JPH0139918B2 - - Google Patents

Description

[Φ]

[Ψ] In these various rings, the groups R ₁ and R ₁ ' bonded to the nitrogen atom in the ring are substituted or unsubstituted alkyl groups, aryl groups, or alkenyl groups. In such a ring, the group R ₁ bonded to the nitrogen atom,
There is no particular restriction on the number of carbon atoms in R ₁ '. In addition, when this group further has a substituent, examples of the substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamido group, an alkylsulfonamide group, an alkoxycarbonyl group, an alkylamino group, an alkylcarbamoyl group, It may be any of an alkylsulfamoyl group, a hydroxyl group, a carboxy group, a halogen atom, etc. Among these, unsubstituted alkyl groups or alkyl groups substituted with alkylcarbonyloxy groups, hydroxyl groups, etc. are particularly preferred. Further, two substituents R ₂ , R ₃ , R ₂ ′, and R ₃ ′ are preferably bonded to the 3-position of the indolenine ring. In this case, two substituents R ₂ bonded to the 3-position,
R ₃ , R ₂ ′, and R ₃ ′ are preferably an alkyl group or an aryl group. Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred. On the other hand, other substituents R ₄ and R ₄ ' may be bonded to a predetermined one of the rings represented by Φ ⁺ and Ψ. Such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, and aryloxycarbonyl groups. group, alkylcarbonyloxy group, alkylamide group, arylamide group, alkylcarbamoyl group, arylcarbamoyl group,
Alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, cyano group, nitro group, etc.
Various substituents may be used. The number of these substituents (p, p') is 1
It is said to be around 4. Note that when p and p' are 2 or more, the plurality of R ₄ and R ₄ ' may be different from each other. The cyanine dye cation has a non-fused indolenine ring, has excellent solubility, coating properties, and stability, and exhibits an extremely high reflectance. On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetracarbocyanine dye, and in particular, the formula [L]
It is preferable that it is any one of ~[L]. Formula [L] Formula [L] Formula [L] Formula [L] Formula [LV] Formula [L] Formula [L] Formula [L] Formula [L] Here, Y represents a hydrogen atom or a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxycarbonylpiperazine groups. Preferable examples include di-substituted amino groups such as, alkylcarbonyloxy groups such as acetoxy groups, alkylthio groups such as methylthio groups, cyano groups, nitro groups, and halogen atoms such as Br and Cl. Furthermore, R ₈ and R ₉ each represent a hydrogen atom or a lower alkyl group such as a methyl group. And l is 0 or 1. In addition, in these formulas [L] to [L], tricarbocyanine linking groups, especially formulas [L], [L
], [L], and [L] are preferred. Specific examples of the indolenine cyanine dye of the present invention are listed below. Note that the skeleton rings of Φ ⁺ and Ψ are as described above.

【table】

【table】

[Table] Such indolenine cyanine dye cations are ^- , Br ^- , ClO ₄ ^- , BF ₄ ^- ,

【formula】

It is known as a conjugate with an acid anion such as [Formula]. Further, these combinations of indolenine cyanine dye cations and acid anions can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compounds, page 432, Dai Organic Kagaku (Asakura Shoten). That is, first, the corresponding Φ′−CH ₃ (Φ′ is the above Φ
) is heated with excess R ₁ (R ₁ is an alkyl group or an aryl group) to introduce R ₁ into the nitrogen atom in Φ′ and form Φ−CH ₃ ⁻
get. Alternatively, according to Fisher's conventional method or the method of Harald et al. (Synthesis, 958, 1981),
Obtain indolenine derivatives from acetylene alcohol. Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst. Alternatively, pyridine may be cleaved according to the ZINCK reaction to obtain glutaconaldehyde, and this may be reacted with a quaternary salt of an indolenine derivative to obtain tricarbocyanine. These indolenine cyanine dye cations usually take the form of a monomer, but may take the form of a polymer if necessary. In this case, the polymer has two or more molecules of indolenine cyanine dye cations, and may be a condensate of these indolenine cyanine dye cations. For example, single or co-condensates of the above indolenine cyanine dye cations having one or more functional groups such as -OH, -COOH, -SO ₃ H, etc., or combinations thereof with dialcohols. , dicarboxylic acid or its chloride, diamine,
There are cocondensation components such as di- or triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other dyes. Alternatively, the indolenine cyanine dye cation 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, metal crosslinking agents include alkoxides such as titanium, zircon, and aluminum; chelates such as titanium, zircon, and aluminum (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and esters thereof, ketoalcohols, aminoalcohols, enolic Examples include those with active hydrogen compounds as ligands), sialates of titanium, zircon, aluminum, etc. Furthermore, -OH group, -OCOR group and -
One or more indolenine cyanine dye cations having at least one COOR group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and others. It is also possible to use a spacer component or another dye bonded with 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. In addition, the indolenine cyanine dye cation 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. If necessary, indolenine cyanine dye cations are linked via a spacer component or the like. On the other hand, as the quencher anion constituting the conjugate, various quencher anion forms can be used, but in particular, the quencher anion has a property that reduces regeneration deterioration and has good compatibility with the dye-binding resin. Therefore, an anion of a transition metal chelate compound is preferable. In this case, the central metal is preferably Ni, Co, Cu, Mn, Pd, Pt, etc., and the following compounds are particularly preferred. 1) Bisphenyldithiol system represented by the following formula Here, R ¹ to R ⁴ represent hydrogen or 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 Ni, Co, or Cu. , represents a transition metal atom such as Pd or Pt. Furthermore, other ligands may be bonded above and below M. Examples of this include the following:

[Table] 2) Bisdithio-α-diketone system represented by the following formula

[Formula] Here, R ⁵ to R ⁸ represent a substituted or unsubstituted alkyl group or aryl group, and M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. In addition, in the following description, ph is a phenyl group, φ is a 1,4-phenylene group, and φ' is
The 1,2-phenylene group, benz, represents that adjacent groups on the ring bond to each other to form a condensed benzene ring.

[Table] 3) What is shown by the following formula Here, M represents a transition metal atom, and Q ¹
teeth,

[expression] or

Represents [formula]. M Q Q ^- 3-1 Ni Q ¹² Q ^- 3-2 Ni Q ¹² Q ^- 3-3 Co Q ¹² Q ^- 3-4 Cu Q ¹ ₂ Q ^- 3-5 Pd Q ¹² 4) Represented by the following formula thing Here, M represents a transition gold atom, A is S,

[expression] or

[Formula], R ¹¹ and R ¹² are CN, CN, and
COR ¹³ , COOR ¹⁴ , CONR ¹⁵ , R ¹⁶ or
SO ₂ R ¹⁷ is represented, R ¹³ to R ¹⁷ each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q ² is an atomic group necessary to form a 5- or 6-membered ring. represents.

【table】 \
CN
5) What is shown by the following formula Here, M represents a transition metal atom. M Q ^- 5-1 Ni Other items described in Japanese Patent Application No. 127075/1982. 6) Thiocatechol chelate system represented by the following formula Here, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt. Further, the benzene ring may have a substituent. 7) What is shown by the following formula Here, R ¹⁸ represents a monovalent group, and l is
0 to 6, and M represents a transition metal atom. M R ¹⁸ l Q ^- 7-1 Ni H 0 Q ^- 7-2 Ni CH ₃ 1 8) Thiobisphenolate chelate system represented by the following formula

[Formula] Here, M is the same as above, R ⁶⁵ and
R ⁶⁶ represents an alkyl group. R ⁶⁵ , R ⁶⁶ M Q ^- 8-1 t-C ₈ H ₁₇ Ni Q ^- 8-2 t-C ₈ H ₁₇ Co Among the above quencher anions, the phenylbisdithiol type in 1) above is most preferred. This is because reproduction deterioration due to read light is further reduced and light resistance is extremely high. Next, specific examples of the photostabilized cyanine dye used in the present invention will be given.

【table】

[Table] Such photostabilized cyanine dyes of the present invention are
For example, it is manufactured as follows. First, a cationic cyanine dye combined with an anion is prepared. In this case, the anion (An ^- ) is I ^- ,
Br ^- , ClO ₄ ^- , BF ₄ ^- ,

【formula】

[Formula] etc. are sufficient. Such cyanine dyes are known and synthesized according to conventional methods. That is, for example,
Large Organic Chemistry (Asakura Shoten) Nitrogen-containing heterocyclic compounds I
The method described on page 432, etc., or Hara1d
The method of et al. and ZINCK may be followed. On the other hand, an anionic quencher bonded to a cation is prepared. The cation (Cat ⁺ ) in this case is particularly
Tetraalkylammoniums such as N ⁺ (CH ₃ ) ₄ and N ⁺ (C ₄ H ₉ ) ₄ are preferred. In addition, these quenchers are based on a patent application filed in 1982.
Synthesized according to No. 166832, Japanese Patent Application No. 163080/1980, etc. Next, equimolar amounts of these cyanine dyes and quenchers are dissolved in a polar organic solvent. The polar organic solvent used is preferably N,N-dimethylformamide or the like. Further, its concentration may be approximately 0.01 mol/l. Thereafter, an aqueous solvent, particularly water, is added to the mixture to cause double decomposition and to obtain a precipitate. The amount of water to add is 10
It is sufficient to have a large excess of twice or more. In addition, the reaction temperature is preferably about room temperature to 90°C. In addition, if the cyanine dye is highly soluble, such as p-toluenesulfonate or p-chlorobenzenesulfonate, the desired stabilized dye will precipitate by dissolving it in methanol or the like and mixing it. It's coming. Then, both liquid phases are separated, filtered and dried,
If recrystallized with DMF-ethanol, etc., a photostabilized cyanine dye can be obtained. In addition to the above method, a neutral intermediate of the quencher cation may be dissolved in methylene chloride, etc., and an equimolar amount of cyanine dye may be added thereto, concentrated, and recrystallized. . Alternatively, according to Japanese Patent Application No. 57-166832, nickel may be oxidized while blowing air to form an anionic salt. Next, an example of synthesis of the photostabilized cyanine dye of the present invention will be given. Synthesis Example 1 (Synthesis of D1) 1,3,3,1',3',3'-hexamethylindolinotricarbocyanine iodide [Iodide of NK-125 D ⁺ 22, manufactured by Japan Photosensitive Color Research Institute] (0.0005
mole, 0.25 g) and bis(3,4,6-trichloro-1,2-dithiophenolate)nickel()tetra-n-butylammonium [manufactured by Mitsui Toatsu Co., Ltd., PA-1006 Q ^- 1-8 tetra Butylammonium salt [0.0005 mol, 0.39 g) was dissolved in 20 ml of N,N'-dimethylformamide, kept at 70°C for 3 hours, poured into cold water, filtered the precipitate, washed with water and dried under reduced pressure. 1,3,3,1',3',3'-hexamethylindolinotricarbocyanine bis(3,4,6-trichloro-1,2-dithiophenolate) nickel () [D1] was obtained. Yield: 0.40g (yield: 88%)
The mixture was heated and dissolved in 10 ml of DMF, 30 ml of hot ethanol was added, and the mixture was allowed to stand for recrystallization. mp 181-182°C (reddish brown) The content of Ni was determined by atomic absorption spectrometry, and the following results were obtained. Ni content (%) Calculated value 6.15 Measured value 6.07 Calculated value as dye stabilizer 1:1 mixture 4.43 Synthesis example 2 (Synthesis of D2) Iodide of D ⁺ 22 [NK- manufactured by Japan Photosensitive Color Research Institute
125] and the tetrabutylammonium salt of Q ^- 1-12 [NIR C-2 manufactured by Teikoku Kagaku Sangyo Co., Ltd.] were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D2. Yield 91% mp Gradual decomposition (black color) Ni content (%) Calculated value 7.04 Measured value 6.93 Synthesis example 3 (Synthesis of D15) Perchlorate of D ⁺ 19 [NK-2905 manufactured by Nippon Kanko Color Research Institute] and Q ^- Tetrabutylammonium salt of 1-12 [NIR C- manufactured by Teikoku Kagaku Sangyo Co., Ltd.
2] in the same manner as in Synthesis Example 1 to obtain a photostabilized dye.
Got D15. Yield 80% mp 240℃ (decomposition) (black-green) Ni content (%) Calculated value 4.85 Measured value 4.77 Synthesis example 4 (Synthesis of D4) Iodide of D ⁺²² [NK- manufactured by Japan Photosensitive Color Research Institute
125] and the tetrabutylammonium salt of Q ^- 1-3 [PA-1005 manufactured by Mitsui Toatsu Co., Ltd.] were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D4. Yield 95% mp 219-220℃ (green) Ni content (%) Calculated value 6.63 Measured value 6.51 Synthesis example 5 (Synthesis of D7) 1,1′, obtained by the method of Harald and ZINCK
3,3,3',3'-hexamethyl-5,5'-dichloroindolinotricarbocyanine iodide [D ⁺ 2
iodide] and the tetrabutylammonium salt of Q ^- 1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D7. Yield 75% mp 205-208℃ Ni content (%) Calculated value 5.73 Measured value 5.81 Synthesis example 6 (Synthesis of D16) 1,1′,3,3,3′, obtained in the same manner as above
3'-hexamethyl-5,5'-diethylhydroxycarbonyl indolinotricarbocyanine p-
Toluenesulfonate (p-toluenesulfonate of D ⁺ 20) and the tetrabutylammonium salt of Q ^- 1-8 were mixed in methanol to obtain photostabilized dye D16. Yield 70% mp 192-194℃ Ni content (%) Calculated value 5.34 Measured value 5.49 Synthesis example 7 (Synthesis of D14) 1,1',3,3,3',3'-hexamethyl- obtained in the same manner 5,5′-dimethylsulfonylindolinotricarbocyanine perchlorate (D ⁺ 19
perchlorate) and the tetrabutylammonium salt of Q ^- 1-8 in the same manner as in Synthesis Example 1 to obtain photostabilized dye D14. Yield 82% mp 234-236°C Ni content (%) Calculated value 5.28 Measured value 5.25 The λmax of the absorption spectrum of each photostabilized dye in dichloroethane was almost the same as that of the raw cyanine dye. Such a binder may be combined with other dyes to form a recording layer within the range that does not impair the effects of the present invention. The recording layer may contain a resin if necessary. The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin. Among these, thermoplastic resins that can be particularly preferably used include the following. ) Polyolefins 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. Polymer, 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 acid 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. ) Styrene type polymers such as α-methylstyrene, p-methylstyrene, 2,5-dichlorostyrene, α,β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, For example, a copolymer of α-methylstyrene and methacrylic acid ester. ) Coumaron-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, and picolite obtained from β-pinene. ) Acrylic resin Particularly preferred is one containing an atomic group represented by the following formula. 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 number of carbon atoms in the alkyl group is preferably 1 to 8, and when R ₂₀ is a substituted alkyl group, the alkyl group The substituent for substituting 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 -Methyl methacrylate 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 copolymers For example, copolymers with acrylic esters, vinyl ethers, 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 is nylon 6,
Nylon 6-6, Nylon 6-10, Nylon 6-
In addition to regular homonylons such as 12, nylon 9, nylon 11, nylon 12, and nylon 13, nylon 6/6-6/6-10, nylon 6/6-6/12,
It may also be a polymer such as nylon 6/6-6/11, 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, and ethylene glycol, Condensates and co-condensates with glycols such as tetramethylene 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 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, such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, and mixtures thereof. ) 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 C ₅ type, C ₉ type, C ₅ - C ₉ copolymer type, dicyclopentadiene type, or copolymers or modified products of these. ) Blends of two or more of the above) or blends with other thermoplastic resins. In addition, the molecular weight etc. of 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. Incidentally, such a recording layer may additionally contain other quenchers such as those described in Japanese Patent Application No. 181368/1983. 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. To deposit such a recording layer, on the substrate,
What is necessary is just to apply|coat using a predetermined solvent and to dry. 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. The material of the substrate on which such a recording layer is provided is not particularly limited as long as it is substantially transparent to writing light and reading light, and may be any of various resins, glass, etc. 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. It is preferable to form a base layer on these substrates in order to improve solvent resistance, wettability, surface tension, thermal conductivity, etc. The material of the underlayer is preferably an oxide formed by applying an organic complex compound or an organic polyfunctional compound such as Si, Ti, Al, Zr, In, Ni, Ta, etc. and drying it by heating. In addition, various photosensitive resins can also be used as the base layer. 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. In addition, two substrates with recording layers coated on one surface are used, and the recording layers are placed facing each other with a predetermined gap between them, and the substrate is sealed to prevent dust and scratches. You can also avoid it. Specific Effects of the Invention The medium of the present invention irradiates recording light in pulses while traveling or rotating. 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 are performed through the substrate from the substrate side. 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 readout 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. Furthermore, the light resistance is improved, and there is little deterioration of characteristics due to storage in a bright room. Further, there is little deterioration in characteristics even when erasing and rewriting are performed. Furthermore, storage stability is improved. In this case, in the present invention, since the dye cation and the quencher anion are ionically bonded, these effects are even greater than when the dye and quencher are used as a mixture. Furthermore, writing and reading can be performed satisfactorily 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 Using dye D shown in Table 1 below, it was dissolved in a predetermined solvent, and a titanium chelate compound [T-
50 (manufactured by Nippon Soda Co., Ltd.)] was coated and hydrolyzed to form a base layer (0.01 μm) on an acrylic disc substrate with a diameter of 30 cm, and a layer of 0.06 μm thick was coated to obtain various media. In this case, in Table 1, NC is the nitrogen content
11.5-12.2%, nitrocellulose with a viscosity of 80 seconds based on JIS K 6703, and its content is 10wt.
%. Separately, for comparison, perchlorate of D ⁺ 22 (D′22) and tetrabutylammonium salt of Q ⁻ 1−8 (Q1−8) and perchlorate of D ⁺ 22 (D′22) and A medium containing a mixture of tetrabutylammonium salts of Q ^- 1-12 (Q ^- 1-12) was prepared. In addition, the dye used was No. exemplified above. I used the one from While rotating each medium thus produced at 900 rpm, writing was performed from the back side of the substrate using a semiconductor laser (830 nm). In this case, the condenser output is 10 mW and the frequency is 2 MHz. Next, a semiconductor laser (830 nm, condensing part output: 1 mW) was used as the readout light, and the reflected light through the substrate was detected and measured with a spectrum analyzer manufactured by Heuretsu Patscard Co., Ltd. with a band width of 30 KHz.
The C/N ratio was measured. In addition, the 1mW laser readout light is 1μsec wide.
After being irradiated as a 3 KHz pulse for 5 minutes in a static state and after being stored at 40° C. and 88% RH for 1500 hours, the change in reflectance (%) from the back side of the substrate was measured. These results are shown in Table 1.

[Table] From the results in Table 1, the effects of the present invention are clear.

Claims (1)

[Claims] 1. A recording layer comprising a light-stabilized cyanine dye consisting of a combination of a cyanine dye cation and a quencher anion represented by the following general formula [] is formed on a substrate. optical recording medium. General formula [] {In the above general formula [], Z and Z' each represent an atomic group necessary to complete a substituted or unsubstituted indolenine ring, and R ₁ and R ₁ ' each represent a substituted or unsubstituted indolenine ring. represents an alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and Q ^- represents a quencher anion. }