TW202012547A - Compound and manufacturing method thereof - Google Patents

Abstract

Provided is a compound represented by formula (I). [In the formula, R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; T1 and T2 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; any one of Y1 and Y2 represents a monovalent aromatic group that may have a substituent, and the other represents a monovalent aromatic group which may have a substituent, a hydrogen atom, a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-).].

Description

Compound and its manufacturing method

The present invention relates to novel compounds and methods for making them.

Display devices such as liquid crystal display devices or organic electroluminescence (organic EL) display devices are undergoing color tone adjustment and improving color purity. Patent Document 1 describes that a squarylium-based compound is used as a filter for a plasma display panel that can effectively filter neon light emitted from a plasma display.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-183522

An object of the present invention is to provide a novel compound useful for an optical filter of a display device and the like and a method for manufacturing the same.

The present invention provides the compounds shown below and their production methods.

[1] A compound represented by formula (I).

[式中，R¹至R⁴分別獨立地表示氫原子或可具有取代基之碳數1至6的1價烴基。

[In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

Either Y ^{1 or} Y ² represents a monovalent aromatic group that may have a substituent, and the other represents a monovalent aromatic group that may have a substituent, a hydrogen atom, a halogen atom, or a carbon number that may have a substituent 1 A monovalent hydrocarbon group up to 6 (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-)].

[2] A compound represented by formula (II).

[式中，

[Where,

R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

Either X ^{1 or} X ² represents any group selected from Group A, and the other represents any group selected from Group A, a hydrogen atom, or a monovalent carbon number of 1 to 6 which may have a substituent Hydrocarbon group (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-).

Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ . ]

[3] A method for producing a compound represented by formula (Ia), which comprises

The step of reacting the compound represented by formula (IIa), the compound represented by formula (III-1a) and the compound represented by formula (III-2a) in the presence of a nickel catalyst or a palladium catalyst.

[式中，

[Where,

R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

Y ^1a and Y ^2a each independently represent a monovalent aromatic group which may have a substituent. ]

[式中，

[Where,

R ¹ to R ^{4 have the} same meaning as described above.

T ¹ and T ^{2 have the} same meaning as described above.

X ^1a and X ^2a each independently represent any group selected from Group A.

Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ . ]

Y ^1a -Z ¹ (III-1a)

Y ^2a -Z ² (III-2a) [In formula (III-1a) and formula (III-2a),

Y ^1a and Y ^{2a have the} same meaning as described above.

Z ¹ and Z ² each independently represent a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group. ]

[4] A method for producing a compound represented by formula (Ib), which comprises

The step of reacting the compound represented by formula (IIb) with the compound represented by formula (III-1b) in the presence of a nickel catalyst or a palladium catalyst.

[式中，

[Where,

R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

Y ^1b represents a monovalent aromatic group which may have a substituent.

X ^2b represents a hydrogen atom or a C1-C6 monovalent hydrocarbon group which may have a substituent (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted to -O- or- CO-). ]

[式中，

[Where,

R ¹ to R ^{4 have the} same meaning as described above.

T ¹ and T ^{2 have the} same meaning as described above.

X ^1b represents any group selected from group A.

Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ .

X ^2b has the same meaning as described above. ]

Y ^1b -Z ¹ (III-1b) [where,

Y ^1b has the same meaning as described above.

Z ¹ represents a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group. ]

The compound of the present invention can be suitably used for optical filters of display devices and the like.

1, 2‧‧‧ image display component

10‧‧‧Optical filter

11‧‧‧Adhesive layer for image display device

12‧‧‧phase retardation film

13‧‧‧Adhesive layer

14‧‧‧The first protective film

15‧‧‧ Polarizing film

16‧‧‧Second protective film

20‧‧‧Optical laminate

21‧‧‧Adhesive layer for image display element

24‧‧‧The first protective film

25‧‧‧ Polarizing film

26‧‧‧Second protective film

Fig. 1 (a) and (b) are schematic cross-sectional views showing an example of an optical filter.

Fig. 2 (a) is a schematic cross-sectional view showing an example of an organic EL display device, and (b) is a schematic cross-sectional view showing an example of a liquid crystal display device.

(Compound represented by formula (I))

The present invention relates to a compound represented by the following formula (I) (hereinafter also referred to as "compound (I)").

[式中，R¹至R⁴分別獨立地表示氫原子或可具有取代基之碳數1至6的1價烴基；

[In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent;

T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent;

Either Y ^{1 or} Y ² represents a monovalent aromatic group which may have a substituent, and the other represents a monovalent aromatic group which may have a substituent, a hydrogen atom, a halogen atom, or a carbon number which may have a substituent 1 A monovalent hydrocarbon group up to 6 (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-)].

In the compound (I), in addition to the symbol represented by the formula (I), there are, for example, tautomers of a resonance structure represented by the following formula. Compound (I) contains all tautomers.

In the formula (I), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms in R ¹ to R ⁴ include monovalent saturated hydrocarbon groups or monovalent unsaturated hydrocarbon groups.

Examples of monovalent saturated hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; isopropyl, isobutyl, second butyl, and third butyl groups , Isopentyl or neopentyl and other branched chain alkyl groups; cyclopropyl, cyclopentyl or cyclohexyl and other alicyclic saturated hydrocarbon groups.

Examples of the monovalent unsaturated hydrocarbon group include: a phenyl group belonging to an aromatic hydrocarbon group; a monovalent unsaturated aliphatic hydrocarbon group such as vinyl group, propenyl group, butenyl group, or pentenyl group; cyclopropenyl group, cyclopentenyl group, or Monovalent alicyclic unsaturated hydrocarbon group such as cyclohexenyl group.

In the formula (I), examples of the substituent of the C 1 to C 6 monovalent hydrocarbon group which may have a substituent among R ¹ to R ⁴ include, for example, halogen atom, hydroxyl group, amino group, nitro group, and sulfamoyl Group, sulfonic acid group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

In the formula (I), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in T ¹ and T ² include those exemplified in R ¹ to R ⁴ .

In formula (I), any one of Y ¹ and Y ² may be a monovalent aromatic group which may have a substituent, and each of them may independently be a monovalent aromatic group which may have a substituent. Among Y ¹ and Y ² , one is a monovalent aromatic group, the other may be a hydrogen atom, a halogen atom, or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, and the hydrocarbon group contains -CH ₂ -may be substituted with -O- or -CO-.

Examples of the monovalent aromatic group which may have a substituent in Y ¹ and Y ² include a monovalent aromatic hydrocarbon group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. The monovalent aromatic group may have a single ring structure or a fused ring structure.

The carbon number of the monovalent aromatic hydrocarbon group is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 13. Examples of monovalent aromatic hydrocarbon groups include: phenyl; naphthyl; anthracenyl; phenanthrenyl; pyrenyl; stilbene and the like. In addition, the monovalent aromatic hydrocarbon group includes a group in which hydrogen contained in the above group is substituted with a hydrocarbon group such as an alkyl group (-CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-), an aryl group, It may be, for example, tolyl, xylyl, tricresyl, propylphenyl, butylphenyl, hexylphenyl, biphenyl, bitriphenyl, propylbiphenyl, and the like.

The carbon number of the monovalent aromatic heterocyclic group is usually 2 to 30, preferably 4 to 20, and more preferably 4 to 10.

唑、異

唑、噻唑、異噻唑、咪唑、吡唑、呋呫、三唑、

二唑、異

唑、四唑、哌喃、吡啶、噻喃、嗒

、嘧啶、吡

、三

、苯并呋喃、異苯并呋喃、苯并噻吩、吲哚、異吲哚、中氮茚 (indolizine)、吲哚啉、異吲哚啉、苯并哌喃、異苯并哌喃、色滿、異色滿、苯并哌喃、喹啉、異喹啉、喹

、苯并咪唑、苯并噻唑、苯并噻二唑、吲唑、萘啶、喹

啉、喹唑啉、喹唑啶、噌啉(Cinnoline)、呔

、嘌呤、喋啶、咔唑、二苯并哌喃(xanthene)、啡啶、吖啶、β-咔啉、呸啶、啡啉、噻嗯、啡

噻、啡

、啡噻

、啡

等雜環式化合物去除1個氫原子後的基。又，1價芳香族雜環基係包含上述基所含有的氫被烷基、芳基等烴基所取代的基，其可為例如從N-聯苯咔唑去除1個氫原子後的基。 The hetero atom in the monovalent aromatic heterocyclic group represents a nitrogen atom, an oxygen atom, a sulfur atom, or the like. Examples of monovalent aromatic heterocyclic groups include furan, thiophene, pyrrole,

Azole, iso

Azole, thiazole, isothiazole, imidazole, pyrazole, furox, triazole,

Diazole, iso

Azole, tetrazole, piperan, pyridine, thiopyran, ta

, Pyrimidine, pyridine

,three

, Benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindolin, benzopiperan, isobenzopiperan, chroman , Isochroman, benzopiperan, quinoline, isoquinoline, quinoline

, Benzimidazole, benzothiazole, benzothiadiazole, indazole, naphthyridine, quinoline

Quinoline, quinazoline, quinazolidine, cinnoline (Cinnoline), 呔

, Purine, pyridine, carbazole, xanthene, pyridine, acridine, β-carboline, pyridine, morpholine, thien, morphine

Thiocyanine

Fenthione

,coffee

The heterocyclic compound removes one hydrogen atom. In addition, the monovalent aromatic heterocyclic group includes a group in which hydrogen contained in the above group is substituted with a hydrocarbon group such as an alkyl group or an aryl group, and it may be a group obtained by removing one hydrogen atom from N-biphenylcarbazole, for example.

Examples of the substituent in the monovalent aromatic group which may have a substituent include the above halogen atom; hydroxyl group; amine group; nitro group; aryloxy group; arylcarbonyl group; aryloxycarbonyl group; carboxyl group; sulfonic acid group ; Amine; Aminosulfonyl and so on.

In the formula (I), the hydrocarbon group other than the monovalent aromatic group of any of Y ¹ and Y ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and examples include: R ¹ to R ^The monovalent saturated hydrocarbon group which may have a substituent, the monovalent unsaturated aliphatic hydrocarbon group which may have a substituent, or the monovalent alicyclic unsaturated hydrocarbon group which may have a substituent, etc., exemplified in ⁴ .

The -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-. Examples of such groups include -C(=O)CH ₃ and -C(=O)-OCH ₂ CH ₃ .

Examples of the compound (I) include compounds represented by the following formula.

The compound (I) can be used for optical filters in display devices and the like. For example, by adding the compound (I) to a layer that becomes an optical filter, it can be used as an optical filter capable of absorbing light in the vicinity of 580 nm (575 to 590 nm) (preferably light having a maximum absorption wavelength of 580 nm). As a result, the light passing through the optical filter improves the separation between the green light and the red light compared to the light entering the optical filter, and it is expected to improve the color purity of the green light and the red light. Therefore, by applying the optical filter using the compound (I) to a display device or the like, a display device with improved color purity can be obtained.

(Compound represented by formula (II))

The compound represented by the following formula (II) of the present invention (hereinafter also referred to as "compound (II)") can be used as an intermediate for producing compound (I).

[式中，R¹至R⁴分別獨立地表示氫原子或可具有取代基之碳數1至6的1價烴基。

[In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent.

Either X ^{1 or} X ² represents any group selected from Group A, and the other represents any group selected from Group A, a hydrogen atom, or a monovalent carbon number of 1 to 6 which may have a substituent Hydrocarbon group (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-).

Group A: a group consisting of a halogen atom, a borate group and -B(OH) ₂ ].

In the compound (II), in addition to the symbol represented by the formula (II), there is, for example, a tautomer of a resonance structure represented by the following formula. Compound (II) contains all tautomers.

In the formula (II), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent in R ¹ to R ⁴ , T ¹ and T ² may be as described above.

In formula (II), either X ^{1 or} X ² represents any group selected from group A, or both may be any group selected from group A. Among X ¹ and X ² , one is a group selected from any group A, and the other may be a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, the hydrocarbon group contains -CH ₂ -may be substituted with -O- or -CO-.

In the formula (II), the halogen atom in the group A may be as mentioned above.

Examples of the borate group in X ¹ and X ² include groups represented by the following formulas. In the following formula, * represents a bonding bond.

In the formula (II), the hydrocarbon group other than the monovalent aromatic group of any one of X ¹ and X ² is a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, and examples include: R ¹ to R ^The monovalent saturated hydrocarbon group, monovalent unsaturated aliphatic hydrocarbon group, monovalent alicyclic unsaturated hydrocarbon group, etc. exemplified in ⁴ .

-CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-. Examples of such a group include -C(=O)CH ₃ and -C(=O)-OCH ₂ CH ₃ .

The compound (II) may, for example, be a compound represented by the following formula.

(Production method of compound (I) [1])

The compound (I) of the present invention shows that both Y ¹ and Y ² are monovalent aromatic groups which may have a substituent (the compound represented by the following formula (Ia) (hereinafter also referred to as “compound ( Ia)")).

[式中，

[Where,

R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent;

T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent;

Y ^1a and Y ^2a each independently represent a monovalent aromatic group which may have a substituent].

In the formula (Ia), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent in R ¹ to R ⁴ , T ¹ and T ² may be as mentioned above.

The monovalent aromatic group which may have a substituent in Y ^1a and Y ^2a in formula (Ia) may be exemplified by the monovalent aromatic group which may have a substituent represented by Y ¹ and Y ² in the above formula (I) An example of a family base.

The method for producing compound (Ia) may include reacting the compound represented by formula (IIa), the compound represented by formula (III-1a) and the compound represented by formula (III-2a) in the presence of a nickel catalyst or a palladium catalyst A step of.

[式中，

[Where,

R ¹ to R ^{4 have the} same meaning as described above;

T ¹ and T ^{2 have the} same meaning as described above;

X ^1a and X ^2a independently represent any group selected from group A;

Group A: a group consisting of a halogen atom, a borate group and -B(OH) ₂ ].

Y ^1a -Z ¹ (III-1a)

Y ^2a -Z ² (III-2a) [In formula (III-Ia) and formula (III-2a),

Y ^1a and Y ^{2a have the} same meaning as above;

Z ¹ and Z ² each independently represent a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group].

In the formula (IIa), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent in R ¹ to R ⁴ , T ¹ and T ² may be as mentioned above.

The halogen atom and the borate group in the group A of X ^1a and X ^2a in the formula (IIa) may be as described above.

In the formula (III-1a) and the formula (III-2a), the halogen atom and the borate group in Z ¹ and Z ² may be as described above.

Examples of the alkyl sulfonate groups in Z ¹ and Z ² include methane sulfonate groups, ethane sulfonate groups, trifluoromethane sulfonate groups, and the like, which may have a halogen atom and a carbon number of 1 to 6. Alkylsulfonate group. Examples of halogen atoms include those exemplified above.

Examples of the arylsulfonate groups in Z ¹ and Z ² include arylsulfonates having 6 to 18 carbon atoms, such as benzenesulfonate groups, p-toluenesulfonate groups, and benzylsulfonate groups. base.

Preferably, Z ¹ and Z ² are each independently a halogen atom, a borate group, or -B(OH) ₂ .

Examples of the compound represented by formula (IIa) include compounds represented by the following formula.

Examples of the compounds represented by formula (III-1a) and formula (III-2a) include: 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl)phenol, 3,4,5-trimethoxyphenylboronic acid, 4-hexylphenylboronic acid, 4-hexyloxyphenylboronic acid, 4-(dimethylamino) ) Phenylboronic acid, 4-(diphenylamino) phenylboronic acid, 4'-propyl-4-biphenylboronic acid, 6-ethoxy-2-naphthaleneboronic acid, 9,9-dimethyl stilbene-2- Boric acid, benzo[b]thiophene-2-boronic acid, 9-ethylcarbazole-3-boronic acid, 9-(4-biphenyl)carbazole-3-boronic acid namalol, 4-third butylbenzene Boronic acid, 4-methoxy-3,5-dimethylphenylboronic acid, 4-carboxyphenylboronic acid coronaol, 1-thienylboronic acid, 4-methyl-1-naphthaleneboronic acid, etc.

In the step of producing compound (Ia), it is preferable to use the compound represented by formula (IIa), the compound represented by formula (III-1a) and the formula (III-2a) in the presence of a palladium catalyst or a nickel catalyst The coupling method of the compound shown is the best coupling method in the presence of a palladium catalyst.

Examples of the palladium catalyst include: palladium (0) triphenylphosphine, palladium (0) ginseng (dibenzylideneacetone), palladium (II) acetate, palladium (II) dichlorobistriphenylphosphine and Potassium hexachloropalladium (IV), etc.

Examples of nickel catalysts include: (triphenylphosphine) nickel (0), [bis(1,5-cyclooctadiene)] nickel (0), and dichloro[1,3-bis(diphenylphosphine Group) propane] nickel (II), bis (2,4-pentanedione) nickel (II), bis (triphenylphosphine) nickel (II) dichloride and nickel halide (II), etc.

The use amount of the palladium catalyst or the nickel catalyst is preferably 0.1 mol% or more and 50 mol% or less with respect to 1 mol of the compound represented by the formula (IIa).

The use amount of the compound represented by formula (III-1a) is preferably 1 mole or more and 5 moles or less, more preferably 1.1 moles or more and 3 moles relative to 1 mole of the compound represented by formula (IIa) the following.

The use amount of the compound represented by the formula (III-2a) is preferably 1 mole or more and 5 moles or less, more preferably 1.1 moles or more and 3 moles relative to the compound represented by the formula (IIa) at 1 mole. the following.

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

烷、二甲氧基乙烷等醚系溶劑；氯苯、二氯苯、氯仿等鹵烴溶劑；甲醇、乙醇、異丙醇、丁醇等醇溶劑；硝基苯等硝基烴溶劑；甲基異丁基酮等酮溶劑；N,N-二甲基甲醯胺、1-甲基-2-吡咯啶酮等醯胺溶劑等，該等亦可混合使用。該等之中，較佳為四氫呋喃。又，亦可藉由在如使用鈀催化劑之偶合反應之與水的2相系或混合系中的反應來進行。有機溶劑的使用量，相對於式(IIa)所示之化合物1質量份，較佳為10質量份以上200質量份以下，更佳為20質量份以上150質量份以下。 From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; hydrocarbon solvents such as hexane, cyclohexane, and decahydronaphthalene; tetrahydrofuran, 1,4-bis

Ether, dimethoxyethane and other ether solvents; chlorobenzene, dichlorobenzene, chloroform and other halogenated hydrocarbon solvents; methanol, ethanol, isopropanol, butanol and other alcohol solvents; nitrobenzene and other nitro hydrocarbon solvents; A Ketone solvents such as isobutyl ketone; amide solvents such as N,N-dimethylformamide and 1-methyl-2-pyrrolidone, etc., which can also be used in combination. Among these, tetrahydrofuran is preferred. In addition, it can also be carried out by a reaction in a two-phase system or a mixed system with water such as a coupling reaction using a palladium catalyst. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 150 parts by mass or less with respect to 1 part by mass of the compound represented by formula (IIa).

In addition, a base may be added to the reaction of the compound represented by formula (IIa), the compound represented by formula (III-1a), and the compound represented by formula (III-2a). The base is preferably soluble in the solvent used in the reaction. Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate; butyl lithium, potassium tributoxide, sodium tributoxide, and sodium methoxide , Sodium ethoxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and other organic bases. The method of mixing alkali includes, for example, a method of adding an alkali solution while stirring the reaction solution in an inactive environment such as argon or nitrogen, or a method of adding a reaction solution to an alkali solution.

The amount of the base used is preferably 2 moles or more and 20 moles or less relative to 1 mole of the compound represented by formula (IIa).

The method of obtaining the compound (Ia) belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used. For example, a method of filtering and taking out precipitated crystals after cooling. The crystals taken out by filtration are preferably washed with water or the like and then dried. In addition, it can be further refined by conventional methods such as recrystallization and column chromatography according to needs.

(Production method of compound (I) [2])

In the compound (I) of the present invention, Y ¹ is a monovalent aromatic group which may have a substituent, Y ² is a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent (the hydrocarbon group is a monovalent aromatic group other than aromatic group, -CH hydrocarbon which contains ₂ - may be substituted with -O- or -CO-) of the compounds of the case where the compound (shown below (the following formula (Ib) also referred to as "compound (Ib )")) manufacturing method.

[式中，

[Where,

R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent;

T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent;

Y ^1b represents a monovalent aromatic group which may have a substituent;

X ^2b represents a hydrogen atom or a C1-C6 monovalent hydrocarbon group which may have a substituent (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted to -O- or- CO-)].

In the formula (Ib), R ¹ to R ⁴ , T ¹ and T ² may have a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, such as: R ¹ to R ⁴ in the above formula (I) Exemplified in.

In the formula (Ib), the monovalent aromatic group which may have a substituent in Y ^1b is exemplified by Y ¹ and Y ² in the above formula (I).

In the formula (Ib), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent in X ^2b may be as exemplified in R ¹ to R ⁴ in the above formula (I).

The method for producing the compound (Ib) may further include the step of reacting the compound represented by the formula (IIb) with the compound represented by the formula (III-1b) in the presence of a nickel catalyst or a palladium catalyst.

[式中，

[Where,

R ¹ to R ^{4 have the} same meaning as described above;

T ¹ and T ^{2 have the} same meaning as described above;

X ^1b represents any group selected from group A.

Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ .

X ^2b means the same as before;]

Y ^1b -Z ¹ (III-1b) [where,

Y ^1b has the same meaning as above;

Z ¹ represents a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group].

In formula (IIb) and formula (III-1b), R ¹ to R ⁴ , T ¹ and T ² , and X ^2b may have a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, and examples include the above formula: Exemplified in R ¹ to R ⁴ in (I).

In the formula (IIb) and the formula (III-1b), the monovalent aromatic group which may have a substituent in Y ^1b may be exemplified by Y ¹ and Y ² in the above formula (I).

In the formula (IIb), the halogen atom and the borate group in X ^1b may be as described above.

Examples of the compound represented by the formula (IIb) include compounds represented by the following formula.

Examples of the compound represented by the formula (III-1b) include the compounds exemplified as the compounds represented by the above formula (III-1a) and formula (III-2a).

In the step of producing compound (Ib), it is preferable to couple the compound represented by formula (IIb) with the compound represented by formula (III-1b) in the presence of a palladium catalyst or a nickel catalyst, and the best method is Coupling method performed in the presence of a palladium catalyst. Examples of the palladium catalyst and nickel catalyst include those mentioned above.

The use amount of the compound represented by formula (III-1b) is preferably 1 mole or more and 5 moles or less, more preferably 1.1 moles or more and 3 moles relative to 1 mole of the compound represented by formula (IIb) the following.

The use amount of the palladium catalyst or the nickel catalyst is preferably 0.1 mol% or more and 50 mol% or less with respect to 1 mol of the compound represented by formula (IIb).

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of organic solvents include those exemplified above. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 150 parts by mass or less with respect to 1 part by mass of the compound represented by formula (IIb).

The method of obtaining the compound (Ib) belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used, and examples thereof include the above-mentioned methods.

(Production method of compound (I) [3])

The production method of the compound (I) of the present invention may include a squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) represented by the following formula (IV) or formula (IV -1) The compound represented by (hereinafter also referred to as compound (IV-1)), the compound represented by the following formula (V1) (hereinafter also referred to as "pyrrole-based compound (V1)") and the following formula (V2 ) The step of reacting the compound shown (hereinafter also referred to as "pyrrole-based compound (V2)").

[式(IV-1)、式(V1)及式(V2)中，

[In formula (IV-1), formula (V1) and formula (V2),

R ¹ to R ^{4 have the} same meaning as described above;

Either Y ^{1 or} Y ² represents a monovalent aromatic group that may have a substituent, and the other represents a monovalent aromatic group that may have a substituent, a hydrogen atom, a halogen atom, or a carbon number that may have a substituent 1 A monovalent hydrocarbon group up to 6 (the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-);

T ¹ and T ^{2 have the} same meaning as described above;

R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 4 carbons].

In the formula (V1) and the formula (V2), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent among R ¹ to R ⁴ , T ¹ and T ² may be as mentioned above.

In formula (V1) and formula (V2), the monovalent aromatic group which may have a substituent in Y ¹ and Y ² , a halogen atom, and a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent are exemplified as described above By.

Examples of the pyrrole-based compound (V1) and the pyrrole-based compound (V2) include compounds represented by the following formulas.

In the step of producing compound (I), a method of dehydrating and condensing squaric acid, pyrrole-based compound (V1) and pyrrole-based compound (V2) in an organic solvent is preferred. Examples of the organic solvent include those described above, and a mixed solvent of butanol and toluene is preferred.

In the step of reacting squaric acid, pyrrole-based compound (V1) and pyrrole-based compound (V2), the amount of squaric acid used is preferably 1 mol in total with respect to pyrrole-based compound (V1) and pyrrole-based compound (V2). It is 0.45 moles or more and 0.6 moles or less, more preferably 0.47 moles or more and 0.51 moles or less.

The use amount of the pyrrole-based compound (V2) is preferably 1 mole or more and 1.5 mole or less relative to 1 mole of the pyrrole-based compound (V1).

The reaction of the compound or compound (IV-1) represented by the formula (IV) with the pyrrole-based compound (V1) and the pyrrole-based compound (V2) is achieved by combining the compound or compound (IV-1) represented by the formula (IV) ) Is mixed with the azole-based compound (V1) and the azole-based compound (V2). In the reaction system, the compound represented by the formula (IV) or the compound (IV-1), the azole-based compound (V1), and the azole-based compound (V2) can be reacted together. Alternatively, a method of first mixing the compound represented by formula (IV) or compound (IV-1) with a pyrrole-based compound (V1) and then mixing the pyrrole-based compound (V2) may also be a method of first using the formula ( IV) The compound or compound (IV-1) shown is mixed with the azole compound (V2), and then the azole compound (V1) is mixed.

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent include those exemplified above. The amount of the organic solvent used is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 8 parts by mass or more and 160 parts by mass or less with respect to 1 part by mass of squaric acid.

The method for obtaining the compound (I) belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods such as the above-mentioned methods can be used.

The pyrrole-based compound (V1) can be obtained by reacting the following formula (V1') (hereinafter also referred to as "pyrrole-based compound (V1')") with a halogenating agent, and then reacting the reaction product with the following formula (III- 1) The compound shown (hereinafter also referred to as "compound (III-1)") is produced by reaction. Further, for example, the pyrrole-based compound (V2) can be obtained by reacting a compound represented by the following formula (V2') (hereinafter also referred to as "pyrrole-based compound (V2')") with a halogenating agent, and then reacting the reaction product It is produced by reacting with a compound represented by the following formula (III-2) (hereinafter also referred to as "compound (III-2)"). Moreover, since the compound (III-1) and the compound (III-2) are reacted at the expected position, (V1') and (V2') may have a protecting group such as an ethoxycarbonyl group at a position where the reaction is not expected After the reaction, the desired pyrrole compound (V1) and pyrrole compound (V2) can be produced by deprotection.

[式(V1’)及式(V2’)中，

[In formula (V1') and formula (V2'),

R ¹ to R ^{4 have the} same meaning as described above;

T ¹ and T ^{2 have the} same meaning as described above].

In the formula (V1′) and the formula (V2′), the C 1 to C 6 monovalent hydrocarbon groups which may have a substituent in R ¹ to R ⁴ , T ¹ and T ² may be as described above.

Y ¹ -Z ¹ (III-1)

Y ² -Z ² (III-2) [In formula (III-1) and formula (III-2),

Y ¹ and Y ^{2 have the} same meaning as above;

Z ¹ and Z ² each independently represent a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group].

In formula (III-1) and formula (III-2), the monovalent aromatic group which may have a substituent in Y ¹ and Y ² , a halogen atom, and a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent As mentioned above.

In the formula (III-1) and the formula (III-2), the halogen atom, the borate group, the alkylsulfonate group or the arylsulfonate group in Z ¹ and Z ² may be as described above.

Examples of the pyrrole-based compound (V1') and pyrrole-based compound (V2') include 2,4-dimethylpyrrole.

Examples of the compound (III-1) and the compound (III-2) include 4-hexylphenylboronic acid and the like.

Examples of the halogenating agent include N-fluorosuccinimide (NFS), N-chlorosuccinimide (NFS), N-chlorosuccinimide (NCS), and N-bromosuccinimide (NXS). (NBS), N-iodosuccinimide (NIS), N-chlorophthalimide, N-chlorodiethylamine, N-chlorodibutylamine, N-chlorocyclohexylamine, chlorine, iodine trichloride , Aluminum trichloride, tellurium (IV) chloride, molybdenum chloride, antimony chloride, ferric chloride (III), titanium tetrachloride, phosphorus pentachloride, thionyl chloride, N-bromophthalimide , N-bromobistrifluoromethylamine, bromine, 1,2-dibromoethane, boron tribromide, copper bromide, silver bromide, tertiary butyl bromide, bromine oxide, etc., preferably N-halogen Succinimide.

In the steps of producing the pyrrole-based compound (V1) and the pyrrole-based compound (V2), the reaction product obtained by reacting the pyrrole-based compound (V1') or the pyrrole-based compound (V2') with a halogenating agent and the compound (III-1) or The reaction of the compound (III-2) is preferably a method of coupling in the presence of a palladium catalyst or a nickel catalyst, and most preferably a method of coupling in the presence of a palladium catalyst. Examples of the palladium catalyst and nickel catalyst include those mentioned above.

The reaction between the reaction product of the pyrrole-based compound (V1') or the pyrrole-based compound (V2') and the halogenating agent with the compound (III-1) or the compound (III-2) is carried out in the presence of a palladium catalyst, and the reaction is introduced by the halogenating agent When the substituent of the product is a halogen atom, Z ¹ in the compound (III-1) or Z ^{2 in} the compound (III-2) is preferably a borate group or -B(OH) independently ₂ . When the above reaction is carried out in the presence of a nickel catalyst and the substituent introduced into the reaction product by a halogenating agent is a halogen atom, it is preferred that Z ¹ and Z ² are each independently a halogen atom. In addition, when the above reaction is carried out in the presence of a palladium catalyst and the substituent introduced into the reaction product by a halogenating agent is converted into a borate group or -B(OH) ₂ by a general method, Z ¹ and Z ^{2 are} preferred Each is independently an alkylsulfonate group or an arylsulfonate group.

In the reaction of a pyrrole-based compound (V1') or a pyrrole-based compound (V2') with a halogenating agent, it is preferably a halogenating agent relative to 1 mole of the pyrrole-based compound (V1') or the pyrrole-based compound (V2'). It is 1 mole or more and 5 moles or less, more preferably 1.05 moles or more and 3 moles or less.

The reaction temperature is preferably -80°C to the boiling point of the solvent. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent include those exemplified above. The amount of the organic solvent used is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 8 parts by mass or more and 50 parts by mass or less based on 1 part by mass of the pyrrole-based compound (V1') or the pyrrole-based compound (V2'). .

The method for obtaining the reaction product of the pyrrole-based compound (V1') or the pyrrole-based compound (V2') and the halogenating agent belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used, and the methods described above can be cited.

In the reaction between the reaction product of the pyrrole-based compound (V1') and the halogenating agent and the compound (III-1), the amount of the compound (III-1) used is preferably 1 mole relative to the pyrrole-based compound (V1'). 1 mol or more and 5 mol or less, more preferably 1.1 mol or more and 3 mol or less.

In the reaction between the reaction product of the pyrrole-based compound (V2') and the halogenating agent and the compound (III-2), the amount of the compound (III-2) used is preferably 1 mole relative to the pyrrole-based compound (V2'). 1 mol or more and 5 mol or less, more preferably 1.1 mol or more and 3 mol or less.

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

The method for obtaining the pyrrole-based compound (V1) or the pyrrole-based compound (V2) belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used, and the methods described above can be cited.

(Production method of compound (I) [4])

The method for producing the compound (I) of the present invention where Y ¹ is a monovalent aromatic group which may have a substituent and Y ² is a halogen atom (hereinafter also referred to as "compound (Ic)") will be described.

Compound (Ic), X ^2b may be by the compound of the above formula (Ib) as shown in the hydrogen atom, the hydrogen atom of the halide X ^2b represents produced. Halogenation can be performed using, for example, the above-mentioned halogenating agent.

(Production method (1) of compound (II))

The production method of the compound (II) of the present invention is, for example, in the case where the compound (II) is a compound in which X ¹ and X ² in the formula (II) are halogen atoms (hereinafter also referred to as "compound (IIc)"), It includes the following two steps: reacting the squaric acid represented by the above formula (IV), the pyrrole-based compound (V1′) and the pyrrole-based compound (V2′) to obtain the compound represented by the following formula (II′) ( Hereinafter also referred to as "compound (II')") and the step of reacting compound (II') with a halogenating agent to obtain compound (IIc).

[式中，

[Where,

R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent;

T ¹ and T ² each independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent].

In the formula (II′), the C 1 to C 6 monovalent hydrocarbon group which may have a substituent in R ¹ to R ⁴ , T ¹ and T ² may be as mentioned above.

Examples of the halogenating agent include those mentioned above.

Examples of the compound (II') include compounds represented by the following formula.

In the step of reacting the squaric acid, the pyrrole-based compound (V1') and the pyrrole-based compound (V2'), the amount of squaric acid used is 1 in total relative to the pyrrole-based compound (V1') and the pyrrole-based compound (V2') Molar is preferably 0.45 mol or more and 0.6 mol or less, more preferably 0.47 mol or more and 0.51 mol or less.

The amount of the pyrrole compound (V2') used is preferably 1 mole or more and 1.5 mole or less relative to 1 mole of the pyrrole compound (V1').

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. As the organic solvent, those exemplified above can be used. The amount of the organic solvent used is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 8 parts by mass or more and 100 parts by mass relative to the total 1 part by mass of the pyrrole-based compound (V1') and the pyrrole-based compound (V2'). the following.

The method for obtaining the compound (II') belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used, and for example, the above-mentioned method can be used.

The reaction of the compound (II') with the halogenating agent is preferably such that the halogenating agent is 2 mol or more and 6 mol or less, more preferably 2.2 mol or more and 5 mol or less with respect to 1 mol of the compound (II'). The reaction temperature is preferably -80°C to the boiling point of the solvent. The reaction time is preferably 1 hour to 20 hours, and more preferably 3 hours to 15 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. As the organic solvent, those exemplified above can be used. The amount of the organic solvent used is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less with respect to 1 part by mass of the compound (II').

The method for obtaining the compound (IIc) belonging to the target compound from the reaction mixture is not particularly limited, and various conventional methods can be used, and for example, the above-mentioned method can be used.

(Production method (2) of compound (II))

The production method of the compound (II) of the present invention is in the case where X ¹ and X ² in the formula (II) are a borate group or a compound of -B(OH) ₂ (hereinafter also referred to as "compound (IId)") , For example, the compound (IIc) [the compound of formula (II) where X ¹ and X ² are halogen atoms] is reacted with a magnesium slice to prepare a Grignard intermediate, and then 2-isopropoxy- 4,4,5,5-Tetramethyl-1,3,2-dioxaborolane and other methods of its action; in the presence of a base, using a palladium catalyst to make compound (IIc) and bis (pinacol ester ) Diboron reaction, thereby borate esterification; boron oxidation by hydrolysis after trimethoxyborane or triisopropoxyborane, etc.

(Optical filter)

The compound (I) can be used for optical filters such as display devices. The optical filter is usually a layer formed of a composition containing a thermoplastic resin or a thermosetting resin having translucency (preferably optically transparent), and can be, for example, a film. The optical filter only needs to have a layer containing the compound (I) (hereinafter also referred to as a "color correction layer"), which may be a color correction film composed of a single-layer structure of the color correction layer, or may include Multilayer structure of the color correction layer. When the optical filter has a multi-layer structure, it may contain one color correction layer or two or more color correction layers, and the compound (I) contained in the two or more layers may be the same as or different from each other .

When the optical filter is a laminate, the color correction layer may be an adhesive layer or a resin layer other than the adhesive layer (hereinafter simply referred to as "resin layer"). When the color correction layer is an adhesive layer, the two layers included in the optical filter may be bonded to each other, or may be used to bond the optical filter to other members such as image display elements. The adhesive layer may be an adhesive layer formed with an adhesive composition, an adhesive layer formed with an adhesive composition, or a layer formed with an adhesive composition and an adhesive composition.

When the color correction layer is a single-layer optical filter (color correction film), or when it is a resin layer other than the adhesive layer in the multi-layer optical filter, the color correction film or resin layer contains a compound ( The method of I) is not particularly limited. For example, [i] a method of kneading with a resin that becomes a color correction film or a resin layer and heat-forming into a film, [ii] a resin that becomes a color correction film or a resin layer, or a monomer and compound of the resin (I ) A method of dispersing or dissolving in an organic solvent, and then forming into a film by casting. In addition, [iii] a coating liquid that disperses or dissolves the compound (I) in a binder resin or an organic solvent may be applied to the resin base film and used as a resin layer, or the resin base may be applied from the resin layer The film is peeled off and used as a color correction film. The thickness of the color correction film and the resin layer is not particularly limited, and may be, for example, 1 μm to 200 μm.

When the color correction film or the resin layer contains the compound (I), its content is not particularly limited. For example, the compound (I) may be 0.001 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the matrix polymer serving as the color correction film or resin layer. It is 10 parts by mass or less, preferably 3 parts by mass or less, and more preferably 0.5 parts by mass or less.

When the color correction layer is an adhesive layer, the method of containing the compound (I) in the adhesive layer is not particularly limited, as long as the compound (I) is added when preparing the adhesive composition or adhesive composition to be an adhesive layer . The thickness of the next layer is not particularly limited, and may be, for example, 1 μm to 100 μm.

When the subsequent layer contains the compound (I), its content is not particularly limited. For example, with respect to 100 parts by mass of the matrix polymer included in the adhesive layer as the adhesive composition and/or adhesive composition, the compound (I) may be 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more It is preferably 0.05 parts by mass or more, and may be 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 0.5 parts by mass or less.

The optical filter can be used for display devices such as organic electroluminescence (organic EL) display devices and liquid crystal display devices, and can be used by being attached to the viewing side of the image display element of the display device. In this case, the optical filter preferably has an adhesive layer and a resin layer other than the adhesive layer, and preferably at least one of the adhesive layer and the resin layer is a color correction layer containing the compound (I).

When the optical filter is a laminate, the laminate structure is not particularly limited, and it may have, for example, the laminate structure shown in (a) and (b) of FIG. 1. Fig. 1 (a) and (b) are schematic cross-sectional views showing an example of an optical filter. The optical filter 10 shown in FIG. 1(a) can be used for an organic EL display device. The optical filter 10 may include, for example, an adhesive layer 11 for an image display element, a retardation film 12, an adhesive layer 13, a first protective film 14, a polarizing film 15, and a second protective film 16, in this order. The adhesive layer 11 and the adhesive layer 13 for the image display device both correspond to the aforementioned adhesive layer, and the retardation film 12, the first protective film 14, the polarizing film 15 and the second protective film 16 all correspond to the aforementioned resin layer.

In the optical filter 10, the first protective film 14, the polarizing film 15 and the second protective film 16 become polarizing plates, and the first protective film 14 and the second protective film 16 may be on the side of the bonding surface with the polarizing film 15 With the next layer. The adhesive layer 11 for the image display element is used for bonding to the light-emitting layer of the organic EL display device that includes the organic EL element and belongs to the image display element. In the adhesive layer 11 for the image display element, the surface on the side opposite to the retardation film 12 may be provided with a separator (release film) not shown in the figure.

The optical filter 20 shown in FIG. 1(b) can be used for a liquid crystal display device. The optical filter 20 may include, for example, an adhesive layer 21 for an image display element, a first protective film 24, a polarizing film 25, and a second protective film 26 in this order. The adhesive layer 21 for the image display element corresponds to the above-mentioned adhesive layer, and the first protective film 24, the polarizing film 25, and the second protective film 26 all correspond to the above-mentioned resin layer.

In the optical filter 20, the first protective film 24, the polarizing film 25, and the second protective film 26 become a polarizing plate, and the first protective film 24 and the second protective film 26 are also on the bonding surface side with the polarizing film 25 There may be an adhesive layer. The adhesive layer 21 for the image display element is used to attach to the liquid crystal cell of the image display element of the liquid crystal display device. A separator (release film) not shown in the figure may be provided on the surface of the adhesive layer 21 for the image display element opposite to the first protective film 24.

At least any one of the resin layers and the adhesive layers of the optical filters 10 and 20 shown in FIGS. 1 (a) and (b) may contain the compound (I). In the optical filter 10 shown in FIG. 1(a), for example, one or more of the adhesive layer 11, the adhesive layer 13, the first protective film 14, and the second protective film 15 for the image display element may be Contains the above compound (I). In the optical filter 20 shown in FIG. 1(b), for example, one or more of the adhesive layer 21 for image display elements, the first protective film 24, and the second protective film 25 may contain the compound (I) .

The optical filters 10 and 20 shown in (a) and (b) of FIG. 1 are only examples, and may have a laminated structure other than the above. For example, the surfaces of the second protective films 16 and 26 opposite to the polarizing films 15 and 25 may have a layer composed of a film with an anti-glare function or a film with a surface reflection preventing function. In addition, the first protective films 15 and 25 may have a function as a phase difference film, and the second protective films 16 and 26 may also have an anti-glare function, a surface reflection prevention function, a function of a phase difference film, and the like. In addition to the layers of the optical filters 10 and 20 shown in FIGS. 1 (a) and (b), a color correction layer containing the compound (I) may be additionally provided at an arbitrary position.

Since the above optical filter contains the compound (I), it can absorb light in the vicinity of 580 nm (575 to 590 nm) (preferably light having a maximum absorption wavelength of 580 nm). With this, by stacking the above optical filter on the viewing side of the image display element of the display device, light having an absorption wavelength in the wavelength region around 580 nm (575 to 590 nm) can be absorbed from the light incident on the optical filter, and The light passing through the optical filter can enhance the color purity of green light and red light compared to the light entering the optical filter. A conventional display device that does not use the above optical filter has insufficient separation between green light and red light, but a display device using the above optical filter can be expected to improve the separation between green light and red light.

Hereinafter, each member that becomes an optical filter will be described in detail.

(Next layer)

Examples of the adhesive composition that can be used for the adhesive layer include water-based adhesives, active energy ray-curable adhesives, and combinations of these. Examples of the water-based adhesive include polyvinyl alcohol-based resin aqueous solutions and water-based two-component urethane-based latex adhesives. The active energy ray-curable adhesive is an adhesive that is hardened by irradiating active energy rays such as ultraviolet rays, and examples thereof include: a polymerizable compound and a photopolymerizable initiator, a photoreactive resin, and an adhesive. Resin and photoreactive crosslinking agent etc. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth)acrylic monomers, and photocurable urethane monomers, and Oligomers derived from such monomers. Examples of the photopolymerization initiator include substances containing active species such as neutral radicals, anionic radicals, and cationic radicals that are generated by irradiation with active energy rays such as ultraviolet rays. In addition, in this specification, "(meth)acrylic system" means "at least 1 type of an acrylic system and a methacrylic system."

As an adhesive composition that can be used for the adhesive layer, a conventionally known adhesive composition can be used. Examples of the adhesive composition include (meth)acrylic adhesives, urethane adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, and polyethers. Adhesives, fluorine adhesives, rubber adhesives, etc. Also, it may be an energy ray-curable adhesive, a thermosetting adhesive, or the like. Among these, from the viewpoint of transparency, adhesion, reliability, etc., it is preferable to use a (meth)acrylic adhesive.

The acrylic adhesive is not particularly limited, but a polymer containing (meth)acrylate as the main component (containing 50% by mass or more) may be a homopolymer of (meth)acrylate, or It may be a copolymer of (meth)acrylate and other (meth)acrylates. Examples of (meth)acrylates include butyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, isooctyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl ester, 2-phenoxyethyl (meth)acrylate. In addition, polymers mainly composed of these (meth)acrylates can also be copolymerized with polar monomers. Examples of polar monomers include (meth)acrylic acid, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylamide, (meth)acrylic acid Monomers such as 2-(N,N-dimethylamino) ethyl ester, glycidyl (meth)acrylate and the like having polar functional groups such as carboxyl group, hydroxyl group, amide group, amine group, and epoxy group. The (meth)acrylic resin used for the acrylic adhesive can use a weight average molecular weight (Mw) of 100,000 or more, preferably 600,000 or more, and generally 2.5 million or less.

These acrylic adhesives can be used alone, but are usually used in combination with crosslinking agents. Examples of the cross-linking agent include: those that form a metal salt of a carboxylic acid with a carboxyl group as a divalent or multivalent metal ion, those that form an amide bond with a carboxyl group as an amine compound, and epoxy compounds or diols Compounds that form an ester bond with a carboxyl group and those that form an amide bond with a carboxyl group as an isocyanate compound. Among them, isocyanate compounds are preferably used.

Among the isocyanate-based compounds, preferably used are: xylylene diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; the addition of polyhydric alcohols such as glycerin or trimethylolpropane and these isocyanate compounds Compounds; compounds that make these isocyanate compounds into dimers, trimers, etc., or mixtures of these; mixtures of two or more of the isocyanate compounds mentioned above.

Examples of suitable isocyanate compounds include toluene diisocyanate, an adduct obtained by reacting a polyol with toluene diisocyanate, a dimer of toluene diisocyanate, and a terpolymer of toluene diisocyanate. Methylene diisocyanate, an adduct obtained by reacting a polyol with hexamethylene diisocyanate, a dimer of hexamethylene diisocyanate, and a terpolymer of hexamethylene diisocyanate.

The content of the crosslinking agent in the acrylic adhesive is usually 0 parts by mass or more and 5 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin.

The acrylic adhesive may further contain a silane compound. When the acrylic adhesive contains a silane compound, the adhesion between the resulting adhesive layer and optical members such as glass substrates can be improved.

Examples of the silane compound include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-aminopropyl triethoxy silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Propyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, 3-glycidoxypropyl ethoxy dimethyl silane, etc. Two or more kinds of silane compounds can also be used.

The silane compound may be a polysiloxane oligomer type. If the polysiloxane oligomer is represented in the form of (monomer) oligomer, for example: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane- Tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane Copolymers, 3-propenyl propylpropyl trimethoxysilane-tetramethoxysilane copolymers, vinyl trimethoxysilane-tetramethoxysilane copolymers, etc.

The content of the silane compound in the acrylic adhesive is generally 0.01 parts by mass or more and 10 parts by mass or less, preferably 0.05 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic resin. 0.1 parts by mass or more and 2 parts by mass or less. If the content of the silane compound is 0.01 parts by mass or more, the effect of improving the adhesion between the adhesive layer and the optical member such as the glass substrate is easily obtained. In addition, when the content of the silane compound is 10 parts by mass or less, the silane compound can be suppressed from seeping out from the adhesive layer.

The acrylic adhesive may further contain an ionic compound as an antistatic agent to impart antistatic properties. Ionic compounds are compounds with inorganic cations or organic cations and inorganic anions or organic anions. The acrylic adhesive may also contain two or more ionic compounds.

Examples of inorganic cations include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], potassium cation [K ⁺ ], or beryllium cation [Be ²⁺ ], magnesium cation [Mg ²⁺ ], Calcium cation [Ca ²⁺ ] and other alkaline earth metal ions.

Examples of organic cations include imidazolium cations, pyridinium cations, pyrrolidinium cations, ammonium cations, ammonium cations, and phosphonium cations.

Examples of the inorganic anion include such as: chlorine anions [Cl ^-], bromine anion [Br ^-], iodide anion [I ^-], tetrachloroaluminate anion [AlCl ₄ ^-], heptachlor aluminum anions [Al ₂ Cl ^_7--], tetrafluoroborate anion [BF ₄ ^-], hexafluorophosphate anions [PF ₆ ^-], perchloric acid anion [ClO ₄ ^-], nitrate anions [NO ₃ ^-], hexafluoroarsenate anion [AsF ₆ ^-], hexafluoroantimonate anion [SbF ₆ ^-], niobium hexafluorophosphate anion [NbF ₆ ^-], six tantalum fluoride anion [TaF ₆ ^-], dicyanamide anion [(CN) ₂ N ^- ]Wait.

Examples of the organic anions include such as: acetate anion [CH ₃ COO ^-], trifluoroacetate anion [CF ₃ COO ^-], methane sulfonate anion [CH ₃ SO ₃ ^-], trifluoromethanesulfonate anion [CF ₃ SO ₃ ^-], p-toluenesulfonate anion _{[p-CH 3 C 6 H} 4 SO 3 -], bis (sulfo-fluoro-acyl) imide anion ^{_{[(FSO 2) 2 N -}} ], bis (trifluoromethane sulfo acyl) imide anion _{[(CF 3 SO 2) 2} N -], reference (trifluoromethane sulfonic acyl) methane anion _{[(CF 3 SO 2) 3} C -], dimethyl phosphinate anion [ ^{_{(CH 3) 2 POO -]}} , ( poly) hydrogen fluoride anion ^{_{[F (HF) n -]}} (n is 1 or about 3 or less), thiocyano anion [SCN ^-], perfluoro butane sulfonate anion ^{_{[C 4 F 9 SO 3 -}} ], bis (pentafluoroethane sulfonic acyl) imide anion _{[(C 2 F 5 SO 2} ) 2 N -], perfluoro butyrate anion [C ₃ F ₇ COO ^-], (trifluoromethane sulfonic acyl) (carbonyl trifluoromethanesulfonyl) imide anion _{[(CF 3 SO 2) (} CF 3 CO) N -] and the like.

Specific examples of the ionic compound can be selected from the combination of the aforementioned cationic component and anionic component.

Examples of ionic compounds having organic cations include N-octylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, and N-butyl-4-methyl Pyridinium hexafluorophosphate, N-decylpyridinium bis(fluorosulfonyl)imide, N-hexylpyridinium bis(trifluoromethanesulfonyl)imide, N-octylpyridinium bis(tris (Fluoromethanesulfonyl) imine and other pyridinium salts, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl -3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazole Imidazolium salts such as onium methanesulfonate; N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, N -Butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and other pyrrolidinium salts; tetrabutylammonium hexafluorophosphate, tetrabutylammonium p-toluenesulfonate and other 4 grade ammonium salt.

Examples of ionic compounds having inorganic cations include lithium bromide, lithium iodide, and sodium hexafluorophosphate.

The ionic compound is preferably solid at room temperature from the viewpoint of maintaining antistatic properties. The ionic compound preferably has a melting point of 30°C or higher, and further 35°C or higher. On the other hand, if the melting point is too high, the compatibility with the (meth)acrylic resin deteriorates, so the melting point of the ionic compound is preferably 90°C or lower, more preferably 70°C or lower, and even more preferably less than 50 ℃.

The content of the ionic compound in the acrylic adhesive is preferably 0.1 parts by mass or more and 8 parts by mass or less, more preferably 0.2 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic resin. It is preferably 0.5 parts by mass or more and 5 parts by mass or less, and particularly preferably 1 part by mass or more and 5 parts by mass or less. When the content of the ionic compound is 0.1 parts by mass or more, it is beneficial to improve antistatic performance, and 8 parts by mass or less is beneficial to maintain the durability of the adhesive layer.

In the adhesive composition or the adhesive composition, various additives may be further blended. Examples of the additives include heavy-duty agents, adhesiveness-imparting resins, antioxidants, ultraviolet absorbers, defoamers, anticorrosive agents, and light diffusing agents such as fine particles.

(Resin layer)

Examples of the resin layer include a polarizing film; a protective film provided to protect the surface of the polarizing film; a retardation film; an optical compensation film other than the retardation film; a film with an anti-glare function and an anti-glare surface having a concave-convex shape Reflective film; reflective film with reflective function on the surface; semi-transparent reflective film with both reflective and penetrating function; light diffusion film; hard coating film; color correction film, etc. The optical filter may contain one kind or two or more kinds of the above resin layers.

Examples of the polarizing film include those in which iodine is aligned in the polyvinyl alcohol-based resin layer, or those in which a liquid crystal compound and a dichroic dye are aligned, and the like.

In the case where the resin layer is other than the polarizing film, the material is not particularly limited, but examples include chain polyolefin resins (polyethylene resins, polypropylene resins, etc.), and cyclic polyolefin resins (degraded Camphene resins, etc.) and other polyolefin resins; cellulose ester resins such as triethyl cellulose, diethyl cellulose, and cellulose acetate propionate; polyethylene terephthalate, polyethylene naphthalate Polyester resins such as diesters; polycarbonate resins; (meth)acrylic resins such as (meth)acrylic acid and polymethyl (meth)acrylate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate ; Polystyrene resin; These mixtures, copolymers, etc. These resins may also contain one or more of the following additives: lubricants, plasticizers, dispersants, heat stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antioxidants, microparticles, etc. Light diffuser, etc.

(Display device)

The above optical filter can be suitably used for display devices such as organic EL display devices, liquid crystal display devices, inorganic electroluminescence (inorganic EL) display devices, electron emission display devices, and the like. Compared with the image display element of the display device, by arranging the optical filter on the viewing side, it can absorb the light near the wavelength of 580 nm (575 to 590 nm) among the light incident on the optical filter (preferably the largest Absorbs light with a wavelength of 580nm). As a result, the light passing through the optical filter has higher color purity than the case where it does not pass through the optical filter, so the color gamut that can be expressed by the display device can be expanded. A conventional display device that does not use the above-mentioned optical filter has insufficient separation between green light and red light, but a display device using the above-mentioned optical filter can be expected to improve the separation between green light and red light.

2 (a) and (b) are schematic cross-sectional views showing an example of a display device provided with an optical filter. The display device shown in FIG. 2(a) is an organic EL display device including the optical filter 10 shown in FIG. 1(a) and the image display element 1 including a light-emitting layer of an organic EL element. The optical filter 10 can be disposed on the viewing side of the image display element 1 through the adhesive layer 11 for the image display element.

The display device shown in FIG. 2(b) is a liquid crystal display device including the optical filter 20 shown in FIG. 1(b) and the image display element 2 of a liquid crystal cell containing a liquid crystal layer. The optical filter 20 can be disposed on the viewing side of the image display element 2 through the adhesive layer 21 for the image display element.

[Example]

The following shows examples and comparative examples to explain the present invention more specifically, but the present invention is not limited to these examples. In Examples, Comparative Examples, Application Examples, and Comparative Application Examples, "%" and "parts" are% by mass and parts by mass unless otherwise stated.

[Identification of compounds]

The structure of the compound was identified by mass analysis (LC; model 1200 manufactured by Agilent, mass; model LC/MSD manufactured by Agilent).

[Measurement of maximum absorption wavelength]

For a solution obtained by dissolving the compound obtained in the Examples and Comparative Examples (the compound represented by formula (I)) in the solvent shown in Table 1, an ultraviolet-visible light spectrometer (V-650DS; manufactured by Japan Spectroscopy Co., Ltd.) was used. (Quartz unit, photohydrocarbon length; 1cm) Measure the maximum absorption wavelength.

For the adhesive sheets obtained in the application examples and the comparative application examples, the maximum absorption wavelength was measured using the above-mentioned ultraviolet-visible light spectrometer.

[Example 1 (compound represented by formula (II))]

3.0 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.), 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 parts, 175 parts of 1-butanol and 290 parts of toluene were mixed. The resulting mixture was stirred at a temperature of 110°C for 3 hours while removing the generated water using a Dean-Stark tube. After the reaction was completed, the solvent was distilled off, 300 parts of ion-exchanged water was added, and the precipitated solid was filtered and taken out. The filtered solid was washed with methanol/ion exchanged water. The obtained solid was dried under reduced pressure at a temperature of 60°C for 12 hours to obtain 4.0 parts of the compound represented by formula (A-1).

In the presence of 200 parts of tetrahydrofuran, after cooling 2.3 parts of compound (A-1) in an ice bath, 3.2 parts of N-bromosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred in an ice bath 3 hour. After warming the obtained reaction mass (reaction liquid) to room temperature, an aqueous solution of sodium thiosulfate was added to terminate the reaction. The solvent was distilled off, and the obtained solid was washed with methanol/ion exchange water. The obtained solid was dried to obtain 3.6 parts of the compound represented by formula (A-2). Mass analysis was performed on the obtained compound.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 424.9

Accurate quality: 423.9

[Example 2 (compound represented by formula (I)]]

0.85 parts of the compound represented by the formula (A-2) obtained in Example 1, 89 parts of tetrahydrofuran, and 70 parts of ion-exchanged water were mixed. Add 1mol/L of cesium carbonate aqueous solution 6 parts, ginseng (dibenzylideneacetone)-dipalladium (0) 0.37 parts, tri-tert-butylphosphonium tetrafluoroborate 0.46 parts, 2,6-dimethyl- 1.49 parts of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was refluxed for 2 hours. After the reaction was completed, a 10% aqueous acetic acid solution was added to stop the reaction. 10% saline was added, and the organic layer was concentrated after liquid separation. The resulting solid was recrystallized with 100 parts of a solution of toluene/1-butanol=1/1 to obtain 0.4 parts of the compound represented by formula (A-3). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 509.2

Accurate quality: 508.24

[Example 3 (compound represented by formula (I)]]

In addition to using 3,4,5-trimethoxyphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-bis in Example 2 Except for oxaborolan-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-4). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 601.3

Accurate quality: 600.25

[Example 4 (Compound represented by formula (I)]]

In addition to using 4-hexylphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 in Example 2 -Group) except phenol, synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-5). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 589.4

Accurate quality: 588.37

[Example 5 (compound represented by formula (I)]]

In addition to using 4-hexyloxyphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane in Example 2 Except for 2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-6). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI ⁺ : m/z=[M+H] ⁺ 621.4

Accurate quality: 620.36

[Example 6 (compound represented by formula (I)]]

In addition to using 4-(dimethylamino)phenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxane in Example 2 Except for heteroborane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-7). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 507.3

Accurate quality: 506.27

[Example 7 (compound represented by formula (I)]]

In addition to using 4-(diphenylamino)phenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxa in Example 2 Except for borane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-8). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 754.3

Accurate quality: 754.33

[Example 8 (compound represented by formula (I)]]

In addition to using 4'-propyl-4-biphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxane in Example 2 Except for heteroborane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-9). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 657.3

Accurate quality: 656.34

[Example 9 (compound represented by formula (I)]]

In addition to using 6-ethoxy-2-naphthaleneboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxa in Example 2 Except for borane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-10). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 609.3

Accurate quality: 608.27

[Example 10 (compound represented by formula (I)]]

In addition to using 9,9-dimethyl stilbene-2-boronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-bis in Example 2 Except for oxaborolan-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-11). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 653.3

Accurate quality: 652.31

[Example 11 (compound represented by formula (I)]]

In addition to using benzo[b]thiophene-2-boronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxa in Example 2 Except for borane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-12). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 533.1

Accurate quality: 532.13

[Example 12 (compound represented by formula (I)]]

In addition to using 9-ethylcarbazole-3-boronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxa in Example 2 Except for borane-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-13). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 655.3

Accurate quality: 654.30

[Example 13 (compound represented by formula (I)]]

In addition to the use of 9-(4-biphenyl)carbazole-3-boronic acid cannapol to replace 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1 in Example 2 , 3,2-dioxaborolan-2-yl)phenol, was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-14). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 903.4

Accurate quality: 902.36

[Comparative Example 1]

In addition to using 3-ethyl-2,4-dimethylpyrrole in place of 2,4-dimethylpyrrole in the synthesis method of the compound represented by the formula (A-1) in Example 1, the formula ( The compound represented by A-1) is synthesized in the same manner to obtain the compound represented by formula (B-1). The maximum absorption wavelength was measured for the obtained compound. Table 1 shows the measured maximum absorption wavelength.

[Comparative Example 2]

The compound represented by formula (A-1) was obtained in the order of the synthesis method of the compound represented by formula (A-1) in Example 1. The maximum absorption wavelength was measured for the obtained compound. Table 1 shows the measured maximum absorption wavelength.

[Example 14 (compound represented by formula (I)]]

In addition to using 4-tert-butylphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaboron in Example 2 Except for alkyl-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-15). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 533.3

Accurate quality: 532.3

[Example 15 (compound represented by formula (I)]]

In addition to using 4-methoxy-3,5-dimethylphenylboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3 in Example 2 ,2-dioxaborolan-2-yl)phenol, was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-16). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 537.2

Accurate quality: 536.3

[Example 16 (compound represented by formula (I)]]

In addition to using 4-carboxyphenylboronic acid cannapol to replace 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborol in Example 2 Except for alkyl-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-17). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 509.5

Accurate quality: 508.2

[Example 17 (Compound represented by formula (I)]]

In addition to the use of 1-thianthraboric acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- in Example 2 The compound represented by the formula (A-18) was obtained in the same manner as in Example 2 except for phenyl)phenol. Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 697.2

Accurate quality: 696.1

[Example 18 (compound represented by formula (I)]]

In addition to using 4-methyl-1-naphthaleneboronic acid instead of 2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaboron in Example 2 Except for alkyl-2-yl)phenol, it was synthesized in the same manner as in Example 2 to obtain a compound represented by formula (A-19). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 549.2

Accurate quality: 548.3

[Example 19 (compound represented by formula (II)]]

11.89 parts of 3,4-dibutoxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) and 38.9 parts of 1-butanol were mixed, and heated and stirred at 110°C. To the resulting mixture, 5.0 parts of 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and heated to reflux for 3 hours. The resulting mixture was cooled to room temperature, the precipitated crystals were filtered, and the solution was separated from the crystals. Regarding the obtained crystals, 327 parts of hexane was used and repulp washing was carried out. As a result, a light green solid was obtained.

In an aqueous solution adjusted with 7.1 parts of concentrated hydrochloric acid and 40 parts of distilled water, 48.3 parts of acetic acid and the above solid were mixed, and heated and refluxed at 110°C for 2 hours. As a result, the color changed from pale green to pale orange, and the reaction was stopped. The resulting reaction liquid was cooled to room temperature, and the light orange powder was filtered. The obtained powder was reslurried and washed with 164 parts of hexane to obtain 5.65 parts (yield 56.2%) of the compound represented by the formula (C-1) as pale yellow.

Combine 1.39 parts of the compound represented by formula (C-1), 1.0 part of 3-acetoxy-2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.6 parts of 1-butanol and 35.7 parts of toluene Mix, heat and reflux at 110°C for 3 hours. The resulting reaction liquid was cooled to room temperature, the precipitated crystals were filtered, and the solution was separated from the crystals. Using 327 parts of hexane, the crystals were reslurried and washed to obtain 0.96 parts of the compound represented by the purple formula (C-2) (yield: 85.3%).

0.80 parts of the compound represented by the formula (C-2) and 59.5 parts of dehydrated tetrahydrofuran were mixed, nitrogen substitution was carried out at ice temperature (5°C) and stirred for 30 minutes.

0.94 parts of N-bromosuccinimide was added to the resulting mixture, and stirred at ice temperature (5°C) for 2 hours. Pure water was added to the resulting reaction liquid, and filtered to obtain crystals. The obtained crystals were redissolved in tetrahydrofuran, pure water was added, and the crystals were precipitated to obtain 0.91 parts of the compound represented by the formula (A-20) in black purple (yield: 90.7%). Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 389.2

Accurate quality: 388.04

[Example 20 (compound represented by formula (I)]]

In a four-necked flask, 0.195 parts of the compound represented by the formula (A-20), 22.2 parts of tetrahydrofuran, and 17.5 parts of pure water were added, and nitrogen was introduced at 80° C. for 60 minutes to perform bubbling. To the resulting mixture, 0.092 parts of ginseng (dibenzylideneacetone) palladium, 0.116 parts of [tri(third butyl)phosphonium] tetrafluoroborate, and 1.5 parts of a 1 mol/L cesium carbonate aqueous solution were added. A solution obtained by dissolving 0.243 parts of benzofuran-2-boronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 6.66 parts of tetrahydrofuran was added dropwise over 10 minutes while stirring the reaction liquid at an oil bath temperature of 80°C. And stir for 2 hours. 100 parts of a 10% by mass acetic acid aqueous solution was added to the resulting mixture, and stirred for 15 minutes under a nitrogen atmosphere.

To the resulting mixture, 0.3 part of 10% saline was added, and a liquid separation operation was performed to differentiate the organic layer. The organic layer was dried using an evaporator to obtain crude refined product 1 in the form of tar. The crude refined product 1 was extracted with methanol, and then methanol was removed, thereby obtaining a crude product 2. For the obtained crude product 2, 100 parts of a toluene/butanol = 1/1 solution was used for heating and dissolution, and recrystallization was performed to obtain 0.07 parts of the compound represented by the formula (A-21) (yield 32.8%).

Mass analysis was performed on the obtained compound, and the maximum absorption wavelength was measured. Table 1 shows the measured maximum absorption wavelength.

(Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 427.1

Accurate quality: 426.16

[Table 1]

[Application example 1]

(Manufacture of (meth)acrylic resin)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 81.8 parts of ethyl acetate as a solvent, 69.8 parts of butyl acrylate as a monomer, 20 parts of methyl acrylate, and 2-hydroxyethyl acrylate 1 were added Parts, a mixed solution of 8 parts of 2-phenoxyethyl acrylate, 1 part of 2-methoxyethyl acrylate, and 0.2 parts of acrylic acid, while replacing the air in the reaction vessel with nitrogen to make it free of oxygen, The temperature rose to 55°C. All the solutions obtained by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate were added to the resulting mixed solution. For the resulting mixture, after maintaining the internal temperature at 55°C for 1 hour, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr while maintaining the internal temperature at 55°C. When the concentration of the acrylic resin became 35%, the addition of ethyl acetate was stopped and polymerization was carried out for 8 hours. Finally, ethyl acetate was added so that the concentration of the (meth)acrylic resin was 20% to prepare an ethyl acetate solution of the (meth)acrylic resin. With respect to the obtained (meth)acrylic resin, the weight average molecular weight (Mw) and polydispersity (Mw/Mn) were measured. As a result, the weight average molecular weight (Mw) was 1.4 million, and the polydispersity (Mw/Mn) was 5.1.

(Preparation of Adhesive Composition 1)

For the solid content of the (meth)acrylic resin obtained in the production of the (meth)acrylic resin, 100 parts, a crosslinking agent ("CORONATE HXR" (hexamethylene di Isocyanate modified polyisocyanate)) 0.6 parts, silane compound ("KBM-403" (3-glycidoxypropyltrimethoxysilane) obtained from Shin-Etsu Chemical Co., Ltd.), 0.5 parts 3 parts of N-hexyl-4-methylpyridinium phosphorous hexafluoride as an electrostatic agent, 0.1 parts of the compound represented by formula (A-5), and then ethyl acetate is added so that the solid content concentration is 14%, A solution of adhesive composition 1 was prepared.

(Preparation of adhesive sheet 1)

Using an applicator, apply the adhesive composition 1 to the first separator film made of polyethylene terephthalate film that has undergone release treatment ("PLR-382190" obtained from LINTEC Corporation) The mold release surface was dried at 100°C for 1 minute to prepare an adhesive layer. The thickness of the resulting adhesive layer was 20 μm. On the obtained adhesive layer, the second separator film ("PLR-251130" obtained from LINTEC Co., Ltd.) composed of polyethylene terephthalate film subjected to mold release treatment was applied for release. Treat the surface as an adhesive sheet 1. One side of the separator film of the obtained adhesive sheet 1 was peeled off, it was bonded to one side of alkali-free glass (EagleXG manufactured by Corning Corporation), and the maximum absorption wavelength was measured using an ultraviolet-visible light spectrometer (UV-2450 manufactured by Shimadzu Corporation). The results are shown in Table 2. In addition, the absorbance of the above-mentioned separator film and alkali-free glass at a wavelength of 400 nm to 700 nm is almost zero.

[Application example 2]

An adhesive composition 2 was prepared in the same manner as in the preparation of the adhesive composition 1 except that the compound represented by the formula (A-6) was used instead of the compound represented by the formula (A-5). Except for using the obtained adhesive composition 2, the adhesive sheet 2 was produced by the same method as the production of the adhesive sheet 1, and the maximum absorption wavelength was measured. The results are shown in Table 2.

[Application Examples 3 to 11]

The adhesive compositions 5 to 11 were prepared in the same manner as in the preparation of the adhesive composition 1 except that the compounds shown in Table 2 were substituted for the compounds shown in the formula (A-5). Except that the obtained adhesive compositions 5 to 11 were used, the adhesive sheets 5 to 11 were produced by the same method as the production of the adhesive sheet 1, and the maximum absorption wavelength was measured. The results are shown in Table 2.

[Comparative Application Example 1]

An adhesive composition 3 was prepared in the same manner as the preparation of the adhesive composition 1 except that the compound represented by the formula (B-1) was used instead of the compound represented by the formula (A-5). Except for using the obtained adhesive composition 3, the adhesive sheet 3 was produced by the same method as the production of the adhesive sheet 1, and the maximum absorption wavelength was measured. The results are shown in Table 2.

[Comparative Application Example 2]

An adhesive composition 4 was prepared in the same manner as in the preparation of the adhesive composition 1 except that the compound represented by the formula (A-1) was used instead of the compound represented by the formula (A-5). Except for using the obtained adhesive composition 4, the adhesive sheet 4 was produced by the same method as the production of the adhesive sheet 1, and the maximum absorption wavelength was measured. The results are shown in Table 2.

[Table 2]

[Comparative Application Example 3]

The adhesive composition 14 was prepared by the same method as the preparation of the adhesive composition 1 except that the compound represented by the formula (A-5) was not used. Except for using the obtained adhesive composition 14, the adhesive sheet 14 was produced by the same method as the production of the adhesive sheet 1.

(Calculate the reproducible color gamut range)

For the adhesive sheet 5 of Application Example 3, when the adhesive sheet 5 is applied to a panel with a universal backlight and a universal color filter based on the obtained absorption spectrum, the reproducible color gamut range in the panel is calculated by simulation [ %]. In addition, the general-purpose backlight used for simulation is a blue LED mixed with YAG phosphor, and the general-purpose color filter is a standard display based on sRGB. In addition, regarding the reproducible color gamut range [%], the reproducible range of colors relative to the DCI P3 color specification was calculated using the CIE1976 color system and compared.

In the case where the adhesive sheet 14 is used instead of the adhesive sheet 5, the calculation is performed in the same manner. Using the range of reproducible colors of the adhesive sheet 14 as a reference, the range of reproducible colors is calculated according to the following formula.

Color reproducible range [%] = (range of reproducible colors when using adhesive sheet 5)/(range of reproducible colors when using adhesive sheet 14) × 100

For the adhesive sheet 3 and the adhesive sheet 4, the reproducible color gamut range is calculated in the same manner as above. The results are shown in Table 3.

(Calculation of backlight transmittance)

Through simulation, the amount of backlight penetration when the adhesive layer 5 is applied to a panel with a universal backlight and a universal color filter is calculated. In addition, the general-purpose backlight used for simulation is a YAG phosphor mixed with Blue LED, and the general-purpose color filter is a standard display based on sRGB.

For the case where the adhesive sheet 14 is used instead of the adhesive sheet 5, the calculation is performed in the same manner. Using the penetration amount of the backlight in the case of using the adhesive sheet 14 as a reference, the transmittance of the backlight when the adhesive sheet 5 is used in the panel is calculated according to the following formula. The results are shown in Table 3.

Backlight penetration rate [%] = (the amount of backlight penetration when using the adhesive sheet 5) / (the amount of backlight penetration when using the adhesive sheet 14) × 100

For the adhesive sheet 3 and the adhesive sheet 4, the transmittance of the backlight is also calculated in the same manner as described above. The results are shown in Table 3.

[table 3]

The compound of the present invention is mixed with a (meth)acrylic resin solution to prepare an adhesive sheet, whereby an optical filter having a maximum absorption wavelength in the wavelength region around 580 nm (wavelength 575 to 590 nm) can be produced. In addition, by applying an adhesive sheet (optical filter) containing the compound (I) to a display device, the separability of the green light and the red light in the transmitted light can be improved, so that the reproducible color can be expanded Domain scope. In addition, the reduction in backlight transmittance can also be suppressed.

[Application Example 12 (Preparation of Photocurable Adhesive Solution 1)]

For 80 parts of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, mix 20 parts of 1,4-butanediol diglycidyl ether, photocationic polymerization initiator 3 1 part, 1 part of the compound represented by formula (A-16), and defoaming, thereby preparing photocurable adhesive liquid 1.

[Application Example 13 (Preparation of Photocurable Adhesive Solution 2)]

The photocurable adhesive liquid 2 is prepared by adding the compound represented by the formula (A-18) in place of the compound represented by the formula (A-16) in the same manner as the photocurable adhesive liquid 1.

[Application Example 14 (Production of Polarizing Plate 1)]

The surface of triacetyl cellulose film [trade name "FUJITEC TG60UL", manufactured by FUJIFILM (made by FUJIFILM Co., Ltd.)] with a thickness of 60 μm containing an ultraviolet absorber was subjected to corona discharge treatment, using a coating rod, on the corona discharge treatment surface, The photocurable adhesive liquid 1 was applied so that the film thickness after curing the photocurable adhesive liquid 1 prepared above was about 2 μm. A polyvinyl alcohol-iodine-based polarizer with a thickness of 28 μm was bonded to the adhesive layer formed by the coating. In addition, the surface of the 50 μm-thick retardation film [trade name “ZEONOR”, manufactured by ZEON Japan) made of cyclic polyolefin resin was subjected to corona discharge treatment, and a coated rod was used to discharge the corona discharge. The treated surface was coated with the photocurable adhesive liquid 1 so that the film thickness after curing the photocurable adhesive liquid 1 was about 2 μm. The polarizer side of the polarizer on which the triacetyl cellulose film prepared above was adhered on one side was attached to the adhesive layer formed by the coating to prepare a laminate. From the retardation film side of the laminate, an ultraviolet irradiation device with a conveyor belt ("D bulb" manufactured by Fusion UV Systems is used for the lamp source) was used to irradiate ultraviolet rays so that the accumulated light amount was 200 mJ/cm ² . Then the agent hardens. In this way, the polarizing plate 1 in which the protective film is bonded to both sides of the polarizer is produced. The obtained polarizing plate was cut to 40 mm × 40 mm, and the measurement light was incident from the surface opposite to the retardation film. Using an ultraviolet visible light spectrometer (Shimadzu Corporation UV-2450), the measurement was performed at a wavelength of 400 nm to 700 nm. Within the range of the polarizing plate in the transmission axis direction. In the obtained spectrum, the wavelength with the smallest transmittance is taken as the maximum absorption wavelength. The results are shown in Table 4.

[Application Example 15 (Production of Polarizing Plate 2)]

A polarizing plate 2 having protective films bonded to both sides of a polarizer is produced in the same manner as the polarizing plate 1 except that the photo-curing adhesive liquid 2 is used instead of the photo-curing adhesive liquid 1. The obtained polarizing plate was cut into 40 mm×40 mm, and the maximum absorption wavelength was obtained using the same method as the polarizing plate 1. The results are shown in Table 4.

[Table 4]

10‧‧‧Optical filter

11‧‧‧Adhesive layer for image display device

12‧‧‧phase retardation film

13‧‧‧Adhesive layer

14‧‧‧The first protective film

15‧‧‧ Polarizing film

16‧‧‧Second protective film

20‧‧‧Optical laminate

21‧‧‧Adhesive layer for image display element

24‧‧‧The first protective film

25‧‧‧ Polarizing film

26‧‧‧Second protective film

Claims (4)

A compound represented by formula (I);

In the formula, R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent; T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; Either Y ^{1 or} Y ² represents a monovalent aromatic group that may have a substituent, and the other represents a monovalent aromatic group that may have a substituent, a hydrogen atom, a halogen atom, or a carbon number that may have a substituent 1 A monovalent hydrocarbon group up to 6, the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-. A compound represented by formula (II);

In the formula, R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent; T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; Either X ^{1 or} X ² represents any group selected from Group A, and the other represents any group selected from Group A, a hydrogen atom, or a monovalent carbon number of 1 to 6 which may have a substituent A hydrocarbon group, the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-; Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ . A method for producing a compound represented by formula (Ia), which includes The step of reacting the compound represented by formula (IIa), the compound represented by formula (III-1a) and the compound represented by formula (III-2a) in the presence of a nickel catalyst or a palladium catalyst;

In the formula, R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent; T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; Y ^1a and Y ^2a each independently represent a monovalent aromatic group which may have a substituent;

In the formula, R ¹ to R ^{4 have the} same meaning as described above; T ¹ and T ^{2 have the} same meaning as described above; X ^1a and X ^2a independently represent any group selected from group A; Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ ; Y ^1a -Z ¹ (III-1a) Y ^2a -Z ² (III-2a) formula (III-1a) and formula (III-2a), Y ^1a and Y ^{2a have the} same meaning as above; Z ¹ and Z ² each independently represent a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group. A method for producing a compound represented by formula (Ib), which includes The step of reacting the compound represented by formula (IIb) with the compound represented by formula (III-1b) in the presence of a nickel catalyst or a palladium catalyst;

In the formula, R ¹ to R ⁴ independently represent a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent; T ¹ and T ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent; Y ^1b represents a monovalent aromatic group which may have a substituent; X ^2b represents a hydrogen atom or a C 1 to C 6 monovalent hydrocarbon group which may have a substituent, the hydrocarbon group is a group other than a monovalent aromatic group, and -CH ₂ -contained in the hydrocarbon group may be substituted to -O- or- CO-;

In the formula, R ¹ to R ^{4 have the} same meaning as described above; T ¹ and T ^{2 have the} same meaning as described above; X ^1b represents any group selected from group A; Group A: a group consisting of halogen atoms, borate groups and -B(OH) ₂ ; X ^2b has the same meaning as described above; Y ^1b -Z ¹ (III-1b) where, Y ^1b has the same meaning as above; Z ¹ represents a halogen atom, a borate group, -B(OH) ₂ , an alkylsulfonate group or an arylsulfonate group.

Images