TW200306334A - Optical recording material - Google Patents

Abstract

An 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 group; 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 3-6-membered ring that connected to each other; 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 group, or a cyano group; Y1 and Y2 are each independently an organic group; Anm- is an m-valent anion; m is 1 or 2; and (p) is a coefficient keeping the charge neutral).

Description

200306334 (ii) Description of the invention: TECHNICAL FIELD The present invention relates to an optical recording material used in an optical recording medium that records information by using a thermal information image generated by a laser or the like. More specifically, it relates to an optical recording material Optical recording materials used in optical recording media for high-density optical recording and playback such as wavelengths in the near infrared region and lasers with low energy. The prior art optical recording medium has been widely used due to its excellent features such as large memory capacity and recording or playback without contact. WORM, CD-R, DVD-R and other write-once optical discs can focus laser light on a small area of the optical recording layer, change the properties of the optical recording layer and record, and according to the difference between the amount of reflected light and the unrecorded part Play. The optical recording layer of the optical recording medium represented by the optical disk is easy to form the optical recording layer. Organic pigments can be used, especially cyanin-based compounds, which have high sensitivity and can respond to high speed. They are being widely studied. . At present, among the above-mentioned optical discs, the wavelength of the semiconductor laser used for recording and playback, CD-R is 750 to 830nm, DVD-R is 620 to 690nm, and higher density optical discs below 600nm are also being developed. In development. The cyanocyanine compounds corresponding to these optical discs are disclosed in, for example, Japanese Patent Application Laid-Open No. 59-55795, Japanese Patent Application Laid-Open No. 5-173282, Japanese Patent Application Laid-Open No. 10-278426, Japanese Patent Application Laid-Open No. 11-53761, Japanese Patent Application Laid-Open No. Japanese Patent Application No. 11-170695, Japanese Patent Application Publication No. 1 1-22733 Japanese Patent Application Publication No. 11-277904, Japanese Patent Application Publication No. 11-34499, Japanese Patent Application Publication No. 2000-108510, Japanese Patent Application Publication No. 83018.doc 200306334 2000-289335 It has been reported in Japanese Patent Publication No. 2001-506933. However, the aforementioned cyanocyanine compounds have problems in terms of thermal decomposition properties. High-speed recording must have low thermal interference. For optical recording materials, those with low decomposition temperature and rapid thermal decomposition are more suitable. However, the characteristics of each of the anthocyanin compounds reported above are insufficient. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an anthocyanin-based optical recording material suitable for an optical recording medium capable of high-speed recording. In order to realize the sensitivity that can correspond to high-speed recording, and to consider the effectiveness in optimizing the thermal decomposition behavior and optimizing the absorption wavelength, the inventors have repeatedly reviewed the results and found that anthocyanins with specific molecular structures The compound can solve the above-mentioned problems, and thus has reached the present invention. Based on the above findings, the present invention provides an optical recording material, which is characterized by containing a compound represented by the following general formula (I) or (II), and provides an optical recording medium, which is characterized in that an optical recording material is formed on a substrate. film.

83018 doc 200306334 (wherein ring A and ring B represent a benzene or fluorene ring which may have a substituent; R1 represents an alkyl group having 1 to 4 carbon atoms; R2 and R3 represent an alkyl group or benzyl group with 1 to 4 carbon atoms Or groups connected to each other to form a 3 to 6 member ring; X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, 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 having a valence of m and m represents an integer of 1 or 2; and p represents a coefficient for keeping the charge neutral). The present invention provides an anthocyanin-based optical recording material suitable for use in an optical recording medium capable of high-speed recording. Embodiments Detailed Description of the Invention Embodiments of the present invention will be described in detail below. The anthocyanin-based compound represented by the general formula (I) or (II) of the present invention is characterized in that it has a fluorenyl group at a specific site and has a lower decomposition temperature than other anthocyanin-based compounds used in optical recording materials. And the absorption wavelength is most moderate. Also, Japanese Patent Application Laid-Open No. 5-173282, Japanese Patent Application Laid-Open No. 10-278426, Japanese Patent Application Laid-Open No. 11-22733, and Japanese Patent Application Laid-Open No. 11-277904 describe that the formula (I) and The general formula of the anthocyanin-based compound, which is part of the concept of the compound represented by (II). In these reports, although it is described that aralkyl is used as a substituent bonded to the third position of the indole skeleton, no specific examples are given of benzyl, and it is not described that benzyl or aralkyl is introduced into flowers. Method in cyanoside compounds and effects of fluorenyl groups In the general formula (I) or (II) above, ring A and ring B may have substituents 83018.doc 200306334 benzene ring «ring substituent, may Fluorine, chlorine, bromine and fluorene, methyl ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, isopentyl, third pentyl Alkyl, hexyl, cyclohexyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, third octyl and 2-ethylhexyl and other alkyl groups, phenyl'fluorenyl, 2-tolyl ,% Tolyl, 'tolyl, 4-ethylenyl, 3-isopropylphenyl and other aryl groups, methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butyl Alkoxy groups such as oxy and third butoxy, alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, second butylthio, and third butylthio, Nitro and amine groups. Examples of the alkyl group having 1 to 4 carbon atoms represented by & include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, and isobutyl. The alkyl group having 1 to 4 carbon atoms represented by R2 & R3 is, for example, methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, and isobutyl. 3- to 6-membered rings formed by linking, for example, cyclopropyldiyl, cyclobutadiene, ^ diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3-dimethylcyclobutene_ι , Ι_diyl, cyclopentyl 4, ^ diyl, cyclohexanediyl, tetrahydrofuran_4,4-diyl, thiopyran_4, renyl, hexahydropyridine-4,4-di Group, N-substituted hexahydropyridine-4,4-diyl, morpholine-2,2-diyl, morpholine-3,3-diyl, N-substituted morpholine-2,2-di And N-substituted morpho-4-3,3-diyl, etc., wherein the 1 substituent is as exemplified in ring a. The function atom represented by 'X' is, for example, fluorine, chlorine, bromine, iodine, etc., and the alkyl group having 1 to 4 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, or second The substituents of butyl, third butyl and isobutyl, phenyl and benzyl are the same as those mentioned for ring A. The organic group represented by γι and γ2 is not particularly limited, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, 83018.doc -10- 200306334 second butyl, third butyl, Isobutyl, pentyl, isopentyl, third pentyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, heptyl, isoheptyl, third heptyl, n-octyl, iso Octyl, third octyl and 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 17 Alkyl and octadecyl, etc., ethyl fluorenyl, i β methyl ethyl fluorenyl, 2-methyl ethylenyl, propyl fluorenyl, butyl fluorenyl, isobutyl fluorenyl, pentenyl, hexenyl, heptenyl, octene Alkyl, decyl, pentadecyl, and 1-pyridinyl gamma-3-yl, phenyl, fluorenyl, 2-tolyl, 3-tolyl, 4-tolyl, 4-ethyl P-phenylene, 3-cumyl, 4-cumyl, 4-butylphenyl, 4-butylene, 4-second butylphenyl, 4-hexylphenyl, 4-cyclohexyl Phenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-xylyl, 2,4-bis Tolyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,4-di-tert-butylphenyl, and cyclohexylphenyl And other alkyl groups, such as benzyl, phenethyl, 2-phenylpropan-2-yl, dityl, trityl, phenethyl, and propyl, and these hydrocarbon groups are related to Sulfur bond inserters, such as 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethylmethoxyethoxyethyl, methoxyethoxyethoxyethyl, & quot Oxybutylphenoxyethyl, 2-methylthioethyl, 2-phenylthioethyl, etc., and moreover, these groups 5F can be dry oxy, fluorenyl, nitro, cyano or primary . The above-mentioned Anm. The anion represented, for example, ^ ^ 如 such as chloride anion, ^ anion, hydrogen and fluorin "anion, perchlorine anion, chloric acid anion, thiocyanate anion, hexafluoro anion, six Inorganic anions such as ammonium fluoride anion and boron tetrafluoride anion, benzene coke 83018.doc 200306334 acid anion, toluenesulfonic acid anion-Dingjiu Yiluanjia; ^ organic anions such as bismuth anion, octyl phosphate anion, ten Dibasic phosphoric acid anion, octadecyl phosphoric acid, phenyl, anion, 4-based phosphate anion, and methylene wu (4,6 · _second butylphenyl) carboxylic acid anion, etc. Anions, etc .; divalents such as phthalic acid anion and benzoic acid anion, etc. Also, 'quencher anions (queneher such as Ii) or ferrocene or metallocene compound anions such as ferrocene or iuteocene with an anionic group such as carboxyl, phosphonic acid, or sulfonic acid on the cyclopentadiene ring. ≪ Stop Ions are, for example, those represented by the following general formula (A) or (B), such as Japanese Patent Application Laid-Open No. 60-234892, Japanese Patent Application Laid-Open No. 5_43814, Japanese Patent Application Laid-Open No. 6-239028, Japanese Patent Application Laid-Open No. 9_3009988 Anion described in Kaiping No. 10-45767 and the like.

(In the formula, M 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; Z represents an alkyl group, An aryl group, a dialkylamino group, a diarylamino group, a hexahydro 17-pyridyl group, or a morpholinyl group which may be substituted by an i element atom, a and b each represent 0 to 4; R6, R7, R8, and R9 are each independently Ground means alkyl, alkphenyl, alkoxyphenyl or halogenated phenyl). 83018.doc -12- 200306334 In the above general formula 咐 or (command, about x, it is better to use gas source (because of the thermal decomposition characteristics, especially thermal decomposition temperature, suitable for high recording), and also, about Y1 'to The same base as R1 is preferred (due to the system, fewer steps and lower costs). Also, R2 and R3 are preferably connected to each other in the shape of <3 ~ 6 shells (because of its UV absorption is particularly suitable for recording the laser light used.) According to the above general formula ⑴ 砉 + & &gt; human t, 、, formula U) π &lt; specific examples of compounds, such as the following compounds No. 1 ~ 5 1 is shown. For example, Ding Jieyi, Dan You, and the following examples are represented by anthocyanin cations which omit the anions.

83018.doc -13-200306334

83018.doc -14- 200306334

83018.doc 15- 200306334 In addition, specific examples of the compound represented by the above general formula (II) are the compounds of the above-exemplified compounds No. 1 to 5 1 having a polymethine (p0yymethine) chain carbon number of 5 . The anthocyanin-based compound represented by the above-mentioned general formula (I) or represented by the present invention is not limited by its production method. The manufacturing method of these anthocyanin compounds, for example, when IU and Y1 are the same, can be performed in the following ways. In the case where R1 and Y1 are different from each other, it is possible to synthesize ¥ 1 to be introduced into a hydrazine compound in advance, and then use it as a raw material to produce it in the same manner as the following.

(In the formula, ring A, ring B, R1, R2, R3, X, Y2, Anm_, and p are the same as those in the general formula (I) or (II). 'D represents a halogen or a substituted S-blue oxy group.) The element represented by the above D is chlorine, bromine or iodine, and the substituted sulfonyloxy group is benzenesulfonyloxy, 4-toluenesulfonyloxy or 4-chlorobenzenesulfonyloxy and the like. 83018.doc -16- 200306334 As the above-mentioned cyanine compound as the optical recording material of the present invention, as long as it can be commonly used in the optical recording layer of an optical recording medium and the optical recording layer can be formed, it is not particularly limited. . _ In general, lower alcohols such as methanol and ethanol, methyl cellosolve, ethyl cellosolve, butyl / cereal, and butyl: polyethylene: alcohol, etc. can be used, Ketones such as acetone, methyl ethyl ketone, methyl xyl butyl ketone, cyclohexanone, and diacetone alcohol; esters such as ethyl acetate, butyl acetate, and methoxyacetic acid acetate; 2,2,3, 3_ Tetrapropanol and other gasified alcohols such as wheat, toluene and xylene, hydrocarbons, chloroform, dichloroethane, chloroform and other organic solvents such as chlorinated hydrocarbons. , Spray or dip coating method on the coating substrate. Other methods, such as steaming and spraying. The thickness of the optical recording layer is generally from 0.001 to 10 / z m, and a range of # m is preferred. The optical recording material of the present invention is preferably 50 to 100% by weight. The optical recording layer of the optical recording medium contains, and the amount of the optical recording layer is considered to be the above-mentioned optical recording layer. In addition to the optical recording material of the present invention, other cyanine compounds, azo "物 or 酉 太 stuffed flower green # series compounds and other compounds used in the recording layer of materials; may also include resins such as polyethylene, polyester, polystyrene, or carbonates; and; contain surfactants, antistatic agents , Lubricating agents, flame retardants, free radical trapping agents such as hlndered amine, ferrocene derivatives and other cavitation agents, dispersants, oxidation inhibitors, crosslinking agents, or imparting light properties, Furthermore, the optical recording layer described above may also contain an aromatic nitroso compound, a stopper agent such as singlet oxygen 83018.doc -17- 200306334, an amine it (aminium) compound, an imine diamond «m) compound, A carbodiimide compound or a transition metal chelate compound, etc. The amount of use thereof is preferably 0 to 50% by weight of the optical recording layer. To provide the base material f of such an optical recording layer, Record) light and output The light of broadcast) is not particularly limited as long as it is substantially transparent. For example, resins such as polymethyl methacrylate, polyethylene terephthalate, or polycarbonate can be used. Χ 'The shape Any shape, such as film, tube, ribbon, or sheet, is used according to the material. In addition, gold, silver, aluminum, or copper can also be used on the optical recording layer, and reflection can be formed by evaporation or sputtering. Film, or a protective layer made of acrylic resin or ultraviolet curable resin, etc. The optical recording material of the present invention is suitable for recording and playing optical recording media that uses a semiconducting field to shoot field, especially for high-speed recording. Optical discs such as DVD-R are particularly preferred. Hereinafter, the present invention will be explained in more detail through manufacturing examples, manufacturing examples, evaluation examples, and examples. However, the present invention is not affected by the following examples and the like. [Production Example 1] (Production of Intermediate Compound A) In a reaction flask substituted with nitrogen, 4-tolylhydrazine hydrochloride 3 9.7§ and ethanol 117.2§ were added, and the nitrogen flow was 70. (: below (Note the fever) 4- Phenylmethyl ketone 40.8g. 114.7g of 35% hydrochloric acid aqueous solution was added dropwise and refluxed for 2 hours. After cooling, 500g of toluene and 500g of water were added, and 50% sodium hydroxide was added. The aqueous solution was adjusted to pH 8 or higher, and then oil-water separation was performed. The oil phase was washed three times with 500 g of warm water, and dehydrated and desolvated. 83018.doc -18-200306334 was known that the residue was crystallized with 117e2 g of ethanol and filtered. The obtained crystals were dried under vacuum at 80 ° C to obtain 35.6§ (yield 60.8%) of white crystals. 11.8 g of the obtained white crystals, 28 4 g of methyl iodide and 19 6 g of methanol were added to a reaction flask. , In an autoclave at 100. The reaction was continued for 5 hours. After the solvent was removed, 40 g of ethyl acetate was added and the mixture was refluxed for 30 minutes. After cooling to room temperature, the crystals were collected by filtration and dried under vacuum at 80 ° C to obtain 11.4 g of yellow crystals as intermediate eight (yield 58.3%). . [Production Example 2] (Production of intermediate compound b) In a nitrogen-substituted reaction flask, 34.9 g of 4-methoxyphenylhydrazine hydrochloride and 100 g of ethanol were added. Under a nitrogen flow and 8 (rc (note the heat generation conditions) ), 3 6 g of 3-phenethyl methyl ketone was added dropwise. After refluxing for 1 hour, the sulfuric acid parent% was added dropwise to reflux for another 2 hours. After cooling, 2000 g of toluene and 2000 g of water were added, and then added. A 50% sodium hydroxide aqueous solution was adjusted to pH 8 or higher, and then oil-water separation was performed. The oil phase was washed three times with 200 g of warm water, and dehydrated and desolvated. The obtained residue was crystallized with 100 g of toluene and filtered to obtain The crystals thus obtained were dried under vacuum at 80 C to obtain 25.4 g of white crystals (yield 50.5%). The obtained white crystals 10.1 g, 28.4 g of iodide methyl group and 19.6 g of methanol were added to the reaction flask, and The reaction was carried out 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 crystals were filtered off at 80 t: vacuum drying to obtain 9.5 g (yield 58.3%) of yellow crystals of intermediate b. [Production Example 3] (Production of intermediate compound C) In a nitrogen-substituted reaction flask, 79.1 g of 2-fluorenylhydrazine and 274.1 g of ethanol were added, and under a nitrogen stream, 88 9 g of 3-phenethylmethyl ketone was added dropwise at 55 °. 83018.doc -19- 200306334 k mix After 30 for 4 miles, pay attention to the heat generation, and simultaneously drop in 49 g of sulfuric acid, and return for 1 hour. After cooling, add 1000 g of toluene and 1000 g of water, and then add 50% sodium hydroxide aqueous solution. Adjust to pH 8 or higher, and then perform oil-water separation. The oil phase was washed three times with 500 g of warm water, and dehydrated and desolvated. The obtained residue was crystallized from 137 g of toluene, and the crystals obtained by filtration were obtained at 80 °. Drying of Shiba 'to obtain 72e4g of white crystals (yield 53.4%). 13.6g of white crystals obtained, 28.4§ of methyl iodide and 214g of methanol were added to the reaction flask, in an autoclave at 100 ° C It was allowed to react for 15 hours. After the solvent was removed, crystallization was performed with a mixed solvent of 100 g of ethyl acetate and 6.0 g of methanol. The crystals were collected by filtration and dried at 14 ° C to obtain crude crystals of intermediate c (HPLC purity 60%). ) 6.9 (yield 32.3%). [Production Example 4] (Production of intermediate compound d) Add 57 g of phenylhydrazine sulfate and 221 g of ethanol to the flask. Under a nitrogen stream and 70 (note the heat generation), drop 1-7-glycidyl methyl ketone. Then add 4 · 9 g of sulfuric acid. Add dropwise and reflux for 8 hours. After cooling, add 250g of toluene and 300g of warm water, add 50% sodium hydroxide aqueous solution to adjust the pH to 8 or more, and then perform oil-water separation. Wash the oil phase with 300g of warm water three times. Dehydration and desolvation. The obtained residue was crystallized with 300 g of ethanol, and the crystals obtained by filtration were dried under vacuum at 80 ° C. to obtain 116.1 g of white crystals (yield 52.5%). The obtained white crystals 22, 1 g, 56.8 g of methyl iodide, and 37.7 g of methanol were charged into a reaction flask, and reacted in an autoclave at 100 ° C for 16 hours. After the solvent was removed, 380 g of methanol was added and dissolved by heating, and then 3.8 g of ethyl acetate was added. After cooling to room temperature, crystallization was performed. The crystals were collected by filtration and dried under vacuum at 80 ° C to obtain 17.5 g (yield 46.4%) of white crystals as an intermediate 83018.doc -20-200306334 D. [Production Example 5] (Production of Intermediate Compound E) In a reaction flask substituted with nitrogen, 19.0 g of 4-isopropylphenylhydrazine hydrochloride and 54.0 g of ethanol were added. Under a nitrogen stream and 70 ° C (note Its fever), 18.1 g of 3-phenethyl methyl ketone was added dropwise. After refluxing for 1 hour, 2.0 g of sulfuric acid was added dropwise, followed by refluxing for another 1 hour. After cooling, 120 g of toluene and 20 g of water were added, and a 50% aqueous sodium hydroxide solution was added to adjust the pH to 8 or more, and then oil-water separation was performed. The oil phase was washed three times with 60 · 0 g of warm water, and dehydrated and desolvated. The obtained residue was crystallized from 100 g of toluene, and the crystals obtained were collected by filtration, and dried at 80 ° C, and dried to obtain 18.1 g of light-colored crystals (yield 67.4%). 10.5 g of the obtained light brown crystals, 28.4 g of methyl iodide, and 16.8 m of methanol were added to a reaction flask, and reacted in an autoclave at 100 t for 5 hours. After the solvent was removed, 40.0 g of ethyl acetate was added and refluxed for 30 minutes. After cooling to room temperature, the crystals were collected by filtration and dried under vacuum at 80 C to obtain 103 g of yellow crystals as an intermediate (yield 59.6%). [Production Example 1] (Production of compound No. 4 phosphorous hexafluoride salt) In a reaction flask substituted with nitrogen, 5 g of intermediate A 4, 3.9 g of intermediate a represented by the following formula, and acetic anhydride 3 were added. 1§ and 15 g of pyridine were reacted at 50 t for 3 hours. Add 50.0 g of chloroform, 50 g of water, and 5.5§ potassium potassium hexafluoride, and stir for 30 minutes for salt exchange. After removing the aqueous layer, 5Q g of water and 0 g of potassium potassium hexafluoride were added, and after stirring for 30 minutes, the water phase was removed, and the oil phase was washed with 50.0 g of water three times. After drying with anhydrous sulfuric acid, The solvent was removed under reduced pressure to obtain a residue. 30.0 g of methanol was added to the residue and crystallized, and the crystal 1 was washed and collected, and then dried under vacuum to obtain the target compound, which is 83018 doc -21- 200306334 compound No. 4 hexafluoro 2.5 g of green crystals of phosphorus salt (yield 38.9%). For this compound, the following analysis was performed to confirm the structure and the like. Intermediate a

&lt; Analysis result &gt; Purity: HPLC measurement; 99.3% Structural analysis: i-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 ^ 7.〇5; m; 3) (7.07-7.09; d; 1) (7.17-7.19; 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) Characteristics of CD optics: λ max was measured using UV spectrum of chloroform solvent; 593nm-ε; 1.17x105 [Production Example 2] (Production of Compound No. 7 Phosphorus hexafluoride salt) In a reaction flask substituted with nitrogen, intermediate B 4 · 1 g, intermediate a 4.5 g, acetic anhydride 3.1 g and pyridine 15.8 g were added at 50 ° C. (: Reaction for 3 hours. Add 50.0 g of rat imitation, 50 g of water, and 5 · 5 g of 7T fluorinated scales, and allow 30 minutes for salt replacement. After removing the water layer, add water 5 0.00g and potassium hexafluoride 1.0g. After stirring for 30 minutes, the aqueous phase was removed, and the oil phase was washed twice with water 500§, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue is obtained. 83018.doc -22- 200306334 To the residue was added methanol 1 and 4 knives to crystallize each 100 g. After washing and filtering the crystals, it was dried under vacuum at 140 C to obtain Of the target compound, no. 7 phosphorous hexafluoride salt, 2.4 g of green crystals (yield: 35 7%). For this compound, the following analysis was performed to confirm the structure, etc. &lt; Analysis result &gt; G purity: HPLC measurement; 99.1% tritium structure analysis: h-NMR measurement (chemical transfer PPm; multiplicity; number of protons) 0-83; s; 3) (2.00; s; 3) (2.06; s; 3) (3.49; s; 3) 0.55-3.58; 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) (D optical characteristics: using chloroform Solvent uv spectrum measurement λ max; 602 nm, ε; 1.09 × 1 005 [Production Example 3] (Production of compound ν〇 · 34 phosphorous hexafluoride salt) In the reaction flask which has been replaced with nitrogen, an intermediate is added The body c 6.〇g, ν5ν, _ diphenylsulfonium; L4g, 2elg of acetic anhydride and Uelg of pyridine, reacted at 55t for 2 hours. Add 20.0g of chloroform, 40.0g of water and 39g of potassium hexafluoride, mix in Minutes for salt exchange. After removing the water layer, water 5 (h0g and potassium hexafluoride 1.0 g) was added, and after stirring for 30 minutes, the water phase was removed, and the oil phase was washed twice with 40.0 g of water. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure to obtain a residue. To this residue was added methanol 40.0§ for crystallization, and the filtered 83018.doc -23- 200306334 was crystallized from 5.0 g of dimethylformamide. It was dissolved by heating in a medium, and methanol was added thereto for recrystallization. Vacuum drying was performed at 8 ° C. to obtain 0.6 g of green crystals of the target compound version 34 phosphorous hexafluoride salt (yield 10.6%). For the I compound, the following analysis was performed to confirm the structure and the like. &lt; Analysis results &gt; 0) Purity: HPLC measurement; 98.0 / 〇❽ structure analysis: ^ -NMR measurement (chemical transfer ppm; multiplicity; number of protons) (2.19; s; 6) (3〇56; s; 6) (3.68 ^ 3.72; d; 2) (4.20 ^ 4.24; d; 2) (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) ㊁Optical properties: λ max; 608 nm &gt;ε; 1.23 × 10 5 [production example 4] (manufacturing of compound No. 36 phosphorous hexafluoride salt) using chloroform solvent 糸 used In a nitrogen-substituted reaction flask, intermediates D 7 · 58, N, N diphenylphenylhydrazone 2.Gg, liver acetate 3.lg, and 158 g were added, and 25.0 g of chloroform and 25.50 of water were added at the stage of 3 J reaction. g and 55 g of potassium hexafluoride for 30 knives and 4 miles of salt. After the water layer was removed, water and potassium hexafluoride (LOg I) were added for 30 minutes. The water phase was removed, and the oil phase was washed with water for 25 times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. To obtain a residue, methanol was added to the residue, and the crystals were prepared and washed. The crystals were washed and dried under vacuum to obtain 2.2 g of red crystals of the target compound n03 "% fluoride salt. (Yield 33 6%). For this compound, 83018 doc -24-200306334 was subjected to the following analysis to confirm the structure, etc. &lt; Analysis result &gt; CD purity: HPLC measurement; 100% ㊁ Structure analysis: i-NMR measurement (chemical Transfer ppm; Multiplicity; Proton number) (1.91; s; 6) (3.40 ~ 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 ~ 7e76; d; 2) (8.60 ~ 8.66; t; 1 ) (D optical properties: λ max was measured using UV spectrum of chloroform solvent; 561 nm, ε; 1.42χ 105 [Production Example 5] (Production of compound No. 41 phosphorous hexafluoride salt)) Add intermediate D to the reaction flask 5 jg, 3.8 g of intermediate b 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. After warming to 50 ° C, 30.0 g of chloroform, 30 g of water and hexafluoro 5.5 g of potassium phosphide, stirred for 30 minutes for salt exchange. After removing the aqueous layer, 30.0 g of water and 1.0 g of potassium hexafluoride were added. After stirring for 30 minutes, the water phase was removed, and the oil phase was washed with 30.0 g of water. It was cleaned three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a residue. To the residue was added 2.0 g of dimethylformamide and the solution dissolved by heating was added. 20.0 g of methanol was added for crystallization. The crystals were recrystallized using 4.0 g of dimethylformamide and 20 Ag of methanol. The crystals were washed and filtered, and then dried under vacuum at 140 ° C to obtain the target compound No. 41, a phosphorous hexafluoride salt. 1.4 g of dark green crystals (yield 20.9%). For this compound, the following analysis was performed to confirm the structure and the like. 83018.doc -25- 200306334

&lt; Analysis results &gt; CD purity: HPLC measurement; 99.0% G) Structural analysis: W-NMR measurement (chemical transfer ppm; multipleness; number of protons) (1.66 ^ 1.89; br; 4) (1.80; s; 3) (2.49 ^ 2.62 br + 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) (? ^ 174; t; 1) (7.181 to 7.84; d; 1) (7.16 to 817; called 2) (8.33 to 8) · 37; called 2) CD optical characteristics: 1 using chloroform solvent; ¥ Spectral measurement of Amax; 579nm, ε; 1.00x5 [Production Example 6] (Production of compound No. 43 hexafluoride scale salt) in In a reaction flask substituted with nitrogen, intermediate A, 4.9 g of intermediate c represented by the following formula, 31 g of acetic anhydride, and 58 g of pyridine were added, and reacted at 50 ° C. for 3 hours. 500 g of chloroform, water, and potassium hexafluoride were added to make it quinone, and salt exchange was performed for 30 minutes. After removing the water layer, 50.0 g of water and 1.0% potassium hexafluoride 1.0§ were added, and after stirring for 30 minutes, the water phase was removed, and the oil phase was washed three times with water, dried over anhydrous sodium sulfate, and then removed under reduced pressure. Solvent to obtain residual 83018.doc -26- 200306334 Product 1 3GGg of methanol was added to the mixture and crystallized. After washing and washing the crystals, it was dried under vacuum at 140 t it to obtain the compound No. 43 as the target substance. 4, 3 g of green crystals of fluorinated% salt (yield. For this compound, the following analysis was performed to confirm the structure, etc.)

&lt; Analysis results &gt; 0) Purity: HPLC measurement; 99.3% Q) Structural analysis: iH-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 ^ 3.45 d; 1K3.52 ~ 3.56; d; 1) (4.30; s; 3) (6.44 ~ 6.48; d; D (6.52 ^ 6.55; d; 1) (6.64 ~ 6.66; d; 2) (6.88 ~ 6.96; m; 4) (7.09 ^ 7-11; d; 1) (7.42; s; 1) (7.42-7.57; m; 2) ) (7.78-7.80; d · 1) (7.96 ~ 7.99; d; 2) (8.06 ~ 8.08; d; Mu%; ^ 〇 (8.66-8.73; t; 1) ❻Optical characteristics ·· use UV spectrum measurement of chloroform solvent λ max; 596 nm, ε; 1.34χ 1 〇 Production Example 7] (Production of Compound No. 44 hexafluoride transsalt) The intermediate was added to the reaction flask in which the tritium gas was replaced E 4 2 g, tj: body C4,9g, acetic anhydride 3.lg and pyridine 15.8g, and 50.0g of chloroform, 50g of water and 5.5g of potassium hexafluoride were added in the reaction for 3 days. 〇83018.doc -27- 200306334 Salt exchange. After removing the water layer, add 50.0 g of water and 1.0 g of potassium hexafluoride. Stir: After stirring for 30 minutes, remove the water phase and use the oil phase with water. 5 0. 0 g washed three times' dried with anhydrous sodium sulfate After drying, the solvent was removed under reduced pressure to obtain a residue. 30.0 g of methanol was added to the residue and crystallized. The crystals collected by filtration were washed and then dried under vacuum at 140 ° C to obtain the compound of interest ο. · 44 g of green crystals of 44 phosphorous hexafluoride salt (yield 46.3 ° /.). For this compound, the following analysis was performed to confirm the structure, etc. &lt; Analysis result &gt; Purity: HPLC measurement; 99.5% structure analysis · iH -NMR measurement (ppm of chemical transfer; multiplicity; number of protons) (1.30 ~ 1.3 5; t; 6) (1 β 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 ~ 6 · 83; d; 2) (7.03 ~ 7.12; m) 4) (7.27 ~ 7.30; d; 1) (7.62 ~ 7 · 72; m; 3) (7.92 ~ 7.94; d; 1) (8.10 ~ 8 · 13; d; 1) (8.20 ^ 8.22; d; 1) (8.72 ~ 8.74; d; 1) (8.83 ~ 8.90; t; 1) Optical characteristics: λ max was measured using UV spectrum of a chloroform solvent; 597 nm, ε; 1.1 5χ 105 [Production Example 8] (penta-methyl cyanine: y: production of a compound) in Reactions that have been replaced with nitrogen 3.9 g of intermediate A, 4.5 g of intermediate d represented by the following formula, 3.1 g of acetic anhydride, and 5.8 g of pyridine were added to the flask, and reacted at 25 ° C for 10 hours. After adding 30.0 g of chloroform, 30 g of water and 5.5 g of potassium hexafluoride, salt exchange was performed at 50 ° C for 30 minutes. After removing the water layer, water-28- 83018.doc 200306334 30.0 g and potassium hexafluoride i.og were added, and after stirring for 30 minutes, the water phase was removed, and the oil phase was washed three times with 30.0 g of water. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure to obtain a residue. Methanol was added to the residue at 45 ° C, and the crystals were 'washed and filtered to obtain the crystals' and dried under vacuum at 150 ° C to obtain a fifth-order methyl compound of the following formula: 4.7 g of 52 green crystals of phosphorous hexafluoride salt (yield 70.4%). For this compound, the following analysis was performed to confirm the structure and the like.

&lt; Analysis results &gt; 0) Purity: HPLC measurement; 100% Q) Structural analysis: iH-NMR measurement (chemical transfer Ppm; multiplicity; number of protons) (1.79; S; 3) (1β96 ~ 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; (6.31 ~ 6 · 36; d; 1) (6.55 ~ 6 · 63; m; 3) (6.95 ~ 7.05; 4) (713 ~ 7 · 15; d; 1) (7.48 ~ 7 · 50 ; t; 1) (7 · 58; s; 1) (7.64 ~ 7.70; t; 1) (7.73 ~ 7.76; d; 1) (8.04 ~ 8 · 09; t; 2) (8.23 ~ 8.26 ; d; ”(8.41 to 8.49; m; 2) (D optical characteristics · UV spectrum measurement using methanol solvent 83018.doc -29- 200306334 λ max; 667nm, ε; 2.26χ 105 [Evaluation example] For the compounds obtained in the above-mentioned production examples and the comparative compounds 1 to 5 shown below, differential thermal analysis in a nitrogen gas flow was performed to evaluate the thermal decomposition temperature and the rapidity of thermal decomposition. The thermal decomposition temperature was determined by the heating peak temperature of DTA. For comparative evaluation, the rapidity is evaluated by the temperature and the range of the melting from DSC to the end of exothermic decomposition. The results are shown in Tables 1 to 4.

Table 1 Anthocyanin compounds Anion Thermal decomposition temperature (° C) Anionic Thermal decomposition temperature (° 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 Comparison Compound No. 2 pf6- 276.5 25.0 83018.doc -30- 200306334 Table 2 Anionic thermal decomposition temperature (° C) of cyanine 'compound cationic anthocyanin compound Thermal decomposition rapidity (° C) 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 Huayinru Compound Cationic Anthocyanin Compound Anion Thermal Decomposition Temperature CC) Rapid Thermal Decomposition (.C) 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 Anthocyanin Compound Cationic Anthocyanin Taste Compound Anion Thermal Decomposition Temperature CC) Rapid Thermal Decomposition (.C) 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 Tables 1 to 4 above, it was confirmed that the anthocyanin-based compound introduced with a fluorenyl group at the third position of the present invention can be decomposed at a low temperature. And, the rapidity of thermal decomposition is excellent. These properties are suitable for high-speed recording. [Examples 1 to 6] (Manufacturing and Evaluation of Recording Media) On a 12 cm diameter polycarbonate disc substrate provided with a substrate ((KOI // m) (the substrate is coated with a titanium chelate compound (T-50: (Manufactured by Soda Co., Ltd., Japan) and water 83018 doc -31-200306334 solution), the anthocyanin compounds obtained in the above-mentioned manufacturing examples 1 to 3, 5 or 7 to 8 were applied by a spin coating method to dissolve in 2, 2, 3 A solution of 3,4-tetrafluoropropanol (concentration 2%) to form an optical recording layer with a thickness of 100 nm to obtain an optical recording medium. For these optical recording media, UV was measured at the wavelength of the recording light used for the optical recording disc. Spectral absorption is evaluated. The λ max intensity of each recording medium is taken as 1. If its relative intensity value is less than 0 · 15, it indicates that the recording and playback characteristics are deteriorated; if it exceeds 0.5, it indicates that the optical recording layer is The light resistance is deteriorated, and the storage stability of the record is deteriorated. Therefore, the relative light intensity exhibited in the preferred range of 0.1 5 to 0.50 is used as the recording light wavelength. The results are shown in Table 5. Table 5 Anthocyanin compounds λ max nm Optimum recording light wavelength (relative intensity) Example 1 Compound Noβ4 PF6_ salt 610 635nm (0〇477) 5650nm (0.208) Example 2 Compound No. 7 PF6_ salt 619 650nm (0305) 9660nm (0.188) Example 3 Compound Noβ3 34 PFf salt 620 650nm (0 (316)-660nm (0.181) Example 4 Compound No. 41 PF, salt 594 620nm (0444)-635nm (0.180) Example 5 Compound No. 44 pf6i 610 635nm (0e455)-650nm (0.200) Example 6 Compound No. 52 pf6i 706 770nm (0e292), 780nm (0. 180), 790 (0.151) 83018.doc -32-

Claims (1)

200306334 Patent application park: 1. An optical recording material, which is used for forming the optical recording layer of the optical recording layer on the substrate &quot; the recorded optical layer in the recorded red, which contains the following general formula (I) or (II) Compounds ... (In the formula, ^ and ㈣ are benzene rings or benzo rings which may have a substituent, R1 is a benzene group having 1 to 4 carbon atoms; R2 and ㈣, $ group, or a carbon number 4 are connected to each other to form 3 to 6 A member of a ring group; X is a hydrogen atom, a halogen atom, a fluorenyl group of a carbon number, a phenyl group which may have a substituent, a aryl group which may have a substituent, or cyanite Y1 and Y2 are each independently an organic group; Anm is m-valent anion and m is an integer of 1 or 2. • The positive number of fen ^ a, and p is the coefficient that keeps the charge neutral.) 2. For example, in the first coin of the scope of the patent application, "Jiuzi Jizhi Materials," in the general formula (I) or (II), R2 and R3 are connected to each other to form a base of 3 to 6 members. For example, the optics + bell Youyouyou green material 申 of the patent application No. 2 range, wherein X in the general formula (I) or (II) is a hydrogen atom. 4. If the optics in the scope of claims 1 to 3 or Y1 in (II) is the same base as R1. A green material, in which the general formula ⑴ 5 ·-an optical recording medium 'is formed on the substrate with a thin film containing the optical recording material of any one of claims 1 to 4. 83018.doc 200306334 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the representative symbols of the elements in this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 83018.doc