TWI382060B - (E, g) type cationic cyanine dyes - Google Patents

Description

(e,g) type cationic cyanine dye

The present invention relates to a (e, g) type cationic cyanine dye which is a high sensitivity recording layer material of a high power red laser wavelength optical storage medium.

Compact Disk (CD) is a storage medium that uses light for recording and reading. It has high recording density (large capacity), small noise, long life, small size, easy to carry, freely replaceable, and low cost. It can be used in a wide range of applications, such as text, graphics, video, sound, video and animation, not only has it been affected by surface dust, but also has become a music, movie, and game. Audio-visual consumer goods have become the most important storage media for computer information today.

Designing new molecular pigments by focusing on semiconductor laser light on an optical disk drive and different absorption wavelengths due to different optical recording medium dyes. The most commonly used optical recording media dyes on the market are the Cyanine series, the Azo series and other heterocyclic series, and the cyanine series dyes continue to be used in the recording layer materials of optical storage media. It plays a pivotal role, and its characteristics are that it has the advantages of easy synthesis, low cost, good solubility in organic solvents, and easy processing of the disc process.

The ( e,g ) type cationic cyanine dye provided as the high-sensitivity recording layer material of the high-speed red laser wavelength optical storage medium is as shown in the chemical formula (1):

Wherein: the left benzo ring type indol e (e -Benzoindole) represents a connected benzo ring (benzo) on the [4,5] position of the indole primary structure (or position e); g type rightward Benzocycloindole ( g- Benzoindole) represents a benzo ring attached to the [6,7] position (or g position) of the main structure of the ruthenium; R ¹ and R ² are independent of each other. Represents a C ₁ -C ₈ alkyl group; R ³ and R ⁴ independently of each other represent a C ₁ -C ₈ alkyl group; R ⁵ and R ^{6 are} joined together to form a 3-6 member ring ; R ⁷ is one of a group selected from the group consisting of hydrogen, alkyl, alkoxy, halogen, nitro, substituted amine; X ^- is an anion.

The maximum absorption wavelength of the general cyan dye is the shortest ( e,e ) type (λmax.~580nm), the ( e,g ) type is the second (λmax.~590nm), and the ( g,g ) type is the longest (λmax. ~600nm) as shown in chemical formulas (2) to (4).

The ( e,g ) type cationic cyanine dye provided by the invention has a longer absorption wavelength in the spectral analysis, is at 590 nm, has good thermochemical properties, and has good solubility, and the solid film formed by spin coating is red. The laser wavelength has a high and appropriate absorbance value, so it has a high sensitivity to absorb the laser light energy and convert it into heat energy, and promote thermal cracking to form a pit, thereby achieving the purpose of high-speed recording.

Please refer to FIG. 1 to FIG. 3, and the following is the (e, g) type cationic cyanine dye (( e, g )- as the high-sensitivity recording layer material of the high-speed red laser wavelength optical storage medium. The description of the embodiment of TYPE CYANINE DYES) includes: such as a chemical reaction formula: As shown, the present invention firstly obtains an intermediate (7) by condensation reaction of the g -type benzocyclononane salt chemical formula (5) with the benzhydrin formula (6); further, the intermediate (7) is obtained. Further, the condensation reaction is further carried out with the chemical formula (8) of the e -benzophenone oxime salt; finally, ion-exchange reaction (ion-exchange) is carried out to obtain a high yield ( e, g ) type cationic cyanine dye chemical formula (1). .

[Examples]

The detailed description of the synthesis by the above-mentioned chemical reaction formula is described, and the relevant characteristics of the optical recording medium dye are specified, and of course, the scope of the claimed invention is not limited thereto. The above-mentioned synthesis method is only a concrete and feasible exemplary technical content.

Specifically, the chemical formulas of the g -type benzocyclophosphonium salt (5) and the e -type benzocyclononane salt (8a-d) used in the present examples are as follows:

Step 1: Perform a condensation reaction, placing 0.1 mol of g -benzophenone quinone (5) and 0.15 mol of benzamidine (6) in 150 ml of isopropanol and heating to 100 ° C. Stirring was carried out for 6 hours under reflux. Then, it was filtered to dryness at room temperature, and dried to obtain intermediate (7) in a yield of about 82%.

Step 2: further carry out the condensation reaction, and 0.02 mol of e -benzophenone sulfonium salt (8a-d) and 0.02 mol of intermediate (7) were placed in 75 ml of dichloromethane, respectively, and dropped into 2.8 g of three After ethylamine and 2.8 g of acetic anhydride, the mixture was reacted at 40 ° C for 5 hours to obtain a purple solution.

Step 3: Perform ion-exchange (ion-exchange), add the above purple solution to 80 g of 10% sodium perchlorate (or potassium hexafluorophosphate) aqueous solution, stir rapidly at room temperature for 30 minutes, and then stand for stratification. After the water layer is omitted, repeat the above-mentioned displacement reaction step twice to ensure the reaction is complete, then add anhydrous magnesium sulfate to remove water, filter and concentrate to obtain the viscous liquid, and then add 150 ml of isopropanol and heat to 50 ° C to stir. After 1 hour, and then gradually reduced to room temperature and stirred for 3 hours, filtered and dried to obtain a high yield (total two-step total yield of 63-80%) of ( e,g ) type cationic cyanine dye (1a-d), The chemical formula is shown below:

The ( e,e ) type cyanine dye (9-10) of the comparative example has the chemical formula shown below:

The above-mentioned ( e, g ) type cationic cyanine dye (1a-d) and the comparative example were dissolved in methanol (concentration: 5 ppm), and the results were measured by ultraviolet-visible spectrometer (UV-Vis) as shown in the following table: UV -Vis maximum absorption wavelength table

The above-mentioned ( e,g ) type cationic cyanine dye (1a-d) and a comparative example are dissolved in tetrafluoropropanol (concentration: 1%), spin-coated on a polycarbonate sheet, and dried to form a solid film. The results measured by UV-Vis spectrometer (UV-Vis) are shown in the following table: Solid-state film UV-Vis maximum absorption wavelength table

This result shows that such ( e,g ) type cationic cyanine dye has a long optical absorption wavelength and good solubility in tetrafluoropropanol, and is suitable for red laser light region (laser wavelength of 600-680 nm). Optical storage media recording layer material for higher sensitivity applications.

The solid state film is tested for weathering stability by placing the test piece in a high temperature and high humidity weathering tester (the system environment is set to a relative humidity of 80% and a temperature of 60 ° C), and the UV-Vis is measured after 150 hours. The absorbance of the test piece at 635 nm has a weather stability of S = A ₁₅₀ /A ₀ (where A ₀ is the original absorbance value and A ₁₅₀ is the absorbance of 150 hours). The results of the measurement are shown in the following table:

This result shows that such ( e, g ) type cyanine dye has high weather stability.

The above ( e, g ) type cationic cyanine dye (1a-d) and the comparative example, the results measured by a thermogravimetric analyzer (TGA) are shown in the following table: initial pyrolysis temperature table

This result shows that such ( e,g ) type cationic cyanine dye has an initial pyrolysis temperature in the temperature range required for the optical storage medium recording layer material, and has a high cracking rate, and is suitable for a red laser light region (600-680 nm). Laser wavelength recording of optical storage media recording layer materials for high-speed read and write applications.

The above description of the embodiments is intended to be illustrative of the invention and is not intended to limit the scope of the invention.

From the above detailed description, it will be apparent to those skilled in the art that the present invention can achieve the foregoing objects and is in accordance with the provisions of the Patent Law.

Figure 1 is a diagram showing the ultraviolet-visible absorption spectrum of the dye (1a) in a methanol solution according to an embodiment of the present invention.

2 is an ultraviolet light of a solid film of the dye (1a) according to an embodiment of the present invention - See light absorption spectrum

Figure 3 is a graph showing the results of thermogravimetric analysis of the dye (1a) of the embodiment of the present invention.

Claims (3)

An ( e,g ) type cationic cyanine dye as shown in the chemical formula (1), which can be used for a recording layer material of an optical storage medium of a red laser light region (laser wavelength of 600-680 nm), E leftward indole ring type benzo (e -Benzoindole) represents a connected benzo ring (benzo) on the [4,5] position of the indole primary structure (or position e); g type benzo rightward G- Benzoindole represents a benzo ring attached to the [6,7] position (or g position) of the main structure of the ruthenium; R ¹ and R ² are independent of each other. C ₁ -C ₈ alkyl; R ³ and R ⁴ are mutually independent of each other to represent a C ₁ -C ₈ alkyl group; R ⁵ and R ^{6 are} bonded together to form a 3-6 member ring; ⁷ is selected from hydrogen, alkyl, alkoxy, halo, nitro, wherein one of the groups substituted alkyl group of the group; X ^- is an anion. A recording layer of an optical storage medium of a red laser light region (laser wavelength of 600-680 nm) comprising a cationic cyanine dye compound of the formula ( e, g ) of the formula (1) as defined in claim 1 . A material for an optical storage medium recording layer of a red laser light region (laser wavelength of 600-680 nm) comprising a ( e, g ) type cationic cyanine of the chemical formula (1) as defined in claim 1 Dye compound.