KR100398087B1 - New azo metal complex having heterocyclic ring, and use thereof - Google Patents

Abstract

The present invention relates to azo-based metal complexes of the following formula (2) having a novel structure prepared by reacting azo dyes containing various derivatives of the formula (1) with various metal ions, and their application.

In Formulas 1 and 2, X, Y, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and M are as defined in the detailed description of the invention, respectively.

Description

Azo metal complex containing hetero ring and use thereof {New azo metal complex having heterocyclic ring, and use}

In the present invention, the azo-based metal complex of the following formula (2) is prepared and applied to an optical recording medium having a low manufacturing cost and easy to synthesize.

[Formula 2]

In Formula 2, X and Y are each S or N, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom (-H), a carboxylic acid group (-COOH), or a methoxy group ( -OCH ₃ ), M is a metal ion is Ni, Zn, Co or Cu.

The present invention relates to an optical recording medium using an azo dye and a metal complex thereof as the optical recording material. Such optical recording media include a read only memory for reproducing recorded information according to a function, a write once read many (WORM) for recording only once, and an erase for rewriting and rewriting after recording. It is classified as Erasable. The recordable optical recording medium records and reproduces by reflectance change due to physical deformation, phase change, magnetic property change, and the like before and after recording. CD-R (Compact Disk Recordable) is the most widely known recordable optical recording medium. In order to improve the characteristics of the optical recording medium and to facilitate the manufacture of various optical recording materials have been proposed and some practical use. Examples of the optical recording material for CD-R include cyanine dyes (Japanese Patent Laid-Open No. 58-125246), phthalocyanine dyes (European Patent No. 667751), azo dyes (US Pat. No. 5,441,844), and double salts. (US Pat. No. 4,626,490) and the like are known.

In recent years, as the amount of information gradually increases, a digital versatile disk recordable (DVD-R) has been proposed that increases the capacity of stored information. The DVD-R employs a red diode laser in the 630-670 nm wavelength range as a light source and reduces the bit size and track spacing to increase the storage capacity by 6 to 8 times compared to the case of CD-R to improve recording density. . In order to be used as an optical recording material for DVD-R, high refractive index and proper absorption characteristics in recording wavelength, excellent solubility in organic solvents, uniformity and stability of recording sites, as well as easy synthesis and low material cost Etc. are required. Examples of the optical recording material for DVD-R include cyanine dyes (Japanese Patent Application Laid-open No. Hei 10-149583 and Japanese Patent Application Laid-open No. Hei 9-208560). But. In the case of conventional dye materials, phthalocyanine dyes are difficult to synthesize and have high manufacturing costs, and cyanine dyes are weak to light or heat. As such, the existing dyes still have much room for improvement in view of the above-described properties.

The technical problem to be achieved in the present invention is that it is relatively easy to synthesize, compared to the existing phthalocyanine or cyanine, the production yield is high, and the new structure of the azo-based metal complex and the azo-based metal complex compound exhibiting excellent optical and thermal properties An optical recording medium manufactured using the recording material is provided.

In order to achieve the above technical problem, the present invention firstly prepares an azo dye represented by the following Chemical Formula 1.

Synthesis Example 1

The method for producing the azo dye represented by compound A is as follows.

2.2 g (0.01 mol) of aminobenzimidazole represented by Chemical Formula 3 was dissolved in 17 mL of sulfuric acid at 0 ° C., and then cooled to −20 ° C. Slowly add a solution of 0.83 g (0.012 mol) of sodium nitrite to a small amount of water and stir for 20 to 30 minutes. When a yellow solid is formed, 1.65 g (0.01 mol) of diethylaminophenol represented by the formula (4) is added to the agitator to be coupled. After stirring for 20-30 minutes, 10 mL of ice water is added. After stirring this solution for 30 minutes, the mixture is neutralized to pH 6. When a reddish brown solid is produced, the resultant is filtered by suction, reprecipitated with alcohols, and then vacuum dried at 40 to 60 ° C. The yield is 77%. 0.3 g of the A pigment was dissolved in 10 mL of tetrafluoropropane, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer (Scinco, S-2100 / 2000). As a result, the maximum absorption wavelength (λ _max ) of the A pigment was 489 nm. ¹ H NMR (Varian, 400 MHz): CDC1 ₃ , ppm, δ 1.17 (t, 3H), δ 3.35 to 3.59 (m, 2H), δ 6.15 (s, 1H), δ 6.65 (d, 1H), δ 7.55 (d, 1H), δ 7.80 (d, 1H), δ 8.21 (d, 1H).

Synthesis Example 2

The method for producing the azo dye represented by the compound B is as follows.

After dissolving 2.3 g (0.01 mol) of the aminocarboxylic benzothiazole represented by Chemical Formula 5 in 17 mL of sulfuric acid at 0 ° C., the temperature is cooled to −20 ° C. 3.8 g of HO ₃ SONO is slowly added to the above solution and then stirred for 2 hours. When a yellow solid is formed, 20 g of ice water is added thereto, stirred for 10 minutes, and a solution dissolved in 20 mL of 1.65 g (0.01 mol) methanol of diethylaminophenol represented by Formula 4 is slowly added thereto, and the mixture is allowed to couple for 2 hours. The mixture is neutralized to pH 5-6. When a reddish brown solid is produced, the resultant is filtered by suction, reprecipitated using a 1: 1 mixture of methanol and water, and then vacuum dried at 40 to 60 ° C. Yield 63%. 0.3 g of the B pigment was dissolved in 10 mL of tetrafluoropropanol, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer. As a result, the maximum absorption wavelength (λ _max ) of the B pigment was found to be 512 nm. ¹ H NMR: DMSO. ppm. δ1.17 (t, 3H), δ3.35-3.59 (m, 2H), δ6.15 (s, 1H), δ6.65 (d, 1H), δ7.55 (d, 1H), δ7.85 (d, 1H), δ 7.95 (d, 1H), δ 8.56 (s, 1H).

Synthesis Example 3

The method for producing the azo dye represented by the compound C is as follows.

After dissolving 2.3 g (0.01 mol) of aminomethoxybenzothiazole represented by Chemical Formula 6 at 8.82 g of sulfuric acid at 0 ° C., the temperature is cooled to −20 ° C. Slowly add a solution of 0.83 g (0.012 mol) of sodium nitrite to a small amount of water and stir for 20 to 30 minutes. When a yellow solid is formed, 1.65 g (0.01 mol) of diethylaminophenol represented by Chemical Formula 4 is dissolved in methanol, and then added to the stirred solution to be coupled. After stirring for 20-30 minutes, 10 mL of ice water is added. After stirring this solution for 30 minutes, the mixture is neutralized to pH 7. When a reddish brown solid is produced, the resultant is filtered by suction, reprecipitated with alcohols, and then vacuum dried at 40 to 60 ° C. The yield is 77%. 0.3 g of the C dye was dissolved in 10 mL of tetrafluoropropanol, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer. As a result, the maximum absorption wavelength (λ _max ) of the C dye was found to be 516 nm. ¹ H NMR: CDCl ₃ , ppm, 1.17 (t, 3H), δ 3.35-3.59 (m, 2H), δ6.15 (s, 1H), δ6.42 (d, 1H), δ7.1 (d , 1H), δ 7.5 (d, 1H), δ 7.82 (d, 1H), δ 8.28 (s, 1H).

In order to achieve the above technical problem, in the present invention, an azo-based metal complex represented by Formula 2 is prepared.

Synthesis Example 4

The method for producing a nickel complex of an azo dye represented by compound A1 is as follows.

Azo dye represented by Formula 7 is Compound A prepared in Synthesis Example 1. 0.5 g of the azo dye prepared in Chemical Formula 7 was dissolved in 10 mL of methanol, and then a solution of 0.07 g of nickel acetate tetrahydrate was slowly added to 0.9 mL of methanol. After stirring for 3 hours, 20 mL of water are added. When a solid is produced, it is produced by suction filtration and vacuum drying at 60 to 80 캜. 0.3 g of the A1 dye was dissolved in 10 mL of tetrafluoropropane, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer. As a result, the maximum absorption wavelength (λ _max ) of the A1 dye was found to be 522 nm.

Synthesis Example 5

The method for producing the cobalt complex compound of the azo dye represented by compound A2 is the same as in Synthesis Example 4. Use cobalt nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the A2 dye was found to be 590 nm.

Synthesis Example 6

The method for producing a zinc complex of an azo dye represented by compound A3 is the same as in Synthesis Example 4. Use cobalt nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the A3 dye was found to be 548 nm.

Synthesis Example 7

The method for producing a copper complex of an azo dye represented by compound A4 is the same as in Synthesis Example 4. Use copper nitrate xhydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the A4 dye was found to be 550 nm.

Synthesis Example 8

The method for producing a nickel complex of an azo dye represented by compound B1 is as follows.

Azo dye represented by Formula 8 is Compound B prepared in Synthesis Example 2. 0.2 g of the azo dye prepared in Chemical Formula 8 was dissolved in 4.5 mL of methanol, and then a solution of 0.07 g of nickel acetate tetrahydrate was slowly added to 0.9 mL of methanol. After stirring for 3 hours, 20 mL of water are added. When a solid is produced, it is produced by suction filtration and vacuum drying at 60 to 80 캜. 0.3 g of the B1 dye was dissolved in 10 mL of tetrafluoropropanol, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer. As a result, the maximum absorption wavelength (λ _max ) of the B1 dye was found to be 590 nm.

Synthesis Example 9

The method for producing the cobalt complex compound of the azo dye represented by the compound B2 is the same as in Synthesis Example 8. Use cobalt nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the B2 pigment was found to be 620 nm.

Synthesis Example 10

The method for producing a zinc complex of an azo dye represented by compound B3 is the same as in Synthesis Example 8. Use cobalt nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the B3 dye was found to be 598 nm.

Synthesis Example 11

The method for producing a copper complex of an azo dye represented by compound B4 is the same as in Synthesis Example 8. Use copper nitrate hydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the B4 dye was 596 nm.

Synthesis Example 12

The method for producing a nickel complex of an azo dye represented by compound C1 is as follows.

Azo dye represented by Formula 9 is Compound C prepared in Synthesis Example 3. After dissolving 1.1 g of the azo dye of Formula 9 in 15 mL of methanol, a solution of 1.49 g of nickel acetate tetrahydrate was slowly added to 4 mL of methanol. After stirring for 3 hours, 20 mL of water are added. When a solid is produced, it is produced by suction filtration and vacuum drying at 60 to 80 캜. 0.3 g of the C1 dye was dissolved in 10 mL of tetrafluoropropanol, and then spin coated onto a substrate to form a dye layer. Subsequently, the absorption spectrum of the prepared thin film was investigated using a UV-VIS spectrophotometer. As a result, the maximum absorption wavelength (λ _max ) of the C1 dye was found to be 541 nm.

Synthesis Example 13

The method for producing the cobalt complex compound of the azo dye represented by the compound C2 is the same as in Synthesis Example 12. Use cobalt nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the C2 pigment was found to be 628 nm.

Synthesis Example 14

The method for producing a zinc complex of an azo dye represented by compound C3 is the same as in Synthesis Example 12. Use zinc nitrate hexahydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the C3 dye was found to be 517 nm.

Synthesis Example 15

The method for producing a copper complex of an azo dye represented by compound B4 is the same as in Synthesis Example 12. Use copper nitrate xhydrate instead of nickel acetate tetrahydrate. The maximum absorption wavelength (λ _max ) of the B4 dye was found to be 537 nm.

As described above, the azo dye represented by Chemical Formula 1 is not only easy to synthesize, but also has excellent synthesis yield. In addition, the azo-based metal complex represented by Formula 2 is also easy to synthesize. Therefore, when the azo-based metal complex compound represented by Chemical Formula 2 is used as the optical recording material, it is advantageous in terms of manufacturing cost of the optical recording material as compared with the case of using the conventional optical recording material.

Claims (3)

Azo metal complex represented by the following formula (2): [Formula 2] In Formula 2, X and Y are each S or N, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom (-H), a carboxylic acid group (-COOH), a methoxy group (- OCH ₃ ), M is a metal ion, Ni, Zn, Co or Cu. An optical recording medium comprising a transparent substrate having a groove and a recording layer formed on the transparent substrate and containing a dye for absorbing laser light, wherein the dye contained in the recording layer is an azo metal complex compound of the following formula (2): Optical recording medium, characterized in that: [Formula 2] In Formula 2, X and Y are each S or N, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom (-H), a carboxylic acid group (-COOH), a methoxy group (- OCH ₃ ), M is a metal ion, Ni, Zn, Co or Cu. The optical recording medium according to claim 2, wherein the azo metal complex of Formula 2 exhibits a maximum absorption at 350 to 650 nm and a refractive index of 1.8 to 2.3 in the wavelength range of 400 to 700 nm.