JP2012214595A - Organic fluorescence dye and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic fluorescence dye manifesting strong luminescence near 400 nm, and an excellent fluorescence property in adding to a resin.SOLUTION: The organic fluorescence dye is a benzotriazole derivative such as 2-(4-methoxyphenyl)-2H-benzotriazole represented by the following general formula, wherein Ris a hydrogen atom, a halogen atom, a 1-8C alkyl group, a 1-8C alkoxyl group or hydroxyl group, and Ris a 1-20C alkyl group.

Description

  The present invention relates to an organic fluorescent dye and a resin composition. More specifically, the present invention relates to an organic fluorescent dye and a resin composition that exhibit strong emission near 400 nm.

  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. in use.

  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 EL 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, the organic fluorescent dye used is required to absorb ultraviolet light or visible light sufficiently and emit strong light. That is, an organic fluorescent dye having a high molar extinction coefficient, which is an index indicating the degree of light absorption by a substance, and high fluorescence quantum efficiency expressed by the ratio of the number of emitted photons to the number of absorbed photons is required. The higher the molar extinction coefficient and the fluorescence quantum efficiency, the higher the fluorescence intensity. In addition, organic fluorescent dyes are often used not only in dyes and organic solvents but also in resins, and it is required that the fluorescent properties of the resins are excellent.

  Many organic fluorescent dyes that have been used so far have a large molar extinction coefficient, but few have a sufficiently high fluorescence quantum efficiency, and organic fluorescence has a large molar extinction coefficient and a large fluorescence quantum efficiency in order to increase the fluorescence intensity. Dyes have been developed. For example, as described in Non-Patent Document 1, oxadiazole derivatives and triazole derivatives have been proposed.

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

  Although it can be said that the molar extinction coefficient of these compounds is large, the fluorescence quantum efficiency cannot be said to be sufficiently large, and is particularly small for blue organic fluorescent dyes emitting near 400 nm. As a result, it is not possible to obtain sufficiently satisfactory light emission for each of the above applications, and concentration quenching occurs when the amount of organic fluorescent dye added is increased to increase fluorescence intensity, or when added to a resin Has a problem that bleed-out tends to occur. Therefore, an object of the present invention is to provide an organic fluorescent dye that exhibits strong light emission at around 400 nm and has excellent fluorescence characteristics when added to a resin.

一般式（１）
［式中Ｒ_１は水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基又はヒドロキシル基を表す。式中Ｒ_２は炭素数１〜２０のアルキル基を表す。］ In the present invention, use of a benzotriazole derivative compound represented by the following general formula (1) as an organic fluorescent dye and a fluorescent resin composition is a main means for solving the above problems.

General formula (1)
[Wherein R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydroxyl group. In the formula, R ₂ represents an alkyl group having 1 to 20 carbon atoms. ]

The benzotriazole derivative compound represented by the general formula (1) is preferably a compound in which R ₁ is a hydrogen atom and R ₂ is an alkyl group having 1 to 8 carbon atoms.

  The benzotriazole derivative of the general formula (1) used for the organic fluorescent dye of the present invention emits light at around 400 nm, has a molar extinction coefficient of about 26000, and a fluorescence quantum efficiency of about 90%. It is useful as an organic fluorescent dye and a resin composition that can solve the above.

  The present invention will be described in detail below. In the present invention, a compound represented by the following general formula (1) is used as the organic fluorescent dye and the resin composition. The compound represented by the 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; a halogen atom such as fluorine, chlorine, iodine; 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, optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms; methoxy group, Ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc. C1-C8 linear or branched alkoxy group or hydroxyl group may be mentioned. R ₂ is 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, n- Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, such as a decyl group, an n-dodecyl group, an n-hexadecyl group, and an n-eicosyl group.

  Examples of the benzotriazole derivative compound general formula (1) used in the organic fluorescent dye of the present invention include the following. 2- (4-methoxyphenyl) -2H-benzotriazole, 5-chloro-2- (4-methoxyphenyl) -2H-benzotriazole, 2- (4-methoxyphenyl) -5-methyl-2H-benzotriazole, 5-methoxy-2- (4-methoxyphenyl) -2H-benzotriazole, 2- (4-methoxyphenyl) -2H-benzotriazol-5-ol, 2- (4-octyloxyphenyl) -2H-benzotriazole 5-chloro-2- (4-octyloxyphenyl) -2H-benzotriazole, 5-methyl-2- (4-octyloxyphenyl) -2H-benzotriazole, 5-methoxy-2- (4-octyloxy) Phenyl) -2H-benzotriazole, 2- (4-octyloxyphenyl) -2H-benzoto Azol-5-ol, 2- (4-eicosyloxyphenyl) -2H-benzotriazole, 5-chloro-2- (4-eicosyloxyphenyl) -2H-benzotriazole, 2- (4-eicosyloxy) Phenyl) -5-methyl-2H-benzotriazole, 2- (4-eicosyloxyphenyl) -5-methoxy-2H-benzotriazole, 2- (4-eicosyloxyphenyl) -2H-benzotriazole-5 All etc.

Among the above substituents, R ₁ is preferably a hydrogen atom and R ₂ is an alkyl group having 1 to 8 carbon atoms. R ₁ is a hydrogen atom _{R 2} is an alkyl group having 1 carbon atoms and 2- (4-methoxyphenyl) -2H- benzotriazole, _{R 1} is hydrogen atom, _{R 2} is an alkyl group having 8 carbon atoms It has been demonstrated in the Examples that 2- (4-octyloxyphenyl) -2H-benzotriazole is a high fluorescence quantum efficiency.

  In the organic fluorescent dye of the present invention, only one compound included in the benzotriazole derivative compound general formula (1) can be used, or two or more compounds included in the compound general formula (1) are mixed. Can also be used. Moreover, it can also be used by mixing with other fluorescent organic compounds.

  The benzotriazole derivative compound general formula (1) used in the organic fluorescent dye of the present invention can be synthesized by a conventionally known method. That is, as shown in the following reaction formulas (Chemical Formula 2 to Chemical Formula 6), nitroanilines are diazotized, coupled with parahydroxybenzoic acid by a conventional method, and the resulting nitrophenylazo compound is reduced to produce benzotriazole. A desired benzotriazole derivative can be synthesized by converting it into a derivative and further alkoxylating with an alkyl halide or a sulfate.

  The organic fluorescent dye is often used by being added to the resin, and the benzotriazole derivative compound used for the organic fluorescent dye of the present invention is also added to the resin and used. The resin to which the benzotriazole derivative compound can be blended is not particularly limited. For example, an α-olefin polymer such as polyethylene, polypropylene, polybutene, polypentene, poly-3-methylbutylene, polymethylpentene, or ethylene- Polyolefin such as vinyl acetate copolymer, ethylene-propylene copolymer, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-anhydrous Maleic acid terpolymer, Vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer Halogen-containing synthesis such as polymers, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plastic polyvinyl chloride Resin, petroleum resin, coumarone resin, polystyrene, copolymer of styrene and other monomers (maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene resin, acrylate-butadiene-styrene resin, methacryl Acid ester-butadiene- Styrene resin such as styrene 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, silicone 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 coatings, polyamide resin Examples thereof include fats, polyurethane resins and unsaturated polyester resins.

  The benzotriazole derivative compound is preferably used in the range of 0.001 to 1.0% by weight, preferably 0.01 to 0.2% by weight, based on the resin. This is because if the addition amount is too small, sufficient light emission cannot be obtained, and if it is too large, bleeding out or concentration quenching occurs.

  The synthesis method of the benzotriazole derivative compound used in the present invention and the characteristics of the compound are shown below. However, the synthesis method is not limited to this.

(Production example)
[Intermediate; Synthesis of 4- (2H-benzotriazol-2-yl) phenol]
A 500 ml four-necked flask is equipped with a ball condenser, thermometer, and stirrer, and 30.4 g (0.220 mol) of orthonitroaniline and 50.8 g (0.324 mol) of 62.5% sulfuric acid are dissolved. And 170 ml of water was added with stirring. To this, 43.4 g (0.226 mol) of 36% sodium nitrite aqueous solution was added dropwise at 3 to 7 ° C., and the mixture was stirred at the same temperature for 2 hours to obtain 290 g of a diazonium salt aqueous solution. Attach a condenser with a ball, a thermometer and a stirrer to a 2000 ml four-necked flask, water 470 ml, sodium hydroxide 10.0 g (0.250 mol), sodium carbonate 11.5 g (0.109 mol), parahydroxybenzoic acid 31.3 g (0.227 mol) of acid 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 generated precipitate was filtered, washed with water, and dried to obtain 49.2 g of 4- (2-nitrophenylazo) phenol.

  A 1000 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, 49.2 g (0.202 mol) of 4- (2-nitrophenylazo) phenol, 175 ml of isopropyl alcohol, 200 ml of water, 17 sodium hydroxide .6 g (0.440 mol) and hydroquinone 0.4 g are dissolved, 60% hydrazine hydrate 18.4 g (0.220 mol) is added dropwise at 70 to 75 ° C., and the mixture is stirred at the same temperature for 2 hours. The pH was adjusted to 3 with 62.5% sulfuric acid, and the resulting precipitate was filtered, washed with water and dried to obtain 30.9 g of 4- (2H-benzotriazol-2-yl) phenol-N-oxide.

  A 1000 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirrer, 30.9 g (0.136 mol) of N-oxide, 300 ml of methyl isobutyl ketone, 150 ml of water, 14.9 g of zinc dust (0.228) The mixture was added dropwise with 53.6 g (0.342 mol) of 62.5% sulfuric acid maintained at 70 to 75 ° C., and stirred at the same temperature for 1 hour. The mixture was allowed to stand to separate and remove the lower aqueous layer, washed with 150 ml of warm water, added with 1.0 g of activated carbon, and stirred to reflux for decolorization. Filtration was performed while hot, and methyl isobutyl ketone was recovered from the filtrate, and then 150 ml of isopropyl alcohol was added, and the mixture was cooled to 25 ° C. The precipitated crystals were filtered, washed with isopropyl alcohol, and then dried to give 4- (2H-benzotriazole 21.3 g of 2-yl) phenol was obtained. The yield was 46% (from orthonitroaniline).

化合物（ａ） [Compound (a); Synthesis of 2- (4-methoxyphenyl) -2H-benzotriazole]

Compound (a)

  A 300 ml four-necked flask is equipped with a condenser with a ball, a thermometer and a stirrer, 12.0 g (0.0568 mol) of 4- (2H-benzotriazol-2-yl) phenol, 60 ml of methyl isobutyl ketone, 9 potassium carbonate 0.4 g (0.0680 mol), 1.2 ml of polyethylene glycol 400, 2.4 g of potassium iodide, and 16.5 g (0.1308 mol) of dimethylsulfuric acid were added and stirred at 120 ° C. for 12 hours under reflux. 80 ml of water was added, and the mixture was allowed to stand at 50 ° C., and the lower aqueous layer was separated and removed, washed with 40 ml of warm water, 0.5 g of activated carbon was added, and the mixture was stirred under reflux to decolorize. Filtration was performed while hot, and methyl isobutyl ketone was recovered from the filtrate, and then 40 ml of isopropyl alcohol was added, and the mixture was cooled to 20 ° C. The precipitated crystals were filtered, washed with isopropyl alcohol and dried to obtain 8.4 g of white crystals. It was. The white crystals were recrystallized from toluene and dried to obtain 4.3 g of 2- (4-methoxyphenyl) -2H-benzotriazole. The yield was 34% (from 4- (2H-benzotriazol-2-yl) phenol). Melting point is 111 ° 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: 99.5%
In the following examples, HPLC measurement was performed under the same measurement conditions as in this example.

化合物（ｂ） [Compound (b); Synthesis of 2- (4-octyloxyphenyl) -2H-benzotriazole]

Compound (b)

  A 1000 ml four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirring device, 46.6 g (0.221 mol) of 4- (2H-benzotriazol-2-yl) phenol, 470 ml of methyl isobutyl ketone, 18 potassium carbonate 3.9 g (0.137 mol), 4.7 ml of polyethylene glycol 400, 9.3 g of potassium iodide, and 37.4 g (0.252 mol) of n-octyl chloride were added and reflux dehydrated at 120 ° C. for 12 hours. 200 ml of water was added, and the mixture was allowed to stand at 50 ° C., and the lower aqueous layer was separated and removed, washed with 200 ml of warm water, added with 2 g of activated carbon, and decolorized by stirring under reflux. Filtration was performed while hot, and methyl isobutyl ketone was recovered from the filtrate, and then 200 ml of isopropyl alcohol was added, and the mixture was cooled to 20 ° C. The precipitated crystals were filtered, washed with isopropyl alcohol and dried to obtain 66.0 g of white crystals. It was. The white crystals were recrystallized from isopropyl alcohol and dried to obtain 52.7 g of 2- (4-octyloxyphenyl) -2H-benzotriazole. The yield was 74% (from 4- (2H-benzotriazol-2-yl) phenol). The melting point was 75 ° C., and the HPLC surface percentage purity was 99.8%.

(Examples 1 and 2)
[optical properties]
Table 1 shows the absorption characteristics in chloroform of the compound (a) (Example 1) and compound (b) (Example 2) obtained in the above synthesis, and the fluorescence characteristics in polystyrene and polypropylene.

(Comparative example)
The compound (c), which is a conventional organic fluorescent dye; 4,4′-bis (2-methoxystyryl) biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) has the same absorption characteristics and fluorescence characteristics as in Examples 1 and 2 above. Table 1 shows.

  From Table 1, Examples 1 and 2 show a high molar extinction coefficient far exceeding 10,000, which is considered useful as an organic fluorescent dye, and show a higher fluorescence quantum efficiency than conventional products that emit light at around 400 nm. In the resin, it shows a high fluorescence quantum efficiency in a wide range of concentrations, indicating that it is an excellent organic fluorescent dye. The absorption spectrum, fluorescence spectrum, and resin film molding conditions of the examples and comparative examples are as follows.

<Absorption spectrum>
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-450 nm
Solvent: Chloroform Concentration: 10 ppm
Cell: 1cm quartz

<Fluorescence spectrum>
Apparatus: FP-6500 (manufactured by JASCO Corporation)
Excitation wavelength: Compound (a), (b) 320 nm, Compound (c) 370 nm

<Polystyrene cast film molding>
Polystyrene raw material: degree of polymerization about 2000 (manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent: Dichloromethane Film thickness: 0.1mm

<Polypropylene hot press film molding>
[Kneading]
Polypropylene raw material: PX600N 4kg manufactured by Sun Allomer Co., Ltd.
Compound: 8g
Extruder: Twin screw extruder KZW31-42MG-01R manufactured by Technobel
Temperature: 180 ° C
[Hot press]
Injection molding machine: Toyo Machine Metal Co., Ltd. S80IV
Temperature: 210 ° C
Film thickness: 1mm

  The organic fluorescent dye of the present invention can be suitably used as an organic fluorescent dye because it has a high molar absorption coefficient and high fluorescence quantum efficiency and exhibits excellent optical properties. Since excellent optical characteristics are exhibited in various resins as well, it can be suitably used particularly in a state dispersed in the resin.

Claims (3)

An organic fluorescent dye containing a benzotriazole derivative represented by the following general formula (1):

General formula (1)
[Wherein R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydroxyl group. In the formula, R ₂ represents an alkyl group having 1 to 20 carbon atoms. ] The organic fluorescent dye according to claim ₁ , wherein R ₁ in the general formula (1) is a hydrogen atom, and R ₂ is an alkyl group having 1 to 8 carbon atoms. The fluorescent resin composition which mix | blended the organic fluorescent dye of any one of Claims 1 and 2 with resin.