JP6326140B2 - Compound, composition, film, optical instrument - Google Patents

Description

  The present invention relates to a compound having a predetermined structure, a composition containing the compound, a film obtained from the composition, and an optical apparatus including the film.

Conventionally, a high refractive index is required for a compound used in an optical material or the like.
For example, Patent Document 1 discloses a triazine ring-containing polymer as a high refractive index material. More specifically, it is disclosed that a polymer having a triazine ring structure as a partial structure exhibits an excellent refractive index.

International Publication No. 2012/111682

2. Description of the Related Art In recent years, an optical material capable of forming a flat film even in a region having a step has been demanded in accordance with a demand for high functionality and miniaturization of an optical device (a solid-state imaging device, a display device, etc.). That is, there is a demand for an optical material that can form a film having excellent refractive index and excellent flatness even in a region having a step. Hereinafter, the excellent flatness of the formed film surface is referred to as excellent surface flatness.
When the present inventors examined the characteristics of the optical material described in Patent Document 1, it was confirmed that the above two characteristics could not be satisfied and further improvement was necessary.

In view of the above circumstances, an object of the present invention is to provide a compound that exhibits a high refractive index and can form a film having excellent surface flatness.
Another object of the present invention is to provide a composition containing the above compound, a film formed from the above composition, and an optical instrument including the above film.

As a result of intensive studies to solve the above problems, the present inventors have found that a desired effect can be obtained by using a compound having a specific structure, and completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A composition comprising a compound represented by the general formula (1) described later.
(2) The composition according to (1), wherein Ar ³ and Ar ⁴ are linked in General Formula (2) described below.
(3) The composition according to (1) or (2), wherein in general formula (1), X represents a residue obtained by removing one hydrogen atom from a compound represented by general formula (3) described later. object.
(4) The composition according to (3), wherein in general formula (3), at least one of Ar ^{1 to} Ar ² and Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group.
(5) The composition according to (3) or (4), wherein in general formula (3), at least one of Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group.
(6) The composition according to any one of (1) to (5), wherein A in Formula (1) includes one or more quaternary carbon atoms.
(7) In general formula (1), A is a group having a partial structure represented by general formula (4) described later, or a group having a partial structure represented by general formula (5) described later. The composition according to any one of (1) to (6).
(8) In the general formula (1), Y is a monovalent organic group having at least one group selected from the group consisting of an acid group and a polymerizable group. A compound according to any one.
(9) The composition according to any one of (1) to (8), wherein a ratio of m to n is 0.5 to 5.0 in the general formula (1). In addition, the said ratio represents m / n.
(10) The composition according to any one of (1) to (9), further comprising a polymerizable compound.
(11) The composition according to (10), wherein the polymerizable compound includes a polymerizable compound having two or more polymerizable groups and having a fluorene skeleton.
(12) A film formed from the composition according to any one of (1) to (11).
(13) An optical apparatus including the film according to (12).
(14) A compound represented by the following general formula (1).
(15) The compound according to (14), wherein Ar ³ and Ar ⁴ are linked in General Formula (2) described below.
(16) The compound according to (14) or (15), wherein in general formula (1), X represents a residue obtained by removing one hydrogen atom from a compound represented by general formula (3) described later. .
(17) The compound according to (16), wherein in general formula (3), at least one of Ar ^{1 to} Ar ² and Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group.
(18) The compound according to (16) or (17), wherein in general formula (3), at least one of Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group.
(19) The compound according to any one of (14) to (18), wherein in formula (1), A contains one or more quaternary carbon atoms.
(20) In general formula (1), A is a group having a partial structure represented by general formula (4) described later or a group having a partial structure represented by general formula (5) described later. , (14)-(19).
(21) In the general formula (1), Y is a monovalent organic group having at least one group selected from the group consisting of an acid group and a polymerizable group. A compound according to any one.
(22) The compound according to any one of (14) to (21), wherein a ratio of m to n is 0.5 to 5.0 in the general formula (1). In addition, the said ratio represents m / n.

ADVANTAGE OF THE INVENTION According to this invention, while showing a high refractive index, the compound which can form the film | membrane excellent in surface flatness can be provided.
Moreover, according to this invention, the optical instrument containing the composition containing the said compound, the film | membrane formed from the said composition, and the said film | membrane can also be provided.

It is sectional drawing for 1 pixel of the one aspect | mode of the display apparatus which uses the composition of this invention as a base material of a color filter. It is a schematic sectional drawing for demonstrating the method of surface flatness evaluation. It is a ¹ H-NMR (Nuclear Magnetic Resonance) chart of A-1.

Below, the compound of this invention etc. are demonstrated.
In the present specification, (meth) acrylate represents acrylate or methacrylate, and (meth) acryloyloxy represents acryloyloxy or methacryloyloxy.
Furthermore, the numerical range expressed using “to” in the present specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  As a characteristic point of the compound of the present invention, one hydrogen atom is removed from the compound represented by the general formula (2) having a high refractive index with the (m + n) -valent linking group represented by A as the center. In that the residues are arranged radially. By taking such a structure, it is presumed that the mobility of the compound itself is improved and the flexibility of the compound is increased. Therefore, when trying to form a film in a region having a step, it is presumed that the mobility of the compound on the film surface is increased, and the flatness of the formed film is increased as a result.

<Compound>
Hereinafter, each group in the compound represented by the general formula (1) will be described in detail.

In general formula (1), A represents a (m + n) -valent linking group.
The molecular weight of the (m + n) -valent linking group represented by A is not particularly limited, but the refractive index of the formed film is more excellent and / or the surface flatness of the formed film is more excellent (hereinafter, 100 or more is preferable, and 200 or more is more preferable because it is simply referred to as “the point where the effect of the present invention is more excellent”. The upper limit is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less, and still more preferably 1000 or less from the viewpoint of synthesis.

(M + n) -valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and It is preferred that a group consisting of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining these structural units (which may form a ring structure).

  The (m + n) -valent linking group is preferably a group represented by any one of the following general formulas.

In the above general formula,
L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T _{3 s} may be the same or different from each other.
L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and four T _{4 s} may be the same or different from each other.
L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five T _{5 s} may be the same or different from each other.
L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and the six T ₆ present may be the same or different from each other.
Incidentally, specific examples and preferred embodiments of the divalent linking group represented by T ₃ through T ₆ is the same as the divalent linking group represented by L ¹ and L ² will be described later.
Specific examples [specific examples (1) to (17) and (35)] of the (m + n) -valent linking group represented by A are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent linking groups are the following (1), (2), (10), from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. (11), (16), (17) and (35).

As one of the preferable embodiments of A, it is preferable that A contains at least one quaternary carbon atom from the viewpoint that the surface flatness of the formed film is more excellent.
Moreover, as the most suitable aspect of A, group which has the partial structure represented by General formula (4), or group which has the partial structure represented by General formula (5) is mentioned.

  In general formula (5), R represents an alkyl group. In general formulas (4) and (5), * represents a bonding position.

L ¹ and L ² each independently represents a single bond or a divalent linking group. When m is 2 or more, the plurality of L ¹ may be the same or different, and when n is 2 or more, the plurality of L ² may be the same or different.
Divalent linking groups include 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 are included, which may be unsubstituted or further substituted.
More specifically, as the divalent linking group, for example, a divalent chain saturated hydrocarbon group (which may be linear or branched and preferably has 1 to 20 carbon atoms), A divalent cyclic saturated hydrocarbon group (preferably having 3 to 20 carbon atoms), a divalent aromatic group (preferably having 5 to 20 carbon atoms, for example, a phenylene group), -O-,- S—, —SO ₂ —, —NR _L —, —CO—, —NH—, —COO—, —CONL _L —, —O—CO—O—, —SO ₃ —, —NHCOO—, —SO ₂ NR _L- , -NH-CO-NH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or the like) can be given. Here, _RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Among them, the divalent linking group represented by ^{L 1} and ^{L 2, -S -, - O} -, - CO-, an alkylene group, and a group composed of a combination of these are preferred.

  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, and a carbon number of 6 such as a phenyl group and a naphthyl group. From 1 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups and the like. Carbonate esters such as alkoxy groups of up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups of 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups and t-butyl carbonate Groups and the like.

X represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (2). That is, X is a group having a structure in which one hydrogen atom is extracted from an arbitrary position in the structural formula represented by the general formula (2) and can be bonded at the position where the hydrogen atom is extracted. The position at which the hydrogen atom is extracted is not particularly limited, and ^one hydrogen atom contained in any of Ar ^{1 to} Ar ⁴ is extracted.

In General Formula (2), Ar ^{1 to} Ar ⁴ each independently represents an aromatic ring group. Ar ^{1 to} Ar ⁴ may be linked to each other via 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), or a group obtained by combining these.
Specific examples of the ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a pyrene ring, a naphthacene ring, and a biphenyl ring. And a terphenyl ring (the three phenyl groups may be connected in an arbitrary connection mode) and the like.
As an aromatic heterocyclic group, the aromatic heterocyclic group which consists of a 5-membered, 6-membered or 7-membered ring or its condensed ring is mentioned, for example. 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 furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, oxadiazole ring, thiazole ring, isothiazole ring, thiadiazole ring, imidazole ring, pyrazole. Ring, triazole ring, furazane ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, Benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, azole Lysine ring, phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring and pteridine ring.

Preferable embodiments of the aromatic ring group represented by Ar ^{1 to} Ar ⁴ include polycyclic aromatic groups. That is, at least one of Ar ^{1 to} Ar ⁴ is preferably a polycyclic aromatic group, and more preferably 2 to ⁴ of Ar ^{1 to} Ar ⁴ are polycyclic aromatic groups.
A polycyclic aromatic group is a group formed by condensing a plurality of aromatic ring groups, and specifically, a polycyclic aromatic hydrocarbon group (polycyclic aromatic hydrocarbon ring group) or a polycyclic aromatic group. Group heterocyclic group.
Here, the polycyclic aromatic hydrocarbon group is a group composed of an aromatic hydrocarbon ring having two or more rings, and more specifically, two or more monocyclic aromatic hydrocarbon rings (benzene). A condensed ring group having a ring). Of these, a group consisting of a ring in which two or more monocyclic aromatic hydrocarbon rings are condensed is preferable.
Specific examples of the ring constituting the polycyclic aromatic hydrocarbon group include a naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, acenaphthylene ring, chrysene ring, fluoranthene ring, pyrene ring, triphenylene ring, tetracene ring, benzopyrene ring, Examples include a picene ring, a perylene ring, a pentacene ring, a hexacene ring, a heptacene ring, and a coronene ring. Among these, a naphthalene ring is preferable.
The polycyclic aromatic heterocyclic group is a group composed of an aromatic heterocyclic ring having two or more rings, more specifically, having two or more rings, and one or more A condensed ring group having a monocyclic aromatic heterocycle. Among them, a group composed of a ring in which one or more monocyclic aromatic hydrocarbon rings and one or more monocyclic heterocycles are condensed, or a ring in which two or more monocyclic heterocycles are condensed. A group is preferred.
Specific examples of the ring constituting the polycyclic aromatic heterocyclic group include acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, kindrin ring, tepenidine ring, A quinindrine ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (representing a carbon atom constituting a carboline ring replaced by a nitrogen atom) ), Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anth Raj thiophene ring, thianthrene ring, phenoxathiin ring, thio fan train 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, for example, furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, oxadiazole ring, thiazole. Ring, isothiazole ring, thiadiazole ring, imidazole ring, pyrazole ring, triazole ring, furazane ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring and the like.

As a preferred embodiment of X, Ar ³ and Ar ⁴ are preferably linked from the viewpoint that the effects of the present invention are more excellent. Here, “Ar ³ and Ar ⁴ are linked” means that Ar ³ and Ar ⁴ are linked through a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as the divalent linking group represented by L ¹ and L ² described above.

  The most preferred embodiment of X represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (3) in that the effect of the present invention is more excellent.

In General Formula (3), 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. Ar ^{5 to} Ar ⁶ each constitute an aromatic ring group in a form containing two carbon atoms in the general formula (3).
Although one hydrogen atom is removed from the compound represented by the general formula (3), the position at which the hydrogen atom is removed is not particularly limited, and any one of Ar ^{1 to} Ar ² and Ar ^{5 to} Ar ⁶ may be used. It may be a group of
Among them, Table at the point where the effect of the present invention is more excellent, it is preferable that a hydrogen atom is removed from any one of Ar ¹ to Ar ^2, for example, when a hydrogen atom is removed from Ar ^1, general formula (3) The residue remove | excluding one hydrogen atom from the compound shown represents group represented by the following general formula (3-1). In the following formulae, “*” represents a bonding position. In General Formula (3-1), Ar ¹ represents a so-called divalent aromatic ring group (arylene group or heteroarylene group).

Among them, in terms of the effect of the present invention is more excellent, it is preferable that at least one of Ar ⁵ and Ar ⁶ is a polycyclic aromatic group, that both Ar ⁵ and Ar ⁶ are polycyclic aromatic group More preferred.
The definition of the polycyclic aromatic group is as described above.

Ar ^{1 to} Ar ⁴ may contain a substituent.
Examples of the substituent include halogen atoms, alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, and aryl groups. , Heteroaryl group, cyano group, hydroxy group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heteroaryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino Group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl Or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ) , A phosphato group (—OPO (OH) ₂ ), a sulfato group (—OSO ₃ H), or a group in which these groups are combined.

Y represents a monovalent organic group. Although the structure of the organic group is not particularly limited, for example, an acid group, a polymerizable group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group A group selected from the group consisting of a group having an alkyleneoxy chain, an imide group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an isocyanate group and a hydroxyl group ( Hereinafter, a monovalent organic group having at least one functional group X) is preferred.
The monovalent organic group may be a polymer chain (polymer skeleton).
The monovalent organic group may contain two or more functional groups X described above. As an aspect in which two or more of the functional groups X described above are included, a chain saturated hydrocarbon group (which may be linear or branched and preferably has 1 to 10 carbon atoms), a cyclic saturated hydrocarbon 2 or more functional groups X are bonded to each other via a group (preferably having 3 to 10 carbon atoms), an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group), and the like. An embodiment in which an organic group is formed, and a mode in which two or more functional groups X are bonded via a chain saturated hydrocarbon group to form a monovalent organic group is preferable.
In addition, two or more functional groups X described above may be included in the polymer chain. In that case, the functional group X may be directly bonded to the main chain of the polymer chain as a side chain of the polymer chain, or the functional group X is bonded to the main chain of the polymer chain via a divalent linking group. Also good.

  Preferred examples of the “acid group” 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 boric acid group. Group, sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, phosphonic acid group, phosphinic acid group are more preferable, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, phosphinic acid group Are more preferred, and carboxylic acid groups are particularly preferred.

Examples of the “polymerizable group” include a radical polymerizable group and a cationic polymerizable group.
As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferable examples thereof include a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization. Specifically, Examples thereof include a vinyl group and a (meth) acryloyloxy group. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, the alicyclic ether group, the cyclic acetal group, the cyclic lactone group, the cyclic thioether group, the spiro orthoester group, the vinyloxy group, and the like. Examples include groups. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.

As the “urea group”, for example, —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 or more carbon atoms) And an aryl group having a carbon number of 7 or more.) —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom, from 1 carbon atom) An alkyl group having up to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms is more preferable, and —NHCONHR ¹⁷ (where R ¹⁷ is a hydrogen atom, 1 to 10 carbon atoms). Or an alkyl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms) is particularly preferable.

As the “urethane group”, for example, —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each Independently, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms) may be mentioned as preferred examples, and -NHCOOR ¹⁸ , -OCONHR ²¹ ( Here, R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. NHCOOR ^18, -OCONHR ^{21 (wherein,} each independently R ^{18, R 21} is an alkyl group having from 1 to 10 carbon atoms, carbon atoms Or aryl group, or a number of 7 or more aralkyl group having a carbon.), Etc. are particularly preferred.

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.
Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ are each independently Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), a formula (a2 And the like.

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group or a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl having 1 to 10 carbon atoms; Represents a group, a phenyl group, or a benzyl group. Amidinyl group represented by formula (a2) [in formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group or a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, Represents a phenyl group or a benzyl group. Amidinyl group represented by formula (a2) [in formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

The “alkyl group” may be linear or branched, preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms, and 10 to 10 carbon atoms. 18 alkyl groups are more preferred.
The “aryl group” is preferably an aryl group having 6 to 10 carbon atoms.
As the “group having an alkyleneoxy chain”, the terminal preferably forms an alkyloxy group, and more preferably an alkyloxy group having 1 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but preferably comprises an alkyleneoxy group having 1 to 6 carbon atoms. The alkylene group, for _{example, -CH 2 CH 2 O -,} - CH 2 CH 2 CH 2 O- and the like.
The alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
The alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the “carboxylic acid group” include groups composed of ammonium salts of carboxylic acids.
In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group), an acyl group (such as an acetyl group or a trifluoroacetyl group), and the like.

Examples of the “heterocyclic group” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, Preferred examples include groups consisting of dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, etc. It is done.
Examples of the “imide group” include succinimide, phthalimide, naphthalimide and the like.

  The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group, trialkoxysilyl group, but is preferably trialkoxysilyl group, such as trimethoxysilyl group, triethoxysilyl group, etc. Is mentioned.

As described above, the monovalent organic group may be a polymer chain (polymer skeleton). The polymer chain means a group derived from a polymer, and it is preferable that the polymer chain can be bonded at a polymer main chain part.
The polymer chain can be selected from known polymers according to the purpose.
Among the polymers, polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products or copolymers thereof (for example, , Polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, and graft copolymers may be used). At least one selected from the group consisting of: a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, and a modified product or copolymer thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
When the organic group is the above polymer chain, the compound has a long molecular chain, and the flatness of the formed film is improved due to a decrease in the glass transition temperature.
The polymer chain may contain various functional groups (for example, acid groups such as carboxylic acid groups, polymerizable groups, and the like). The various functional groups may be arranged in the side chain portion in the polymer chain or may be bonded to the polymer seed chain via a divalent linking group. The definition of a bivalent coupling group is as the above-mentioned.

Among them, Y is selected from the group consisting of an acid group and a polymerizable group in that developability can be imparted to the cured film and / or the strength of the formed film is improved. It is preferably a monovalent organic group having at least one group.
Note that the organic group represented by Y may contain two or more acid groups or two or more polymerizable groups.
In particular, when an acid group is contained, the compound can be suitably applied to development processing, which is preferable.

m represents an integer greater than or equal to 2, and 2-6 are preferable, 2-5 are more preferable, and 3-4 are more preferable at the point which the effect of this invention is more excellent.
n represents an integer greater than or equal to 0, and 0-5 are preferable and 1-4 are more preferable at the point which the effect of this invention is more excellent.
In addition, the total number of m + n is not particularly limited, but 3 to 10 is preferable and 3 to 6 is more preferable in that the effect of the present invention is more excellent.
Especially, it is preferable that ratio (m / n) of m with respect to n is 0.5-5.0, and it is more preferable that it is 1-3 with the point which the effect of this invention is more excellent.

(Method for synthesizing compounds)
The method for synthesizing the compound represented by the general formula (1) is not particularly limited. However, paragraphs 0114 to 0140 and 0266 to 0348 and 0266 to 0348 of JP 2007-277514 A It can be synthesized according to the synthesis method described in paragraphs 0145 to 0173 and 0289 to 0429).
In particular, a method of reacting a compound having a plurality of mercapto groups with a compound having a carbon-carbon double bond such as a (meth) acryloyloxy group or a vinyl group (thiol-ene reaction method) is preferable.

  Specific examples of the compound having a plurality of mercapto groups [specific examples (18) to (34), (36)] include the following compounds.

  Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred compounds are the above (18), (19), (27), (28), (33), (34) and (36).

  The above is commercially available (for example, (33) is dipentaerythritol hexakis (3-mercaptopropionate): Sakai Chemical Industry Co., Ltd.).

Also used to obtain the general formula (1) in the "L ¹ -X 'portion, carbon - The compound having a carbon double bond, for example, compounds represented by the following general formula (6) Is mentioned.

In general formula (6), the definitions of Ar ^{1 to} Ar ⁴ are as described above.
L _A represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as the divalent linking group represented by L ¹ and L ² described above.
W is a group containing a carbon-carbon double bond, and examples thereof include a (meth) acryloyloxy group and a vinyl group.

A suitable solvent used in the thiol-ene reaction method is not particularly limited, and may be any solvent as long as it can dissolve the above-described reaction substrate. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 2-ethylhexanol, 1 -Methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene.
These solvents may be used as a mixture of two or more.

<Composition>
The composition of this invention contains the compound represented by the said General formula (1). In addition, in a composition, the compound represented by General formula (1) may use only 1 type, and may use 2 or more types together.
When the film formed from the composition of the present invention is used as a high refractive index film, the content of the compound represented by the general formula (1) contained in the composition is more excellent in the effects of the present invention. Therefore, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 30% by mass or more is more preferable with respect to the total solid content in the composition. The upper limit is not particularly limited, but may be 100% by mass. When other optional components described later are included, the upper limit is often 80% by mass or less, and in many cases is 60% by mass or less.
In addition, solid content intends the component which forms the film | membrane mentioned later, and a solvent is not contained.

<Other optional components>
The composition may contain other compounds other than the compound represented by the general formula (1), such as a polymerizable compound, a polymerization initiator, a surfactant, a silane coupling agent, and inorganic particles. , A solvent, a polymerization inhibitor and the like may be contained.
Hereinafter, representative examples of optional components that may be contained in the composition will be described in detail.

(Polymerizable compound)
A polymerizable compound may be contained in the composition. By using a polymerizable compound and being subjected to a curing treatment, the strength of the formed film is improved.
The kind in particular of a polymeric compound is not restrict | limited, A well-known polymeric compound can be used. The kind in particular of the polymeric group contained in a polymeric compound is not restrict | limited, The polymeric group etc. which Y in General formula (1) mentioned above can take are mentioned.
The number of the polymerizable groups in the polymerizable compound is not particularly limited, but it is preferable that two or more polymerizable groups are included in that the strength of the formed film is more excellent. In other words, a polyfunctional polymerizable compound is preferable.
In the composition, only one type of polymerizable compound may be contained, or two or more types of polymerizable compounds may be contained.
Although it does not restrict | limit especially as a polymeric compound, For example, the compound containing an ethylenically unsaturated bond is mentioned. As examples of the compound containing an ethylenically unsaturated bond, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, the contents of which are incorporated herein.
Examples of the compound containing an ethylenically unsaturated bond include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available KAYARAD D-330). Manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol, propylene glycol Structures through Lumpur residues are preferred. These oligomer types can also be used.
Also, paragraphs [0107] to [0118] of JP2012-251125A (corresponding international publication 2012/153826) and paragraphs of JP2012-255148A (corresponding international publication 2012-157784). The polymerizable compounds described in [0114] to [0128] can be used, and the contents thereof are incorporated in the present specification.
Furthermore, a polymerizable compound having a cationic polymerizable group (particularly an epoxy group) is also preferably used.

  One preferred embodiment of the polymerizable compound is a polymerizable compound having two or more polymerizable groups and having a fluorene skeleton. The fluorene skeleton is a skeleton containing at least a fluorene structure, and the aromatic ring group in the fluorene structure may be a so-called monocyclic structure (benzene ring) or a polycyclic structure (polycyclic aromatic ring structure).

  As a most suitable aspect of a polymeric compound, the polymeric compound represented by the following general formula (M1) is mentioned.

In the general formula (M1), Ar ^{11 to} Ar ¹⁴ each independently represents an aromatic ring group which may have a substituent, and one or more of Ar ^{11 to} Ar ¹⁴ have a polymerizable group. Contains substituents. Ar ^{11 to} Ar ¹⁴ may be connected to each other, and Ar ¹³ and Ar ¹⁴ are preferably connected to each other.
The definition of the aromatic ring group represented by Ar < ¹¹ > -Ar < ¹⁴ > is synonymous with the definition of the aromatic ring group represented by Ar < ¹ > -Ar < ⁴ > in General formula (2), and its suitable aspect is also the same.
Moreover, it is preferable that the said polymeric group which the substituent which Ar < ¹¹ > -Ar < ¹⁴ > has is a radically polymerizable group or a cationically polymerizable group (especially epoxy group).

One or more of Ar ^{11 to} Ar ¹⁴ include a substituent having a polymerizable group. Especially, it is preferable that 2-4 of Ar < ¹¹ > -Ar < ¹⁴ > contains the substituent which has a polymeric group at the point which the intensity | strength of the film | membrane formed is more excellent, and 2 or 3 among Ar < ¹¹ > -Ar < ¹⁴ >. It is more preferable that each includes a substituent having a polymerizable group, and it is particularly preferable that two of Ar ^{11 to} Ar ¹⁴ include a substituent having a polymerizable group.
In addition, although the structure of the substituent which has a polymeric group is not specifically limited, The group represented with the following general formula (M2) is preferable at the point which the effect of this invention is more excellent.
The general formula (M2) * _-L B -V
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 the divalent linking group represented by L ¹ and L ² described above.
V represents a polymerizable group. The definition of the polymerizable group is as described above.

In the general formula (M1), Ar ^{11 to} Ar ¹⁴ may be connected to each other. The ring that is formed when Ar ^{11 to} Ar ¹⁴ are connected to each other is preferably an alicyclic ring. Examples of the linking group when Ar ^{11 to} Ar ¹⁴ are linked to each other include a single bond and —O—, and a single bond is preferable. Ar ¹¹ to Ar ¹⁴ is means one ring containing a linking group when the ^{ring (Ar} 11 ^{to Ar 14} which are formed when connecting to each other are linked to each ^other, Ar 11 ^{to Ar 14} are linked to each other The number of ring members of the condensed ring formed as a result is preferably 5 or 6, and more preferably 5.
If Ar ¹¹ to Ar ¹⁴ are linked to each ^other, Ar 11 is preferably linked are two mutually adjacent of ^{to Ar 14,} it is more preferable ^{that Ar 13} and ^{Ar 14} are linked, Ar It is particularly preferable that only Ar ¹³ and Ar ¹⁴ of ^{11 to} Ar ¹⁴ are linked.

When a polymerizable compound is contained in the composition, the content of the polymerizable compound contained in the composition is 20 to 95 with respect to the total solid content in the composition in that the effect of the present invention is more excellent. % By mass is preferable, 30 to 80% by mass is more preferable, and 35 to 60% by mass is further preferable.
In addition, the mass ratio of the compound represented by the general formula (1) and the polymerizable compound is not particularly limited. On the other hand, it is preferable that content of a polymeric compound is 10-120 mass parts, It is more preferable that it is 10-90 mass parts, It is further more preferable that it is 30-80 mass parts.
In the composition, only one type of polymerizable compound may be used, or two or more types may be used in combination.

(Polymerization initiator)
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either light, heat, or both, but is preferably a photopolymerization initiator. When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
Moreover, when starting superposition | polymerization with a heat | fever, the polymerization initiator decomposed | disassembled at 150-250 degreeC is preferable.
The polymerization initiator is preferably a compound having at least an aromatic group. For example, an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone compound, an oxime compound, Hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, onium salt compounds such as sulfonium compounds, azinium compounds, metallocene compounds, organic boron salt compounds, disulfone compounds, thiol compounds, etc. Can be mentioned.
As the polymerization initiator, the description in paragraphs 0217 to 0228 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
As the oxime compound, commercially available products IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. In addition, as the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.
It is also possible to use an oxime initiator having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24, 36-40 described in paragraph No. 0345 of JP 2014-500852 A, JP The compound (C-3) described in paragraph number 0101 of 2013-164471 gazette is mentioned.
Further, paragraphs [0119] to [0215] of JP2012-251125A (corresponding international publication 2012/153826) and paragraphs of JP2012-255148A (corresponding international publication 2012-157784). The polymerization initiators described in [0129] to [0226] can be used, and the contents thereof are incorporated in the present specification.
When a polymerization initiator is contained in the composition, the content of the polymerization initiator contained in the composition is 0.1% relative to the total solid content in the composition in that the effect of the present invention is more excellent. 10 mass% is preferable, and 0.5-5 mass% is more preferable.

(Surfactant)
Although it does not restrict | limit especially as surfactant, Various surfactants, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant, can be used.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781, F781F (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC- 101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656 PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.
As the surfactant, paragraphs [0256] to [0264] of JP2012-251125A (corresponding to International Publication No. 2012/153826) and JP2012-255148A (corresponding to International Publication No. 2012-157784). No.), the surfactants described in paragraphs [0295] to [0303] and the like can be used, and the contents thereof are incorporated herein.
When a surfactant is contained in the composition, the content of the surfactant contained in the composition is 0.01 with respect to the total solid content in the composition in that the effect of the present invention is more excellent. 10 mass% is preferable, and 0.01-5 mass% is more preferable.

(Silane coupling agent)
The silane coupling agent is not particularly limited. For example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ- Aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-amino Propyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical) Industrial brand name KBM-503) and the like.
When the composition contains a silane coupling agent, the content of the silane coupling agent contained in the composition is 0 with respect to the total solid content in the composition in that the effect of the present invention is more excellent. 0.01 to 10% by mass is preferable, and 0.01 to 5% by mass is more preferable.

(Polymerization inhibitor)
In order to prevent unnecessary polymerization of the polymerizable compound during production or storage of the composition of the present invention, the composition may contain a polymerization inhibitor.
Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, cationic dyes , Transition group compounds such as sulfide group-containing compounds, nitro group-containing compounds, FeCl ₃ , CuCl _{2 and the} like.
When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor contained in the composition is 0.001 with respect to the total solid content in the composition in that the effect of the present invention is more excellent. -1 mass% is preferable and 0.001-0.5 mass% is more preferable.

(Inorganic particles)
The inorganic particles are preferably colorless, white or transparent inorganic particles having a high refractive index, and titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn) or magnesium. Examples thereof include oxide particles of (Mg), and titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles are more preferable.
The primary particle diameter of the inorganic particles is not particularly limited and is preferably 1 to 100 nm, more preferably 1 to 80 nm, and particularly preferably 1 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, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index.
Although the specific surface area is not particularly limited in the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, more preferably 30 to 150 m ² / g.
Moreover, there is no restriction | limiting in particular in the shape of an inorganic particle, For example, a rice grain shape, a spherical shape, a cube shape, a spindle shape, or an indefinite shape is mentioned.
The inorganic particles may be those that have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyol, alkanolamine, stearic acid, silane coupling agent or titanate coupling agent. Of these, stearic acid or a silane coupling agent is preferable.
Moreover, it is also preferable that the surface of the inorganic particles is covered with an oxide such as aluminum, silicon, or zirconia in that the weather resistance is further improved.
As the inorganic particles, commercially available particles can be preferably used.
Inorganic particles may be used singly or in combination of two or more.

(Curing accelerator)
The composition of the present invention preferably contains a curing accelerator, particularly when the polymerizable compound contains a cationic polymerizable group such as an epoxy group.
Examples of the curing accelerator that improves the curing rate include acid anhydrides, bases (aliphatic amines, aromatic amines, modified amines), acids (sulfonic acids, phosphoric acids, carboxylic acids, etc.), polymercaptans, and the like. Among these, an acid anhydride is preferable, and an aliphatic acid anhydride is more preferable.

The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore size of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. Can do.
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm. By setting it as this range, the foreign material mixed in the composition can be removed while the component particles contained in the composition remain.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

<Application>
The use of the compound and composition of the present invention is not particularly limited. For example, a high-refractive member of a display device or a solid-state imaging device (a microlens, a transparent film such as a base layer or an adjacent layer of a color filter, a white pixel of a color filter) , Lenses (glass lenses, digital camera lenses, Fresnel lenses, prism lenses, etc.), optical overcoat agents, hard coat agents, antireflection films, optical fibers, optical waveguides, LED (Light Emitting Diode) sealing materials, LEDs It is useful as a flattening material for solar cells and a coating material for solar cells.

<Membrane>
The film of the present invention is a film obtained from the composition of the present invention. When a component having a polymerizable group (for example, a polymerizable compound) is contained in the composition, a cured film can be obtained by subjecting the composition to a curing 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 over the entire wavelength region of 400 to 700 nm, more preferably 95% or more, and even more preferably 100%. preferable.
Although the thickness in particular of the film | membrane of this invention is not restrict | limited, It is preferable that it is 0.1-20 micrometers, It is more preferable that it is 0.1-10 micrometers, It is further more preferable that it is 0.5-4 micrometers.
The method for curing the composition of the present invention is not particularly limited, and examples thereof include heating and exposure. The apparatus used for heating is not particularly limited, and an air dryer, an oven, an infrared dryer, a heating drum, or the like can be used. The apparatus 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, optical devices such as a solid-state imaging device and a display device.

<Solid-state imaging device>
The film of the present invention can be suitably applied to a solid-state image sensor.
For example, a light receiving element made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (Charge Coupled Device) image sensor, CMOS (Complementary Metal Oxide Semiconductor) image sensor, etc.) is provided on a substrate. In addition, a configuration in which an undercoat film, which is a film of the present invention, is provided under the color filter, and the like.

<Display device>
The film of the present invention can be suitably applied to a display device.
The display device of the present invention is preferably a small and high-definition organic EL display device (for example, a micro OLED) used for a viewfinder or a head mounted display of a digital single lens reflex camera. It is preferable that a display area in which each pixel is arranged in a matrix is provided.
An embodiment of a display device of the present invention will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view of one pixel of one embodiment of a display device using the composition of the present invention as a base material for a color filter. Each pixel generates light of one of the three primary colors (red, green, and blue) by combining a plurality of organic EL elements 20 that generate white light and a color filter 50 (50R, 50G, 50B), for example. It is. The pitch (distance between centers) p of the plurality of organic EL elements 20 is, for example, 30 μm or less, specifically, for example, about 2 μm to 3 μm. That is, this display device is a so-called micro display in which the size of the organic EL element 20 is extremely small. Note that an eyepiece lens (not shown) is provided on the display device, and the user views an image displayed on the display device in an enlarged manner through the eyepiece lens. Therefore, the user can see only a portion of the image displayed on the display device within the range of the eyepiece lens capture angle.
The organic EL elements 20 are arranged in a matrix on the substrate 10 and are covered with a protective film 30. A sealing substrate (not shown) made of glass or the like is bonded to the entire surface of the protective film 30 with an adhesive layer (not shown) in between. A color filter 50 is provided on the surface of the sealing substrate on the substrate 10 side.
The color filter 50 has a transmissive red region (not shown) that faces the plurality of organic EL elements 20. A semi-transmissive area (not shown) is provided in a part of the transmissive color area. Thereby, in this display device, even when the dimension of the organic EL element 20 is small, it is possible to suppress color mixing due to diffraction of light that has passed through the adjacent transmission color region.
Under the color filter 50, an underlayer 40 which is a film of the present invention is provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In addition, about the present Example, after preparing the composition, it filtered all using Nippon Pole DFA4201NXEY (0.45 micrometer nylon filter).

<Synthesis of compounds>
The following A-1 to A-5 were synthesized by a known method. Each compound was identified by ¹ H-NMR. FIG. 3 shows a ¹ H-NMR chart of A-1.

<Synthesis Example 1: A-1 (X)>

(Synthesis of monofunctional fluorene monomer X)
Monofunctional fluorene monomer X was synthesized according to the following synthesis scheme and synthesis method (steps A to D).

(Process A)
While stirring 200 mL of tetrahydrofuran containing 15.8 g (0.2171 mol) of magnesium and shavings (manufactured by Wako Pure Chemical Industries, Ltd.), 134.9 g of 2-bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) A solution of 0.6514 mol) in tetrahydrofuran was added dropwise to prepare a Grignard reagent. Thereafter, the mixture was cooled to 0 ° C., and 600 mL of a tetrahydrofuran (THF) solution of 50 g of 11H-benzo [b] fluoren-11-one (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After dripping, after stirring for 30 minutes, saturated ammonium chloride aqueous solution was dripped, and reaction was stopped. The oil obtained by liquid separation and concentration was purified by column chromatography (hexane / ethyl acetate = 4/1) to obtain 65 g (yield: 83.5%) of the target tertiary alcohol.

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

(Process C)
74 g (0.1527 mol) of naphthol adduct obtained in Step B, 26.9 g (0.3054 mol) of ethylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 42.2 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 740 mL of a dimethylformaldehyde solution (0.3054 mol) was stirred at 110 ° C. for 3 hours. After confirming disappearance of the raw materials, 91 g of an aqueous 18.8% potassium hydroxide solution was added. After confirming the disappearance of the starting ethylene carbonate, water and ethyl acetate were added, and the mixture was separated and concentrated to obtain 68 g of the desired alcohol (yield: 84.3%).

(Process D)
Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (52.1 g, 0.5145 mol) was added to a solution of 68 g (0.1286 mol) of tetrahydrofuran obtained in Step C in 1000 mL of tetrahydrofuran and cooled to 0 ° C. Next, 23.3 g (0.2573 mol) of acrylic acid chloride (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, followed by liquid separation and concentration. Ethyl acetate was added to the resulting oil to make a 30% solution, which was then added dropwise to methanol cooled to 0 ° C. The target monofunctional fluorene monomer X (45 g) (yield: 60.0%) was recovered by filtration.

Monofunctional fluorene monomer X (5 g) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) (manufactured by SC Organic Chemical) 1.68 g of cyclohexanone (manufactured by Wako Pure Chemical) 65 g solution in triethylamine (Wako Pure Chemical) 0.1 g) was added and stirred at 65 ° C. for 12 hours. 0.56 g of itaconic acid (manufactured by Wako Pure Chemical Industries) and 0.01 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the solution, and the mixture was heated and stirred at 90 ° C. Two hours later, 0.01 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After completion of the reaction, the reaction solution was added dropwise to methanol, and the precipitated A-1 (X) was recovered by filtration (7 g, yield 97%). The obtained A-1 (X) was dissolved in cyclohexanone to obtain a 33.6% solution of A-1 (X).
In A-1 (X), m = 4 and n = 2.

In addition, A-1 (Y) where m = 3 and n = 3 in the same manner as the production procedure of A-1 (X) except that the amounts of monofunctional fluorene monomer X and itaconic acid used were changed. Manufactured.
Further, A-1 (Z) where m = 2 and n = 4 in the same manner as in the production procedure of A-1 (X) except that the amounts of the monofunctional fluorene monomer X and itaconic acid used were changed. Manufactured.

<Synthesis Example 2: A-2>

Fluorenone X was synthesized according to the following scheme.
A solution of 50 g of 5-bromo-1-indanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 32 g of o-phthalaldehyde in 1500 mL of methanol was heated to 40 ° C. and completely dissolved. Thereto, 100 mL of methanol of 40 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped while being kept at 30 ° C. or lower. After dropping, the mixture was heated at 55 ° C. for 2 hours and then cooled to 0 ° C. By filtration, 37 g of the desired fluorenone X was obtained.

  Except for using 11H-benzo [b] fluoren-11-one in place of the above fluorenone X, and in place of DPMP pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) (manufactured by SC Organic Chemical). Prepared A-2 according to the same procedure as in Synthesis Example 1. In A-2, m was 2 and n was 2.

<Synthesis Example 3: A-3>

  A-3 was synthesized according to the same procedure as in Synthesis Example 1 except that Karenz MT NR1 (manufactured by Showa Denko) was used instead of DPMP. In A-3, m was 2 and n was 1.

<Synthesis Example 4: A-4>

(Synthesis of Compound X)
Compound X was synthesized according to the following scheme.
A solution of 50 g of 5-bromo-1-indanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 32 g of o-phthalaldehyde in 1500 mL of methanol was heated to 40 ° C. and completely dissolved. Thereto, 100 mL of methanol of 40 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped while being kept at 30 ° C. or lower. After dropping, the mixture was heated at 55 ° C. for 2 hours and then cooled to 0 ° C. Filtration gave 37 g of the desired fluorenone.
Under a nitrogen atmosphere, a solution of 30 g of the obtained fluorenone and 20 g of 2-naphthaleneboronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 500 mL of THF was added with a solution of 250 g of water of 35 g of potassium carbonate (manufactured by Wako Pure Chemical Industries) and heated to 65 ° C. Thereto was added 1.1 g of tetrakis (triphenylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry). After stirring with heating for 5 hours, 500 mL of methanol was added to the organic layer obtained by liquid separation. Compound X, which was the target product that had precipitated, was obtained by filtration (31 g, yield 90%).

  Synthesis except that the above compound X was used in place of 11H-benzo [b] fluoren-11-one and 2- (4-bromophenyl) -benzothiazole (manufactured by Tokyo Chemical Industry) was used in place of 2-bromonaphthalene. A monofunctional fluorene monomer Y was synthesized according to the same procedure as in Example 1 (Synthesis of monofunctional fluorene monomer X).

Monofunctional fluorene monomer Y (5 g) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) (manufactured by SC Organic Chemical) 1.68 g of cyclohexanone (manufactured by Wako Pure Chemical) 65 g solution in triethylamine (Wako Pure Chemical) 0.1 g) was added and stirred at 65 ° C. for 12 hours. The solution was dropped into 650 mL of methanol and filtered to obtain a solid. After the obtained solid was dissolved in 17 g of cyclohexanone, 0.56 g of itaconic acid (manufactured by Wako Pure Chemical Industries) and 0.01 g of V-601 (manufactured by Wako Pure Chemical Industries) were added, and the mixture was heated and stirred at 90 ° C. Two hours later, 0.01 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After completion of the reaction, the reaction solution was added dropwise to methanol, and the precipitated compound was recovered by filtration (7 g, yield 97%).
Next, to the cyclohexanone solution (16 g) of the obtained compound (7 g), glycidyl methacrylate (0.84 g) (manufactured by Wako Pure Chemical Industries), tetrabutylammonium bromide (0.29 g) (manufactured by Wako Pure Chemical Industries), p-Methoxyphenol (0.01 g) (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 90 ° C. for 12 hours to obtain a cyclohexanone solution of A-4. In A-4, m was 3, and n was 3.

<Synthesis Example 5: A-5>

  Instead of 11H-benzo [b] fluoren-11-one (manufactured by Tokyo Chemical Industry), 9-fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and bromobenzene was used instead of 2-bromonaphthalene, and 2-naphthol was used. A-5 was synthesized according to the same procedure as in Synthesis Example 1 except that phenol was used instead of. In addition, m in A-5 was 3, and n was 3.

<Synthesis Example 6: A-6 (X)>

Monofunctional fluorene monomer Y was synthesized in the same manner as in Synthesis Example 4.
Monofunctional fluorene monomer Y (3.65 g) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) (manufactured by SC Organic Chemical) 0.90 g of cyclohexanone (manufactured by Wako Pure Chemical Industries) 0.19 g (manufactured by Koyo Pure Chemical) was added and stirred at 65 ° C. for 12 hours. The solution was dropped into 500 mL of methanol and filtered to obtain a solid. After the obtained solid was dissolved in 16 g of cyclohexanone, 1.05 g of acrylic acid (manufactured by Tokyo Chemical Industry), 1.11 g of 130A (manufactured by Kyoeisha Chemical Co., Ltd.) and 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was added and heated and stirred at 90 ° C. Two hours later, 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After completion of the reaction, the reaction solution was added dropwise to methanol, and the precipitated compound was recovered by filtration (6.5 g, yield 97%).
Next, with respect to the cyclohexanone solution (16 g) of the obtained compound (6.5 g), glycidyl methacrylate (0.30 g) (manufactured by Wako Pure Chemical Industries), tetrabutylammonium bromide (0.13 g) (manufactured by Wako Pure Chemical Industries, Ltd.) ), P-methoxyphenol (0.01 g) (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 90 ° C. for 12 hours to obtain a cyclohexanone solution of A-6 (X). In A-6 (X), m was 4 and n was 2 (Mw: 7800, Mn: 5000).
In addition, A-6 (Y) in which m is 3 and n is 3 was also synthesized by adjusting the amount of the compound used.

<Synthesis Example 7: A-7>

Monofunctional fluorene monomer Y was synthesized in the same manner as in Synthesis Example 4.
In a 50 g solution of monofunctional fluorene monomer Y (3.65 g) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) (SC Organic Chemical) (0.90 g) in a 50 g solution Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.19 g was added and stirred at 65 ° C. for 12 hours. The solution was added dropwise to 500 mL of methanol to obtain a solid obtained by filtration. After the obtained solid was dissolved in 16 g of cyclohexanone, 1.14 g of M-5300 (Kyoeisha) and 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries) were added to the solution, and the mixture was heated and stirred at 90 ° C. Two hours later, 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After completion of the reaction, the reaction solution was added dropwise to methanol, and the precipitated compound (A-7) was recovered by filtration (6.5 g, yield 97%). In A-7, m was 4 and n was 2 (Mw8500, Mn6500).

<Synthesis Example 8: A-8>

Monofunctional fluorene monomer Y was synthesized in the same manner as in Synthesis Example 4.
In a 50 g solution of monofunctional fluorene monomer Y (3.65 g) and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) (SC Organic Chemical) (0.90 g) in a 50 g solution Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.19 g was added and stirred at 65 ° C. for 12 hours. The solution was added dropwise to 500 mL of methanol to obtain a solid obtained by filtration. After dissolving the obtained solid in 16 g of cyclohexanone, 1.05 g of acrylic acid (manufactured by Tokyo Chemical Industry) and 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries) were added to the solution, and the mixture was heated and stirred at 90 ° C. Two hours later, 0.12 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After completion of the reaction, the reaction solution was added dropwise to methanol, and the precipitated compound was recovered by filtration (5.3 g, yield 95%).
Next, to the cyclohexanone solution (16 g) of the obtained compound (5.3 g), glycidyl methacrylate (2.67 g) (manufactured by Wako Pure Chemical Industries), tetrabutylammonium bromide (0.30 g) (manufactured by Wako Pure Chemical Industries, Ltd.) ), P-methoxyphenol (0.01 g) (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 90 ° C. for 12 hours to obtain a cyclohexanone solution of A-8. In addition, m in A-8 was 4, and n was 2 (Mw8000, Mn6000).

The M-1 was synthesized according to the following procedure.
11H-benzo [b] fluoren-11-one (manufactured by Tokyo Chemical Industry) 100 g, 2-naphthol 156.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.), 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6 1.9 g of toluene was added to 9 g, and the mixture was heated and stirred at 60 ° C. After dissolution, 166.9 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at 60 ° C. for 2 hours. Then, water and ethyl acetate were added, and liquid separation and concentration were performed. The obtained concentrate was purified by column chromatography to obtain 101 g of the desired naphthol adduct (yield: 46.5%).
71.1 g of ethylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 111.5 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a solution of 101 g of the resulting naphthol adduct 101 g of dimethylformamide (DMF) at 110 ° C. For 2 hours. After confirming disappearance of the raw materials, 245 g of a 18.5% aqueous solution of potassium hydroxide was added. After confirming the disappearance of the starting ethylene carbonate, water and ethyl acetate were added, followed by liquid separation and concentration to obtain 100 g (yield: 84.0%) of the target alcohol.
95.0 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a solution of 69 g of tetrahydrofuran in 69 g of tetrahydrofuran, and the resulting alcohol was cooled to 0 ° C. Next, 42.5 g of acrylic acid chloride (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, followed by liquid separation and concentration. Ethyl acetate was added to the resulting oil to make a 30% solution, which was then added dropwise to methanol cooled to 0 ° C. The target M-1 (57 g) (yield: 70.0%) was recovered by filtration.

The C-1 was synthesized with reference to the synthesis method described in Patent Document 1 (paragraph 0083).
C-2 was synthesized according to the following procedure.
To 7.2 g of cyclohexanone heated to 90 ° C. under nitrogen, 10 g of vinylnaphthalene (manufactured by Alfa Aesar), 2.0 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.85 g of V-601 (Wako Pure Chemical ( 10.8 g of a cyclohexanone solution (manufactured) was added dropwise over 2 hours. After stirring for 2 hours, 0.4 g of V-601 was added, and the mixture was further stirred for 5 hours. There, 2.63 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.30 g of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.005 g of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) Was added, and a cyclohexanone solution of C-2 was obtained by stirring overnight (Mw: 5400, Mn: 3200).

  In addition, Toagosei Co., Ltd. Aronix TO-2349 was used as "M-2" mentioned later.

The polymerizable compound M-4 was synthesized with reference to Comparative Example 5 in JP2014-208804A.
As “M-5”, EHPE3150 manufactured by Daicel Corporation was used.
As “P-1”, a cyclohexanedicarboxylic acid anhydride manufactured by Tokyo Chemical Industry Co., Ltd. was used.
As “P-2”, phthalic anhydride manufactured by Tokyo Chemical Industry Co., Ltd. was used.

<Preparation of compositions 1-11>
A 33.6% solution (5.0 parts by mass) of the compound A-1, a polymerizable compound M-1 (1.3 parts by mass), a polymerizable compound M-2 (0.33 parts by mass), IRGACURE OXE01 (manufactured by BASF) 0.16 parts by mass, additive Megafac F-781F (manufactured by DIC, fluorine-containing polymer surfactant) 0.17 parts by mass, and KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) Composition 1 by mixing 0.02 parts by mass, 0.01 parts by mass of p-methoxyphenol (manufactured by Wako Pure Chemical Industries), and propylene glycol 1-monomethyl ether 2-acetate (PGMEA) (13 parts by mass). Was prepared.
The compositions 2 to 11 were prepared in the same procedure as the composition 1 by changing the type of the compound represented by the general formula (1) and the polymerizable compound as shown in Table 1 described later.

<Evaluation of refractive index>
Each composition was applied onto a silicon wafer by spin coating, and then heated on a hot plate at 100 ° C. for 2 minutes to obtain a photosensitive film having a thickness of 1 μm. Next, a cured film was prepared by irradiating ultraviolet rays of 10 mW / cm ² using Execute 3000 (manufactured by HOYA Corporation).
About the obtained film | membrane, it measured using the refractive index (wavelength: 500 nm) (apparatus: Dainippon Screen Mfg. Co., Ltd. ellipso type film thickness measuring apparatus RE series, RE-3320). And the refractive index was evaluated from the following criteria. The results are shown in Table 1. Practically, it is preferably A to C.
-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 1.55 or more and less than 1.60-D: Refractive index is less than 1.55

<Evaluation of flatness>
The flatness evaluation method will be described in detail with reference to FIG.
First, as shown in FIG. 2, a substrate 110 having a groove with a depth D1 of 1400 nm and a width W of 3000 nm is prepared, and each composition is applied onto the substrate 110 by spin coating. In addition, in the case of application | coating, it adjusted so that the thickness of T1 of the cured film 120 obtained by the procedure mentioned later might be set to 200 nm.
Then, it heated at 100 degreeC on the hotplate for 2 minutes, and obtained the photosensitive film | membrane. Subsequently, the cured film was produced by irradiating ultraviolet rays of 10 mW / cm ² using Execute 3000 (manufactured by HOYA Corporation).
The maximum value of the depth D2 of the concave portion of the cured film located on the groove of the obtained cured film was measured using a scanning probe microscope (AFM Nano Scope IV manufactured by Veeco Instruments), and the flatness was evaluated from the following criteria did. The results are shown in Table 1. Practically, it is preferably A to B.
A: Depth D2 is less than 600 nm B: Depth D2 is 600 nm or more and less than 800 nm C: Depth D2 is 800 nm or more

As shown in Table 1, the film obtained from the composition containing the compound of the present invention exhibited excellent refractive index and surface flatness.
In particular, a comparison between Example 7 and other examples confirmed that the refractive index is more excellent when any of Ar ^{1 to} Ar ^{4 in} the general formula (2) is a polycyclic aromatic group. .
Moreover, it is confirmed from the comparison between Example 2 and Example 5 that when A in the general formula (1) is a group having a partial structure represented by the general formula (4), the surface flatness is more excellent. It was done.
In Comparative Examples 1 to 3 using the composition not containing the compound of the present invention, it was impossible to achieve both refractive index and surface flatness.

<Preparation of compositions 12-21>
30.0% solution (5.0 parts by mass) of the above compound A-6 (X), polymerizable compound M-1 (0.5 parts by mass), and polymerizable compound M-2 (0.38 parts by mass) ), 0.13 parts by mass of a curing accelerator P-1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.16 parts by mass of IRGACURE OXE01 (manufactured by BASF), and additive Megafac F-781F (manufactured by DIC, fluorine-containing polymer) Type surfactant) 0.17 parts by mass, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.02 parts by mass, p-methoxyphenol (manufactured by Wako Pure Chemical Industries) 0.01 parts by mass, and cyclohexanone (13 parts by mass) Part) was mixed to prepare composition 12.
The compositions 13 to 21 were prepared in the same procedure as the composition 12 by changing the type of the compound represented by the general formula (1) and the polymerizable compound as shown in Table 2 described later.

  <Evaluation of flatness> described above was performed using the obtained compositions (compositions 12 to 21).

<Production method of evaluation sample (thick film substrate for microlenses)>
FFEM CT-4000 was applied to a glass substrate by spin coating. Then, heat processing was implemented at 220 degreeC for 1 hour, and the glass substrate with a base layer was produced. The film thickness of the underlayer was 0.1 μm.
The obtained composition (compositions 12-21) was apply | coated by the spin coat method on the glass substrate with a base layer. Then, after performing prebaking at 100 degreeC for 2 minutes, it heat-processed at 265 degreeC for 10 minutes, and performed post-baking. The film thickness of the obtained cured film was 3 μm.

  The refractive index of the obtained cured film was measured by the method described in <Evaluation of Refractive Index> described above. Further, the flatness was evaluated by the method described in <Evaluation of flatness> described above.

<Evaluation of heat resistance>
The transmittance | permeability in wavelength 400nm of a cured film was measured using the evaluation sample obtained above, and it evaluated in accordance with the following references | standards.
A: 95% or more B: 90% or more and less than 95% C: 80% or more and less than 90% D: less than 80%

<Evaluation of solvent resistance>
After the evaluation sample obtained above is immersed in cyclohexanone for 5 minutes, the residual ratio of the cured film (%) [{(the mass of the cured film before immersion−the mass of the cured film after immersion) / the cured film before the immersion] Mass} × 100]. The results are shown in Table 1. Practically, 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%

<Evaluation of crack>
Using the evaluation sample obtained above, the cured film was observed with an optical microscope and evaluated according to the following criteria.
A: No crack B: Small crack C: Large crack D: Film cannot be formed

As shown in Table 2, the film obtained from the composition containing the compound of the present invention exhibited excellent refractive index and surface flatness.
In addition, it was confirmed from the comparison with Example 9 and 10 that solvent resistance is more excellent when a polymeric compound has an epoxy group.
Moreover, it was confirmed from the comparison with Example 12 and 13 that solvent resistance and a crack are more excellent when the acid group (carboxylic acid group) has couple | bonded the polymer chain via the coupling group.

DESCRIPTION OF SYMBOLS 10 Substrate 20 Organic EL element 30 Protective film 40 Underlayer 50R Red color filter 50G Green color filter 50B Blue color filter 100 Display device (micro OLED)
110 Substrate 120 Cured film

Claims (16)

The composition containing the compound represented by General formula (1).

In general formula (1), A represents a (m + n) -valent linking group. L ¹ and L ² each independently represents a divalent linking group containing —S— . X represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (3). Y represents a monovalent organic group having at least one group selected from the group consisting of an acid group and a polymerizable group . m represents an integer of 2 or more, and n represents an integer of 1 to 4 .

In General Formula (3), Ar ^{1 to} Ar ² and Ar ^{5 to} Ar ⁶ each independently represent an aromatic ring group. Note that at least one of Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group.   The composition of Claim 1 in which A contains one or more quaternary carbon atoms in General formula (1). In General Formula (1), A is a group having a partial structure represented by General Formula (4) or a group having a partial structure represented by General Formula (5). The composition as described.

In general formula (5), R represents an alkyl group. In general formulas (4) and (5), * represents a bonding position.   The composition of any one of Claims 1-3 whose ratio of m with respect to n is 0.5-5.0 in General formula (1). The ratio represents m / n. The composition of any one of Claims 1-4 whose total number of m + n is 3-10 in General formula (1). In General Formula (1), L ¹ and L ² are each independently a group selected from the group consisting of —S— or —S—, —O—, —CO—, and an alkylene group. The composition according to any one of claims 1 to 5 , which is a group in which Furthermore, the composition of any one of Claims 1-6 containing a polymeric compound. The composition according to claim 7 , wherein the polymerizable compound includes a polymerizable compound having two or more polymerizable groups and having a fluorene skeleton. The film | membrane formed from the composition of any one of Claims 1-8 . An optical instrument comprising the film according to claim 9 . The compound represented by General formula (1).

In general formula (1), A represents a (m + n) -valent linking group. L ¹ and L ² each independently represents a divalent linking group containing —S— . X represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (3). Y represents a monovalent organic group having at least one group selected from the group consisting of an acid group and a polymerizable group . m represents an integer of 2 or more, and n represents an integer of 1 to 4 .

In General Formula (3), Ar ^{1 to} Ar ² and Ar ^{5 to} Ar ⁶ each independently represent an aromatic ring group. Note that at least one of Ar ^{5 to} Ar ⁶ is a polycyclic aromatic group. The compound of Claim 11 in which A contains one or more quaternary carbon atoms in General formula (1). In the formula (1), A is a group having a partial structure represented by the general formula (4) or, a group having a partial structure represented by the general formula (5), in claim 11 or 12 The described compound.

In general formula (5), R represents an alkyl group. In general formulas (4) and (5), * represents a bonding position. In the general formula (1), the ratio of m for n is 0.5 to 5.0 A compound according to any one of claims 11 to 13. The ratio represents m / n. In the general formula (1), the total number of m + n is 3 to 10, A compound according to any one of claims 11 to 14. In General Formula (1), L ¹ and L ² are each independently a group selected from the group consisting of —S— or —S—, —O—, —CO—, and an alkylene group. The compound according to any one of claims 11 to 15 , which is a group in which