JPH0448639B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical recording media, particularly heat mode optical recording media. Prior Art Optical recording media have the characteristic that the recording medium does not deteriorate due to wear since the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out. Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom. This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium, which is called a pit. There is a pit-forming type in which writing is performed by forming small holes, information is recorded using the pits, and reading is performed by detecting the pits with a readout light. Until now, most of these pit-forming type media, especially those using a semiconductor laser as a light source that can make the device smaller, have a recording layer made of a material mainly composed of Te. However, in recent years, it has become clear that Te-based materials are harmful.
In addition, due to the need for higher sensitivity and lower manufacturing costs, Te
In place of conventional recording media, there are an increasing number of proposals and reports on media that use recording layers made of organic materials mainly containing dyes. For example, for He-Ne lasers, squalirium dye [JP-A No. 56-46221, VBJipson
and CRJones, J.Vac.Sci.Tech-nol., 18 (1)
105 (1981)] and metal phthalocyanine dyes (Japanese Unexamined Patent Publication Nos. 57-82094 and 57-82095). There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Application Laid-Open No. 86795/1986). In both of these, the recording layer is made into a thin film by vapor deposition of dye, and there is no major difference from the Te type in terms of medium production. However, the reflectance of the dye-deposited film to the laser is generally small, and the current conventional method of obtaining a readout signal from a change (decrease) in the amount of reflected light due to the pit cannot obtain a large S/N ratio. Can not. In addition, it is possible to use a transparent substrate carrying a recording layer as a medium with a so-called air sandwich structure in which the recording layers are integrated so that they face each other, and write and read data through the substrate without reducing the writing sensitivity. Although it is advantageous in that the recording layer can be protected and the recording density can be increased, such a recording/reproducing method is also not possible with a dye-deposited film. This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate) and a relatively high surface reflectance (4% for polymethyl methacrylate), and the reflection through the substrate of the recording layer. Rate is,
For example, with polymethyl methacrylate, the reflectance is about 60% or less, so it cannot be detected with a recording layer that exhibits only a low reflectance. Readout S/ of recording layer made of dye deposited film
In order to improve the N ratio, a vapor-deposited reflective film of Al or the like is usually interposed between the substrate and the recording layer. In this case, the vapor-deposited reflective film increases the reflectance and increases the S/
The purpose is to improve the N ratio, and the reflective film is exposed by pit formation and the reflectance increases, or in some cases, the reflective film is removed to reduce the reflectance. As a matter of course,
Recording and playback through the substrate is not possible. Similarly, JP-A-55-161690 describes a recording layer consisting of IR-132 dye (manufactured by Kodatsu) and polyvinyl acetate, and JP-A-57-74845 discloses a recording layer consisting of 1,1'-
A recording layer consisting of diethyl-2-2'-tricarbocyanine iodide and nitrocellulose, as well as KYLaw, et al., Appl.Phys.Lett. 39
(9) 718 (1981) contains 3,3'-diethyl-12-
A medium is disclosed in which a recording layer made of a dye and a resin is formed by a coating method, such as a recording layer made of acetylthiatetracarbocyanine and polyvinyl acetate. However, these cases also have the same drawback as the dye-deposited film in that a reflective film is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the back side of the substrate. In this way, in order to realize a medium with an organic material-based recording layer that is capable of recording and reproducing through the substrate and is compatible with a medium that has a recording layer made of Te-based material, it is necessary to use an organic material. It is necessary for it to exhibit a large reflectance. However, conventionally, there are very few examples of exhibiting high reflectance with a single layer of organic material without stacking reflectance. It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance [P. Kivits, etal.
Appl.Phys.Part A 26 (2) 101 (1981), JP-A-Sho
No. 55-97033], but the writing sensitivity is low, probably due to the high sublimation temperature. It has also been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes exhibit high reflectance (Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics, 1p-p-9 (1980)). A proposal based on this was made in JP-A-58-112790, but these dyes have low solubility in solvents, are easily crystallized, and are more sensitive to readout light, especially when applied as a coating film. It is extremely unstable and immediately decolorizes, making it unusable for practical use.In view of these circumstances, the present inventors first
No. 57-134397, which proposes the use of indolenine-based cyanine dyes that have high solubility in solvents, little crystallization, thermal stability, and high reflectance of paint films as a single layer film. , 57-134170
issue). In addition, long-chain alkyl groups can be introduced into the molecules of other cyanine dyes such as indolenine, thiazole, quinoline, and selenazole to improve solubility and prevent crystallization. (Patent Application No. 57-182589, same)
57-177776, etc.). Furthermore, we have proposed adding a quencher to the cyanine dye in order to improve photostability and, in particular, to prevent decolorization (reproduction deterioration) caused by readout light (Japanese Patent Application No. 166832/1983, 168048 etc.). By the way, as one of the dyes, a dye represented by the following general formula [] is known. (Tokuko Showa 31
−5920, U.S. Patent No. 1845404, U.S. Patent No. 3652283
No. 3384487, Special Publication No. 57-46056, etc.). General formula [] {In the above general formula [], Z represents an atomic group necessary to complete the indolenyl group which may have a fused ring. R ₁ represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group. L ₁ and L ₂ each represent a substituted or unsubstituted methine group. l is an integer of 1, 2 or 3. R ₂ represents a monovalent group. k is 0 or an integer from 1 to 5. However, k
is 2 or more, a plurality of R ₂ may be different or the same. X ^- represents an anion. n is 0 or 1. } These dyes are used especially for silver halide photography. The present inventors formed a recording layer using these dyes to create an optical recording medium, and confirmed that writing and reading could be performed through the substrate even with a single layer film without laminating a reflective layer. . However, it has been found that during readout after writing, the dye is bleached by repeated irradiation with readout light, resulting in significant reproduction deterioration in which the readout S/N ratio deteriorates, making it impractical for practical use. OBJECTS OF THE INVENTION The main object of the present invention is to provide an optical recording medium having a recording layer containing a dye represented by the above general formula [], in which reproduction deterioration is improved. These objects are achieved by the invention described below. That is, the present invention provides an optical recording medium having a recording layer formed of a dye composition on a substrate, wherein the dye consists of a compound represented by the following general formula [], a quencher is contained in the dye composition, and The present invention is an optical recording medium characterized in that deterioration of the dye due to reproduction light is prevented. General formula [] {In the above general formula [], Z represents an atomic group necessary to complete the indolenyl group which may have a fused ring. R ₁ represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group. L ₁ and L ₂ each represent a substituted or unsubstituted methine group. l is an integer of 1, 2 or 3. k is 0 or an integer from 1 to 5. However, when k is 2 or more, a plurality of R ₂ may be different or the same. X ^- represents an anion. n is 0 or 1. } Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The dye used in the present invention is represented by the above general formula []. In the above general formula [], Z represents an atomic group necessary to complete the indolenyl group which may have a fused ring. That is, Z is preferably as follows. In the above general formula [], R ₁ is a substituted or unsubstituted alkyl group (e.g. methyl, ethyl,
butyl, octyl, etc.), aryl groups (eg, phenyl, etc.), or alkenyl groups (eg, allyl, metaallyl, etc.). There is no particular restriction on the number of carbon atoms in R ₁ . In addition, when these are substituted, examples of the substituent include an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxycarbonyl group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, an aryl It may be any of carbonyloxy group, arylamide group, arylsulfonamide group, aryloxycarbonyl group, arylamino group, arylcarbamoyl group, arylsulfamoyl group, hydroxyl group, carboxy group, sulfonic acid group, halogen atom, etc. . Note that when n described below is 0, R ₁ is a substituted alkyl group, a substituted aryl group, or a substituted alkenyl group, and may have a negative charge. Furthermore, in formulas [Φ] to [Φ], two substituents R ₃ and R ₄ are preferably bonded to the 3rd position. In this case, the two substituents R ₃ and R ₄ bonded to the 3-position are preferably an alkyl group or an aryl group. Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred. Furthermore, another substituent R ₅ may be bonded to a predetermined position in these rings. Such substituents include halogen atoms, alkyl groups, aryl groups, heterocyclic residues, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, and aryloxycarbonyl groups. group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino group, carboxylic acid group, sulfonic acid group, alkylsulfonyl group, arylsulfonyl The substituents may be various substituents, such as a group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, a nitro group, or a hydroxy group. And the number of these substituents (p, q, r)
is usually about 0 or 1 to 4. In addition,
When p, q, and r are 2 or more, a plurality of R ₅ may be different from each other. L ₁ and L ₂ are methine groups that may be substituted, but are usually CH. l may be 1, 2 or 3. R ₂ represents a monovalent group, p=0, 1, 2,
3, 4 or 5. In this case, when p≧2, the plurality of R ₂ may be the same or different. Note that p is 1 or more, particularly 1 or 2, one of which is bonded to the p-position and the other one is bonded to the m-position, and R ₂ bonded to the p-position is a substituted Alternatively, it is preferably an unsubstituted dialkylamino group or an alkyloxy group. In this case, the substituents include a sulfonic acid group, a cyano group,
These include halogen atoms and carboxylic acid groups. In addition, when n is 0 and no anion is present, one of R ₂ , especially at the p-position.
R ₂ may be substituted with SO ₃ ^- , etc. to form an inner salt. Furthermore, the anion represented by X ^- is
I ^- , Br ^- , ClO ₄ ^- , BF ₄ ^- ,
[Formula] [Formula] etc. And n is 0 or 1. Next, specific examples of styryl dyes represented by the general formula [] will be listed. [Table] [Table] When l=1 or 2, such dyes are disclosed in Japanese Patent Publication No. 31-5920, U.S. Patent No. 1845404, U.S. Pat.
Synthesized according to No. 3652283, No. 3384487, Japanese Patent Publication No. 57-46056, etc. In addition, in the case of l=2 and 3, J.Chemical
Society, 1266 (1961), Berichte, 94 , 838
(1961), Bulletin of the Chemical Society of
Japan, 43 , 1586 (1970), the methine chain is extended to form an α,β-unsaturated aldehyde, and then synthesized according to the above method. Further, such a dye is usually contained in the recording layer in the form of a monomer, but may be contained in the form of a polymer if necessary. In this case, the polymer has two or more molecules of a dye, and may be a condensate of these dyes. For example, single or co-condensates of the above dyes having one or more functional groups such as -OH, -COOH, -SO ₃ H, etc., or with these, dialcohols, dicarboxylic acids, or their salts. There are cocondensation components such as diamines, di- and triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other pigments. Alternatively, the dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dye. In this case, the metal crosslinking agents include alkoxides of titanium, zircon, aluminum, etc., chelates of titanium, zircon, aluminum, etc. (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and their esters, ketoalcohols, aminoalcohols, enols) acylates of titanium, zircon, aluminum, etc.). Furthermore, -OH group, -OCOR group and -
One or more dyes having at least one COOR group (wherein R is a substituted or unsubstituted alkyl group or aryl group);
Alternatively, it is also possible to use a compound in which this and other spacer components or other dyes are bonded through a -COO- group through a transesterification reaction. In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum as a catalyst. Additionally, the dyes described above may be bound to a resin. In such a case, a resin having a predetermined group is used, and the side chain of the resin is subjected to a condensation reaction, transesterification reaction, or crosslinking, as in the case of the polymer described above. The dyes are linked via a spacer component, etc., if necessary. Such dyes may be used in combination with other dyes to form the recording layer as long as the effects of the present invention are not achieved. The recording layer may contain a resin if necessary. The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin. Among these, resins that can be particularly suitably used include the following. Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc. Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer,
Acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-maleic anhydride copolymer, ethylene propylene terpolymer (EPT), etc. In this case, the polymerization ratio of the comonomers can be arbitrary. Vinyl chloride copolymer For example, vinyl acetate-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, copolymer of acrylic acid ester or methacrylic acid ester and vinyl chloride acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer, ethylene or propylene-vinyl chloride copolymer, ethylene-
Such as vinyl chloride graft polymerized to vinyl acetate copolymer. In this case, the copolymerization ratio can be arbitrary. Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc. In this case, the copolymerization ratio can be arbitrary. Polystyrene Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-acrylic ester- Acrylamide copolymer, styrene-butadiene copolymer (SBR), styrene-
Vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2,5-dichlorostyrene, α,β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as , a copolymer of α-methylstyrene and methacrylic acid ester. Coumarone-indene resin A copolymer of coumaron-indene-styrene. Terpene resin or picolite For example, terpene resin which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene. Acrylic resin In particular, those containing an atomic group represented by the following formula are preferred. formula In the above formula, R ₁₀ represents a hydrogen atom or an alkyl group, and R ₂₀ represents a substituted or unsubstituted alkyl group. In this case, in the above formula,
R ₁₀ is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group. Further, R ₂₀ may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R ₂₀ is a substituted alkyl group, the alkyl group preferably has 1 to 8 carbon atoms. The substituent for the group is preferably a hydroxyl group, a halogen atom, or an amino group (particularly a dialkylamino group). The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one type of atomic group represented by the above formula is used. Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units. Polyacrylonitrile Acrylonitrile copolymer For example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer, acrylonitrile-methacrylate acid methyl copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-
Butyl acrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. Diacetone acrylamide polymer Diacetone acrylamide polymer made by acetone acting on acrylonitrile. Polyvinyl acetate Vinyl acetate copolymer For example, a copolymer with acrylic acid ester, vinyl ether, ethylene, vinyl chloride, etc. The copolymerization ratio may be arbitrary. Polyvinyl ether For example, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc. Polyamide In this case, the polyamide includes nylon 6,
Nylon 6-6, Nylon 6-10, Nylon 6-
12, nylon 9, nylon 11, nylon 6-12,
In addition to regular homonylon such as nylon 13, nylon 6/6-6/6-10, nylon 6/6-6/
12, a polymer such as nylon 6/6-11, or modified nylon in some cases. Polyester For example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, ethylene glycol, and tetrabasic acids. Condensates and co-condensates with glycols such as methylene glycol and hexamethylene glycol are suitable. Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable. Furthermore, for example, a modified gliptal resin, which is a condensation product of phthalic anhydride and glycerin, is esterified and modified with a fatty acid, a natural resin, etc., and the like can also be suitably used. Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used. In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary. Polyurethane resin A thermoplastic polyurethane resin with urethane bonds. Particularly suitable are polyurethane resins obtained by condensation of glycols and diisocyanates, particularly polyurethane resins obtained by condensation of alkylene glycol and alkylene diisocyanate. Polyether Styrene-formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc. Cellulose derivatives Various esters and ethers of cellulose, or mixtures thereof, such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylhydroxyethylcellulose. Polycarbonate For example, various polycarbonates such as polydioxydiphenylmethane carbonate and dioxydiphenylpropane carbonate. Ionomers Na, Li, methacrylic acid, acrylic acid, etc.
Zn, Mg salt, etc. Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde. Xylene resin For example, a condensate of m-xylene or mesitylene and formalin, or a modified product thereof. Petroleum resins _C5 type, _C9 type, _C5 - _C9 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof. A blend of two or more of the above) to), or a blend with other thermoplastic resins. Note that the molecular weight of the self-oxidizing, thermoplastic, etc. resin may be various. Such a resin and the above-mentioned dye are usually formed in a wide range of weight ratio of 1:0.1 to 100. A quencher is contained in such a recording layer. This reduces reproduction deterioration of the S/N ratio due to repeated irradiation with readout light. In addition, light resistance is improved by storage in a bright room. Various quenchers can be used, but in particular, the quencher reduces regeneration deterioration,
A transition metal chelate compound is preferred because it has good compatibility with the dye-binding resin. In this case, the central metals are Ni,
Co, Cu, Mn.Pd, Pt, etc. are preferred, and the following compounds are particularly preferred. 1 Acetylacetonate chelate system Q1-1 Ni () acetylacetonate Q1-2 Cu () acetylacetonate Q1-3 Mn () acetylacetonate Q1-4 Co () acetylacetonate 2 Bisdithio- expressed by the following formula α-diketone system Here, R ⁽¹⁾ to ^{R (4)} represent a substituted or unsubstituted amkyl group or aryl group, and M is
Represents transition metal atoms such as Ni, Co, Cu, Pt, and Pd. In this case, M has a negative charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion. In addition, in the following description, ph stands for phenyl group, φ stands for 1,4-phenylene group, and φ' stands for 1,2-phenylene group.
-Phenylene group, benz represents that adjacent groups on the ring bond to each other to form a condensed benzene ring. [Table] 3 Bisphenyldithiol system represented by the following formula Here, R ⁽⁵⁾ and R ⁽⁶⁾ represent hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as Cl, or an amino group such as a dimethylamino group or a diethylamino group, and M is , represents transition metal atoms such as Ni, Co, Cu, Pd, and Pt. Furthermore, M in the above structure has a negative charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion, and furthermore, other ligands may be bonded above and below M. It's okay. Examples of this include the following: [Table] [Table] In addition, those described in JP-A-50-45027 and the patent application dated September 5, 1982. 4 Dithiocarbamate chelate system represented by the following formula Here, R ⁽⁹⁾ and R ⁽¹⁰⁾ represent an alkyl group. Further, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. R ⁽⁹⁾ , R ⁽¹⁰⁾ M Q4−1 C ₄ H ₉ Ni 5 Compound represented by the following formula Here, M represents a transition metal atom, and Q ₁
represents [formula] or [formula], and Cat represents a cation. [Table] Other items described in Japanese Patent Application No. 58-125654. 6 Compound represented by the following formula Here, M represents a transition metal atom, A represents S, [Formula] or [Formula], and R ⁽¹¹⁾ and R ⁽¹²⁾ are CN, CO, respectively.
R ⁽¹³⁾ , COOR ⁽¹⁴⁾ , CONR ⁽¹⁵⁾ , R ⁽¹⁶⁾ or SO ₂
R ^{( 17) represents} a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q ² represents a 5- or 6-membered ring. Cat represents a cation, and n is 1 or 2. 【table】 \
CN
In addition, those described in Japanese Patent Application No. 58-127074. 7 Compound represented by the following formula Here, M represents a transition metal atom, Cat
represents a cation, and n is 1 or 2. M Cat Q7-1 Ni 2 [(n-C ₄ H ₉ ) ₃ N Q7-2 Ni 2 [n-C ₁₆ H ₃₃ (CH ₃ ) ₃ N] In addition, the thing. 8 Bisphenylthiol system Q8-1 Ni-bis(octylphenyl) sulfide 9 Thiocatechol chelate system represented by the following formula Here, M represents a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc. In addition, M has a negative charge and is a cation (Cat).
and the benzene ring may have a substituent. M Cat Q9−1 Ni N ⁺ (C ₄ H ₉ ) ₄ 10 Compound represented by the following formula Here, R ⁽¹⁸⁾ represents a monovalent group, l is 0 to 6, M represents a transition metal atom, and Cat represents a cation. [Table] Other items described in Japanese Patent Application No. 58-143531. 11 Compounds represented by both formulas below Here, in the above general formulas [] and [], R ⁽²⁰⁾ , R ⁽²¹⁾ , R ⁽²²⁾ and R ⁽²³⁾ each represent a hydrogen atom or a monovalent group, and R ⁽²⁴⁾ , R ⁽²⁵⁾ , R ⁽²⁶⁾ and R ⁽²⁷⁾ represent a hydrogen atom or a monovalent group, but R ⁽²⁴⁾ , R ⁽²⁵⁾ and R ⁽²⁵⁾
R ⁽²⁶⁾ , R ⁽²⁶⁾ and R ⁽²⁷⁾ may be combined with each other to form a 6-membered ring. Moreover, M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 145294/1982. 12 Compound represented by the following formula Here, M represents Pt, Ni or Pd, and X ₁ , X ₂ , X ₃ , and X ₄ each represent 0 or S
represents. [Table] Other items described in Japanese Patent Application No. 145295/1982. 13 Compound represented by the following formula Here, R ⁽³¹⁾ is a substituted or unsubstituted alkyl group or aryl group, and R ⁽³²⁾ , R ⁽³³⁾ , R ⁽³⁴⁾ and R ⁽³⁵⁾ are hydrogen atoms or monovalent groups. , but R ⁽³²⁾ and R ⁽³³⁾ , R ⁽³³⁾ and
R ⁽³⁴⁾ , R ⁽³⁴⁾ and R ⁽³⁵⁾ may be combined with each other to form a 6-membered ring. Moreover, M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 151928/1982. 14 Compounds represented by both formulas below Here, R ⁽⁴¹⁾ , R ⁽⁴²⁾ , R ⁽⁴³⁾ and R ⁽⁴⁴⁾ each represent a hydrogen atom or a monovalent group,
R ⁽⁴¹⁾ and R ⁽⁴²⁾ , R ⁽⁴²⁾ and R ⁽⁴³⁾ , and R ⁽⁴³⁾ and R ⁽⁴⁴⁾ may be combined with each other to form a 6-membered ring. Furthermore, R ⁽⁴⁵⁾ and R ⁽⁴⁶⁾ are hydrogen atoms or 1
Represents a valence group. Furthermore, M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 151929/1982. 15 Compound represented by the following formula Here, R ⁽⁵¹⁾ , R ⁽⁵²⁾ , R ⁽⁵³⁾ , R ⁽⁵⁴⁾ , R ⁽⁵⁵⁾ ,
R ⁽⁵⁶⁾ , R ⁽⁵⁷⁾ and R ⁽⁵⁸⁾ each represent a hydrogen atom or a monovalent group, but R ⁽⁵¹⁾ and R ⁽⁵²⁾ , R ⁽⁵²⁾ and R ⁽⁵³⁾ , R ⁽⁵³⁾ and R ⁽⁵⁴⁾ , R ⁽⁵⁵⁾
and R ⁽⁵⁶⁾ , R ⁽⁵⁶⁾ and R ⁽⁵⁷⁾ , and R ⁽⁵⁷⁾ and R ⁽⁵⁸⁾ may be bonded to each other to form a 6-membered ring. R ⁽⁵⁹⁾ represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. X represents halogen. M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 153392/1982. 16 Salicylaldehyde oxime system represented by the following formula Here, R ⁽⁶⁰⁾ and R ⁽⁶¹⁾ represent an alkyl group, and M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. [Table] 17 Thiobisphenolate chelate system represented by the following formula Here, M is the same as above, R ⁽⁶⁵⁾ and
R ⁽⁶⁶⁾ represents an alkyl group. Further, M has a negative charge and may form a salt with a cation (Cat). [Table] 18 Phosphonous acid chelate system represented by the following formula Here, M is the same as above, R ⁽⁷¹⁾ and
R ⁽⁷²⁾ represents a substituent such as an alkyl group or a hydroxyl group. R ⁽⁷¹⁾ , R ⁽⁷²⁾ M Q18-1 3-t-C ₄ H ₉ , 5-t-C ₄ H ₉ , 6
−OH Ni 19 Compounds represented by the following formulas Here, R ⁽⁸¹⁾ , R ⁽⁸²⁾ , R ⁽⁸³⁾ and R ⁽⁸⁴⁾ represent hydrogen atoms or monovalent groups, but R ⁽⁸¹⁾ , R ⁽⁸²⁾ and R ⁽⁸²⁾ R ⁽⁸³⁾ , R ⁽⁸³⁾ and R ⁽⁸⁴⁾ may be bonded to each other to form a 6-membered ring. R ⁽⁸⁵⁾ and R ⁽⁸⁸⁾ each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. R ⁽⁸⁶⁾ represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group or aryl group. R ⁽⁸⁷⁾ represents a substituted or unsubstituted alkyl group or allul group. Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 153393/1983. 20 Compound represented by the following formula Here, R ⁽⁹¹⁾ and R ⁽⁹²⁾ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N-alkylcarbamoyl group,
It represents an N-arylcarbamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and M represents a transition metal atom. [Table] Other items described in Japanese Patent Application No. 58-155359. In addition, other quenchers include the following. 21 Benzoate Q21-1 Existing chemical substance 3-3040 [Tinuvin-
120 (manufactured by Ciba Geigy)] 22 Hindered amine Q22-1 Existing chemical substance 5-3732 [SANOLLS
-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Each of these quenchers has a
It is contained in an amount of about 0.01 to 12 mol, particularly about 0.1 to 1.2 mol. Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used. As a result, reproduction deterioration becomes extremely small. In this case, the difference between the two is preferably 0 or 350 nm or less. In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method. And the thickness of the recording layer is usually 0.03~10μm
It is considered to be a degree. In addition, such a recording layer may contain other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and antioxidants. , a crosslinking agent, etc. may be contained. In order to form such a recording layer, it is usually enough to coat the substrate with a predetermined solvent and dry it. Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carbitol acetate, and butyl carbitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. , aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, and alcohol systems. There is no particular restriction on the material of the substrate on which such a recording layer is provided, and it may be made of any of various resins, glass, ceramics, metals, etc., but it must be substantially transparent to writing light and reading light. Preferably. Further, its shape may be a tape, a drum, a belt, etc. depending on the intended use. Note that the base body usually has a tracking groove. Further, as the resin material for the substrate, a substrate without grooves, such as polymethyl methacrylate acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyether sulfone, methylpentene polymer, etc., is suitable. These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, etc. As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, and the like can be used. Further, various uppermost protective layers, half mirror layers, etc. can be provided on the recording layer, if necessary. However, it is preferable that the recording layer is a single layer film and that a reflective layer is not laminated above or below the recording layer. The medium of the present invention may have the above-mentioned recording layer on one surface of such a substrate, or may have recording layers on both surfaces thereof. Also,
Two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, and they are sealed to prevent dust and scratches. You can also do it like this. Specific effects of the invention When the medium of the invention is running or rotating,
Recording light is irradiated in a pulsed manner. At this time, due to the heat generated by the dye in the recording layer, the dye melts and pits are formed. The pits thus formed are read out by detecting the reflected or transmitted light of the readout light, particularly the reflected light, while the medium is running or rotating. In this case, recording and reading may be performed from the substrate side or from the recording layer side, but it is preferable to perform the recording and reading through the substrate. It is also possible to erase the pits once formed in the recording layer with light or heat and rewrite. Note that the recording or reading light can be a semiconductor laser, He-Ne laser, Ar laser, He
-Cd laser etc. can be used. Specific Effects of the Invention According to the present invention, reproduction deterioration caused by read light is extremely reduced. In addition, the light resistance has been significantly improved, and there is extremely little deterioration in characteristics due to storage in a bright room. Further, there is little deterioration in characteristics even when erasing and rewriting are performed. Furthermore, writing and reading can be performed through the substrate without laminating a reflective layer. It also has good solubility and little crystallization. Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. Example 1 Dye D, Resin R, and Quencher Q shown in Table 1 below were dissolved in a predetermined solvent in the proportions shown in Table 1, and 0.07 Various media were obtained by coating the film to a thickness of μm. In this case, in Table 1, NC is the nitrogen content
It is nitrocellulose with a viscosity of 11.5-12.2% and 80 seconds based on JIS K 6703. Furthermore, the dyes used were those of the numbers exemplified above. In addition, the quenchers used are indicated by the numbers listed above. Table 1 shows the R/D weight ratio and Q/D
The weight ratio is also written. For each medium created in this way, do this
While rotating at 1800 rpm, recording light from a He-Ne laser (632.8 nm) or AlGaAs-GaAs semiconductor laser (830 nm) was focused to 1 μmφ (focusing section output 10 mW) and irradiated in a pulse train at a predetermined frequency. Each medium was irradiated with write light with a different pulse width, and the pulse width at which an extinction ratio of 1.4 was obtained was measured, and the reciprocal of the pulse width was taken as the write sensitivity. The results are shown in Table 1. In this case, the extinction ratio is the degree of attenuation of the reflectance of the readout light on the medium surface, which will be described later, at the pit portion. Separately, writing was performed with a pulse width of 100 nsec. A 1 mW He-Ne laser or semiconductor laser readout light is irradiated as a 1 μsec width, 3 KHz pulse to determine the initial peak-to-peak C/N ratio on the disk surface and the irradiation for 5 minutes on the disk surface that has stopped rotating. After that, the change (%) in reflectance from the back side of the substrate was measured. These results are shown in Table 1. [Table] From the results shown in Table 1, the effects of the present invention are clear.

Claims (1)

[Claims] 1. An optical recording medium having a recording layer made of a dye composition on a substrate, wherein the dye consists of a compound represented by the following general formula [ ], and the dye composition contains a quencher. . An optical recording medium characterized in that the dye is prevented from being degraded by reproduction light. General formula [] {In the above general formula [], Z represents an atomic group necessary to complete the indolenyl group which may have a fused ring. R ₁ represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group. L ₁ and L ₂ each represent a substituted or unsubstituted methine group. l is an integer of 1, 2 or 3. R ₂ represents a monovalent group. K is 0 or an integer from 1 to 5. However, k
is 2 or more, a plurality of R ₂ may be different or the same. X ^- represents an anion. n is 0 or 1. } 2. The optical recording medium according to claim 1, wherein a resin is contained in the dye composition. 3. The optical recording medium according to claim 1 or 2, wherein the quencher is a transition metal chelate compound. 4. The optical recording medium according to any one of claims 1 to 3, which is configured to perform writing and reading from the back side of the base. 5. The optical recording medium according to any one of claims 1 to 3, wherein the recording layer is not laminated with a reflective layer.