TWI333968B - - Google Patents

Description

1333968 Correction and replacement of April 28, 1999, invention description: [Technical field of invention] Guangyue Ί 舰 之 靖 财 , 特 特 特 特 特 特 特 特 特 特 特 - - - - - - - - - - - - - - - - - - - - - - Application of the district. [Prior Art] <§*, DlSk; CD) is a storage medium that uses light to record and read. You can have a small amount of noise, small life, long life, small size, and easy to carry. Change the second? f low 1 and read * can be affected by surface dust, etc., its wide range of use can be recorded and read shouting including text, graphics, video, sound, video and motion 要 to SKii music, movies, The video (four) of the game has become the computer information of today.

= Designing new molecular pigments by using semiconductor laser light on an optical disc to produce different uv's due to different optical recording medium dyes. Future dye development trends are toward higher density and shorter wavelengths, while HD-DVD-R (405/410 nm; recording density 15-30 GB), used in CD-R (780 nm; recording density 700 MB) and DVD- R (635/655nm; records similar to *5 long dyes, the most important property requirements of which are selected, the dyeing properties should have the following characteristics: clear thermal decomposition threshold, higher rate, and stable recording Solution (4) π Μ g The color molecular structure of HD-DVD-R (according to the laser wavelength of 4〇5nm) ί, in the patent published by f, such as China's No. 0931彳3527 Recording material =", No. 93137842 "Materials for optical recording media" and European patent ep1149873, the cyanine series of dyes, and the second is China's No. 9113797 媒体 media dye, high-density blue light recording media And its manufacturing method", No. 91138145 咼 density optical disc and its compound for recording" and the German patent DE1〇1〇9243 disclosed in the enone series of dyes, the three are as in China 094126297 Antipyrine azo metal complex dye and It is equivalent to the application of the optical data recording, the dye composition of the metal-comp丨ex series disclosed in Japanese Patent No. JP2001271001, and the US Patent No. US20030138728, the four of which are, for example, US Patent No. 20030091931, US20040259031 and Japan. The composition of the heterocyclic (Heterocyde) series of dyes disclosed in JP200301986 and the like, and the five of them are the squa "丨丨" disclosed in "Application of the use of a prismatic acid in the optical layer for optical data recording", No. 94118〇98. Um) series of dyes. Among them, the cyanine series dyes have been developed since the CD-R, and have been developed by the DVD-R, and have continued to play a role in the recording layer materials of optical storage media. The trick is that such dyes have the advantages of easy synthesis, low cost, good solubility in organic solvents, and easy processing of the disc process." 1333968

Correction and replacement on April 28, 1999 [Invention content] Application of enamel layer material

-s χζ

Where the benzene of the [4,5], [5,6] or [6,7] position of the A (1) lion part is in the [2, 2] or [3, 4] position of the ° part Connected benzocyclopurine or 1 dentate dentate group attached to any co-light double bond C (halc〇, C!-C4 calcination (^l), CrC4 alkoxy (tetra) koxy), deterministic (n丨) Tro), a second compound of an amine group (〇1 old 丨|^丨3 anthraquinone 110) or a hydrogen group; R1 and R2^ independently represent a CrC8 alkyl group (a|k丨) or benzyl (benzyl); R3 and R4 independently of each other represent a Ci_C8 alkyl (8) ky |) or benzyl; X- is an anion.

B η is S. [Embodiment] Hereinafter, the detailed technical content of the present invention will be described with reference to the drawings. In summary, the pyrrole cyanine dyes provided by the present invention are prepared by condensation and displacement reactions of an onium salt and an aldehyde pyrrole derivative, and the reaction formula is:

That is, the condensation of the sulfonium salt of the chemical formula (2) with the aldehyde pyrrole of the chemical formula (3) is carried out, and the ion exchange reaction is continued after the reaction. (ion-exchange), thereby obtaining a high yield of the pyrrole-containing cyanine dye 〇1333968 having the chemical structure formula (1)

(2c) @d) (3a) (2a) (2b) Amendment of April 28, 1999, when the condensation is carried out, 0.01 mol of + salt (2a_d) and 0.02 m 1-methyl-2· ligated batch (3a) was placed in 30 ml of dimethyl 'acetamide, while adding a few drops of hexahydropyridine and glacial acetic acid as a catalyst, heating to 80 ° C for 12 hours . The reaction mixture was then poured into 1 mL of pure water and extracted three times with 1 〇〇m|diqi methane to obtain an intermediate product of & color solution. 'The intermediate product obtained after the completion of the condensation reaction is subjected to ion displacement reaction (j〇n_exchange)', that is, the intermediate product is added to 100 ml of 1〇〇/0 hexafluorodisc acid solution, and rapidly stirred at room temperature. After 30 minutes', then the layer was drained and the water layer was removed. Then the 'replacement step was repeated twice to ensure that the reaction was complete. Then add anhydrous magnesium sulfate to remove the water. After the $, get the 'sticky liquid, re-re- Add 15Qm of alcohol, heat to 5〇tg K瞎 gradually down to room temperature and stir for 3 hours, then filter and dry to obtain high yield (human 1' hit rate 65-85%) containing pyrrole cyanine dye (1a- d) 'Chemical structure as shown below picture Ai Xiang ~ closed 1333968 _ • . April 28, 2017 revised replacement

(1a) (1b) (1c) (1d) The result is measured by ultraviolet-visible spectrometer (UV-Vis) in a ratio of spheroidal cyanine dye (1a-d) dissolved in methanol (concentration: 5 ppm). As shown in the following table: Maximum absorption wavelength of pyrrole cyanine dye 〇ad) Table Maximum absorption wavelength (Xmax.) 8 (l/mol.cm) 1a 478nm 6·15”0Λ7 1b 484nm 5.93*10Λ7 1c 494nm 5.41 *10Λ7 1d 502nm 4.56*10Λ7 This contains "pyrazine cyanine dye (1a-d)' dissolved in tetrafluoropropanol (concentration 1〇/〇), spin-coated, after drying on polycarbonate sheet The results of the solid-state film with UV-Vis are as follows: Synthesis example Maximum absorption wavelength (Xmax.) AO/A1 ratio ※ 1a 458nm 0.507 1b 492nm 0.143 1c 508nm 0.204 1d 518nm 0.228 1333968

※ Among them, AO is the absorbance of the solid film at a wavelength of 405 nm; A1 is the absorbance of the chiral thin amine at the maximum absorption wavelength. The net result is that such a pyrrole cyanine dye has an appropriate optical absorption wavelength, and The solubility in fluoropropanol is good for the application of the wind storage medium recording layer material suitable for the blue laser light region (about 405 nm laser wavelength). The results of the thermogravimetric analyzer (TGA) measured by the pyrrole cyanine dye (1a-d) are shown in the following table:

Synthesis Example Initial Cracking Temperature (Tid) Weight Loss Rate ^ (4) Cracking Rate ~ (sm/t:)*2 1a 256.22V 73.7% 0.94%/〇C ' 1b 223.46〇C 72.8% 0.86%/〇C ' 1c 252.58〇C 74.7% 1.07%/°C id Λ iL . 219.83〇C 70.5% 0.52%/〇C percentage value*2 The reduction rate is expressed as a sample in a thermogravimetric analyzer, mainly degrading the mass and heating Celsius per degree. Weight loss rate' This result shows that this kind of pyrrole-containing cyanine dye has an initial pyrolysis temperature in the temperature range required for the material of the optical storage medium recording layer, and has an appropriate weight loss rate and a high cracking rate, and is suitable for the blue laser light region ( Optical storage medium recording layer material of about 405 nm laser wavelength) is used for low-speed to high-speed reading and writing. _ [Simplified illustration of the illustration] The first figure is the ultraviolet light and visible light absorption spectrum of the dye (1a) in the synthesis example of the present invention. The figure is the ultraviolet light of the solid film of the dye (1a) of the synthesis example of the present invention - The third chart of the visible light absorption spectrum is the result of the thermogravimetric analysis curve of the dye (1a) of the synthesis example of the present invention.

Claims (1)

Amendment and patent application scope on April 28, 1999: A cationic pyrrole cyanine dye as shown in chemical formula (1), which can be used in the recording layer of optical storage medium for blue laser light region (laser wavelength of 405 nm) Use of materials s represents a halo, a G-α alkyl group, a Ci-Ci alkoxy group, a nitro group, and a diakiry lamino group attached to the fluorene moiety benzene ring. Or a hydrogen group; the private R2 independently of each other represents a q-Co alkyl or benzyl; 匕 and R4 are independently of each other and represent a qG alkyl or benzyl group ( Benzyl); X- is an anion. A cation-containing pyrrole cyanine dye represented by the chemical formula (2), which can be used for a recording layer material of an optical storage medium for a blue laser region (a laser wavelength of 405 nm) S represents a halo, OC4 alkyl, GG, alkoxy, nitr〇, dialkylamino or hydrogen group attached to the pyrrole; Respectively independent of each other - a Ci_C8 alkyl or benzyl; $ and 仏, which independently represent a Ci_G alkyl (alk丨) or benzyl (ben U; X- is an anion . The use of the cation-containing pirocyanine dye as shown in the figure can be used for the recording layer material of the optical storage medium for the blue laser region (the laser wavelength of 4^m) r3 r4 X r2 where U of the A (3) part , 5], [5, 6] or [6, 7] position connected stupid ring 1-333968 April 28, 1999 Correction replacement S represents a halogen (halo), G connected on 11 -C4 alkyl, (VC4 alkoxy, nitro, dialkylamino or hydrogen), and each other independently represents a G-C8 alkyl (alkyl Or benzyl; ^ and hydrazine independently of each other to represent an alkyl or benzyl group; X- is an anion. 4. A cation-containing pyrrole as shown in formula (4) Cyanine dye, which can be used for the recording layer material of optical storage medium for blue laser light region (laser wavelength of 405 nm) R3 R4 X (4) Represents a benzo ring (Benzo) attached at the [2,3] or [3,4] position of the β-ha ha moiety; S represents a halo group attached to the quinone moiety benzene ring (halo) , alkyl, Ci-Ci alkoxy, nitro, dialkylamino or hydrogen; 吣 and R2 are independent of each other to represent a GG alkyl (aikyl) Or benzyl; R3 and R4 are mutually independent of each other to represent a CK: 8 alkyl or benzvi X- is an anion. ^ Two kinds of recording layers that can be used for optical storage media in the blue laser region (the laser wavelength of 4〇5nm), which are 5. (5)-(4) of the chemical formulas defined in items 1, 2, 3 or 4. 1333968 _ 'Amended on April 28, 1999, the replacement of the seven, the designated representative map: (a) The representative representative of the case is: Figure (1). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Wherein A represents a benzo ring (Benzo) attached at the [4, 5], [5, 6] or [6, 7] position of the oxime moiety; B represents a [2, 2] moiety in the oxime moiety Or a benzo ring attached at the [3,4] position; η is 0 or 1 S represents a halo, alkyl, CrC4 alkoxy group attached to any conjugated double bond C Alkoxy, nitro, dialkylamino or argon; Ri and R2 mutually independently represent a CrCe alkyl or benzyl; R3 and R4 Independent of each other represents a CtC8 alkyl or benzyl; X- is an anion.