TW201035080A - Otical recording material - Google Patents

Abstract

To provide an optical recording material containing a cyanine compound in accordance with an optical recording medium which can cope with high speed recording. The optical recording material is used in the optical recording layer of the optical recording medium in which the layer is formed on a substrate and contains a compound expressed by formula (I) or formula (II) (the ring A and the ring B are each a benzene or naphthalene ring which can have a substituent; R1 is a 1-4C alkyl group; R2 and R3 are each a 1-4C alkyl group, a benzyl group, or a group forming a 3-4-membered ring by being connected; X is a hydrogen atom, a halogen atom, a 1-4C alkyl group, a phenyl group which can have a substituent, a benzyl group which can have a substituent, or a cyano group; Y1 and Y2 are independently an organic group; An m is an m-valent anion; m is 1 or 2; and (p) is a coefficient keeping the charge neutral).

Description

201035080 VI. Description of the Invention: [Technical Field] The present invention relates to an optical recording material used in an optical recording medium for recording information by using a thermal information image generated by a laser or the like, and more specifically, An optical recording material used in an optical recording medium having high-density optical recording and playback by a laser having a wavelength of visible light and a near-infrared region and a low-energy laser. [Prior Art] The optical recording medium has been popularized because it generally has a large feature such as a large memory capacity and can be recorded or played without contact. WORM, (3) Rhyme DVD-R and other recordable optical discs, which can concentrate the laser light on a small area of the optical recording layer, 'change the characteristics of the optical recording layer, record' and play according to the difference between the amount of reflected light and the unrecorded portion. . In the optical recording layer of an optical recording medium typified by an optical disk, it is easy to form an optical recording layer, and an organic dye can be used, and the compound of the cyanine-based compound has high sensitivity and can be widely studied in response to high speed. Now, in the above-mentioned optical disc, the wavelength of the semiconductor laser used for recording and playback is CD-R of 750 to 83 〇 nm, DVD-R is 620 to 690 nm, and higher density of 6 〇〇 nm or less. The disc is also under development. In the case of the cyanine-based compound of the above-mentioned optical disk, for example, JP-A-59-55795, JP-A-5-173282, JP-A-Heisei No. Hei. No. Hei. 〇 〇 695 、 特 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 It has been reported in the bulletin No. 289335 and the special issue _ Yun 933. However, the above-mentioned cyanine compounds have problems in thermal decomposition characteristics. High-speed recording requires small thermal interference. As an optical recording material, it is suitable for those with low decomposition temperature and rapid thermal decomposition. However, the various cyanine compounds reported above are insufficient in this respect. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an optical recording material containing an anthocyanin-based compound suitable for use in an optical recording medium compatible with high-speed recording. The present inventors have found that an anthocyanin having a specific molecular structure can be found by realizing the sensitivity to high-speed recording and considering the optimization of the thermal decomposition behavior and the optimization of the absorption wavelength. The compound can solve the above problems, and thus the present invention has been achieved. The present invention is based on the above findings and provides an optical recording material characterized by having a compound represented by the following formula (I) or (II), and an optical recording medium characterized by forming the optical body on the substrate. Record the film of the material.

(wherein ring A and ring B represent a stupid ring or an anthracene ring which may have a substituent; R1 represents an alkyl group having 1 to 4 carbon atoms; and R2 and han 3 represent an alkyl group having a carbon number of 44, fluorenyl or 148536 .doc 201035080 is bonded to each other to form a group of 3 to 6 membered rings; X represents a hydrogen atom, a halogen atom, a carbon number of 1 to 4, a phenyl group which may have a substituent, a benzyl group or a cyano group which may have a substituent Y1 and Y2 each independently represent an organic group; Anm· represents an anion of m valence and m represents an integer of 1 or 2; and p represents a coefficient which maintains neutrality of charge). The present invention provides an optical recording material containing an anthocyanine compound suitable for use in an optical recording medium capable of high speed recording. [Embodiment] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The anthocyanin-based compound represented by the above formula (I) or (II) of the present invention is characterized in that it has a mercapto group at a specific site and has a lower decomposition temperature than other indigo-based compounds used for an optical recording material. And the absorption wavelength is optimal. In the above-mentioned general formula (1) and/or according to the present invention, it is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. (11) A general formula of a cyanine compound which is a part of the concept of a compound. In these reports, although an aralkyl group is described as a substituent bonded to the third position of the anthracene skeleton, the radical is not specifically illustrated, and the introduction of a mercapto or aralkyl group into the flower is also not described. The method of the lanthanide compound and the effect of the sulfhydryl group. In the general formula (I) or (II), the substituents of the benzene ring or the ring which may have a substituent represented by the ring A and the ring B may be fluorine, chlorine, indigo, etc., methyl, B. Propyl, isopropyl, butyl, t-butyl tert-butyl, isobutyl 148536.doc 201035080 base, pentyl, isopentyl, third amyl, hexyl, cyclohexyl, heptyl, isethylene Alkyl groups such as benzyl, tert-heptyl, n-octyl, isooctyl, trioctyl and 2-ethylhexyl, phenyl, naphthyl, 2-nonylphenyl, 3-phenylphenyl, 4-nonylbenzene An aryl group such as 4-vinylphenyl or 3-isopropylphenyl, an anthracenyloxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group and a third butoxy group. An alkoxy group such as an alkoxy group, an anthracenethio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a second butylthio group or a third butylthio group, a nitro group and an amine group. Ri represents an alkyl group having a hindrance of 1 to 4, and examples thereof include an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, and an isobutyl group. The alkyl group having a carbon number of 1 to 4 represented by R2AR3 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, an isobutyl group or the like, and the rulers 2 and 113 are linked. And the 3~6 member ring formed, for example, cyclopropene_1, bis-diyl, cyclobutane 4,^diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3-dimethylcyclobutane -M-diyl, cyclopentyl-1,1-diyl, cyclohexa-1,1-diyl, tetrahydrofuran-4,4-diyl, thiopyran-4,4-diyl, hexahydropyridine -4,4-diyl, N-substituted hexahydropyridine _4,4-diyl, morphine-2,2-diyl, morpholine-3,3-diyl, N-substituted morphine _2,2_diyl and N_substituted morpholine-3,3-diyl and the like, wherein the N-substituent is as exemplified at ring A. Further, the halogen atom represented by X is, for example, fluorine, gas, bromine or iodine, or an alkyl group having 1 to 4 carbon atoms, and is, for example, a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a second group. The substituents of the butyl group and the isobutyl group, the phenyl group and the benzyl group are as defined at the ring A. And the organic group represented by ¥2 is not particularly limited and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, a pentyl group, Isoamyl, third amyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, heptyl, isoheptyl, 148536.doc 201035080 third heptyl, n-octyl, isooctyl, Third octyl and 2-ethylhexyl, fluorenyl, isodecyl, fluorenyl, decyl, thirteenth, fourteen, fifteen, fifteen, sixteen, and seventeen An octadecyl group, an alkyl group, a vinyl group, a methyl group, a 2-f-ethyl group, an acryl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, Alkenyl groups such as decenyl, pentadecenyl and 1-phenylpropan-3-yl, phenyl, naphthyl, 2-tolyl, 3-tolyl, 4-tolyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4- Octyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-xylyl, 2,4-dimethylphenyl, 2,5-di An alkaryl group such as phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl or cyclohexylphenyl, a benzyl group, An aralkyl group such as phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, trityl, styryl or phenylallyl, and the alkyl group is inserted as an ether bond or a thioether bond, For example, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, oxiranyloxyethyl, 3-methoxylated a group, a 2-phenoxyethyl group, a 2-methylthioethyl group, a 2-phenylthioethyl group, etc., and further, these groups may be substituted by an alkoxy group, an alkenyl group, a nitro group, a cyano group or a halogen atom. . Further, the anion represented by the above-mentioned Anm-, for example, a valence anion such as a gas anion 'bromine anion, an iodine anion, and a fluoride anion, a peroxy acid anion, a gas acid anion, a thiocyanate anion, a phosphorus hexafluoride Anionic anion, ammonium hexafluoride anion and boron tetrafluoride anion, organic sulfonate anion such as sulfonate anion, toluenesulfonic acid anion and trifluorosulfonate anion, octyl phosphate anion, dodecyl phosphate Anion, 18 148536.doc 201035080 Burning base acid anion 'phenyl benzene acid anion, sulfhydryl anion, and bismuth (4,6-second butytyl) ruthenium anion and other organic squama anions Etc.; a divalent person such as a phthalic acid anion and a hydrazine acid anion, etc., may also use a quenching anion having a function of de-exciting (activating) the active molecule in an excited state, as needed. Or a metallocene compound such as ferr〇Cene or lute〇cene having an anionic group such as a carboxyl group or a phosphonic acid or a sulfonic acid; Anions. The above-mentioned sudden-stop anion is, for example, represented by the following general formula (A) or (B), for example, JP-A-60-234892, JP-A-5-43814, JP-A-6-239028, and JP-A 9-39988 An anion described in, for example, Japanese Laid-Open Patent Publication No. Hei 10-45767.

(wherein 'Μ denotes a nickel atom or a copper atom; r4 and 5 represent a halogen atom, an alkyl group having a hindrance of 1 to 8, an aryl group having a carbon number of 6 to 30 or a -S〇2-Z group; and Ζ represents an alkyl group; An aryl group, a dialkylamino group, a diarylamino group, a hexahydro-b-b-pyridyl group or a ruthenium-f-linyl group which may be substituted by a dentate atom; a and b each represent 〇~4; R6, R7, R8 and R9 Each independently represents an alkyl group, an alkylphenyl group, an alkoxyphenyl group or a halogenated phenyl group). In the above formula (I) or (II), 'with respect to X, a hydrogen atom is preferred (because of thermal decomposition characteristics, especially thermal decomposition temperature, suitable for high-speed recording); and, regarding 148536.doc 201035080 Y1, with R1 The same basis is preferred (due to fewer manufacturing steps and lower cost). Further, it is preferable that R2 and R3 are 3 to 6 member rings formed by being joined to each other (the UV absorption is particularly suitable for recording the laser light used). Specific examples of the compound represented by the above formula (I) of the present invention are shown in the following compounds Nos. 1 to 51. Further, the examples shown below are represented by an anionic anthocyanin cation.

148536.doc -9- 201035080

148536.doc -10- 201035080

148536.doc -11 - 201035080 Further, the compound represented by the above formula (π) is, for example, a compound of the above-exemplified compound Νο·1 to 51 having a polymethylidene (p〇iymethine) chain of 5 carbon atoms. The cyanine compound represented by the above formula (1) or (11) according to the present invention is not limited by the production method thereof. The production method of these anthocyanin-based compounds can be carried out, for example, in the same manner as in the case of hydrazine. Further, in the case where R1 and Y1 are different from each other, it is possible to synthesize ¥1 into a ruthenium compound, and use it as a raw material, and manufacture it in the same manner as the following.

(wherein '% A, ring B, W, R2, R3, χ, γ2, Anm- and p are the same as the above formula (I) or (II), and D represents a halogen or a substituted fluorenyloxy group.) "Deletion of halogen such as gas, bromine or iodine, substituted sulfomethoxy group such as benzoquinone oxy, 4 _ phenyl alcohol or benzene decyloxy. 148536.doc -12 - 201035080 上述 The above-described anthocyanine compound which is an optical recording material of the present invention is not particularly limited as long as it can be applied to an optical recording layer of an optical recording medium, and is generally not limited. It is possible to use an ether alcohol such as a lower alcohol such as methanol or ethanol, a methyl cellosolve, an ethyl cellosolve, a butyl cellosolve or a butyl dipolyglycol ether, acetone or mercaptoethyl hydrazine. , methyl isobutyl hydrazine, cyclohexyl yl and dipropyl alcohol, etc., acetonitrile acetate, vinegar acetate and methoxyacetic acid vinegar, 2,2,3,3_tetrapropanol A solution of a gasification such as a hydrocarbon such as benzene, toluene or xylene, or an organic solvent such as a chlorinated hydrocarbon such as a gas, a dichloroethane or a chloroform, by a shaft coating, spraying or dipping A fish coating method applied to a substrate, etc. Other methods, such as steaming and spattering, etc. The thickness of the optical recording layer is usually 0.001 to 10/zm, and 0.01 to 5 Å. The range is preferred. Further, when the optical recording layer of the optical recording medium contains the optical recording material of the present invention, it is preferably used in an amount of 50 to 100% by weight based on the optical recording layer. Further, in addition to the optical recording material of the present invention, the above-mentioned optical recording layer may be used as an optical recording layer compound such as an anthocyanin compound, an azo compound or a glare compound, as needed; , polyester, polystyrene or resin with carbonate; and may contain surfactant, antistatic agent, slip agent, flame retardant, hindered amine (hindered _ne), etc., ferrocene scavenger, ferrocene A pore formation accelerator such as a derivative, a dispersant, an oxidation preventive agent, a crosslinking agent, or a light resistance imparting agent. Furthermore, the optical reading layer may also contain an aromatic nitroso compound, an aminium compound, or an iminium compound as a single stop oxygen 148536.doc -13· 201035080. , a sulfoximine compound or a transition metal chelate compound. The amount of use thereof is preferably 5% to 5% by weight of the optical recording layer. The base material of the optical recording layer is not particularly limited as long as it is substantially transparent to the input (recording) light and the output (playback) light, and for example, polymethyl methacrylate or poly can be used. A resin such as ethylene terephthalate or polycarbonate, or glass. Further, the shape may be any shape such as a film shape, a cylindrical shape, a belt shape or a sheet shape depending on the application. Further, the optical recording layer may be formed of gold, silver, aluminum, copper, or the like by a vapor deposition method or a sputtering method, or may be formed by an acrylic resin or an ultraviolet curable resin. Floor. The optical recording material of the present invention is suitable for use in an optical recording medium using a semiconductor laser for recording and playback, and is particularly preferably a high-speed recording type optical disk or a DVD-R optical disk. Hereinafter, the present invention will be described in more detail by way of Production Examples, Production Examples, Evaluation Examples and Examples. However, the present invention is not limited by the following examples and the like. [Production Example 1] (Production of Intermediate Compound A) 4-methylphenylphosphonium hydrochloride 39.7S and 117.2 g of ethanol were added to a reaction flask which had been replaced with nitrogen, and the mixture was heated under nitrogen flow at 70 ° C (note that the heat was generated). In the case, 40.8 g of 3-phenethylmethyl ketone was added dropwise. Further, a 35% hydrochloric acid aqueous solution of 114.7 L was added dropwise and refluxed for 2 hours. After cooling, toluene 5008 and water 500 liters were added, and a 50% aqueous sodium hydroxide solution was added thereto to adjust to pH 8 or higher, and then the oil was separated. The oil phase was washed three times with warm water 5 〇〇g to carry out dehydration and desolvation. The residue obtained by 148536.doc -14·201035080 was crystallized with 117.2 g of ethanol, and crystallized therefrom, and dried under vacuum at 80 ° C to obtain 35 6 g of white crystals (yield 6 〇 8%). 11.8 g of the obtained white crystal, 28.4 g of methyl iodide and 19.6 g of decyl alcohol were placed in a reaction flask, and reacted in an autoclave at 10 (TC for 5 hours. After the solvent was removed, 40 g of ethyl acetate was added and refluxed 30). After cooling to room temperature, the crystals were taken and vacuum-dried at 80 ° C to obtain 11.4 g of a yellow crystal of the intermediate a (yield 58.3%). [Production Example 2] (Production of Intermediate Compound B) Adding 4 g 曱 曱 曱 3 3 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气After refluxing for 1 hour, 5.9 g of sulfuric acid was added dropwise and refluxed for 2 hours. After cooling, 2 g of toluene and 2 g of water were added, and then 50% aqueous sodium hydroxide solution was added to adjust to pH 8 or higher. The oil phase was separated. The oil phase was washed three times with warm water 200 g to carry out dehydration and desolvation. The obtained residue was crystallized with 100 g of toluene, crystallized by filtration, and vacuum dried at 80 ° C to obtain white crystal 25.4. g (yield 50.5%), white crystals obtained 10. lg, bismuth iodide 28.4 g and furfuryl alcohol 19.6 g The reaction flask was placed in a reaction flask and reacted in an autoclave at 100 ° C for 5 hours. After the solvent was removed, 32.0 g of ethyl acetate was added and refluxed for 30 minutes. After cooling to room temperature, the crystal was filtered and vacuumed at 80 ° C. After drying, 9-5 g (yield 58.3%) of the yellow crystals of Intermediate B were obtained. [Production Example 3] (Production of Intermediate Compound C) 2-mercaptopurine 79.1 g was added to a reaction flask which had been replaced with nitrogen. And 274.1 g of ethanol, under nitrogen flow, at 8X: 88.9 g of 3-phenethyl decyl ketone was added dropwise. 148536.doc •15- 201035080 After stirring for 30 minutes, pay attention to the heat, while dropping 49 g of sulfuric acid, reflux 1 hour. After cooling, add hydrazine Benzene l〇〇〇g and water l〇〇〇g, add 50% aqueous sodium hydroxide solution to adjust pH to above 8 and then carry out oil-water separation. Wash the oil phase with warm water 500g three times. Dehydration and desolvation of the solvent were carried out, and the obtained residue was crystallized from 137 g of toluene, and crystallized by filtration to obtain crystals at 8 〇 ((: vacuum drying) gave 72.4 g of white crystals (yield 53.4%). 13.6 g of white crystals, 28.4 g of deuterated methyl group and 21.4 g of methanol were added to the reaction flask in an autoclave. The reaction was carried out for 15 hours at 1 ° C. After the solvent was removed, crystallization was carried out using a mixed solvent of 100 g of ethyl acetate and 6.0 g of decyl alcohol. The crystals were collected by filtration and dried under vacuum at 14 ° C to obtain intermediate C. The crude crystals (HPLC purity: 60%) were 6.9 g (yield: 32.3%). [Production Example 4] (Production of Intermediate Compound D) 157 g of phenyl sulfonate and ethanol were added to a reaction flask which had been replaced with nitrogen. 1 g, 3 7-phenethyl decyl ketone 1 7 8 g was added dropwise under a nitrogen stream at 70 ° C (note the heating). Further, 4.9 g of sulfuric acid was added dropwise and refluxed for 8 hours. After cooling, 250 g of toluene and 300 g of warm water were added, and then a 50% aqueous sodium hydroxide solution was added to adjust to pH 8 or higher, followed by oil-water separation. The oil phase was washed three times with warm water 3 〇〇g to carry out dehydration and desolvation. The obtained residue was crystallized from ethanol 300 g; crystallized at 8 〇. The hydrazine was vacuum dried to obtain 116.1 g of a white crystal (yield: 52 5%). The obtained white crystals 22. lg, 56.8 g of decyl iodide and 37.7 g of decyl alcohol were placed in a reaction flask, and reacted at 100 ° C for 16 hours in a hot pressure dad. After the solvent was removed, 3 〇g of decyl alcohol was added and dissolved by heating. Then, 3.58 g of ethyl acetate was added, and after cooling to room temperature, crystallization was carried out. The crystals were collected by filtration and dried under vacuum at <RTI ID=0.0></RTI> </RTI> <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt; [Production Example 5] (Production of Intermediate Compound E) 19.0 g of 4-isopropylphenylhydrazine hydrochloride and 54.0 g of ethanol were added to a reaction flask which had been replaced with nitrogen, under a nitrogen stream and 70X: In case of fever, 3-phenylethyl decyl ketone 18.g was added dropwise. After refluxing for 1 hour, 2. g of sulfuric acid was added dropwise, followed by reflux for 1 hour. After cooling, 120 g of toluene and 12 g of water were added, and a 5 wt% aqueous sodium hydroxide solution was added thereto to adjust to pH 8 or higher, followed by oil-water separation. The oil phase was washed three times with warm water 60.0 g to carry out dehydration and desolvation. The obtained residue was crystallized by toluene iog, which was crystallized, and crystallized at 8 (c. vac.) to give pale brown crystals of 18. lg (yield: 67%). g, 28.4 g of ruthenium iodide and 16 8 g of methanol were added to the reaction flask, and reacted in an autoclave at l〇〇t for 5 hours. After the solvent was removed, 40.0 g of ethyl acetate was added and refluxed for 3 minutes, and cooled to After room temperature, the crystals were collected by filtration, and dried under vacuum at <RTI ID=0.0># </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Manufacture) 4.5 g of intermediate A, an intermediate a 3_9g of the following formula, 3. ig of acetic anhydride, and 158 g of pyridine were added to a reaction flask which had been replaced with nitrogen, and reacted at 5 ° C for 3 hours. 5〇〇g, water 5〇g and potassium hexafluoride 55g, stir for 30 minutes for salt exchange. After removing the water layer, add 5〇〇g of water and 1.0g of potassium hexafluoride, stir 3〇 After a minute, the aqueous phase was removed, and the oil phase was washed three times with 50.0 g of water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give a residue. 3 〇〇g of methanol was added to the residue, and crystallization was carried out, and the crystals were collected by washing and washing, and then dried at 14 Torr. (: Vacuum drying was carried out to obtain the target compound 148536.doc -17- 201035080 Ν · ο Green crystallization of phosphorus hexafluoride salt 25 g (yield 38.9% ρ for this compound' was analyzed as follows to confirm the structure, etc.

&lt;Analytical result&gt; Purity: HPLC measurement; 99.3% Structural analysis: iH-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1.77; s; 3) (1.79; s; 3) (2.04; s; 3) (3.34; s; 3) (3.37-3.41; d; 1) (3.59-3.63; d; 1) (4.21; s; 3) (6.45-6.50; d; 1) (6.63-6.66; d; 2) (6.99-7.05; m; 3) (7.07-7.09; d; 1) (7.17 to 7.19; d; 1) (7·55; s; 1) (7.58~7.65; m; 2) (7.80~ 7.83; d; 1) (7.92~7.95; d; 1) (8.06~8·09; d; 1) (8.31~8.54; t; 1) (8.63~8.66; d; 1) G) Optical properties: UV spectroscopy using chloroform solvent

[Manufacturing Example 2] (Production of compound Νο·7 hexafluoride salt) An intermediate Β 4.1 g, an intermediate a4.5 g, acetic anhydride 3.1 g and pyridine I5 were added to a reaction flask which had been replaced with nitrogen. 8g, at 50. (: reaction for 3 hours. Add 50.0 g of gas, 50 g of water, and 5.5 g of potassium hexafluoride, and stir for 30 minutes to carry out salt exchange. After removing the water layer, add 50.0 g of water and 10 g of potassium hexafluoride, and stir. After 30 minutes, the aqueous phase was removed, and the oily phase was washed three times with water (5 g), dried over anhydrous sodium sulfate and then evaporated to vacuo to afford residue. 148536.doc -18- 201035080 100 g of methanol was crystallized, and the crystals obtained by washing were washed, and then vacuum-dried at 140 ° C to obtain 2.4 g of a green crystal of the compound n〇7 hexafluoride phosphorus salt (yield 35 7%). For the compound, the following analysis was carried out to confirm the structure, etc. &lt;Analytical result&gt; Θ Purity: HPLC measurement; 99.1% CD structure analysis: W-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1.83; s; (2.00; s; 3) (2.06; s; 3) (3.49; s; 3) (3.55-3.58; d; 1) (3.69-3.72; d; 1) (3.89; s; 3) (4.34; s; 3) (6.56-6.60; d; 1) (6.66-6.69; d; 1) (6.79-6.80; d; 2) (6.95-6.97; d; 1) (7.02-7.09; m; 3) ( 7.12~7.1 5; d; 1)(7.36; s; 1)(7.58-7.66; m; 2) (7.75-7.77; d; 1)(7.91-7.93; d; 1)(8 .06-8.08; d; 1) (8.68~8.78; t+d; 2) (Characteristics of D optics: ν max measured using uv spectrum of a gas-like solvent; 602 nm ' ε ; 1.09 χ 105 [Manufacturing Example 3] ( Preparation of compound Νο.34 phosphorus hexafluoride salt) Intermediate C 6.0g, hydrazine, hydrazine, diphenyl hydrazine 1.4g, acetic anhydride 2.1g and pyridine ll.lg were added to the reaction flask which had been replaced with nitrogen. The reaction was carried out for 2 hours at 55 ° C. 20.0 g of chloroform, 40.0 g of water and 3-9 g of potassium hexafluoride were added, and the mixture was stirred at 50 t for 30 minutes to carry out salt exchange. After removing the water layer, 50.0 g of water and hexafluoride were further added. 1.0 g of potassium phosphate was stirred for 30 minutes, the aqueous phase was removed, and the oil phase was washed three times with 40.0 g of water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give a residue. Crystallization was carried out, and 148536.doc •19-201035080 crystallized by filtration was dissolved in 5.0 g of dimethylamine amine, and methanol was added thereto for recrystallization. Vacuum drying at 8 (TC) gave the desired product. Compound No. 34, phosphorus hexafluoride salt, green crystal 〇. 6 g (yield: 1 6%). The following analysis was carried out for this compound' to confirm the structure and the like. &lt;Analytical result&gt; 0) Purity: HPLC measurement; 98.0% ❻Structural analysis: W-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (2.19; s; 6) (3.56; s; 6) (3.68 -3.72; d; 2) (4.20-4.24; d; 2) Ο (6.49-6.52; d; 4) (6.64~6.68; d; 2) (6.85-6.90; t; 6) (6.94-6.98; t 2)(7.54-7.60; m; 4)(7.75-7.80; t; 2)(8.02-8.09; m; 4)(8.51-8.53; d; 2)(8.82-8.90; t; 3) CD optics Characteristics····························· Intermediate D 7.5 g, hydrazine, hydrazine, -diphenyl hydrazine 2.0 g, acetic anhydride 3.1 g, and pyridine pyridine I5.8 g were added thereto, and reacted at 60 ° C for 3 hours. A gas-like 25-0 g, water 25.0 g, and potassium hexafluorophosphate 5.5 g were added for salt exchange for 30 minutes. After removing the water layer, 'addition of water 25 〇g and potassium hexafluoride l.〇g 'after stirring for 30 minutes, 'removing the aqueous phase, and washing the oil phase with water 25 〇g twice' dried with anhydrous sodium sulfate Thereafter, the solvent was removed under reduced pressure to give a residue. 60.0 g of decyl alcohol was added to the residue to carry out crystallization, and the crystals obtained by filtration were washed, and then vacuum-dried at 140 ° C to obtain a compound of the target compound N〇.36 red crystal of phosphorus hexafluoride 2.2 g (yield 33.6%). For this compound, 148536.doc -20- 201035080 The following analysis was performed to confirm the structure and the like. &lt;Analytical result&gt; 〇) Purity: HPLC measurement; 100% 12 Structural analysis: h-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1.91; s; 6) (3.40 to 3.52; m+s; 2 + 6) (3·59~3·71; m; 2) (6.52~ 6.60; d; 2) (6.64~6.72; m; 4) (6.98~7·09; m; 6) (7.19~7.25 ; d; 2) (7.28-7.39; m; 4) (7.73-7.76; d; 2) (8.60-8.66; t; 1) (Characteristics of D optics: ν Δ ν φ φ φ , ε ; 1·42 χ 105 [Production Example 5] (Production of Compound No. 41 hexafluorinated sulphate salt) 5.4 g of Intermediate D was added to a reaction flask which had been replaced with nitrogen, and Intermediate b 3.8 represented by the following formula g, acetic anhydride anhydride 3.1g and pyridine I5.8g, and reacted at 25 C for 10 hours. After heating to 5 ° C, add chloroform 3 〇 g, water 30 g and potassium hexafluoride 5.5 g, stir 30 Salt exchange was carried out in a minute. After removing the water layer, 30.0 g of water and potassium hexafluoride 丨〇g were added, and after stirring for 3 minutes, the aqueous phase was removed and the oil phase was washed three times with water 30.0 g. After drying, the solvent was decompressed under reduced pressure to obtain a residue. To the residue was added dimethylformamide (2.0 g) to dissolve. The solution was crystallized by adding methanol 〇g. The crystals which were collected by filtration were re-slurried using dimethyl hydrazine, 〇g and methanol (20.0 g), and then crystallized at 140 ° C. Drying under vacuum gave the title compound Compound No. 41 as a dark green crystal 14 of hexafluorophosphate salt in a yield of 20.9%. For this compound, the following analysis was carried out to confirm the structure and the like. 148536.doc •21 - 201035080

&lt;Analytical result&gt; 2 Purity: HPLC measurement; 99.0% 12 Structural analysis: 1H-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1.66 to 1.89; br; 4) (1.80; s; 3) ( 2.49~2.62br+br;4)(2.49~ 2.62; m; 2)(3.38; s; 3)(3.42~3.47;m;2)(4.04;s;3)(6.56~ 6.79,m; 4) (6·98~7·06; m; 3)(7.14~7,17; d; 1)(7.21~7.26; t; 1) (7.31~7.36; t; 1)(7.54~7.59; t; 1 (7.62~7.65; d; 1) (7·69~ 7.74; t; 1) (7.81~7·84; d; 1) (7.86~8.17; m; 2) (8.30~8.37; m; 2) (Charact of D optics: UV spectrum measurement using chloroform solvent λ max ; 579 nm ' £ ; l. 〇〇 xi 〇 5 [manufacturing example 6] (manufacture of compound No. 43 hexafluoride phosphorus salt) In the substituted reaction flask, 3.9 g of the intermediate A, 4.9 g of the intermediate c represented by the following formula, 3. lg of acetic anhydride, and 158 g of pyridine were added, and the mixture was reacted at 5 ° C for 3 hours. Water 5〇g and potassium hexafluoride 5 5g, and change for 30 knives. After removing the water layer, add water and hexafluoride to remove i.Og' and stir for 30 minutes, then remove the water phase, and Wash the oil phase three times with 5 μg of water, using anhydrous sodium sulfate After drying, the solvent was decompressed under reduced pressure to obtain a residue of 148536.doc -22· 201035080. 30 g of decyl alcohol was added to the residue and crystallized, and the crystals were washed and filtered, and then dried at 14 (rc vacuum drying). The target compound No. 43 /, the green crystal of the phosphorous fluoride salt, 43 g (yield 62 9%) was obtained. The following analysis was carried out for this compound to confirm the structure and the like.

&lt;Analytical result&gt; Q) Purity·· HPLC measurement; 99.3% ❻ structure analysis: W-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1.74-1.96; br; 7) (2.09-2.19 br; 6) (2.32; s; 3) (3.36; s; 3) (3.41 to 3.45 d; 1) (3.52 to 3.56; d; 1) (4.30; S; 3) (6.44 to 6.48; d; (6.52~6.55; d; 1) (6.64~6.66; d; 2) (6.88~6.96; m; 4) (7.09~ 〇7·!1; d; 1)(7.42; s; 1)(7.42 -7.57; m; 2) (7.78-7.80; d; 1) (7.96 to 7.99; d; 2) (8.06 to 8.08; d; 1) (8.57 to 8, 59; d; l) (8.66-8.73; t; 1) (|) Optical characteristics: uv spectrum measurement using chloroform solvent; max; 596 nm, ε; 1.34 χ 105 [manufacturing example 7] (manufacture of compound No. 44 hexafluoride phosphorus salt) The reaction flask to which nitrogen was substituted was charged with intermediate Ε 4.2 g, intermediate c 4-9 g, acetic anhydride 3. lg and p 唆1 5.8 g, and reacted at 50 ° C for 3 hours. 50.0 g of chloroform, 50 g of water, and 5.5 g of potassium hexafluoride were added to carry out salt exchange for 3 minutes 148536.doc -23· 201035080. After removing the water layer, 50.0 g of water and potassium hexafluoride Ug' were added and stirred for 30 minutes, then 'the aqueous phase was removed, and the oil phase was washed three times with 5 〇g. 〇g. After drying with anhydrous sodium sulfate, the pressure was reduced. The solvent was removed to give a residue. To the residue, 30.0 g of decyl alcohol was added and crystallization was carried out, and the crystals collected by filtration were washed and dried under vacuum at 140 ° C to obtain a green crystal of the compound Ν〇·44 hexafluoride phosphorus salt as a target compound. 3.3 g (yield 46.3%) The following analysis was performed for this compound to confirm the structure and the like. &lt;Analytical result&gt; Purity: HPLC measurement; 99.5% Structural analysis: W-NMR measurement (chemical transfer ppm; multiplicity; number of protons) (1·30~1·35; t; 6) (1.88-2.08; br 7) (2.24-2.34; br; 6) (3.03-3.07; m; 1) (3.53-3.58; s + d; 4) (3.69-3.73; d; 1) (4.43; s; 3) (6.63 ~6.66; d; 1) (6.68~6.71; d; 1) (6.81 to 6.83; d; 2) (7.03-7.12; m; 4) (7.27-7.30; d; 1) (7.62-7.72; m; 3) (7.92 to 7.94; d; 1) (8.10 to 8.13; d; 1) (8.20 to 8.22; d; 1) (8.72 to 8.74; d; 1) (8.83 to 8.90; t; 1) optical characteristics : UV spectroscopy using a gas-like solvent to determine λ max ; 597 nm, ε ; 1.15×l 〇 5 [Production Example 8] (manufacturing of pentamethyl-type chloroform compound) Adding a middle to a reaction flask which had been replaced with nitrogen The body A was 3.9 g, 4.5 g of the intermediate d represented by the following formula, 3.1 g of acetic anhydride, and 15.8 g of pyridine, and reacted at 25 C for 10 hours. Gas immersion 30 〇g, water 3 〇 g, and potassium hexafluoride 55 g were added, followed by salt exchange at 50 ° C for 30 minutes. After removing the water layer, add water 148536.doc -24- 201035080 30.0g and potassium hexafluoride i.og, stir for 30 minutes, remove the water phase, and wash the oil phase with water 30.0g three: owe, use After drying with sodium sulfate in water, the solvent is removed under reduced pressure to obtain residue 1 which is crystallized by adding 45 MeOH to the residue, and the crystals are washed and dried in vacuo at 15 (t) to give: Green crystal of the pentamethyl type compound Ν〇·52 hexafluoride phosphorus salt represented by the following formula: 4.7 g (yield 70·4%) β For the compound, the following analysis was carried out to confirm the structure and the like.

&lt;Analytical result&gt; 0) Purity: HPLC measurement; 100% G) Structural analysis: W-NMR measurement © (chemical transfer Ppm; multiplicity; number of protons) (1.79; s; 3) (1.96 to 1.99; d; 6) (2.40; s; 3) (3.28; s; 3) (3 48~ 3.52; d; 1) (3.66~3.70; d; 1) (3·73; s; 3) (6.22~6.26·d 1) (6.31 ~ 6.36; d; 1) (6.55~6.63; m; 3) (6.95~7.05; m; 4) (7 13~ 7.15; d; 1) (7.48-7.50; t; 1) (5) (7.64 to 7.70; Q) Characteristics of optics: uv spectrometry using methanol solvent 148536.doc • 25- 201035080 λ max ; 667 nm, ε ; 2.26× 105 [Evaluation example] Comparison of the compounds obtained in the above Production Examples and the following Compounds 1 to 5 were subjected to differential thermal analysis in a nitrogen gas stream to evaluate thermal decomposition temperature and thermal decomposition rapidity. The thermal decomposition temperature was compared and evaluated by the heat peak temperature of DTA, and the rapidity was evaluated by the temperature and magnitude of the melting of the DSC to the end of the thermal decomposition. The results are shown in Tables 1 to 4.

Table 1 Anthocyanin compound cationic anthocyanin compound Anion thermal decomposition temperature (°C) Thermal decomposition rapidity (°c) Evaluation Example 1 Compound No. 4 pf6· 242.5 8.5 Evaluation Example 2 Compound No. 7 pf6- 247.5 12.4 Evaluation Example 3 Compound No. 41 pf6 - 227.1 9.8 Evaluation Example 4 Compound No. 43 pf6 - 252.2 2.7 Evaluation Example 5 Compound No. 44 pf6_ 241.9 13.9 Comparative Evaluation Example 1 Comparative Compound No. 1 pf6- 282.5 19.5 Comparative Evaluation Example 2 Comparative Compound No.2 pf6- 276.5 25.0 148536.doc •26- 201035080 Table 2 Cyanine compound cationic cyanine compound anion thermal decomposition temperature (°c) thermal decomposition rapidity (.〇 Evaluation Example 6 Compound No.34 pf6- 229.1 1.0 Comparative Evaluation Example 3 Comparative Compound No. 3 pf6- 292 2.0 Table 3 Huaqingfen Compound Cationic Huaqing Station Compound Anion Thermal Decomposition Temperature CC) Thermal Decomposition Rapidity (.) Evaluation Example 7 Compound No. 36 pf6· 246.6 4.2 Comparative Evaluation Example 4 Comparative Compound No. 4 pf6-300 10.8 Table 4 Huaqing Taste Compound Cationic Cyan Taste Compound Anion Thermal Decomposition Temperature CC) Thermal Decomposition Rapidity (. Evaluation Example 8 Compound No. 52 pf6- 222.0 50 Comparative Evaluation Example 5 Comparative Compound No. 5 pf6- 247.0 64.3 From the results of the above Tables 1 to 4, it was confirmed that the present invention relates to the third introduction of the genus The compound can be decomposed at a low temperature and has excellent rapidity of thermal decomposition. These properties are suitable for high-speed recording. [Examples 1 to 6] (Manufacturing and evaluation of recording medium) 12 cm in diameter of a bottom layer (0.01 μm) On the carbonate disc substrate (the underlayer is coated with a titanium chelate compound (T-50: manufactured by Nippon Soda Co., Ltd.) and water 148536.doc -27-201035080), and the above-described manufacturing example is coated by a spin coating method. The cyanine-based compound obtained in 3, 5 or 7 to 8 was dissolved in a solution of 2,2,3,3-tetrafluoropropanol (concentration: 2%) to form an optical recording layer having a thickness of 100 nm to obtain an optical recording medium. For these optical recording media, the UV spectral absorption is measured and evaluated at the wavelength of the recording light used for the optical recording disc. The λ max intensity of each recording medium is regarded as 1, and the relative intensity value relative to the recording medium is less than 0.15. Means that the characteristics of recording and playback deteriorated; 0.5, then the light resistance is deteriorated storage of the optical recording layer, the recording stability deteriorates. Therefore, the wavelength at which the relative intensity of the presentation is in the preferred range of 0.15 to 0.50 is taken as the wavelength of the recording light. The results are shown in Table 5. Table 5 Cyanine compound λ max nm Optimum recording light wavelength (relative intensity) Example 1 Compound No. 4 PF6_ Salt 610 635 nm (0.477), 650 nm (0.208) Example 2 Compound No. 7 PF6j 619 650 nm (0.305) 660 nm (0.188) Example 3 Compound No. 34 PF6·Salt 620 650 nm (0.316), 660 nm (0.181) Example 4 Compound No. 41 pf6i 594 620 nm (0.444), 635 nm (0.180) Example 5 Compound No. 44 Pf6·salt 610 635 nm (0.455), 650 nm (0.200) Example 6 Compound No. 52 PF6·salt 706 770 nm (0.292), 780 nm (0.180), 790 (0.151) 148536.doc -28-

Claims (1)

201035080 VII. Patent application scope: 1. The optical δ recording material, the pottery is used for Λ. M. tn /, is used in the optical recording medium on which the optical recording layer is formed on the substrate and the stencil and 4 rib · You Xueyu, who contains the following compounds of general formula (I) or (Π): ' (wherein one of the cyclic oxime and the cyclic oxime is a benzene ring which may have a substituent, the other is a naphthalene ring which may have a substituent, R1 is an alkyl group having a carbon number of i to 4; and R2 and R3 are carbon numbers a group of 1 to 4, a benzyl group or a group of 3 to 6 membered rings; X is a hydrogen atom, a halogen atom, an alkyl group of a carbon number 4, a phenyl group, a fluorenyl group or a cyano group; Y1 and Y2 Each is independently a hydrocarbon group selected from an alkyl group, an alkenyl group, an alkyl group, and a phenyl group which may be inserted by an ether bond and may be substituted with an alkoxy group, an alkenyl group, a nitro group, a cyano group or a halogen atom; An anion, an inorganic anion, an organic sulfonate anion, an organic phosphate anion, and an anion represented by the following formula (A): (wherein, Μ represents a nickel atom or a copper atom; R4 and R5 represent a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms or a -S02-Z group; and Ζ represents an alkyl group, which can be Halogen substituted aryl, dialkylamino, diarylamino, 148536.doc 201035080 2. 3. 4. 5 hexahydroacridinyl or morpholinyl; a &amp; b each represents 〇 ~ 4); m is an integer of 1; and ρ is a coefficient for maintaining a charge neutrality as in the optical recording material of claim i, wherein 'R2 and R3 in the formula (1) or (II) are bonded to each other to form 3 to 6 The base of the staff. An optical recording material according to claim 1, wherein X in the formula (I) or (II) is a hydrogen atom. An optical recording material as claimed in claim 2 wherein X in the formula (1) or (II) is a hydrogen atom. An optical S-recording medium which forms a film comprising an optical recording material according to any one of claims 1 to 4 on a substrate. 148536.doc 201035080 IV. Designated representative map: (1) The representative representative figure of this case is: (none), ^ · '(2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best Chemical formula showing the characteristics of the invention: (none) 148536.doc