JP6131400B2 - Benzotriazole derivative compounds - Google Patents

Description

  The present invention relates to a novel organic fluorescent dye, a fluorescent resin composition using the same, and an organic electroluminescent element material. More specifically, the present invention relates to an organic fluorescent dye exhibiting excellent emission characteristics with an emission wavelength of around 450 nm, a fluorescent resin composition using the organic fluorescent dye, and an organic electroluminescent element material.

  Organic fluorescent dyes are dyes that emit light by absorbing the energy of irradiated light, and because they can convert energy with high efficiency, they can be used in a wide range of fields in the state of dyes, dispersed in organic solvents or resins. It is used.

  Bank notes and important certificates are often marked with an organic fluorescent dye ink with high UV sensitivity, and the mark appears to emit light only when irradiated with UV light, preventing counterfeiting. Helpful. In addition, organic fluorescent dyes are used in paints for the purpose of improving visibility such as road fences, road signs, and interior and exterior of buildings. In addition, when a white background is dyed with a blue fluorescent dye, yellowing, which is a complementary color of blue, can be made inconspicuous, and therefore organic fluorescent dyes are used as fluorescent whitening agents in clothes dyeing or detergents. . In the field of molecular biology, visualization of target molecules and cells by fluorescence is an indispensable technique, and organic fluorescent dyes are used as markers for tracking the dynamics of various cells and molecules.

  A film to which an organic fluorescent dye is added is attached to the surface of the solar cell, and ultraviolet rays can be converted into long-wavelength visible light, thereby efficiently converting into energy. Moreover, by adding an organic fluorescent pigment to the vinyl in the greenhouse, a lot of specific wavelengths can be applied to the plant, and the growth of the plant can be promoted.

  The basic structure of the organic electroluminescent element is a structure in which a light emitting layer is sandwiched between a hole transport layer and an electron transport layer. An electric field is applied to the hole, holes and electrons are injected, electric charges are recombined in the light emitting layer to generate electric energy, and the light emitting layer emits light. An organic fluorescent dye is used as a light emitting material used for the light emitting layer.

  In each of the above applications, it is required that the organic fluorescent dye used absorbs ultraviolet light or visible light sufficiently and emits strong light, and emits light that absorbs so as not to self-absorb the emitted light. There is a demand for a sufficiently wide wavelength of light. That is, the molar extinction coefficient, which is an index indicating the degree of light absorption by a substance, is high, the fluorescence quantum efficiency expressed by the ratio of the number of emitted photons to the number of absorbed photons is high, and the peak of the excitation spectrum and fluorescence spectrum An organic fluorescent dye having a large Stokes shift, which is a difference between wavelengths, is demanded. As the molar extinction coefficient, the fluorescence quantum efficiency, and the Stokes shift increase, the organic fluorescent dye becomes more excellent.

  Organic fluorescent dyes are often used not only in an organic solvent but also in a resin or in a thin film state, and are required to be excellent in solid light emission.

  When used in a resin, there is a demand for an organic fluorescent dye having good compatibility with the resin that does not cause volatilization or bleeding of the organic fluorescent dye itself.

  When an organic fluorescent dye is used as a light emitting material of an organic electroluminescent device, it is usually formed by a vacuum vapor deposition method when it is a low molecular weight material, but the vacuum vapor deposition method has a complicated process and a large area of the device. However, there is a problem that it is difficult to manufacture and the cost is high. In the case of film formation by the wet coating method, the process can be simplified and the area of the element can be increased, and the cost is low. Therefore, an organic fluorescent dye capable of the wet coating method is demanded as a light-emitting material of the organic electroluminescent element. It has been.

  Some organic fluorescent dyes used so far have large molar extinction coefficient, fluorescence quantum efficiency, and Stokes shift, but all of them are few enough, especially blue organic fluorescent dyes that emit near 450 nm. Few. Thus, as a blue organic fluorescent dye having excellent light emission characteristics, for example, as described in Patent Documents 1 to 3, polyimide derivatives, naphthalic acid imide derivatives, polyphenylene derivatives, and the like have been proposed. However, it cannot be said that the molar extinction coefficient, fluorescence quantum efficiency, and Stokes shift of these compounds are all sufficiently large, and it is not possible to obtain light emission that is sufficiently satisfactory for each of the above applications.

  As organic fluorescent dyes having excellent light emission characteristics in resins, for example, as described in Non-Patent Document 1, oxadiazole derivatives, triazole derivatives, and the like have been proposed. However, these compounds, particularly blue organic fluorescent dyes, cannot be said to have sufficiently high light emission characteristics. Further, as described in Patent Document 4, a polyvinyl carbazole derivative has been proposed as a light emitting material of a blue organic electroluminescent element that can be wet-coated. Although these compounds can be formed into a film by wet coating, it cannot be said that the organic electroluminescent element using these compounds has sufficient electroluminescent characteristics.

JP 2010-043048 A JP 2002-212458 A JP 2002-322100 A JP 2005-154404 A

Fine Chemicals February 2011 issue vol.40 No.2 p52

  Under such circumstances, the subject of the present invention is a blue color having an emission wavelength of around 450 nm, which exhibits excellent absorption and emission characteristics in a solution and in a solid state, and can be wet applied as a light emitting material of an organic electroluminescent element. It is to provide an organic fluorescent dye.

一般式（１）
［式中Ｒ_１は、水素原子又は炭素数１〜８のアルキル基を表し、Ｒ_２は炭素数１〜８のアルキル基を表す。Ｒ_３及びＲ_４はそれぞれ独立して、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、ヒドロキシル基、アミノ基、炭素数１〜４の直鎖または分鎖のモノ置換アミノ基、炭素数１〜４の直鎖または分鎖のジ置換アミノ基、ニトロ基、カルボキシル基、炭素数１〜８のアルキルオキシカルボニル基、炭素数１〜３のアルキルカルボキシル基、炭素数１〜８のアルキルカルボキシエステル基、アリール基、アシル基、スルホ基又はシアノ基を表すが、少なくともいずれかは炭素数１〜８のアルコキシ基を表す。］ In the present invention, the most important feature is that the novel compound that can be used for the organic fluorescent dye, the fluorescent resin composition, and the organic electroluminescent device luminescent material is a benzotriazole derivative compound represented by the following general formula (1). To do.

General formula (1)
[Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₂ represents an alkyl group having 1 to 8 carbon atoms. R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a straight chain having 1 to 4 carbon atoms or Branched mono-substituted amino group, straight or branched di-substituted amino group having 1 to 4 carbon atoms, nitro group, carboxyl group, alkyloxycarbonyl group having 1 to 8 carbon atoms, alkyl carboxyl group having 1 to 3 carbon atoms Group, an alkylcarboxyester group having 1 to 8 carbon atoms, an aryl group, an acyl group, a sulfo group or a cyano group, at least one of which represents an alkoxy group having 1 to 8 carbon atoms. ]

In the benzotriazole derivative compound represented by the general formula (1), preferably R ₃ and R ₄ each independently represent a hydrogen atom or a methoxy group, but at least one of them is a methoxy group.

  The benzotriazole derivative compound of the present invention emits light at around 450 nm, has a molar extinction coefficient of about 25000, a fluorescence quantum efficiency of about 70% in solution, 90% or more in resin, and a Stokes shift of 80- 110 nm. Furthermore, it has good compatibility with other resins and element constituent materials, exhibits excellent light emission characteristics in the resin, and can be applied wet as an organic electroluminescent element material. It is useful as a fluorescent dye, a fluorescent resin composition, and an organic electroluminescent element material.

  The present invention will be described in detail below. This invention uses the compound shown by following General formula (1) as an organic fluorescent pigment | dye, a fluorescent resin composition, and an organic electroluminescent element luminescent material. The compounds represented by the following general formula (1) will be described below.

一般式（１）

General formula (1)

In the general formula (1), as an example of the optional substituent, R ₁ is a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-hexyl group, n-octyl group, 2-ethylhexyl group and the like, which may be substituted, may be a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₂ is methyl group, ethyl group, propyl group 1 to 8 carbon atoms which may be substituted, such as a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, etc. A linear or branched alkyl group is mentioned. R ₃ and R ₄ are each independently a hydrogen atom; a halogen atom such as fluorine, chlorine or iodine; a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -C1-C8 linear or branched alkyl group which may be substituted such as butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, isopropoxy 1 to 8 carbon atoms which may be substituted such as a group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, n-octyloxy group and 2-ethylhexyloxy group Linear or branched alkoxy group or hydroxyl group; amino group, monomethylamino group, dimethylamino group, monoethylamino group, die A linear or branched amino group having 1 to 4 carbon atoms which may be substituted, such as a tilamino group, mono-n-propylamino group, di-n-propylamino group, monoisopropylamino group, diisopropylamino group; nitro group; carboxyl Groups: methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl A linear or branched alkyloxycarbonyl group having 1 to 8 carbon atoms which may be substituted, such as a group, 2-ethylhexyloxycarbonyl group;
An alkyl carboxyl group represented by —R ₅ COOH of the following (Chemical Formula 2 to Chemical Formula 4); an alkylcarboxy ester group represented by —R ₆ COOR ₇ of the following (Chemical Formula 5 to Chemical Formula 14); a phenyl group, a benzyl group, An aryl group such as a tolyl group and a xylyl group; an acyl group such as a formyl group, an acetyl group, a propionyl group, a butyryl group, and a benzoyl group; a sulfo group; and a cyano group, at least one of which is an alkoxy group.

Alkyl carboxyl group (—R ₅ COOH)

Alkylcarboxyester group (—R ₆ COOR ₇ )

In the above substituents, R ₃ and R ₄ are each independently a hydrogen atom or an alkoxy group, but when at least one of them is alkoxy, the compatibility with the resin is good, and the film formability is good. preferable.

More preferably, among the above substituents, R ₃ and R ₄ are each independently a hydrogen atom or a methoxy group, but at least one of them is a methoxy group.

  Specific examples of the general formula (1) of the benzotriazole derivative compound of the present invention include the following. Methyl 2- (3,4-dimethoxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3-methoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3-Chloro-5-methoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3-methoxy-5-methyl-4-octyloxyphenyl) -2H-benzotriazole- 5-carboxylate, methyl 2- (3-hydroxy-5-methoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3-amino-5-methoxy-4-octyloxy) Phenyl) -2H-benzotriazole-5-carboxylate Methyl 2- (3-carboxy-5-methoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate, octyl 2- (3-methoxy-4-octyloxyphenyl) -2H-benzotriazole- 5-carboxylate, methyl 2- (3,4,5-trimethoxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3,5-dimethoxy-4-octyloxyphenyl) -2H-benzo Triazole-5-carboxylate, 5-carboxy-2- (3,4-dimethoxyphenyl) -2H-benzotriazole, 5-carboxy-2- (3-methoxy-4-octyloxyphenyl) -2H-benzotriazole, 5-carboxy-2- (3,4,5-trimethoxyphenyl) -2H-benzotriazole, 5-carboxy-2- (3,5-dimethoxy-4-octyloxyphenyl) -2H-benzotriazole.

  Among the compounds exemplified herein, in particular methyl 2- (3,4-dimethoxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3-methoxy-4-octyloxyphenyl) -2H-benzo Triazole-5-carboxylate, methyl 2- (3,4,5-trimethoxyphenyl) -2H-benzotriazole-5-carboxylate, methyl 2- (3,5-dimethoxy-4-octyloxyphenyl) -2H -Benzotriazole-5-carboxylate, 5-carboxy-2- (3,4-dimethoxyphenyl) -2H-benzotriazole, 5-carboxy-2- (3-methoxy-4-octyloxyphenyl) -2H-benzo Triazole, 5-carboxy-2- (3,4,5-trimethoxyphenyl)- H- benzotriazole, 5-carboxy-2- (3,5-dimethoxy-4-octyloxyphenyl) -2H- benzotriazole are preferably used.

The method for synthesizing the general formula (1) of the benzotriazole derivative compound of the present invention is not particularly limited, and it can be synthesized by applying a conventionally known general reaction. For example, it can be synthesized through the reaction formula shown below (Chemical Formula 15 to Chemical Formula 21). However, X represents a halogen atom.

(Organic fluorescent dye)
The organic fluorescent dye is often used by being added to the resin, and when the benzotriazole derivative compound of the present invention is used as the organic fluorescent dye, it is similarly added to the resin and used as a fluorescent resin composition. Specific examples of resins that can be compounded with the benzotriazole derivative compound of the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, polypentene, poly-3-methylbutylene, and polymethylpentene, or ethylene-vinyl acetate copolymers. , Polyolefin such as ethylene-propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride -Ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer Polymer, vinyl chloride-styrene Acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride- Acrylic ester copolymer, vinyl chloride-maleic ester copolymer, vinyl chloride-methacrylic ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internal plastic polyvinyl chloride, petroleum resin, Coumarone resin, polystyrene, copolymer of styrene and other monomers (maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene resin, acrylate ester-butadiene-styrene resin, methacrylate ester-butadiene- Styrene resin Len resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin, polyacrylonitrile, polyphenylene oxide, polycarbonate, modified polyphenylene oxide, polyacetal, phenol resin, urea resin, melamine resin, epoxy resin, silicon Resin, polyethylene terephthalate, reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherimide, polyoxybenzoyl, polyimide, polymaleimide, polyamideimide, alkyd resin, amino resin, Vinyl resin, water-soluble resin, resin for powder coating, polyamide resin, polyurethane resin An unsaturated polyester resin can be exemplified, but is not limited thereto.

  When the amount of the benzotriazole derivative compound of the present invention is too small relative to the resin, sufficient light emission cannot be obtained, and when too large, concentration quenching occurs, so 0.001 to 20% by weight, preferably 0.01 to 10%. It is preferably used in the range of% by weight.

(Organic electroluminescent device luminescent material)
The benzotriazole derivative compound of the present invention can be used as a light emitting material of an organic electroluminescence device, and can be used alone or in combination with other compounds in the light emitting layer. Examples of the compound having a light emitting function other than the benzotriazole derivative compound of the present invention include perylene derivatives, coumarin derivatives, organometallic complexes, pyran derivatives, stilbene derivatives, acridone derivatives, oxazone derivatives, quinacridone derivatives, benzoxazole derivatives, poly- A general low molecular fluorescent material, a low molecular phosphorescent material, a polymer light emitting material, or the like such as an N-vinylcarbazole derivative, a polyfluorene derivative, a polyphenylene vinylene derivative, or the like is used. These light emitting materials may be used alone or in a suitable mixture of two or more.

  Examples of a method for forming a film of a luminescent material on an organic electroluminescent element include a vacuum deposition method and a wet coating method. Compared with the vacuum deposition method, the wet coating method does not require a complicated process, has a low manufacturing cost, and has an advantage of easily increasing the area of the organic electroluminescent device. As the wet coating method, for example, an inkjet method, There are a spin coat method and a dip coat method. In order to perform the wet coating method, it is necessary to dissolve the light emitting material in an organic solvent, and it is desirable to use a material that is easily dissolved in the organic solvent. The benzotriazole derivative compound of the present invention is easily dissolved in an organic solvent, and can form a light emitting layer of an organic electroluminescent device by, for example, a spin coating method.

  When the benzotriazole derivative compound of the present invention is formed on an organic electroluminescent device by a wet coating method, an aliphatic hydrocarbon such as pentane, hexane, heptane, etc. as an organic solvent for dissolving the benzotriazole derivative compound; benzene, toluene, xylene Aromatic hydrocarbons such as cyclohexane and methylcyclohexane; Petroleum solvents such as petroleum ether and petroleum benzine; Halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; Ethyl ether , Ethers such as isopropyl ether, anisole, dioxane, and tetrahydrofuran; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate and butyl acetate; dimethylforma Amides such as amide and dimethylacetamide; acetonitrile; dimethyl sulfoxide; and halogenated benzenes such as chlorobenzene and dichlorobenzene. Only one kind of these may be used, or two or more kinds may be appropriately mixed and used.

  The thickness of the light emitting layer of the organic electroluminescent element is, for example, 5 to 500 nm, preferably 20 to 150 nm.

  The organic electroluminescent element in the present invention has an organic layer such as a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer in addition to the light emitting layer, but has a layer that also serves as two or more layers. May be. In addition to the organic layer, the substrate has a substrate, an anode, and a cathode.

  Inorganic materials such as zirconia-stabilized yttrium and glass as substrates; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, polyimide, polycycloolefin , Polymer materials such as polychlorotrifluoroethylene and polytetrafluoroethylene. As the substrate, only one type of material may be used, or a material in which two or more types are combined may be used.

  Examples of the material used for the anode include metals, metal oxides, and conductive compounds. Specific examples include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), IZO (indium zinc oxide) polythiophene, and polypyrrole. . These may use only one type and may use two or more types together.

  The anode can be formed on the substrate by a method such as vapor deposition or sputtering. Further, the anode may have a single layer structure or a multilayer structure. The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm.

  Examples of the material used for the cathode include metals, metal oxides, and conductive compounds. Specifically, for example, alkali metals such as Li, Na, K, and Cs or alkali metal fluorides, organic salts such as naphthol, alkaline earth metals such as Mg and Ca, or alkaline earth metal fluorides, gold, silver, Examples thereof include platinum, lead, aluminum, a sodium-potassium alloy, a lithium-aluminum alloy, a magnesium-silver alloy, an alloy using two or more of them in combination, and a rare earth metal such as indium and ytterbium. These may use only one type and may use two or more types together.

  For the production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method are used. The cathode may have a single layer structure or a multilayer structure. The thickness of the cathode is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm.

  Specific examples of the compound used for the layer having hole transport and hole injection functions include phthalocyanine derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylenes. And derivatives thereof, polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives. These may use only one type and may use two or more types together.

  The method for forming the layer having hole transport and hole injection functions is not particularly limited, and the layer can be formed by forming a thin film by a vacuum deposition method, a wet coating method, or the like. The thickness of the layer having a hole injecting and transporting function is, for example, 5 to 500 nm, preferably 20 to 150 nm.

  Specific examples of the compound used for the layer having an electron transport and electron injection function include an organometallic complex, an oxadiazole derivative, a triazole derivative, a triazine derivative, a perylene derivative, a quinoline derivative, a diphenylquinone derivative, a nitro-substituted fluorenone derivative, Examples include thiopyrandioxide derivatives, quinoxaline derivatives, and benzimidazole derivatives. These may use only one type and may use two or more types together.

  The method for forming the layer having the electron transport and electron injection functions is not particularly limited, and the layer can be formed by forming a thin film by a vacuum deposition method, a wet coating method, or the like. The thickness of the layer having an electron injecting and transporting function is, for example, 5 to 500 nm, preferably 20 to 150 nm.

  The synthesis method of the benzotriazole derivative compound implemented by this invention and the characteristic of a compound are shown below. However, the synthesis method is not limited to these.

化合物（ａ） Example 1
[Compound (a); Synthesis of 5-carboxy-2- (3,5-dimethoxy-4-octyloxyphenyl) -2H-benzotriazole]

Compound (a)

  A 1000 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirring device, 400 ml of water, 25.6 g (0.242 mol) of sodium carbonate, 78.7 g (0.432) of 4-amino-3-nitrobenzoic acid. Mol) was added and dissolved, and 89.2 g (0.465 mol) of 36% aqueous sodium nitrite solution was added. Attach this solution to a 2000 ml four-necked flask with a ball condenser, thermometer, and stirrer, add 400 ml of water and 168.8 g (1.077 mol) of 62.5% sulfuric acid, and mix to 3-7 ° C. The solution was added dropwise to the cooled product and stirred at the same temperature for 2 hours to obtain a diazonium salt aqueous solution. A 3000 ml four-necked flask is equipped with a condenser with a ball, a thermometer and a stirrer, 880 ml of water, 19.5 g (0.488 mol) of sodium hydroxide, 42.6 g (0.402 mol) of sodium carbonate, 88 of syringic acid 88 .2 g (0.445 mol) was added and mixed, and an aqueous diazonium salt solution was added dropwise at 3 to 7 ° C., followed by stirring at the same temperature for 4 hours. The produced precipitate was filtered, washed with water and dried to obtain 114.7 g of 2,6-dimethoxy-4- (4-carboxy-2-nitrophenylazo) phenol.

  A 1000 ml four-necked flask was equipped with a condenser with a ball, a thermometer, and a stirrer, and 80.0 g (0.230 mol) of 2,6-dimethoxy-4- (4-carboxy-2-nitrophenylazo) phenol, Add 400 ml of isopropyl alcohol, 400 ml of water and 41.6 g (1.040 mol) of sodium hydroxide to dissolve, add 100.0 g (0.925 mol) of thiourea dioxide at 70 to 75 ° C., and continue at the same temperature for 8 hours. The mixture is stirred, adjusted to pH 4 with 62.5% sulfuric acid, and the resulting precipitate is filtered, washed with water and dried to give 5-carboxy-2- (4-hydroxy-3,5-dimethoxyphenyl) -2H-benzotriazole. 36.0 g was obtained.

  A 1000-ml four-necked flask was equipped with a ball condenser, a thermometer, and a stirring device, and 20.0 g (0.0634) of 5-carboxy-2- (4-hydroxy-3,5-dimethoxyphenyl) -2H-benzotriazole was attached. Mol), N, N-dimethylformamide 200 ml, sodium carbonate 9.5 g (0.0896 mol), polyethylene glycol 400 2.5 g, potassium iodide 1.0 g, n-octyl chloride 26.0 g (0.1749 mol) ) And stirred under reflux at 140 ° C. for 4 hours. 500 ml of toluene, 100 ml of water and 20 ml of acetic acid were added and stirred, and the mixture was allowed to stand at 50 ° C., and the lower aqueous layer was separated and removed, followed by washing with 100 ml of water. After recovering toluene, 250 ml of isopropyl alcohol, 250 ml of water and 11.5 g (0.2875 mol) of sodium hydroxide were added and hydrolyzed at 70 to 80 ° C. for 1 hour. The pH was adjusted to 5 with 62.5% sulfuric acid and cooled to 15 ° C. The precipitated crystals were filtered, washed with isopropyl alcohol and dried to obtain 21.4 g of pale yellow green crystals. The pale yellowish green crystals were recrystallized from toluene and dried to obtain 16.6 g of compound (a). The yield was 23% (from 4-amino-3-nitro-benzoic acid). Melting point is 175 ° C.

Moreover, the purity of the compound (a) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMPAX ODS A-212 6.0 × 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: methanol / water = 95/5
Flow rate: 1.0 ml / min
<Measurement results>
HPLC area purity: 99.9%
In addition, the following Example 2 also performed the HPLC measurement on the measurement conditions similar to a present Example.

Moreover, as a result of conducting NMR measurement of the compound (a), a result supporting the above structure was obtained.
The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL ECX-400
Resonant frequency: 400 MHz (1H-NMR)
Solvent: chloroform-d
Tetramethylsilane was used as an internal standard of 1H-NMR, the chemical shift value was represented by δ value (ppm), and the coupling constant was represented by Hertz. Further, s is a singlet, d is a doublet, t is a triplet, dd is a doublet doublet, and m is a short of multiplet. The same applies to all the following examples.
The contents of the obtained NMR spectrum are as follows. In Examples 2 and 4 below, NMR measurement was performed under the same measurement conditions as in this example.
δ = 8.83 (s, 1H, benzotriazol-H), 8.13 (d, 1H, J = 9.0 Hz, benzotriazole-H), 8.00 (d, 1H, J = 9.2 Hz, benzotriazole- H), 7.67 (s, 2H , benzene-H), 4.06 (t, 2H, benzene-O-CH 2 -H), 4.01 (s, 6H, benzene- (O-CH 3) _{2 -H), 1.79 (dd,} 2H, J = 7.6Hz, J = 7.2Hz, J = 7.2Hz, CH 2 -H), 1.48 (m, 2H, CH 2 -H) _{, 1.31 (m, 8H, (} CH 2) 4 -H), 0.89 (t, 3H, CH 3 -H)

化合物（ｂ） (Example 2)
[Compound (b); Synthesis of methyl 2- (3,5-dimethoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate]

Compound (b)

  A 200 ml four-necked flask is equipped with a condenser with a ball, a thermometer and a stirrer, and 5.0 g (0.0117 mol) of compound (a), 50 ml of toluene, 0.5 ml of N, N-dimethylformamide, thionyl chloride 2 .8 g (0.0235 mol) was added, and the mixture was stirred at 60 to 70 ° C. for 1 hour. Toluene and unreacted thionyl chloride were collected under reduced pressure, 50 ml of toluene, 2.8 g (0.0874 mol) of methanol and 1.9 g (0.0240 mol) of pyridine were added, and the mixture was stirred at 60 to 70 ° C. for 1 hour. After adding 30 ml of water and 2 ml of 62.5% sulfuric acid and stirring for 30 minutes, the lower aqueous layer was separated and washed with 30 ml of water. Toluene was recovered under reduced pressure, 50 ml of isopropyl alcohol and 15 ml of toluene were added and cooled to 5 ° C., and the precipitated crystals were filtered, washed with isopropyl alcohol and dried to obtain 4.7 g of white crystals. The white crystals were recrystallized with a mixed solvent of isopropyl alcohol and toluene and dried to obtain 4.1 g of compound (b). The yield was 79% (from compound (a)). The melting point was 106 ° C., and the HPLC surface percentage purity was 99.7%.

Further, as a result of conducting NMR analysis of the compound (b), a result supporting the above structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 8.71 (s, 1H, benzotriazole-H), 8.06 (d, 1H, J = 9.0 Hz, benzotriazole-H), 7.95 (d, 1H, J = 8.8 Hz, benzotriazole- H), 7.65 (s, 2H , benzene-H), 4.05 (t, 2H, benzene-O-CH 2 -H), 4.00 (s, 6H, benzene- (O-CH 3) _{2 -H), 3.99 (s,} 3H, CO-O-CH 3 -H), 1.78 (dd, 2H, J = 8.0Hz, J = 7.2Hz, J = 6.8Hz, CH _{2 -H), 1.48 (t,} 2H, CH 2 -H), 1.32 (m, 8H, (CH 2) 4 -H), 0.89 (t, 3H, CH 3 -H)

化合物（ｃ） (Example 3)
[Compound (c); Synthesis of 5-carboxy-2- (3-methoxy-4-octyloxyphenyl) -2H-benzotriazole]

Compound (c)

  Compound (c) was obtained in 25% yield (from 4-amino-3-nitrobenzoic acid) in the same manner as in Example 1 except that syringic acid was changed to vanillic acid. Melting point is 180 ° C.

Moreover, the purity of the compound (c) was measured by HPLC analysis.
<Measurement conditions>
Device: L-2130 (manufactured by Hitachi High-Technologies Corporation)
Column used: SUMPAX ODS A-212 6.0 × 150 mm 5 μm
Column temperature: 40 ° C
Mobile phase: Methanol / water = 99/1
Flow rate: 1.0 ml / min
<Measurement results>
HPLC area purity: 99.0%
In addition, the following Example 4 also performed the HPLC measurement on the measurement conditions similar to a present Example.

Further, as a result of conducting NMR measurement of the compound (c), a result supporting the above structure was obtained.
The measurement conditions are as follows.
<Measurement conditions>
Equipment: JEOL ECX-400
Resonant frequency: 400 MHz (1H-NMR)
Solvent: DMSO-d6
The contents of the obtained NMR spectrum are as follows.
δ = 8.61 (s, 1H, benzotriazole-H), 8.10 (dd, 1H, J = 8.4 Hz, J = 0.8 Hz, J = 0.8 Hz, benzotriazole-H), 8.00 ( dd, 1H, J = 7.6 Hz, J = 1.6 Hz, J = 1.2 Hz, benzotriazole-H), 7.88 (d, 1H, J = 9.6, benzene-H), 7.87 ( s, 1H, benzene-H), 7.21 (d, 1H, J = 9.6 Hz, benzene-H), 4.06 (t, 2H, benzene-O—CH ₂ —H), 3.93 ( _{s, 3H, -O-CH 3} -H), 1.75 (dd, 2H, J = 8.0Hz, J = 6.8Hz, J = 6.8Hz, CH 2 -H), 1.43 (m _{, 2H, CH 2 -H),} 1.28 (m, 8H, (CH 2) 4 H), 0.87 (t, 3H , CH 3 -H)

化合物（ｄ） Example 4
[Compound (d); Synthesis of methyl 2- (3-methoxy-4-octyloxyphenyl) -2H-benzotriazole-5-carboxylate]

Compound (d)

  The compound (d) was obtained in 81% yield (from the compound (c)) in the same manner as in Example 2 except that the compound (a) was changed to the compound (c). The melting point was 98 ° C., and the HPLC surface percentage purity was 98.8%.

Further, as a result of conducting NMR analysis of the compound (d), a result supporting the above structure was obtained. The contents of the obtained NMR spectrum are as follows.
δ = 8.70 (s, 1H, benzotriazole-H), 8.05 (dd, 1H, J = 7.6 Hz, J = 1.6 Hz, J = 1.2 Hz, benzotriazole-H), 7.94 ( dd, 1H, J = 8.0 Hz, J = 0.8 Hz, J = 0.8 Hz, benzotriazole-H), 7.93 (m, 2H, benzene-H), 7.01 (d, 1H, J = 9.6 Hz, benzene-H), 4.10 (t, 2H, benzene-O—CH ₂ —H), 4.03 (s, 3H, CO—O—CH ₃ —H), 3.99 (s) _{, 3H, benzene-O-CH} 3 -H), 1.90 (t, 2H, CH 2 -H), 1.49 (m, 2H, CH 2 -H), 1.33 (m, 8H, ( _{CH 2) 4 -H), 0.89} (t, 3H, CH 3 -H)

[Optical properties in solvent]
Table 1 shows the absorption and emission characteristics of the compounds (a), (b), (c) and (d) obtained in Examples 1 to 4 in chloroform.

(Comparative example)
Compound (e); 2- (4-octyloxyphenyl) -2H-benzotriazole, compound (f); methyl 2- (4), which is the same benzotriazole derivative compound but having a structure different from that of general formula (1) Table 1 shows the absorption and emission characteristics of -octyloxyphenyl) -2H-benzotriazole-5-carboxylate as in Examples 1-4. In addition, compound (g) which is a conventional organic fluorescent dye; 4,4′-bis (2-methoxystyryl) biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) also absorbs and emits light as in Examples 1-4. The characteristics are shown in Table 1.

  From Table 1, the compound (e) and the compound (f) having a structure different from the general formula (1) have a high molar absorption coefficient and a high fluorescence quantum efficiency, but the maximum emission wavelength is too short as a blue organic fluorescent dye. Therefore, clean blue light emission cannot be obtained, and there is a problem that concentration quenching occurs due to a small Stokes shift. Compound (g), which is a conventional product, has a high molar extinction coefficient and a high fluorescence quantum efficiency, but has a problem that the Stokes shift is small and concentration quenching occurs. The product of the present invention has a molar extinction coefficient far exceeding 10,000, which is considered useful as an organic fluorescent dye, has a fluorescence quantum efficiency of about 70%, which is higher than that of a general organic fluorescent dye, and is around 450 nm at which clean blue emission can be obtained. Since it has the maximum emission wavelength and the Stokes shift is as large as 80 to 110 nm, it is difficult to cause concentration quenching, and shows excellent values in all the optical properties required for blue organic fluorescent dyes. . In addition, the absorption spectrum, emission, and excitation of the compounds (a), (b), (c), (d) obtained in Examples 1 to 4 and the compounds (e), (f), (g) of the comparative examples The measurement conditions of spectrum and fluorescence quantum efficiency are as follows.

<Absorption spectrum>
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm
Concentration: 10ppm
Cell: 1cm quartz

<Emission and excitation spectra>
Apparatus: FP-6600 (manufactured by JASCO Corporation)
Measurement wavelength: 200 to 600 nm
Concentration: 10ppm
Cell: 1cm quartz

<Fluorescence quantum efficiency>
Device: C10027 (manufactured by Hamamatsu Photonics)
Concentration: 10ppm
Cell: 1cm quartz

[Optical properties in film]
Table 2 shows the absorption and emission characteristics of the compound (b) obtained in Example 2 in a polymethyl methacrylate (hereinafter referred to as “PMMA”) film.

  From Table 2, the maximum emission wavelength in the PMMA film is around 450 nm at which clean blue emission can be obtained, the Stokes shift is large at 90 nm or more, and the fluorescence quantum efficiency is 90% or more. It can be seen that the absorption and emission characteristics are excellent. The production conditions, absorption spectrum, emission and excitation spectrum, and fluorescence quantum efficiency measurement conditions of the PMMA film of the compound (b) obtained in Example 2 are as follows.

<PMMA film production>
PMMA: Wako Pure Chemical Industries, Ltd. 10mg
Organic fluorescent dye: 0.5mg
Toluene: 0.7ml
Film formation method: spin coat film thickness: 120 nm

<Absorption spectrum>
Apparatus: UV-3600 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm

<Emission and excitation spectra>
Apparatus: FP-6600 (manufactured by JASCO Corporation)
Measurement wavelength: 200 to 600 nm

<Fluorescence quantum efficiency>
Device: C10027 (manufactured by Hamamatsu Photonics)

[Electroluminescence characteristics]
Using the compound (b) obtained in Example 2, a wet coating type organic electroluminescent device was produced by the following procedure.

  Surface treatment with ozone was performed on an ITO-glass substrate (manufactured by Yamato Vacuum Industries, ITO film thickness 150 nm) that had been subjected to patterning and cleaning treatment in advance. Next, a conductive polymer PEDOT: PSS (manufactured by Heraeus Clevios, CH8000) was applied to the surface of the ITO substrate by a spin coating method and baked at 110 ° C. for 60 minutes to form a hole injection layer having a thickness of 40 nm.

  On the surface of the hole injection layer, compound (b) as a light emitting material, 2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole (PBD) as an electron transport material Then, a toluene solution containing polyvinyl carbazole (PVCz) at a mass ratio of 0.05: 3: 10 as a hole transporting host material was applied by a spin coating method. The coating film was baked at 80 ° C. for 30 minutes to form a light emitting layer having a thickness of 120 nm.

By depositing cesium fluoride on the surface of the light emitting layer under a reduced pressure of 10 ⁻⁴ Pa to form a layer having a thickness of 1 nm, and further depositing aluminum under a reduced pressure of 10 ⁻⁴ Pa, A cathode was formed. In this way, an organic electroluminescent element was obtained. The irradiation area of the organic electroluminescent element was 0.25 cm ² . The obtained organic electroluminescent element was sealed in cavity glass using UV curable resin.

  Evaluation of the obtained organic electroluminescent element was implemented using the C9920-11 luminance orientation characteristic measuring apparatus by Hamamatsu Photonics. The current and emission intensity and the electroluminescence spectrum when voltage was applied were measured, and the maximum luminance, power efficiency, current efficiency, external quantum efficiency, chromaticity coordinates, and EL wavelength were measured to evaluate the characteristics. Table 3 shows the measurement results of the element performance evaluation.

As is clear from Table 3, as the voltage was applied to the organic electroluminescence device, light emission started at 4.5V, and a maximum luminance of 585 cd / m ² was obtained at 15V. The obtained light emission was blue light emission indicating (0.18, 0.14) in chromaticity coordinates determined by the International Lighting Commission CIE.

  The benzotriazole derivative compound of the present invention has a large molar extinction coefficient, fluorescence quantum efficiency and Stokes shift, exhibits excellent optical properties, and further has excellent solid light emission, so that organic fluorescent dyes, fluorescent resin compositions and As an organic electroluminescent element luminescent material, it can utilize suitably.

Claims (5)

A benzotriazole derivative compound represented by the following general formula (1):

General formula (1)
[Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₂ represents an alkyl group having 1 to 8 carbon atoms. R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a straight chain having 1 to 4 carbon atoms or branched mono-alkyl-substituted amino group, a straight-chain or branched di-alkyl substituted amino group having 1 to 4 carbon atoms, a nitro group, a carboxyl group, an alkyl alkyloxycarbonyl group having 1 to 8 carbon atoms, an alkyl carbon number 1 3 alkylcarboxyl group, a Rukirukarubo phosphate of an alkyl ester group having 1 to 8 alkyl carbon atoms, an aryl group, an acyl group, and a sulfo group or a cyano group, at least one alkoxy group having 1 to 8 carbon atoms Represents. ] The benzotriazole derivative compound according to claim 1, wherein R ₃ and R ₄ in the general formula (1) each independently represent a hydrogen atom or a methoxy group, at least one of which is a methoxy group.     An organic fluorescent dye containing the benzotriazole derivative compound according to claim 1.     The fluorescent resin composition which mix | blended the organic fluorescent dye of Claim 3 with resin.     The organic electroluminescent element luminescent material containing the organic fluorescent dye of Claim 3.