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    • 专利摘要:
    An optical recording medium excellent in recording sensitivity, light resistance and durability having an optical recording material of Formula 1 and a recording layer comprising the material is provided. Formula 1 Wherein each X 1 -X 4 is a hydrogen atom, an alkyl group, an aryl group, an alicyclic moiety, an aralkyl group, a heterocyclic ring, a substituted heterocyclic ring, an alkoxy group, an aryloxy group, or an alkylthio group , Each of Y 1 -Y 4 is a hydrogen atom, a halogen atom, a nitro group, a phthalimide methyl group or a sulfonamide group, R 1 and R 2 each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group or a diaryl Amino group, M is Al, Ga, In, Si, Ge or Sn, Z is an azo compound, anthraquinone compound or a metal complex salt compound, n 1 -n 4 is 1-4, m 1 -m 4 is 0-4, k is 1 or 2, l is 0 or 1, K + l is 1 or 2.
    公开号:KR19980702259A
    申请号:KR1019970705656
    申请日:1996-12-24
    公开日:1998-07-15
    发明作者:수이찌 기무라；타다시 오가와；마꼬또 사까모또
    申请人:요시토미 데쭈로；도요 잉크 매뉴팩쳐링 캄파니 리미티드；
    IPC主号:
    专利说明:

    Optical recording materials and optical recording media
    Currently write-once optical discs with editing capabilities are organic, such as cyanine, in which a CD format or CD-ROM format signal is recorded at a wavelength of 780 nm and the data is read by a CD or CD-ROM reproducer. CD-Rs having a gold reflective film formed on a recording film formed of a dye are practically used. However, since cyanine dyes generally have poor light stability, data reliablity is a problem for CD or CD-ROMs having a single-sided structure under direct sunlight exposure.
    Therefore, a method of using physiochemically stable phthalocyanine dyes as a recording film material has been attempted. JP-B-4-53713, JP-A-4-214388 and JP-A-5-1272 suggest the use of phthalocyanine compounds, some of which are actually used. The CR-Rs using the phthalocyanine material have the same characteristics as the CD-R using the cyanine dye and serve as a medium based on an Orange Book, and some of them have better light resistance than the medium using the cyanine dye.
    With the recent increase in the use of CD-ROMs, it is required that CD-R media satisfy both fast-access storage and fast-access reading, There is a need for media capable of double-speed and quad-speed storage as well as random-access storage.Pthalocyanine dyes are recorded in comparison with the above-mentioned cyanine dyes. Since sensitivities are generally poor, phthalocyanine dyes do not meet all of the above requirements, so to improve recording sensitivity, the dye structure can be altered by introducing highly thermally degradable substituents as described in JP-A-7-20550. Or use of a pyrolysis-promoting additive as described in JP-A-59-92448. The technique yields a recording sensitivity that can satisfy fast-access storage. Although successful, they generally come at the expense of durability and light resistance, and as a result of improved recording sensitivity, the unstable shape of the recording pit results in insufficient stability of the storage properties and consequently all commercial use. It is difficult to provide CD-Rs with good compatibility in the available CD players, thus improving the properties of the surface layer of the recording film, as shown in JP-B-5-58915 and JP-A-7-98887. Attempts have been made to stabilize the properties of the stored signal by incorporating drugs that control the shape of the drug or the recording pit, but the recording layer will have a complex structure and the productivity will be lower than when only dyes are used. Since the light resistance itself is poor, another problem arises that the reliability is poor.
    The present inventors have intensively studied to improve such a problem, and as a result, by incorporating a phthalocyanine compound having a specific structure as an organic dye incorporated into the recording layer, it has a recording sensitivity suitable for fast-access storage, and is reliable in terms of light resistance and durability. The present invention has been accomplished by discovering that the optical recording medium having improved and stable recording characteristics can be produced.
    EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
    The present invention relates to an optical recording medium which enables writing and reading of data with laser light. More particularly, it relates to optical recording film materials, recording film compositions and media structures for write-once compact discs (CD-R).
    According to one aspect of the present invention, there is provided a phthalocyanine compound having a specific structure represented by the following formula 1 and used for a recording layer in an optical recording medium formed of four layers including a transparent substrate, a recording layer formed of an organic dye, a reflective layer, and a protective layer. There is provided an optical recording material used as an organic dye.
    Wherein each of X 1 -X 4 independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alicyclic residue, an substituted aliphatic ring residue, an aralkyl group, a substituted aralkyl group, a hetero Ring ring, substituted heterocyclic ring, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group, alkylthio group or substituted arylthio group,
    Each of Y 1 -Y 4 is independently a hydrogen atom, a halogen atom, a nitro group, a phthalimidemethyl group, a substituted phthalimidemethyl group, a sulfonamide group, or a substituted sulfonamide group,
    Each R 1 -R 2 is independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkoxy group, a substituted alkoxy group, an aryloxy group , Substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, alkylamino group, substituted alkylamino group, dialkylamino group, substituted dialkylamino group, arylamino group, substituted Arylamino group, diarylamino group or substituted diarylamino group,
    M is Al, Ga, In, Si, Ge or Sn,
    Z is an azo compound, anthraquinone compound or a metal complex salt compound of any one of the following Formulas 2-6,
    n 1 -n 4 is the number of substituents X 1 -X 4 , each independently an integer of 1-4,
    m 1 -m 4 are the numbers of substituents Y 1 -Y 4 , each independently an integer of 0-4,
    k is an axial substituent. Is the number of -OSO 2 -Z, 1 or 2,
    l is the number of axial substituents, OP-(= 0) R 1 R 2 , which is 0 or 1,
    K + l is 1 or 2.
    In the above formula
    R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group, a substituted alkyl group, an aryl group, Substituted aryl group, cycloalkyl group, substituted cycloalkyl group, aralkyl group, substituted aralkyl group, heterocyclic ring, substituted heterocyclic ring, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group, alkyl Thio group, substituted alkylthio group, arylthio group, substituted arylthio group, amino group, alkylamino group, substituted alkylamino group, dialkylamino group, substituted dialkylamino group, arylamino group or substituted arylamino group,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 -n 7 is the number of substituents R 4 and R 5 , each an integer of 0-5.
    Wherein R 3 -R 6 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 -n 8 is the number of substituents R 4 -R 6 , each an integer of 0-3.
    Wherein R 3 -R 6 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 -n 8 is the number of substituents R 3 -R 6 , each an integer of 0-3.
    Wherein A 1 and A 2 are a benzene ring or a naphthalene ring,
    R 3 -R 6 has the same meaning as R 3 -R 5 in Formula 2,
    n 5 -n 8 is the number of substituents R 3 -R 6 , each an integer of 0-3,
    M 1 is a transition metal atom.
    Wherein R 3 and R 4 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 is an integer of 0-5 as the number of substituents R 4 ,
    M 2 is a transition metal.
    When the phthalocyanine compound has a compound having a sulfonic acid group as the axial substituent, the sulfonic acid and the central metal are ionically bonded to each other, and the axial substituent can improve the reliability with respect to light resistance and durability, and can provide stable recording characteristics. have. Preferably, the phthalocyanine compound has an asymmetric structure in which both the substituent formed of the compound having phosphorus and the substituent formed of the compound having a sulfonic acid group are introduced as axial substituents with respect to the central metal, or these substituents are formed only of a substituent formed of a compound having a sulfonic acid group. Has
    According to two aspects of the present invention, an optical recording medium having a recording layer containing at least one phthalocyanine compound having the above structure is provided.
    The inventors have previously found that phthalocyanine compounds having structures with specific axial substituents, such as phosphoric acid ester groups and phosphinic acid ester groups, to the central metal have significantly superior light resistance (JP-A-214388, Preprint of Announcements of Coloring material Researches, 1994, 11B-12), succeeded in providing an optical recording medium excellent in light resistance. However, the phthalocyanine compounds do not satisfy the recording sensitivity that corresponds to recent fast-access storage.
    To improve recording sensitivity, the dye structure can be altered by introducing a highly pyrolysable bulk substituent as disclosed in JP-A-7-20550 for the purpose of inhibiting the binding of phthalocyanine molecules and enhancing the thermal degradability, or JP-A-59 It is necessary to use a combination of additives that promote pyrolysis as disclosed in -24228. While these technologies can achieve recording sensitivity that can be matched to fast-access storage, in most cases durability and light resistance are sacrificed. In addition, as a result of improved recording sensitivity, the stability of the storage characteristics becomes inadequate due to the unstable shape of the data storage pit, and consequently, it is difficult to provide a CD-R with excellent compatibility with all commercially available CD players. . Thus, as shown in JP-B-58915 and JP-A-7-98887, it is desired to stabilize the characteristics of the stored signal by incorporating a drug that improves the properties of the surface layer of the recording film or a drug that controls the shape of the data storage pit. Attempts are being made. However, as a result, the recording layer has a complicated structure and there is a problem that the productivity is inferior as compared with the case of using the dye alone.
    Sato et al. Have proposed an optical recording medium using a phthalocyanine compound having a specific structure in an axial substituent (JP-A-3-281386). However, the proposed compound is not only able to obtain recording sensitivity that can sufficiently meet fast-access storage, but some implementations of the compound have problems in stabilizing the recording characteristics such as poor light resistance or adverse effects on recording characteristics. It is.
    JP-A-5-279580 and JP-A-6-65514 disclose examples in which an azo compound or a metal complex thereof is used as an optical recording material, which is used in combination with a phthalocyanine compound to improve recording sensitivity. There are other embodiments. However, in any of the embodiments, it is not found to produce an optical recording material by binding to an axial substituent of a phthalocyanine compound as the present invention for the purpose of improving recording characteristics.
    JP-A-7-98887 discloses various metal complexes as chemicals for controlling the shape of the data storage pitch. However, all of them are used as additives for improving recording characteristics of optical recording materials such as phthalocyanine compounds, none of which have a structure integrated into the organic dye used in the recording layer. Furthermore, the metal complex is effective in controlling the shape of the data storage pit by controlling heat generation during the recording time, showing that the recorded signal is improved. However, there is generally a problem in that the light resistance of the metal complex itself is poor. For example, when used in combination with a phthalocyanine compound, in most cases the light resistance of the phthalocyanine compound itself cannot be maintained.
    The present inventors have conducted intensive studies, and as a result, the phthalocyanine compound having a specific structure having an azo compound, an anthraquinone compound, or a metal complex salt compound having any one of Formulas 2-6 through a sulfonic acid group overcomes all three problems. It has been found that it has the recording sensitivity that can meet fast-access storage, is excellent in light resistance and durability, and stabilizes the recording characteristics by forming an appropriate data storage pit during the recording time. Therefore, the present inventors have succeeded in providing an optical recording medium having low cost and high productivity.
    In the present invention, the compound structure of the formula and the substituent for the compound will be described. Halogen atoms in the formula include fluorine, chlorine, bromine and iodo. Alkyl groups which may have substituents are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, 2-ethylhexyl, trichloromethyl, trifluor Chloromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl and 2- Nitropropyl. Aryl groups which may have substituents include phenyl, naphthyl, anthranyl, p-methylphenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2- Methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinolyl and 2-aminoanthraquinolyl It includes. Aliphatic ring residues which may have substituents include cyclopentyl, 2,5-dimethylcyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl and adamantyl. Aralkyl groups that may have substituents include benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl and 2,4-dichlorobenzyl. Heterocyclic ring residues which may have substituents include pyridinyl, 3-methylpyridinyl, pyrazinyl, piperidinyl, N-methylpiperidinyl, pyranyl, morphonyl, N-methylpyrrolinyl and acridinyl It includes. Alkoxy groups which may have substituents are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, ste Aryloxy, 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2-ethoxye Oxy, 2-butoxyethoxy and 2-nitropropoxy. Aryloxy groups which may have substituents are phenoxy, naphthoxy, anthranyloxy, p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy And 2-methyl-4-chlorophenoxy. Alkylamino groups which may have substituents include methylamino, ethylamino, dimethylamino, diethylamino, diisopropyl and cyclohexylamino. Arylamino groups that may have substituents include phenylamino, p-nitrophenylamino, 4-methylphenylamino, diphenylamino and di (4-methoxyphenyl) amino. The compound is only an example, and each group is not limited thereto.
    Typical examples of the phthalocyanine compound of the present invention having a structurally specific axial substituent represented by the formula 1 include the following phthalocyanine compounds (a) to (n).
    Phthalocyanine compound (a)

    Phthalocyanine compound (b)

    Phthalocyanine compound (c)

    Phthalocyanine Compound (d)

    Phthalocyanine Compound (e)

    Phthalocyanine Compound (f)

    Phthalocyanine Compound (g)

    Phthalocyanine Compound (h)

    Phthalocyanine compound (i)

    Phthalocyanine compound (j)

    Phthalocyanine Compound (k)

    Phthalocyanine compound (l)

    Phthalocyanine compound (m)

    Phthalocyanine compound (n)

    The recording layer can be formed by any one of a drying method and a wet method. The drying method includes a vacuum deposition method and a sputtering method. Wetting methods include spin coating, dipping, spraying, roll coating, and Langmuir-Blodgett (LB). The recording film material of the present invention exhibits great solubility in commonly used organic solvents such as alcohol-containing, ketone-containing, cellosolve-containing, halogen-containing, hydrocarbon-containing and chlorofluorocarbon-containing solvents. The recording layer is preferably formed by spin coating from the viewpoint of productivity and uniformity of the recording film. When so-called applications are used, polymeric binders can be added as needed.
    Polymer binders include epoxy resins, acrylic resins, polycarbonate resins, polyester resins, polyamide resins, polyvinyl chloride resins, nitrocellulose resins and phenol resins, and the polymer binders are not limited thereto. The mixing ratio of the polymer binder is not particularly limited, but the amount of the polymer binder based on the dye is preferably 30% or less. In the present invention, the optimum film thickness of the recording layer is not particularly limited since it depends on the type and combination of recording film materials, but preferably 500-3,000 kPa, more preferably 800-1,500 kPa.
    In the present invention, the material for the reflective layer includes metals and alloys such as gold, silver, copper, platinum, aluminum, cobalt and tin, oxides and nitrides containing them as main components, but exhibits a large absolute refractive index and stability. Gold is most preferred because it is excellent in. Large-reflective films of organic compounds can be used in some cases. As a method of forming the reflective film, a drying method such as a vacuum precipitation method or a sputtering method is most preferred, but is not limited thereto. Although the optimal film thickness of a reflective film is not specifically limited, 400-1,600 kPa is preferable.
    Furthermore, a protective layer is formed on the reflective film to protect the disk. As the material for the protective film, an ultraviolet curable resin is preferable, and the protective film is preferably formed by a method in which the ultraviolet curable resin is applied by spin coating and cured by irradiating ultraviolet rays, but the materials and methods are limited thereto. It is not. The film thickness of the protective layer is preferably 2-20 μm, with thinner films showing a reduced effect and thicker films causing poor mechanical properties such as disk warpage due to shrinkage caused when the resin is cured. do.
    The disk substrate used in the present invention preferably has a light transmittance of at least 85% and low optical anisotropy with respect to the write and read signals. Examples of disk substrates include glass, acrylic resins, polycarbonate resins, polyester resins, polyamide resins, thermoplastic resins such as polystyrene resins and polyolefin resins, and substrates formed from thermosetting resins such as epoxy resins and acrylic resins. Among them, a substrate formed of a thermoplastic resin is preferable because it is easy to mold and easy to provide wobble signals for ATIP and guide grooves. Substrates formed of acrylic resins or polycarbonate resins are preferred in view of optical properties, mechanical properties and cost.
    The shape of the guide groove in the substrate is not particularly limited, but may be trapezoidal, U-shaped or V-shaped. The optimum value of the size of the guide groove depends on the type and bonding of the recording film material. In general, the average groove width (width at a position having a height equal to 1/2 of the groove depth) is preferably 0.4-0.6 mu m, and the groove width is preferably 1,000-2,000 mm 3. The disc in the present invention is preferable based on the CD-ROM standard (Red Book) and the CD-R standard (Orange Book), since it must function as a CD or CD-ROM after recording is performed.
    In the present invention, the phthalocyanine compound of formula 1 may be used alone or in combination. For the balance of recording characteristics, other phthalocyanine compounds can be added and used in combination, but the other phthalocyanine compounds need to be excellent in light resistance and durability. Preference is given to phthalocyanine compounds having excellent light resistance as disclosed in JP-A-4-214388, since they have specific axial substituents in the structure in which the phosphate ester and phosphinic ester groups are bonded to the central metal.
    The phthalocyanine compound of formula 1 can be obtained by reacting a phthalocyanine compound having a central metal having a hydroxy group with an sulfoic acid of an azo compound, anthraquinone compound, or a metal complex salt compound, which is introduced as a reactive agent or a halide of sulfonic acid as a reactant in a suitable solvent. have. Furthermore, when the phthalocyanine compound has a central metal which is a trivalent metal such as Al or Ga, the phthalocyanine compound may have a sulfonic acid group even though the phthalocyanine compound has a structure having a specific axial substituent such as a phosphate ester group or a phosphinic ester group. It can form a salt with the said compound which has. In this case, the central metal and the sulfonic acid group are ionically bonded to each other.
    Hereinafter, embodiments of the present invention will be described in detail.
    Synthesis Example 1
    Synthesis of Phthalocyanine Compound (a)
    3.0 g of dihydroxysilicone tetra [2,2'-bis (trifluoromethyl) propyl] propoxy] phthalocyanine was dissolved in 100 ml of N-methylpyrrolidone and 3- (2-chloro-4-hydroxyphenyl 1.0 g of azo) benzenesulfonic acid was added and the mixture was stirred at 80 ° C. for 2 hours under heating. The reaction mixture was poured into 2.0 L of ice water, and the precipitated crystals were collected by filtration, washed with water and dried to obtain a blue powder. The powder was dissolved in 200 ml of chloroform and the insolubles were filtered off. The solvent was distilled off from the filtrate to obtain 1.6 g of cyan powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (a).
    Synthesis Example 2
    Synthesis of Phthalocyanine Compound (b)
    Dihydroxysilicone tetra [2,2'-bis (trifluoromethyl) propoxy] phthalocyanine with hydroxyaluminum tetrabromotetra (2,2,3,3-tetrafluoropropoxy) phthalocyanine and 3 1.2 g of a cyan powder was prepared in the same manner as in Synthesis Example 1, except that-(2-chloro-4-hydroxyphenylazo) benzenesulfonic acid was replaced with 3- (4-diethylaminophenylazo) benzenesulfonic acid. Obtained. The powder was analyzed by FD-MS to identify phthalocyanine compound (b).
    Synthesis Example 3
    3.2 g of hydroxyaluminum octachlorotetra [2,2'-bis (trifluoromethyl) propoxy] phthalocyanine was dissolved in 80 ml of anhydrous sulfolane, 1.0 g of sulfonic acid of the azo dye of the following formula was added, and the mixture was Stir at 100 ° C. for 2 hours. The reaction mixture was poured into 1.0 L of ice water, and the resulting precipitate was collected by filtration and washed with water to obtain a bluish green paste. The paste was dissolved in 600 ml of methanol and the insolubles were filtered off. Then 150 ml of water was added dropwise to the filtrate and the mixture was stirred for 3 hours. The resulting precipitate was collected by filtration, washed with a metal / water (4/1) mixture and dried to yield 0.6 g of a blue green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (c).
    Synthesis Example 4
    Synthesis of Phthalocyanine Compound (d)
    2.8 g of hydroxyaluminum tetrabromotetra (neopentyloxy) phthalocyanine and 0.5 g of pyridine are added to 150 ml of dioxane, then 4.0 g of anthraquinone-2-sulfonic acid chloride is slowly added and the mixture is heated to reflux for 2 hours. It was. After cooling the reaction mixture, the solvent was distilled off under reduced pressure. The residue was dissolved in 400 ml of ethanol and insolubles were filtered off. Then 100 ml of water was added dropwise to the filtrate and the mixture was stirred for 3 hours. The resulting precipitate was recovered by filtration, washed with a metal / water (4/1) mixture and dried to give 1.1 g of a bluish green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (d).
    Synthesis Example 5
    Synthesis of Phthalocyanine Compound (e)
    3.2 g of dihydroxysilicone tetra [2,2'-bis (trifluoromethyl) propoxy] phthalocyanine was dissolved in 10 ml of dimethylaminoacetamide, 1.0 g of sulfonic acid of copper complex salt of the following formula was added, and the mixture was Stir under heating at 90 ° C. for 4 hours. The reaction mixture was poured into 1.0 L of ice water, and the resulting precipitate was collected by filtration and washed with water to obtain a green paste. The paste was dissolved in 800 ml of toluene and the insolubles were filtered off. The residue was then washed with water, dried over magnesium sulfate and the solvent was distilled off to yield 1.6 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (e).
    Synthesis Example 6
    Synthesis of Phthalocyanine Compound (f)
    3.0 g of hydroxyaluminum tetra [(2-methyl) butoxy] phthalocyanine and 1.0 g of n-butylferrocenesulfonic acid were added to 150 ml of toluene, and the mixture was refluxed for 3 hours under heating. The reaction mixture was filtered, and the resulting product was washed with 50 ml of ethanol and dried to obtain 2.2 g of a blue green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (f).
    Synthesis Example 7
    Synthesis of Phthalocyanine Compound (g)
    3.2 g of hydroxyaluminum octachlorotetra [2,2'-bis (trifluoromethyl) propoxy] phthalocyanine and 1.5 g of ferrocenesulfonic acid chloride were dissolved in 150 ml of benzene, 0.5 g of pyridine was added and the mixture was stirred for 3 hours. At reflux under heating. The reaction mixture was cooled down and then diluted with 350 ml of benzene and 300 ml of hexane was added dropwise. The mixture was stirred for 2 hours. The precipitated crystals were collected by filtration, washed with benzene / hexane (2/1) mixed solvent and dried to obtain 2.0 g of a bluish green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (g).
    Synthesis Example 8
    Synthesis of Phthalocyanine Compound (h)
    3.0 g of dihydroxysilicone tetra [2,2'-bis (trimethylfluoromethyl) propoxy] phthalocyanine was dissolved in 100 ml of N-methylpyrrolidone and 3- (4-diethylaminophenylazo) benzenesulfonic acid 2.0 g was added and the mixture was stirred at 80 ° C. for 2 h under heating. The reaction mixture was poured into 2.0 L of ice water and the precipitated crystals were collected by filtration, washed with water and dried to give a dark green powder. The powder was dissolved in 200 ml of chloroform, the insolubles were filtered off, and the solvent in the filtrate was distilled off to obtain 1.6 g of a dark green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (h).
    Synthesis Example 9
    Synthesis of Phthalocyanine Compound (i)
    3.0 g of diphenylphosphinoyloxyhydroxysilicone tetra (2,5-dimethyl-3-pentyloxy) phthalocyanine was dissolved in 100 ml of sulfolane and 1.0 g of 3- (2-hydroxynaphthylazo) benzene was added. The mixture was refluxed under heating at 80 ° C. for 2 hours. The reaction mixture was poured into 2.0 L of ice water, and the precipitated crystals were collected by filtration, washed with water and dried to give a dark green powder. The powder was dissolved in 200 ml of chloroform, the insolubles were filtered off, and the solvent in the filtrate was distilled off to obtain 1.8 g of a dark green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (i).
    Synthesis Example 10
    Synthesis of Phthalocyanine Compound (j)
    3.2 g of diphenylphosphinoyloxyaluminum octachloro-tetra [2,2'-bis (trifluoromethyl) propoxy] phthalocyanine was dissolved in 100 ml of N-methylpyrrolidone and 1.5 g of ferrocenesulfonic acid was added thereto. The mixture was stirred at 25 ° C. for 2 hours. The reaction mixture was poured into 200 ml of ice water, and the resulting precipitate was collected by filtration and washed with water to obtain a green paste. The paste was dissolved in 400 ml of acetone and insolubles were filtered off. 200 ml of octane were then added dropwise to the filtrate and the mixture was stirred for 3 hours. The resulting precipitate was recovered by filtration, washed with octane and dried to give 0.9 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (j). Furthermore, the powder solution dissolved in ethyl cellosolve was also evaluated by electron absorption spectrum so that the maximum absorption peak was obtained by diphenylphosphinoyloxyaluminum octachloro-tetra [2,2'-bis (trifluoromethyl) propoxy. ] 10 nm shifted from the maximum absorption peak of phthalocyanine toward the larger wavelength direction. Therefore, it was found that the reactants of phthalocyanine, ferrocenesulfonic acid, and the center metal Al, as raw materials, have mutual effects by ionic bonding.
    Synthesis Example 11
    Synthesis of Phthalocyanine Compound (k)
    2.8 g of hydroxyaluminum tetra [2,2,3,3-tetrafluoropropoxy) phthalocyanine was dissolved in 100 ml of N-methylpyrrolidone, 3.0 g of ferrocenesulfonic acid was added, and the mixture was 80 ° C. Stir for 2 hours. The reaction mixture was poured into 200 ml of iced water, and the resulting precipitate was collected by filtration and washed with water to obtain a green paste. The paste was dissolved in 400 ml of acetone and insolubles were filtered off. Then 200 ml of octane was added dropwise and the mixture was stirred for 3 hours. The resulting precipitate was recovered by filtration, washed with octane and dried to give 1.3 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (k).
    Synthesis Example 12
    Synthesis of Phthalocyanine Compound (l)
    3.0 g of dihydroxygermanium tetrabromo-tetra-tert-butylphthalocyanine was added to a solution containing 100 ml of xylene and 0.5 g of pyridine, 1.5 g of anthraquinone-β-sulfonic acid chloride was added and the mixture was refluxed for 3 hours under heating. I was. The reaction mixture was cooled and then poured into 300 ml of octane and the resulting precipitate was collected by filtration and dissolved in 50 ml of acetone. Insolubles were filtered off and 50 ml of octane was added to give a green precipitate. The precipitate was collected by filtration, washed with octane and dried to obtain 0.7 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (1).
    Synthesis Example 13
    Synthesis of Phthalocyanine Compound (m)
    3.0 g of hydroxygallium tetra (tert-butyl) phenylthioptalocyanine and 3.0 g of a nickel complex salt sulfonic acid compound having a structure of the following formula are added to 100 ml of N-methylpyrrolidone and the mixture is stirred under heating at 90 ° C. for 3 hours. It was. The reaction mixture was cooled, poured into 200 ml of ethanol, and the resulting precipitate was collected by filtration, washed with ethanol and dried to obtain 3.1 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (m).
    Synthesis Example 14
    Synthesis of Phthalocyanine Compound (n)
    2.5 g of diphenylphosphinoyloxyaluminum tetra (neopentyloxy) phthalocyanine and 1.0 g of butyl ferrocenesulfonic acid were added to 50 ml of methyl cellosolve and the mixture was stirred at 25 ° C. for 4 hours. The insolubles were filtered off and then the solvent was distilled off under reduced pressure. The remainder was filtered with the addition of 50 ml of octane, and the product obtained by filtration was washed with 100 ml of octane and dried to obtain 2.8 g of green powder. The powder was analyzed by FD-MS to identify phthalocyanine compound (n).
    Example 1 and Comparative Example 1
    One of the phthalocyanine compounds (a)-(n) or 100 mg of the comparative phthalocyanine compounds (o) and (p) of the following formula was added to 3 ml of ethyl cellosolve and dissolved in an ultrasonic cleaner. The solution was applied to a 0.2 μ filter and the resulting solution was used to form a dye film with a spin coater at 1,200 rpm on a glass substrate heat-treated under reduced pressure. The formed film was measured for absorbance (Abs.) At the maximum absorption peak ( Max) with a spectrophotometer, and the specific value was taken as 100.
    Then, the glass substrate having the film formed thereon was placed on a photoresist tester and irradiated at 50,000 lux for 150 hours, and then the absorbance was measured at λ max as well, and the film was evaluated based on the ratio of measured value: initial value 100. .
    Phthalocyanine Compound (o)
    Phthalocyanine compound (p)
    Phthalocyanine compoundsBefore photoresist testAfter photoresist test (a)10094 (b)10091 (c)10089 (d)10093 (e)10095 (f)10092 (g)10096 (h)10092 (i)10088 (j)10097 (k)10090 (l)10087 (m)10092 (n)10095 (o)10074 (p)10081
    Table 1 shows that the decrease in the absorbance of the thin film of the phthalocyanine compound of Formula 1 with respect to the initial value is very small compared to the case of using the phthalocyanine compounds (o) and (p) as comparative examples, and the decrease is all within 15%. . Therefore, the axial substituents of the phthalocyanine compounds (a) to (n) show an effective effect in improving the light resistance.
    Example 2
    A kind of 5% by weight ethyl cellosolve solution of phthalocyanine compounds (a) to (n) was prepared, and from this, the spin coater had a guide groove having a width of 1,600 mm, a width of 0.4 m and a pitch of 1.6 m, A film having a thickness of 500 mm 3 was formed on a polycarbonate substrate having a diameter of 1.2 mm, an outer diameter of 200 mm, and an inner diameter of 30 mm. Then, a film having a thickness of 800 Å formed of gold by sputtering on the dye film was formed as a reflective coating. Furthermore, a protective film was formed from the UV curable film on it, and the CD-R disc was obtained. EFM signals were recorded in the medium with a semiconductor laser at a linear speed of 1.2 mm / sec. The recorded signal characteristics were evaluated by the Orange Book.
    The optical disk was then applied to a light resistance tester at 50,000 lux for 100 hours and then pulled out. Recording was performed and the recorded signal characteristics were evaluated in the same manner as above. The results are shown in Table 2 below.
    The recorded signal characteristics evaluated are optimum recording power (PO), maximum reflection value (Rtop, Refraction top) of the pit array, block error rate (BLER) in the pit array and maximum in the longest pit array. And minimum reflectance difference (LLT modulation, IIT modulation).
    Table 2 below shows that optical recording media (CD-R) using phthalocyanine compounds (a) to (n) have stable recording characteristics such as excellent recording sensitivity, a small error ratio and a high modulation degree, in particular with respect to light resistance. Since there is no significant difference in recording characteristics between the untested media and the tested media, the media is fully compatible with fast-access storage and has great reliability.
    Phthalocyanine compounds POmWRtop%BLER up to / 10secIIT modulation (a) (a)Early6.472554 Alrt * 681251 (b) (b)Early5.868562 Alrt * 641458 (c) (c)Early5.567565 Alrt * 661061 (d) (d)Early5.366553 Alrt * 622150 (e) (e)Early5.669562 Alrt * 69559 (f) (f)Early6.072564 Alrt * 72563 (g) (g)Early5.570565 Alrt * 70563 (h) (h)Early6.463554 Alrt * 581750 (i) (i)Early6.861562 Alrt * 571458 (j) (j)Early5.565560 Alrt * 63860 (k) (k)Early5.356553 Alrt * 551850 (l) (l)Early5.654557 Alrt * 512655 (m) (m)Early5.149572 Alrt * 492868 (n) (n)Early5.569565 Alrt * 67562
    Alrt * = after light resistance test
    Example 3 and Comparative Example 2
    A solution in which 150 mg of the phthalocyanine compound (j) was dissolved in 3 ml of ethyl cellosolve was prepared, and a spin coater had a guide groove having a depth of 1,800 mm, a width of 0.4 m and a pitch of 1.6 m, and a thickness of 1.2 mm and an outer diameter. A film having a thickness of 800 mm 3 was formed on a polycarbonate substrate having a diameter of 200 mm and an internal diameter of 30 mm. Gold was then sputtered onto the dye film to form a film having a thickness of 800 mm 3 as a reflective film. Furthermore, a protective film was formed from the UV cured film thereon, and the CD-R disc was manufactured. An EFM signal was recorded in the medium at a line speed of 1.2 mm / sec with a semiconductor laser. The recorded signal characteristics were evaluated by the Orange Book.
    The optical disk was then applied for 100 hours at 50,000 lux with a light resistance tester and then pulled out. The signal characteristics recorded were evaluated in the same manner as above. The results are shown in Table 3 below.
    As a comparative example, a CD-R disc was formed in the same manner as above using a 5% solution of phthalocyanine compound (q) of the following formula. Then, the recording characteristics were evaluated and the light resistance test was performed in the same manner as above. The results are shown in Table 3 below.
    Phthalocyanine compound (q)
    ExampleFurtherance POmWRtop%BLER up to / 10secIIT Modulation Example 3(j)Early5.669565 Alrt * 68564 Comparative Example 2(q)Early6.070562 Alrt * 6021055
    Alrt * = After Light Resistance Test
    Table 3 shows the following facts. Compared with the phthalocyanine compound (q), the phthalocyanine compound (j) shows an improvement in recording characteristics such as modulation degree and error ratio, in particular, the phthalocyanine compound (j) is a medium tested with a medium that has not been tested in the light resistance test. There seems to be very few cars in between. In contrast, after the light resistance test, the phthalocyanine compound (q) showed reduced Rtop, reduced modulation and increased error ratio. That is, the phthalocyanine compound (j) shows an improvement in the recording characteristics than the phthalocyanine compound (q) and shows that the light resistance is improved due to the effect of a specific axial substituent having a sulfonic acid group.
    According to the above, the recording layer contains a phthalocyanine compound having a specific axial substituent having a sulfonic acid group, thereby providing an optical recording medium having a recording sensitivity, an optical recording characteristic fully conforming to fast-access storage, and having excellent light resistance. Can be.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] An optical recording material of the phthalocyanine compound of Formula 1,
    Formula 1

    Wherein each X 1 -X 4 independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alicyclic residue, an substituted aliphatic ring residue, an aralkyl group, a substituted aralkyl group, Heterocyclic ring, substituted heterocyclic ring, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group, alkylthio group or substituted arylthio group,
    Each of Y 1 -Y 4 is independently a hydrogen atom, a halogen atom, a nitro group, a phthalimidemethyl group, a substituted phthalimidemethyl group, a sulfonamide group, or a substituted sulfonamide group,
    Each R 1 -R 2 is independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkoxy group, a substituted alkoxy group, an aryloxy group , Substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, alkylamino group, substituted alkylamino group, dialkylamino group, substituted dialkylamino group, arylamino group, substituted Arylamino group, diarylamino group or substituted diarylamino group,
    M is Al, Ga, In, Si, Ge or Sn,
    Z is an azo compound, anthraquinone compound or a metal complex salt compound of any one of the following Formulas 2-6,
    n 1 -n 4 is the number of substituents X 1 -X 4 , each of which is independently an integer of 1-4,
    m 1 -m 4 is the number of substituents Y 1 -Y 4 , each of which is independently an integer from 0-4,
    k is an axial substituent. Is the number of -OSO 2 -Z, 1 or 2,
    l is the number of axial substituents, OP-(= 0) R 1 R 2 , which is 0 or 1,
    K + l is 1 or 2.
    Formula 2

    Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group, a substituted alkyl group, Aryl group, substituted aryl group, cycloalkyl group, substituted cycloalkyl group, aralkyl group, substituted aralkyl group, heterocyclic ring, substituted heterocyclic ring, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryl jade Period, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, amino group, alkylamino group, substituted alkylamino group, dialkylamino group, substituted dialkylamino group, arylamino group or substituted arylamino group ,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 -n 7 is the number of substituents R 4 and R 5 , each of which is an integer from 0-5.
    Formula 3

    Wherein R 3 -R 6 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 -n 8 is the number of substituents R 4 -R 6 , each of which is an integer from 0-3.
    Formula 4

    Wherein R 3 -R 6 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 -n 8 is the number of substituents R 3 -R 6 , each of which is an integer from 0-3.
    Formula 5

    Wherein A 1 and A 2 are a benzene ring or a naphthalene ring,
    R 3 -R 6 has the same meaning as R 3 -R 5 in Formula 2,
    n 5 -n 8 is the number of substituents R 3 -R 6 , each an integer of 0-3,
    M 1 is a transition metal atom.
    Formula 6

    Wherein R 3 and R 4 have the same meaning as R 3 -R 5 of Formula 2,
    n 5 is the number of substituents R 3 and is an integer from 0-4,
    n 6 is an integer of 0-5 as the number of substituents R 4 ,
    M 2 is a transition metal.
    [2" claim-type="Currently amended] 2. The optical recording material of claim 1, wherein k and l are each 1 in the formula (1).
    [3" claim-type="Currently amended] The optical recording material of claim 1, wherein l is 0 in the formula (1).
    [4" claim-type="Currently amended] An optical recording medium comprising a transparent substrate, four layers of a recording layer, a reflective layer and a protective layer containing the optical recording material recited in claim 1
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    同族专利:
    公开号 | 公开日
    KR100288681B1|2001-05-02|
    EP0811506A1|1997-12-10|
    DE69612189D1|2001-04-26|
    AU1172797A|1997-07-17|
    CN1169128A|1997-12-31|
    TW334528B|1998-06-21|
    DE69612189T2|2001-07-19|
    WO1997023354A1|1997-07-03|
    EP0811506B1|2001-03-21|
    CN1070783C|2001-09-12|
    US5820962A|1998-10-13|
    JP3377531B2|2003-02-17|
    EP0811506A4|1998-04-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1995-12-25|Priority to JP336241/95
    1995-12-25|Priority to JP33624195
    1996-01-16|Priority to JP445196
    1996-01-16|Priority to JP4451/96
    1996-12-21|Application filed by 요시토미 데쭈로, 도요 잉크 매뉴팩쳐링 캄파니 리미티드
    1996-12-24|Priority to PCT/JP1996/003753
    1998-07-15|Publication of KR19980702259A
    2001-05-02|Application granted
    2001-05-02|Publication of KR100288681B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP336241/95|1995-12-25|
    JP33624195|1995-12-25|
    JP445196|1996-01-16|
    JP4451/96|1996-01-16|
    PCT/JP1996/003753|WO1997023354A1|1995-12-25|1996-12-24|Optical recording material and optical recording medium|
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