylformamide (DMF) was stirred at 60 ° C for 2 hours. . After the completion of the reaction, 10 g of water of 1 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to carry out hydrolysis. After adding hydrochloric acid to become acidic, the organic layer was extracted with ethyl acetate, and the mixture was added dropwise to methanol and filtered to obtain 2.5 g of a dicarboxylic acid. To a 17 mL portion of cyclohexanone dicarboxylic acid, 0.43 g of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.2 g of tetrabutylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.), and p-methoxyphenol 0.01 g were added. (Wako Pure Chemicals), stirred at 90 ° C for 12 hours. 1.4 g of acrylonitrile chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.0 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction mixture at 0 ° C and stirred for 1 hour. The reaction liquid was added to methanol and filtered, whereby 4 g of A-1 was obtained.

<Synthesis Example 2: Synthesis method of A-2> (Synthesis of monofunctional oxime monomer X) The monofunctional oxime monomer X was synthesized according to the following synthesis scheme and synthesis method (steps A to D). .

[化8]

(Step A) 2-bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) 124.1 g was added dropwise while stirring 14.6 g (0.5993 mol) of the diced magnesium (manufactured by Wako Pure Chemical Industries, Ltd.) in tetrahydrofuran (200 mL). A solution of 0.5993 mol) in tetrahydrofuran (800 mL) was used to prepare a Grignard reagent. Thereafter, it was cooled to 0 ° C, and 600 mL of a 46 g THF solution of 11H-benzo[b]fluoren-11-one (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition, the mixture was stirred for 30 minutes, and then a saturated aqueous solution of ammonium chloride was added dropwise to terminate the reaction. The oil was separated and concentrated to obtain an oil, and the obtained oil was purified by column chromatography (hexane/ethyl acetate = 4/1) to obtain a target tertiary alcohol 65 g (yield: 90.2%). .

(Step B) 62 g (0.1730 mol) of the tertiary alcohol obtained in the step A and 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) 29.9 g (0.2076 mol), 3-mercaptopropionic acid (Tokyo Chemical Industry Co., Ltd.) Manufactured by the company, 2.8 g (0.02595 mol) of toluene 600 mL solution was heated to 60 °C. To the solution, methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 249.9 g (2.595 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour, and then water and ethyl acetate were added thereto, and liquid separation was carried out to obtain an oil. The obtained oil was purified by column chromatography (hexane/ethyl acetate = 3/1). The target naphthol adduct 77 g (yield: 91.9%) was obtained.

(Step C) 74 g (0.1527 mol) of naphthol adduct obtained in the step B and ethylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 26.9 g (0.3054 mol), potassium carbonate (Wako Pure Chemicals Co., Ltd.) Manufactured by the company, 42.2 g (0.3054 mol) of dimethylformaldehyde solution 740 mL was stirred at 110 ° C for 3 hours. After confirming the disappearance of the raw material, 91 g of a 18.8% aqueous solution of potassium hydroxide was added. After confirming the disappearance of ethylene carbonate as a raw material, water and ethyl acetate were added, and liquid separation and concentration were carried out to obtain 68 g of a target alcohol (yield: 84.3%).

(Step D) To a solution of 68 g (0.1286 mol) of a tetrahydrofuran in a solution of the alcohol obtained in the step C, was added diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 52.1 g (0.5145 mol) and cooled to 0 °C. Next, 23.3 g (0.2573 mol) of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred for 30 minutes. After confirming the disappearance of the raw materials, water and ethyl acetate were added, liquid separation and concentration were carried out to obtain an oil, and ethyl acetate was added to the obtained oil to prepare a 30% solution, which was added dropwise to methanol cooled to 0 ° C. The target monofunctional oxime monomer X (45 g) was recovered by filtration (yield: 60.0%).

0.067 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a solution of the obtained monofunctional oxime monomer X10 g and thiomalic acid 2.57 g (manufactured by Tokyo Chemical Industry Co., Ltd.) in a nitrogen atmosphere at a nitrogen atmosphere. Stir at 90 ° C for 5 hours. The reaction liquid droplets were added to methanol and filtered, whereby 12 g of thiomalic acid addition product was obtained. The obtained thiomalic acid addition body 10 g and glycidyl methacrylate 1.94 g (manufactured by Wako Pure Chemical Industries, Ltd.), tetrabutylammonium bromide 0.88 g (manufactured by Wako Pure Chemical Industries, Ltd.), p-methoxyphenol 0.01 A 50 mL solution of g in cyclohexanone was stirred at 90 ° C for 12 hours. The reaction solution was added dropwise to methanol and filtered, whereby 11.5 g of A-2 was obtained.

<Synthesis Example 3: Synthesis method of A-3> A solution of 100 g of 5-methoxy-1-indanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 83 g of o-phthalaldehyde (300 g) in methanol was heated to 40 ° C. Make it completely soluble. To 100 g of methanol (104 g) of 104 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) while being kept at 40 ° C or lower, the solution was added dropwise to the solution. After the dropwise addition, the mixture was heated at 55 ° C for 2 hours and then cooled to 0 ° C. The target anthrone 59 g was obtained by filtration. To a solution of 50 g of acetic acid in 60 mL of acetic acid, 130 g of a 48% aqueous solution of hydrobromic acid was added, and the mixture was heated to 120 ° C and stirred overnight. After completion of the reaction, 600 mL of water and 600 mL of ethyl acetate were added, and the organic layer was extracted. After washing with an aqueous solution of sodium hydrogencarbonate and water, the solvent was distilled off, whereby 7.5 g of a hydroxyl group was obtained. A solution of 5 g of a hydroxyl group, 4.2 g of methyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8.4 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) in DMF was stirred at 60 ° C for 2 hours. After the completion of the reaction, 10 g of water of 1 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to carry out hydrolysis. After adding hydrochloric acid to become acidic, the organic layer was extracted with ethyl acetate to obtain 6 g of the desired carboxylic acid. 6 g of a carboxylic acid body and a solution of 8.1 g of 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) in toluene (600 mL) were heated to 60 ° C, and then 28 g of methanesulfonic acid was added dropwise. After stirring for 2 hours, water was poured and the organic layer was extracted with ethyl acetate, and purified by column chromatography to obtain 9 g of the target carcass. A solution of 9 g of steroids and a solution of 5.5 g of ethylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.7 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) in DMF 90 ml was heated at 110 ° C for 2 hours. Thereafter, 20 mL of potassium hydroxide 3.5 g of water was added and stirred for 1 hour. Water was injected and the organic layer was extracted with ethyl acetate to obtain 10 g of the target diol. To a solution of 10 g of diol in 100 mL of THF, 13.7 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and cooled to 0 °C. 7.6 g of acrylonitrile chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto. After stirring for 1 hour, water was poured and the organic layer was extracted with ethyl acetate, and washed with aqueous sodium hydrogen carbonate solution and water. The organic layer was added dropwise to methanol and filtered, whereby 8 g of A-3 was obtained.

[Chemistry 9]

[化10]

Further, the A-2 is in two R, and the compound on the upper side in the structural formula is R and the compound on the lower side is the group and the upper side R in the structural formula is the group and the lower side A mixture of compounds of H.

[11]

(B-1) 10 g of benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.9 g of acrylic acid were added dropwise to 7.1 g of cyclohexanone heated to 90 ° C under nitrogen for 2 hours (Tokyo Chemical Industry Co., Ltd.) Manufactured, 0.81 g of V-601 (manufactured by Wako Pure Chemical Co., Ltd.), 10.7 g of a cyclohexanone solution. After stirring for 2 hours, 0.4 g of V-601 was added, and the mixture was further stirred for 5 hours. 0.56 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.064 g of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.005 g of p-methoxyphenol (Wako Pure Chemicals) were added thereto. The company was made to stir overnight, thereby obtaining a cyclohexanone solution (Mw: 5000, Mn: 3000) of the polymer B-1.

(B-2) 10 g of isobutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.4 g of acrylic acid were added dropwise to 7.5 g of cyclohexanone heated to 90 ° C under nitrogen for 2 hours (Tokyo Chemical Industry Co., Ltd.) The company made), 1.03 g of V-601 (manufactured by Wako Pure Chemical Co., Ltd.), 11.2 g of cyclohexanone solution. After stirring for 2 hours, 0.5 g of V-601 was added, and the mixture was further stirred for 5 hours. To this, 0.62 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.070 g of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.005 g of p-methoxyphenol (Wako Pure Chemicals Co., Ltd.) were added thereto. Co., Ltd.) was stirred overnight to obtain a cyclohexanone solution of polymer B-2 (Mw: 5500, Mn: 3200).

In addition, the following "M-1" is Aronix TO-2349 manufactured by Toagosei Co., Ltd. Further, the "C-1" and "C-4" are comparative compounds.

<Preparation of Composition 1 to Composition 6> The compound A-1 (1.3 parts by mass), the polymer B-1 (30% PGMEA (propylene glycol 1-monomethyl ether 2-acetate) solution, 3.9 parts by mass) ), polymerizable compound M-1 (0.3 parts by mass), IRGACURE OXE01 (manufactured by BASF), 0.16 parts by mass, additive Megafac F-781F (manufactured by DIC Corporation), 0.17 parts by mass, KBM-602 (Shin-Etsu Chemical Co., Ltd.) The composition 1 was prepared by mixing 0.02 parts by mass of 0.01 parts by mass of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and PGMEA (13 parts by mass). The composition 2 to the composition 6 were prepared in the same order as the composition 1 by changing the types of the compound A and the polymer as shown in the following Table 1.

<Evaluation of Refractive Index> Each composition was applied onto a silicon wafer by a spin coat method, and then heated at 100 ° C for 2 minutes on a hot plate. A photosensitive film having a film thickness of 1 μm. Then, ultraviolet rays of 10 mW/cm ² were irradiated using Execure 3000 (manufactured by HOYA Co., Ltd.) to prepare a cured film. The obtained film was measured using a refractive index (wavelength: 500 nm) (device: ellipsic film thickness measuring device RE series manufactured by Dainippon Screen Manufacturing Co., Ltd., RE-3320). Then, the refractive index was evaluated in accordance with the following criteria. The results are shown in Table 1. In practical applications, it is preferably A to B. · A: refractive index is 1.65 or more · B: refractive index is 1.60 or more and less than 1.65 · C: refractive index is less than 1.60

<Evaluation of developability> Each composition was applied onto a ruthenium wafer by a spin coating method, and then heated on a hot plate at 100 ° C for 2 minutes to obtain a photosensitive film having a film thickness of 1 μm. The film was arranged in a mask pattern of 4 mm × 3 mm on the substrate via a side square of 1.1 μm, using an i-ray stepper FPA-3000i5+ (Canon Limited) Co., Ltd.) at a wavelength of 365 nm at an exposure amount of 200 mJ / cm ² exposure. To the film after the exposure, a 0.2% by mass aqueous solution of tetramethylammonium hydroxide was used, and puddle development was performed at 23 ° C for 60 seconds. Thereafter, it was rinsed with water using a spin shower, and then washed with pure water. Thereafter, the high-pressure air was used to splash the water droplets, and the silicon wafer was naturally dried, and post-bake was performed at 200 ° C for 300 seconds using a hot plate to obtain a film thickness of 1 μm on the germanium wafer. Transparent pattern (hardened film). Using a length measuring SEM (Critical Dimension-Scanning Electron Microscope (CD-SEM), S-7800H, manufactured by Hitachi, Ltd.), the transparency obtained by observing 30,000 times on the wafer was observed. pattern. Then, the developability was evaluated based on the following criteria. The results are shown in Table 1. In practical applications, it is preferably A to B. A: No residue was confirmed on the pixels. B: A small amount of residue was confirmed on the pixels, but it was within an allowable range. C: A large amount of residue was observed on the pixels.

<Evaluation of Curability> A film was prepared in the same manner as the evaluation of the refractive index. Thereafter, the obtained film was immersed in cyclohexanone for 5 minutes, and then the residual ratio (%) of the film was measured [{(mass of film before immersion - mass of film after immersion) / quality of film before immersion }×100]. The results are shown in Table 1. In practical applications, it is preferably A to B. · A: Residual rate is 95% or more · B: Residual rate is 85% or more and less than 95% · C: Residual rate is less than 85%

[Table 1]

As shown in Table 1, in the examples using the composition of the present invention, the obtained film had a high refractive index and was excellent in developability and hardenability. In particular, according to the comparison between Example 3 and Example 4, it was confirmed that when the polymer to be used contains an aromatic ring group, the refractive index is more excellent. On the other hand, in Comparative Examples 1 to 2 which are compositions which do not contain the compound of the present invention, the desired effects were not obtained. Further, the composition described in Comparative Example 2 corresponds to the composition using C-4 described in Patent Document 1.

10‧‧‧Substrate
20‧‧‧Organic EL components
30‧‧‧Protective film
40‧‧‧ basal layer
50‧‧‧Color filters
50B‧‧‧Blue color filter
50G‧‧‧Green color filter
50R‧‧‧Red color filter
100‧‧‧Display device (micro OLED)
P‧‧‧pitch (center distance)

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a pixel portion of an embodiment of a display device using a composition of the present invention as a base agent for a color filter. 2 is a ¹ H-NMR chart of A-2.

10‧‧‧Substrate

20‧‧‧Organic EL components

30‧‧‧Protective film

40‧‧‧ basal layer

50B‧‧‧Blue color filter

50G‧‧‧Green color filter

50R‧‧‧Red color filter

100‧‧‧Display device (micro OLED)

P‧‧‧pitch (center distance)

Claims (17)

A composition comprising a compound represented by the formula (1), [Chemical Formula 1] In the general formula (1), Ar ¹ to Ar ⁴ each independently represent an aromatic ring group; and at least one of Ar ¹ to Ar ⁴ is a polycyclic aromatic group, and the following requirements 1 or requirements are satisfied. 2, requirement 1: at least one of Ar ¹ to Ar ⁴ has a substituent including an acid group and a polymerizable group; and 2: at least one of Ar ¹ to Ar ⁴ has a substituent including an acid group, and Ar ¹ ～ At least one of Ar ⁴ has a substituent containing a polymerizable group. The composition according to claim 1, wherein in the formula (1), Ar ³ is bonded to Ar ⁴ . The composition according to claim 1 or 2, wherein the compound is a compound represented by the formula (2), [Chemical 2] In the general formula (2), Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ each independently represent an aromatic ring group; and at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ is plural. The cyclic aromatic group satisfies the following requirement 3 or requirement 4, and the requirement 3: at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group and a polymerizable group; and the element 4: Ar ¹ ～ At least one of Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group, and at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent containing a polymerizable group. The composition according to claim 3, wherein in the formula (2), at least one of Ar ⁵ and Ar ⁶ is a polycyclic aromatic group. The composition of claim 1 or 2, wherein the acid group is a carboxylic acid group. The composition according to the first or second aspect of the invention, which further comprises a polymerizable compound other than the compound represented by the above formula (1). The composition according to claim 1 or 2, further comprising a polymer having an acid group and a polymerizable group. The composition of claim 7, wherein the polymer further has an aromatic ring group. The composition according to the first or second aspect of the invention, wherein the substituent comprising an acid group and a polymerizable group is a group represented by the formula (X-1), [Chem. 3] In the formula (X-1), L _X1 , L _X2 and L _X3 each independently represent a single bond or a divalent linking group; W represents a trivalent linking group; V _a represents an acid group; _b represents a polymerizable group; * represents a bonding position. A film formed by the composition according to any one of claims 1 to 9. An optical device comprising the film of claim 10 of the patent application. a compound represented by the formula (1), [Chemical 4] In the general formula (1), Ar ¹ to Ar ⁴ each independently represent an aromatic ring group; and at least one of Ar ¹ to Ar ⁴ is a polycyclic aromatic group, and the following requirements 1 or requirements are satisfied. 2, requirement 1: at least one of Ar ¹ to Ar ⁴ has a substituent including an acid group and a polymerizable group; and 2: at least one of Ar ¹ to Ar ⁴ has a substituent including an acid group, and Ar ¹ ～ At least one of Ar ⁴ has a substituent containing a polymerizable group. The compound according to claim 12, wherein in the formula (1), Ar ³ is bonded to Ar ⁴ . The compound of claim 12 or 13, wherein the formula (1) is represented by the formula (2), [Chem. 5] In the general formula (2), Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ each independently represent an aromatic ring group; and at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ is plural. The cyclic aromatic group satisfies the following requirement 3 or the requirement 4; and the requirement 3: at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group and a polymerizable group; and the element 4: Ar ¹ ～ At least one of Ar ² and Ar ⁵ to Ar ⁶ has a substituent including an acid group, and at least one of Ar ¹ to Ar ² and Ar ⁵ to Ar ⁶ has a substituent containing a polymerizable group. The compound according to claim 14, wherein in the formula (2), at least one of Ar ⁵ and Ar ⁶ is a polycyclic aromatic group. The compound of claim 12, wherein the acid group is a carboxylic acid group. The compound according to claim 12, wherein the substituent comprising an acid group and a polymerizable group is a group represented by the formula (X-1), [Chem. 6] In the formula (X-1), L _X1 , L _X2 and L _X3 each independently represent a single bond or a divalent linking group; W represents a trivalent linking group; V _a represents an acid group; _b represents a polymerizable group; * represents a bonding position.