WO2015141421A1

WO2015141421A1 - Compound, resin, and composition

Info

Publication number: WO2015141421A1
Application number: PCT/JP2015/055498
Authority: WO
Inventors: 誠一人見; 秀知高橋; 直之師岡; あゆみ石山
Original assignee: 富士フイルム株式会社
Priority date: 2014-03-20
Filing date: 2015-02-26
Publication date: 2015-09-24
Also published as: TW201538478A; JP2015183048A; TWI656114B; JP6240536B2

Abstract

The purpose of the present invention is to provide: a compound and a resin that exhibit excellent dissolubility and a high refractive index; and a composition that includes said resin. This compound is a compound represented by general formula (1).

Description

Compounds, resins and compositions

The present invention relates to a compound, a resin and a composition.

Conventionally, solubility and high refractive index are required for compounds (eg, monomers) and resins used in optical materials and the like.
Under such circumstances, Patent Document 1 discloses a monofunctional fluorene compound represented by a predetermined formula (claim 1). According to Patent Document 1, it is described that the fluorene compound is useful as a raw material capable of imparting excellent optical properties (high refractive index and the like) (paragraph [0022]).

JP 2009-13096 A

2. Description of the Related Art In recent years, with the demand for higher functionality and miniaturization of optical components, further improvements in solubility and refractive index have been demanded for compounds and resins used for optical materials and the like.
The present inventors examined the compound described in Patent Document 1, and found that its solubility and refractive index did not necessarily reach the levels required recently, and further improvement is necessary.

Therefore, in view of the above circumstances, an object of the present invention is to provide a compound and a resin that exhibit excellent solubility and a high refractive index, and a composition containing the resin.

As a result of intensive studies to solve the above problems, the present inventors have found that compounds and resins represented by a specific general formula exhibit excellent solubility and a high refractive index, and have completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A compound represented by the following general formula (1).
(2) The compound according to (1) above, wherein at least one of Ar ₃ and Ar _{4 is} a polycyclic aromatic hydrocarbon ring which may have a substituent.
(3) Resin which has a repeating unit represented by General formula (2) mentioned later.
(4) The resin according to (3) above, having a weight average molecular weight of 2,000 to 100,000.
(5) A composition containing the resin according to (3) or (4).

As described below, according to the present invention, a compound and a resin exhibiting excellent solubility and a high refractive index, and a composition containing the above resin can be provided.

It is sectional drawing for 1 pixel of the one aspect | mode of the micro OLED which uses the compound of this invention etc. as a base material of a color filter. It is a ¹ H-NMR chart of A-3. It is a ¹ H-NMR chart of A-4.

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

[Compound]
The compound of the present invention is represented by the following general formula (1).

In the general formula (1), R ₁ represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10. The alkyl group may be linear or branched.

In the general formula (1), L represents a divalent linking group. The divalent linking group is not particularly limited. For example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group, or a propylene group), a divalent group Aromatic hydrocarbon group (for example, phenylene 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—, a single bond or a group combining two or more of these (eg, alkyleneoxy group, alkyleneoxycarbonyl Group, alkylenecarbonyloxy group, etc.). Here, R _L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

As a suitable aspect of L, the bivalent coupling group represented by the following general formula (L) is mentioned, for example.

In the general formula (L), L ₁ represents a single bond, an ester group (—COO—), an amide group (—CONR _L —) or an ether group (—O—). The definition of _RL is as described above.
In the general formula (L), L ₂ represents a single bond or a divalent organic group. The divalent organic group is a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), a linear, branched or cyclic group. A divalent aromatic hydrocarbon group (for example, a phenylene group) or a combination thereof is preferable. The combined groups are ether group (—O—), ester group (—COO—), amide group (—CONR ₂₂₂ —), urethane group (—NHCOO—), urea group (—NH—CO—NH—). It may be a group combined through The definition of _RL is as described above. Specific examples of L ₂ include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and a group in which these groups are substituted with a methoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom, or the like. Furthermore, the group etc. which combined these are mentioned.
In the general formula (L), L ₃ represents a single bond, —CO ₂ —, —CO—, —O—CO—O—, —SO ₃ —, —CONR _L —, —NHCOO—, —O—, —S—, —SO ₂ NR _L —, or —NR _L — is represented. The definition of _RL is as described above.

In the general formula (L), * ₁ represents a bonding position with the carbon atom to which R ₁ in the general formula (1) is bonded.
In the general formula (L), * ₂ represents a bonding position with Ar ₁ in the general formula (1).
That is, when L in the general formula (1) is a divalent linking group represented by the general formula (L), the general formula (1) is represented by the following general formula (1a).

In the general formula (1), Ar ₁ represents an arylene group or a heteroarylene group which may have a substituent (for example, a substituent W described later).
The arylene group is not particularly limited, but an arylene group having 6 to 30 carbon atoms is preferable, and an arylene group having 6 to 20 carbon atoms is more preferable. Specific examples of the ring constituting the arylene 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 group (three phenyl groups may be connected in an arbitrary connection manner).
The heteroarylene group is not particularly limited, but a heteroarylene group comprising a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof, or a heteroarylene group comprising a condensed ring of the above-mentioned arylene group and heteroarylene is preferred. Examples of the hetero atom contained in the heteroarylene group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroarylene 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 Acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring and pteridine ring.
Ar ₁ is preferably a divalent polycyclic aromatic hydrocarbon group or a divalent polycyclic aromatic heterocyclic group which may have a substituent (for example, a substituent W described later). It is more preferably a valent polycyclic aromatic hydrocarbon group. Here, a divalent polycyclic aromatic hydrocarbon group is a divalent group of a polycyclic aromatic hydrocarbon ring (a divalent group formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon ring. Group). Definitions, specific examples and preferred embodiments of the polycyclic aromatic hydrocarbon ring are as described below. A divalent polycyclic aromatic heterocyclic group is a divalent group of a polycyclic aromatic heterocyclic ring (a divalent group formed by removing two hydrogen atoms from a polycyclic aromatic heterocyclic ring). is there. The definition, specific examples and preferred embodiments of the polycyclic aromatic heterocycle are as described below.

In the general formula (1), Ar ₂ represents an aryl group or a heteroaryl group which may have a substituent (for example, a substituent W described later).
The aryl group is not particularly limited, but is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms. Specific examples of the ring constituting the aryl group are the same as those in the case where Ar ₁ is an arylene group.
The heteroaryl group is not particularly limited, but a heteroaryl group composed of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is preferable. Specific examples of the hetero atom contained in the heteroaryl group and the ring constituting the heteroaryl group are the same as those in the case where Ar ₁ is a heteroarylene group.
Ar ₂ is preferably a monovalent polycyclic aromatic hydrocarbon group or monovalent polycyclic aromatic heterocyclic group which may have a substituent (for example, substituent W described later). It is more preferably a valent polycyclic aromatic hydrocarbon group. Here, the monovalent polycyclic aromatic hydrocarbon group is a monovalent group of a polycyclic aromatic hydrocarbon ring (a monovalent group formed by removing one hydrogen atom from a polycyclic aromatic hydrocarbon ring). Group). Definitions, specific examples and preferred embodiments of the polycyclic aromatic hydrocarbon ring are as described below. A monovalent polycyclic aromatic heterocyclic group is a monovalent group of a polycyclic aromatic heterocyclic ring (a monovalent group formed by removing one hydrogen atom from a polycyclic aromatic heterocyclic ring). is there. The definition, specific examples and preferred embodiments of the polycyclic aromatic heterocycle are as described below.

In the general formula (1), Ar ₃ and Ar ₄ each independently represent an aryl ring or a heteroaryl ring which may have a substituent (for example, a substituent W described later).
Specific examples and preferred embodiments of the aryl ring are the same as those in the case where Ar ₂ is an aryl group. Specific examples and preferred embodiments of the heteroaryl ring are the same as those in the case where Ar ₂ is a heteroaryl group.

However, at least one of Ar ₃ and Ar ₄ is a polycyclic aromatic hydrocarbon ring or a polycyclic aromatic heterocycle which may have a substituent (for example, substituent W described later).
Here, the polycyclic aromatic hydrocarbon ring is an aromatic hydrocarbon ring having two or more rings, more specifically, two or more monocyclic aromatic hydrocarbon rings (benzene rings). It is a condensed ring having. Among these, a ring in which two or more monocyclic aromatic hydrocarbon rings are condensed is preferable.
Specific examples of the polycyclic aromatic hydrocarbon ring include naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, acenaphthylene ring, chrysene ring, fluoranthene ring, pyrene ring, triphenylene ring, tetracene ring, benzopyrene ring, picene ring, perylene Ring, pentacene ring, hexacene ring, heptacene ring, coronene ring and the like. Among these, a naphthalene ring is preferable.
The polycyclic aromatic heterocyclic ring is an aromatic heterocyclic ring having two or more rings, more specifically, having two or more rings and one or more monocyclic aromatic rings. A condensed ring having a heterocyclic ring. Among these, 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 is preferable. .
Specific examples of the polycyclic aromatic heterocycle include an acridine ring, a benzoquinoline ring, a carbazole ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, a quindrine ring, a tepenidine ring, a quinindrin ring, and a triphenodi. A thiazine ring, a triphenodioxazine ring, a phenanthrazine ring, an anthrazine ring, a perimidine ring, a diazacarbazole ring (representing any one of carbon atoms constituting a carboline ring replaced by a nitrogen atom), a phenanthroline ring, Dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring Ring, thianthrene ring, phenoxathiin ring, thio fan train ring (naphthothiophene ring) and the like.
The monocyclic heterocyclic ring constituting the polycyclic aromatic heterocyclic ring is not particularly limited, and specific examples thereof include a monocyclic ring among the specific examples of the ring constituting the heteroarylene group when Ar ₁ is a heteroarylene group. Can be mentioned. 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.

At least one of Ar ₃ and Ar ₄ is preferably a polycyclic aromatic hydrocarbon ring which may have a substituent (for example, a substituent W described later).
Further, one of Ar ₃ and Ar _{4 is} a polycyclic aromatic hydrocarbon ring or polycyclic aromatic heterocycle which may have a substituent (for example, substituent W described later), and the other is a substituent ( For example, a monocyclic aromatic hydrocarbon ring or monocyclic aromatic heterocyclic ring which may have a substituent W) described later is preferable. Among them, one of Ar ₃ and Ar _{4 is} a polycyclic aromatic hydrocarbon ring which may have a substituent (for example, substituent W described later), and the other is a substituent (for example, a substituent described later). It is more preferable that it is a monocyclic aromatic hydrocarbon ring which may have W).

The substituent that Ar ¹ to Ar ⁴ has is not particularly limited, but is preferably an aryl group or a heteroaryl group which may have a substituent (for example, substituent W described later), and is represented by the following formula (Z) It is more preferable that it is group represented by these.

In the general formula (Z), Z ₁ represents an arylene group or a heteroarylene group. Of these, an arylene group is preferable.
In the general formula (Z), Z ₂ represents an aryl group or a heteroaryl group. Of these, a heteroaryl group is preferable.
Specific examples of the ring constituting the arylene group and aryl group are the same as those of Ar ¹ to Ar ⁴ described above. Of these, a benzene ring is preferred.
Specific examples of the ring constituting the heteroarylene group and heteroaryl 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, iso Indole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiol Fen ring, carbazole ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring and pteridine ring. Of these, a benzothiazole ring is preferable.
In the general formula (Z), * represents a bonding position.

The molecular weight of the partial structure represented by the following general formula (a) in the general formula (1) is not particularly limited, but is preferably 320 to 2000, more preferably 400 to 1500, and 500 to 1000. More preferably it is.
The number of carbon atoms in the partial structure represented by the general formula (a) is not particularly limited, but is preferably 30 to 100, and more preferably 40 to 70.

A preferred embodiment of the compound of the present invention includes, for example, a compound represented by the following general formula (1b).

In the general formula _(1b), R 1, L, the definition of Ar ₁ and Ar _2, specific examples and preferred embodiments, respectively, _R 1 in the formula (1) described above, L, Ar ₁ and Ar ₂ Is the same.
In the general formula (1b), each R independently represents a hydrogen atom or a substituent (for example, a substituent W described later). Especially, group represented by the general formula (Z) mentioned above is preferable.
In the general formula (1b), p and q each independently represent an integer of 0 or more. However, at least one of p and q is an integer of 1 or more. p and q are preferably integers of 0 to 3, more preferably integers of 0 to 2, and even more preferably 0 or 1.
Note that p and q represent the number of connected benzene rings. For example, when p = 0 and q = 1, the general formula (1b) represents the following general formula (1b-1).

It is preferable that p and q are integers different from each other because the solubility of the compound represented by the general formula (1b) is more excellent. q is preferably an integer greater than p.

The reason why the compound of the present invention exhibits the desired effect is not clear, but is estimated as follows. That is, as shown in the general formula (1) described later, in the compound of the present invention, at least one of two rings (aryl ring or heteroaryl ring) condensed to a 5-membered ring is a polycyclic aromatic ring (polycyclic aromatic carbonization). A hydrogen ring or a polycyclic aromatic heterocycle). Therefore, the planarity of the whole molecule is low and the density of carbon atoms is high. As a result, the compounds of the present invention are believed to exhibit excellent solubility and high refractive index. These are because the solubility and refractive index are insufficient when both of the two rings condensed to a 5-membered ring are monocyclic benzene rings as shown in Comparative Examples described later. Also guessed.

(Substituent W)
It describes about the substituent W in this specification.
Examples of the substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, Heteroaryl group, cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heteroaryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino Groups (including anilino groups), ammonio groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, Lucapto 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 hetero Ring 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 ), phosphato Examples thereof include a group (—OPO (OH) ₂ ), a sulfato group (—OSO ₃ H), and other known substituents.

The compound of the present invention can be synthesized by a known method or a combination of known methods. Although the specific example of the compound of this invention is shown below, it is not limited to these.

[resin]
The resin of the present invention has a repeating unit represented by the following general formula (2).

In the general formula _{_{(2), R 1, L}} , Ar 1, Ar 2, Ar 3 and the definition of Ar _4, specific examples and preferred embodiments, respectively, _R 1 in the above-mentioned general formula (1), L , Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are the same.

The resin of the present invention may have a repeating unit other than the repeating unit represented by the general formula (2).
The ratio of the repeating unit represented by the general formula (2) to the entire repeating unit in the resin of the present invention is not particularly limited, but is preferably 30 mol% or more, more preferably 50 mol% or more, and 70 mol. % Or more is more preferable, and 90 mol% or more is particularly preferable. The upper limit is not particularly limited, but is 100 mol% (homopolymer).

The molecular weight of the resin of the present invention is not particularly limited, but the weight average molecular weight (Mw) is preferably 1,000 to 100,000, and more preferably 1,000 to 30,000.
In this specification, the weight average molecular weight is a polystyrene equivalent value measured by GPC (eluent: THF).

As a preferred embodiment of the resin of the present invention, for example, a resin represented by the following general formula (2b) can be mentioned.

In the general formula _(2b), R 1, L, the definition of Ar ₁ and Ar _2, specific examples and preferred embodiments, respectively, _R 1 in the formula (1) described above, L, Ar ₁ and Ar ₂ Is the same.
In the general formula (2b), the definitions, specific examples and preferred embodiments of R, p and q are the same as R, p and q in the general formula (1b).

The reason why the resin of the present invention exhibits the desired effect is not clear, but the reason similar to the reason why the above-described compound of the present invention exhibits the desired effect is presumed.

(Synthesis method)
The method for synthesizing the resin of the present invention is not particularly limited, and a preferred embodiment includes a method of polymerizing the above-described compound of the present invention as a monomer. In addition, unless it is contrary to the meaning of this invention, monomers other than the compound of this invention can be used as a copolymerization component.
Such a monomer is not particularly limited. For example, methyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate , Unsubstituted (meth) acrylic esters such as stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, 2- (par Halogen-substituted (meth) acrylic acid esters such as fluorohexyl) ethyl acrylate and 2-chloroethyl (meth) acrylate, butyl (meth) acrylamide, isopropyl (meth) acrylamide, octyl (meth) acrylamide, 2-ethyl (Meth) acrylamides such as silacrylamide and dimethyl (meth) acrylamide, styrenes such as styrene and α-methylstyrene, vinyl compounds such as N-vinylcarbazole, vinyl acetate, N-vinylacetamide, N-vinylcaprolactam, Other examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and the like.

[Composition]
The composition of the present invention is a composition containing the above-described resin of the present invention.
The composition of the present invention may contain other components as long as it is not contrary to the gist of the present invention. Such components include solvents, initiators, monomers, dispersants, plasticizers, heat stabilizers, mold release agents, and the like. Examples of these components include the contents after paragraph [0013] of JP 2012-251125 A (corresponding international publication 2012/153826) and JP 2012-255148 A (corresponding international publication 2012-2012). No. 157784), the contents of paragraph [0019] onward can be incorporated, and these contents are incorporated in the present specification.
The content of the resin of the present invention in the composition of the present invention is not particularly limited, but is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and 30 to 90% by mass. More preferably.

[Usage]
The use of the compound of the present invention, the resin of the present invention, and the composition containing the above resin (hereinafter also referred to as the compound of the present invention) is not particularly limited. For example, lenses (glasses lenses, lenses for digital cameras, Fresnel lenses) , Prism lenses, etc.), optical overcoat agent, hard coat agent, antireflection film, optical fiber, optical waveguide, LED sealing material, LED flattening material, micro-OLED substrate, solar cell coating material It is.
In addition, the compound of this invention is useful as a monomer for synthesize | combining resin which has a repeating unit represented by General formula (2).

[Micro OLED]
Next, a micro OLED (micro organic light emitting diode) using the compound of the present invention as a base material for a color filter will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of one pixel of one embodiment of a micro OLED using the compound of the present invention as a base material for a color filter.
The micro OLED 100 includes a substrate 10, an organic EL element 20, a protective film 30, a base layer 40, and color filters (red color filter: 50R, green color filter: 50G, blue color filter: 50B). Here, the underlayer 40 is a layer formed using the compound of the present invention.
The pitch (center-to-center distance) p of the organic EL element 20 is, for example, 30 μm or less, and preferably 1 to 5 μm. That is, the dimension of the organic EL element 20 is extremely small.
The protective film 30 has a thickness of 0.5 to 10 μm, for example, and is made of, for example, silicon nitride.
The method for forming the underlayer 40 is not particularly limited, and examples thereof include a method of applying and curing the compound of the present invention.
The micro OLED 100 may include other members (for example, a reflector or the like). In the case where irregularities are generated on the surface of the protective film 30 due to the provision of a reflector or the like, the base layer 40 also functions as a planarizing layer. That is, the compound of the present invention is also useful as a leveling agent.

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Synthesis of compounds>
The following A-1 to A-4 (compounds of Examples 1, 3, 5 and 7) and C-1 (compound of Comparative Example 1) were synthesized by a known method. Each compound was identified by NMR. FIG. 2 shows a ¹ H-NMR chart of A-3. FIG. 3 shows a ¹ H-NMR chart of A-4.

The specific synthesis scheme and synthesis method (steps A to D) for A-3 are shown below. Other compounds were synthesized by the same method.

(Process A)
While stirring 15.8 g (0.2171 mol) of magnesium, shaving (manufactured by Wako Pure Chemical Industries, Ltd.) with 200 mL of tetrahydrofuran, 134.9 g (0.8 .mu.m) of 2-bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) is stirred. A solution of 6514 mol) in tetrahydrofuran (600 mL) was added dropwise to give a Grignard reagent. Thereafter, the mixture was cooled to 0 ° C., and 600 mL of a THF solution containing 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 (83.5%) of the desired tertiary alcohol.

(Process B)
62 g (0.1730 mol) of 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 77 g of the desired naphthol adduct. (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 (84.3%) of the desired alcohol.

(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. 45 g (60.0%) of the desired compound (A-3) thus obtained was recovered by filtration.

<Resin synthesis>
Using the obtained compounds (A-1 to A-4 and C-1) as monomers, resins (respective resins in Examples and Comparative Examples) were synthesized by a known method.
Resin of Example 2: A-1 homopolymer (Mw: 7300)
Resin of Example 4: Homopolymer of A-2 (Mw: 6500)
Resin of Example 6: A-3 homopolymer (Mw: 7500)
Resin of Example 8: A-4 homopolymer (Mw: 7900)
Resin of Comparative Example 2: C-1 homopolymer (Mw: 6000)

The Mw is a polystyrene equivalent value measured by GPC (solvent: THF). The GPC measurement conditions are shown below.
・ Main body: HLC-8220GPC (Tosoh)
Column: a guard column (HZ-L), TSK gel Super (HZM-M), TSK gel Super (HZ4000), TSK gel Super (HZ3000), TSK gel Super (HZ2000) connected Eluent: tetrahydrofuran Liquid feeding conditions: Sample pump 0.35 mL / min, reference pump 0.2 mL / min
-Column temperature control: 40 ° C
・ Measurement sample: 0.1 wt% concentration (0.5 μm membrane filter filtration)
・ Injection amount: 10 μm
・ Measurement time: 26 minutes

The specific synthesis method for the homopolymer A-3 and the homopolymer C-1 is shown below. Other homopolymers were synthesized by the same method.

(Synthesis of A-3 homopolymer)
4.26 g of a 40 wt% cyclohexanone solution of A-3 (2 g) (3.43 mmol) and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.158 g (0.686 mmol) into 0.9 g of a cyclohexane solution at 80 ° C. It was dripped over 2 hours. After dropping, the mixture was stirred for 2 hours, and then V-601 (0.079 g) (0.345 mmol) was added. Furthermore, after stirring at 90 degreeC for 2 hours, it stirred at 100 degreeC for 1 hour, and stirred for 2 hours. Finally, 1.67 g of cyclohexanone was added to obtain a 30% cyclohexanone solution of A-3 homopolymer. Residual monomer was not observed by NMR.

(Synthesis of C-1 homopolymer)
10.1 g of 15 wt% cyclohexanone solution of 0.21 g (0.92 mmol) of C-1 (2 g) (3.43 mmol) and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 3.4 g of cyclohexane solution at 80 ° C. It was dripped over 2 hours. After dropping, the mixture was stirred for 2 hours, and then V-601 (0.101 g) (0.46 mmol) was added. After further stirring for 2 hours, the temperature was raised to 100 ° C. and stirring was performed for 2 hours. A C-1 homopolymer 15% cyclohexanone solution was obtained. Residual monomer was not observed by NMR.

<Evaluation of solubility>
The solubility (saturated solution concentration) of each compound and homopolymer in cyclohexanone was examined, and the solubility was evaluated from the following criteria. The results are shown in Table 1. A or B is preferable, and A is more preferable.
・ A: Solubility is 30 wt% or more ・ B: Solubility is more than 20 wt% and less than 30 wt% ・ C: Solubility is 20 wt% or less

<Evaluation of refractive index>
A propylene glycol monomethyl ether acetate solution (5 wt%) was prepared for each compound and homopolymer, spin-coated, and dried at 100 ° C. for 2 minutes to prepare a film. Next, the refractive index (wavelength: 500 nm) of the obtained film was measured (apparatus: Ellipso film thickness measuring apparatus RE series, RE-3320 manufactured by Dainippon Screen Mfg. Co., Ltd.).
And the refractive index was evaluated from the following criteria. The results are shown in Table 1. A or B is preferable, and A is more preferable.
-A: Refractive index is 1.70 or more-B: Refractive index is more than 1.65 and less than 1.70-C: Refractive index is 1.65 or less

As can be seen from Table 1, Examples 1, 3, 5 and 7 which are compounds represented by the general formula (1) described above and the general formulas described above are compared with the compounds of Comparative Example 1 which are known compounds. Examples 2, 4, 6 and 8, which are resins having a repeating unit represented by (2), exhibited excellent solubility and a high refractive index. Among them, Examples 1, 2 and 1 in which one of Ar ₃ and Ar _{4 in} the general formula (1) or (2) is a polycyclic aromatic hydrocarbon ring and the other is a monocyclic aromatic hydrocarbon ring. 5 to 8 showed better solubility. Among them, Examples 5 to 8 in which Ar ₁ in the general formula (1) or (2) is a divalent polycyclic aromatic hydrocarbon group showed a higher refractive index.

Further, using each compound (A-1 to A-4 and C-1) and methyl methacrylate as monomers, a copolymer of each compound and methyl methacrylate (each compound / methyl methacrylate = 80 mass% / 20% by mass) and the solubility and refractive index were evaluated as described above. The copolymer using A-1 to A-4 was superior to the copolymer using C-1. High solubility and high refractive index.

The display device (micro OLED) of the above-described embodiment shown in FIG. 1 is prepared by using the compounds and homopolymers of the above-described examples and copolymers of each of the above-described compounds and methyl methacrylate for the underlayer of the color filter. Then, it was confirmed that the compounds and resins of the present invention are useful for display devices (micro OLED).

DESCRIPTION OF SYMBOLS 10 Board | substrate 20 Organic EL element 30 Protective film 40 Underlayer 50R Red color filter 50G Green color filter 50B Blue color filter 100 Micro OLED

Claims

A compound represented by the following general formula (1). Here, R 1 is a hydrogen atom or an alkyl group, L is a divalent linking group, Ar 1 is an arylene group or heteroarylene group which may have a substituent, and Ar 2 may have a substituent. A good aryl group or heteroaryl group, Ar 3 and Ar 4 each independently represent an optionally substituted aryl ring or heteroaryl ring. However, at least one of Ar 3 and Ar 4 is an optionally substituted polycyclic aromatic hydrocarbon ring or polycyclic aromatic heterocycle.
The compound according to claim 1, wherein at least one of Ar 3 and Ar 4 is a polycyclic aromatic hydrocarbon ring which may have a substituent.
Resin which has a repeating unit represented by following General formula (2). Here, R 1 is a hydrogen atom or an alkyl group, L is a divalent linking group, Ar 1 is an arylene group or heteroarylene group which may have a substituent, and Ar 2 may have a substituent. A good aryl group or heteroaryl group, Ar 3 and Ar 4 each independently represent an optionally substituted aryl ring or heteroaryl ring. However, at least one of Ar 3 and Ar 4 is a polycyclic aromatic hydrocarbon ring or a polycyclic aromatic heterocycle which may have a substituent.
The resin according to claim 3, having a weight average molecular weight of 2,000 to 100,000.
A composition containing the resin according to claim 3 or 4.