JPH0119355B2 - - 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 development in a dark room. 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 [Unexamined Japanese Patent Publication No. 56-46221 VBJipson
and CRJones, J.Vac.Sci.Technol., 18 (1)105
(1981)] and metal phthalocyanine dyes (Unexamined Japanese Patent Publication No. 1983)
- No. 82094, No. 57-82095). There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Application Laid-open No. 86795/1983). 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 certain refractive index (1.5 for polymethyl methacrylate) and a certain high surface reflectance (4% for polymethyl methacrylate). This is because, for example, in the case of polymethyl methacrylate, the reflectance is about 60% or less, and therefore 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 discloses a recording layer consisting of IR-132 dye (manufactured by Kodatsu Co., Ltd.) and polyvinyl acetate, and JP-A-57-74845 discloses 1,
A recording layer composed of 1'-diethyl-2,2'-tricarbocyanine iodide and nitrocellulose, and further KYLaw, et al., Appl.Phys.Lett. 39 (9)
718 (1981) describes a medium 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 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate. is disclosed. 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 allows recording and reproduction 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 a single layer of organic material exhibiting high reflectance without laminating a reflective layer. It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits slightly high reflectance [P. Kivits, et al.,
Appl.Phys.Part A 26 (2)101 (1981), Japanese Patent Publication No. 55
- No. 97033], but the writing sensitivity is low, probably due to the high sublimation temperature. In addition, cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes have been reported [Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics, 1p-P-9 (1980)], and a proposal based on this was published in JP-A-58. ―
No. 112790, however, these dyes have low solubility in solvents, tend to crystallize, and are extremely unstable against readout light, resulting in immediate decolorization, especially when applied as a coating, making them impractical for practical use. It cannot be offered to In view of these actual circumstances, the present inventors first
It is proposed that indolenine cyanine dyes, which have high solubility in solvents, little crystallization, thermal stability, and high reflectance of paint films, be used as a single layer film (Patent Application No. 1983). ―No. 134397, 57―
No. 134170). Furthermore, in indolenine-based cyanine dyes, it has been proposed that long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization (Japanese Patent Application No. 182589/1989). 57-177776, etc.). Furthermore, in order to improve photostability, and especially to prevent decolorization (reproduction deterioration) caused by readout light, we have proposed adding a quencher to indolenine-based cyanine dyes [Japanese Patent Application No. 168048/1983] JP-A No. 59-55795), etc.]. By the way, cyanine dyes are usually bonded to an anion such as ClO ₄ ^- . Further, a typical transition metal chelate compound quencher is bonded to a cation such as an ammonium ion. Therefore, these unnecessary counter-anions and counter-cations are present in the recording layer, and acid, alkali, etc. are likely to be generated by hydrolysis, which poses a problem in terms of moisture resistance. Furthermore, the molecular weight of unnecessary portions increases, and the absorbance and reflectance per unit weight decrease, which is disadvantageous in terms of increasing sensitivity. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording layer containing an indolenine-based cyanine dye, which exhibits extremely little reproduction deterioration and good moisture resistance. The goal is to provide a medium. These objects are achieved by the invention described below. That is, the present invention provides an optical recording characterized in that a recording layer containing a photostabilized 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. It is a medium. General formula [] {In the above general formula [], Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring, or benzindolenine ring, but Z
_The ring completed _by It represents a polymethylene linking group for forming a cyanine dye, and Q ^- represents a quencher anion. } Please note that the applicant's earlier application, JP-A-60-
No. 118749 discloses a photostabilized cyanine dye according to the present invention, but the claims do not mention that this dye is used in an optical recording medium. In addition, Japanese Patent Application Laid-Open No. 59-55795, which is an earlier application of this application,
No. 59-78341 discloses an optical recording medium having a recording layer containing a mixture of an indolenine cyanine dye and a quencher. There is no disclosure regarding the dye. Furthermore, JP-A-59-85791, JP-A No. 59-24692,
No. 58-194595, No. 58-218055, No. 58-114989
JP-A-57-11090, JP-A No. 56-92095, JP-A No. 56-92095, and JP-A No. 58-112790 and JP-A No. 58-105442 mention that indolenine cyanine dyes are used in optical recording media.
No. 58-175693 discloses the use of a quencher, but does not even suggest the photostabilized cyanine dye of the present invention. Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The recording layer of the optical recording medium of the present invention contains a photostabilized cyanine dye consisting of a combination of an indolenine cyanine dye cation and a quencher anion. In this case, there is no restriction on the ionic valence of the indolenine cyanine dye cation and the quencher anion, and various combinations are possible, but usually both are monovalent. That is, if the indolenine cyanine dye cation is D ⁺ and the quencher anion is Q ^- ,
Typically, the conjugate is D ⁺ Q ^- . The cation of the indolenine cyanine dye constituting the ionic bond in the present invention is not particularly limited, and various cations can be used. However, as cations of these various pigments,
Those having high writing sensitivity and high reading S/N ratio when incorporated in the recording layer are those represented by the following general formula []. General formula [] {In the above general formula [], Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring, or dibenzoindolenine ring,
The ring completed by Z and Z′ cannot both be an indolenine ring, R ₁ and R ₁ ′ each represent a substituted or unsubstituted alkyl group, aryl group, or alkenyl group, and L is It represents a polymethylene linking group for forming a cyanine dye, X ^- represents an acid anion, and m is O or 1. } In the above general formula [], Z and Z' represent an indolenine ring to which an aromatic ring such as a benzene ring or a naphthalene ring may be fused, particularly an indolenine ring, benzoindolenine ring or dibenzoindolenine ring. Represents the atomic group necessary for completion. The ring completed by these Z (hereinafter Φ ⁺ ) and
The rings completed by Z' (hereinafter referred to as Ψ) may be the same or different, but are usually the same, and various substituents may be bonded to these rings. And, as the skeletal rings of these Φ ⁺ and Ψ, the following formulas [Φ] ~ [Ψ] and [Ψ] ~
Preferably, it is represented by [Ψ]. However, when Z is [Φ], Z′ is [Φ
] will never occur. 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. Furthermore, 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, the 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, an unsubstituted alkyl group having 1 or 2 carbon atoms, particularly 1, is preferred. On the other hand, other substituents R ₄ and R ₄ ' may be bonded to predetermined positions in the ring 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. Then, the number of these substituents (p, q, r,
s, t) are usually 0 or about 1 to 4. Note that when p, q, r, s, and t are 2 or more, the plurality of R ₄ and R ₄ ' may be different from each other. The cyanine dye cation has a fused or non-fused indolenine ring, and has a high solubility,
It has excellent coating properties and stability, and exhibits extremely high reflectance. On the other hand, L represents a polymethylene linking group for forming a cyanine dye such as simple cyanine, carbocyanine, dicarbocyanine, tricarbocyanine or tetracarbocyanine dye,
In particular, any one of formulas [L] to [L] is preferred. 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 group, especially formula [L], [L
], [L] and [L] are preferred.

[Table] Such indolenine cyanine dye cations are I ^- , 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, p. 432, Dai Organic Kagaku (Asakura Shoten). That is, first, the corresponding Φ′ ^- -CH ₃ (Φ′ represents the ring corresponding to the above Φ) is heated with excess R ₁ I (R ₁ is an alkyl group or an aryl group) to convert R ₁ to Φ ′ to obtain Φ―CH ₃ I ^- . Alternatively, Fisher's conventional method or
Indolenine derivatives are obtained from acetylene alcohol according to the method of Harald et al. (Synthesis, 958, 1981). 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, Cu. , represents transition metal atoms such as Pd and 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 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 is

[expression] or

represents [formula] vinegar.

[Table] 4 What is shown by the following formula Here, M represents a transition metal atom, A is S,

[expression] or

[Formula], R ¹¹ and R ¹² are CN, COR 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 ^. represents the atomic group necessary to form .

[Table] 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, Pt, etc. 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.

[Table] 8 Thiobisphenolate chelate system represented by the following formula Here, M is the same as above, R ⁶⁵ and
R ⁶⁶ represents an alkyl group.

[Table] Among the above quencher anions,
The phenylbisdiol type mentioned 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
The method described on page 432 or the method of Harald et al. and ZINCK may be followed. On the other hand, an anionic quencher bonded to a cation is prepared. In this case, the cation (Cat ⁺ ) is, in particular,
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 1983.
Synthesized according to No. 166832, Japanese Patent Application No. 163080, 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/. 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. Additionally, if the cyanine dye is highly soluble, such as p-toluenesulfonate or p-chlorobenzenesulfonate, the desired stabilizing dye will precipitate if it is dissolved in methanol or the like and mixed. come. 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, nickel may be oxidized while blowing air to form an anionic salt according to Japanese Patent Application No. 166832/1983. 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'-hexamethyl-4,
5,4',5'-dibenzoindotricarbocyanine perchlorate (0.00025 mol, 0.153 g) [E.
Kodak HDITC-15073 D ⁺ 1 perchlorate] and PA-1006 (0.00025 mol, 0.197 g)
[Tetrabutylammonium salt of Q ^- 1-8] is N,
Dissolved in 20ml of N′-dimethylformamide at 70°C.
After keeping for 3 hours, pour into cold water, filter the precipitate,
Wash with water, dry under reduced pressure, double decompose, and light stabilize the dye.
Got D1. Yield: 0.23g (yield: 87%) Recrystallized from DMF-ethanol. mp 177-179℃ (gray-green) Ni content (%) Calculated value 5.56 Measured value 6.20 Calculated value as a mixture 4.2 Synthesis example 2 (Synthesis of D2) Perchlorate of D ⁺ 1 [15073 manufactured by E. Kodak]
and the tetrabutylammonium salt of Q ^- 1-12 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D2. Yield 89% mp 210-212℃ (dark green) Ni content (%) Calculated value 6.28 Measured value 6.41 Synthesis example 3 (Synthesis of D3) Perchlorate of D ⁺ 2 [manufactured by Japan Photosensitive Color Research Institute]
NK-2865] and the tetrabutylammonium salt of Q ^- 1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D3. Yield 75% mp 137-140℃ (black-green) Ni content (%) Calculated value 4.69 Measured value 4.10 Synthesis example 4 (Synthesis of D4) Perchlorate of D ⁺ 3 [manufactured by Japan Photosensitive Color Research Institute]
NK-2866] and the tetrabutylammonium salt of Q ^- 1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D4. Yield 88% mp 73-75℃ (black-green) Ni content (%) Calculated value 3.83 Measured value 4.22 Synthesis example 5 (Synthesis of D5) Perchlorate of D ⁺ 4 [manufactured by Japan Photosensitive Color Research Institute]
NK-2873] and the tetrabutylammonium salt of Q ^- 1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D5. Yield 100% mp 217-218℃ (reddish-purple) Ni content (%) Calculated value 4.70 Measured value 4.55 Synthesis example 6 (Synthesis of D6) Bromide of D ⁺ 5 [NK made by Japan Photosensitive Color Research Institute]
-2902] and the tetrabutylammonium salt of Q ^- 1-8 in the same manner as in Synthesis Example 1 to create a photostabilized dye.
Got D6. Yield 92% mp Gradual decomposition (dark green) Ni content (%) Calculated value 4.90 Measured value 4.97 Synthesis example 7 (Synthesis of D7) Bromide of D ⁺ 5 [Nippon Kanko Shiki Kenkyusho NK]
-2902] and the tetrabutylammonium salt of Q ^- 1-2 [NIR C-1 manufactured by Teikoku Kagaku Sangyo Co., Ltd.] were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D7. Yield 97% mp 183-184℃ (black-green) Ni content (%) Calculated value 5.75 Measured value 5.88 Synthesis example 8 (Synthesis of D8) Perchlorate of D ⁺ 6 [manufactured by Japan Photosensitive Color Research Institute]
NK-2910] and the tetrabutylammonium salt of Q ^- 1-12 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D8. Yield 81% mp 193-194℃ (dark green) Ni content (%) Calculated value 4.62 Measured value 4.75 Synthesis example 9 (Synthesis of D9) Perchlorate of D ⁺ 7 [manufactured by Japan Photosensitive Color Research Institute]
NK-2921] and the tetrabutylammonium salt of Q ^- 1-12 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D9. Yield 88% mp 140℃ (decomposition) (black-green) Ni content (%) Calculated value 5.57 Measured value 5.48 Synthesis example 10 (Synthesis of D11) Perchlorate of D ⁺ 9 [manufactured by Japan Photosensitive Color Research Institute]
NK-2880] and the tetrabutylammonium salt of Q ^- 1-12 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D11. Yield Yield 96% mp 209℃ (bright orange) Ni content (%) Calculated value 6.28 Measured value 6.32 Synthesis example 11 (Synthesis of D12) Perchlorate of D ⁺ 1 [manufactured by E.Kodak]
HDITC-15073] and the tetrabutylammonium salt of Q ^- 1-7 [PA-1003 manufactured by Mitsui Toatsu Co., Ltd.] were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D12. Yield 71% mp 200-201℃ (green) Ni content (%) Calculated value 5.22 Measured value 5.35 The absorption spectrum λmax of each photostabilized dye in dichloroethane is almost the same as that of the raw cyanine dye. It was hot. Such a conjugate may be combined with other dyes to form a recording layer within a 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 terpolyphore (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 ester or methacrylic 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 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. 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. 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 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-
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, 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, glyptal resin, which is a condensate of phthalic anhydride and glycerin, is esterified and modified with a fatty acid, a natural resin, etc., and the like is also preferably 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 For example, 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 _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. 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. or aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, alcohol systems, etc. may be used. 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. In addition, resin materials for the base include polymethyl methacrylate, acrylic resin, epoxy resin,
Non-grooved substrates such as polycarbonate resins, polysulfone resins, polyethersulfones, methylpentene polymers, etc. are 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 a 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 recording layer described above 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 distance between them, and the substrate is sealed to prevent dust and scratches. You can also prevent it from sticking. 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, especially 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 also 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. Further, even without laminating a reflective layer, writing and reading can be performed satisfactorily through the substrate. 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 Nitsuso)] was coated and hydrolyzed to form a base layer (0.01 μm) on an acrylic disk 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, a medium containing a mixture of D ⁺ 1 perchlorate (D'1) and Q ^- 1-8 tetrabutylammonium salt (Q1-8) 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 Pats Card 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 3KHz 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】

[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 the indolenine ring, benzindolenine ring, or dibenzoindolenine ring,
Neither ring completed by Z and Z' becomes an indolenine ring, R ₁ and R ₁ ' each represent a substituted or unsubstituted alkyl group, aryl group or alkenyl group, and L is , represents a polymethylene linking group for forming a cyanine dye, and Q ^- represents a quencher anion. } 2. The optical recording medium according to claim 1, wherein the quencher anion is an anion of a transition metal chelate. 3. The optical recording medium according to claim 1 or 2, wherein Q ^- is represented by the following general formula []. General formula [] {In the above general formula [], M represents a transition metal atom, and R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group or a dialkylamino group. } 4 Claims 1 to 3, in which two alkyl groups are bonded to the 3-position of the indolenine ring, benzindolenine ring, or dibenzoindolenine ring completed by Z and Z'. The optical recording medium according to any one of. 5 R ₁ and R ₁ ′ are each a hydroxy group,
5. The optical recording medium according to claim 1, which is an alkyl group substituted with a sulfo group, a carboxy group, an alkyloxycarbonyl group, or an alkylcarbonyloxy group, or an unsubstituted alkyl group. 6. The optical recording medium according to any one of claims 1 to 5, wherein the number of methine groups in 6L is 7 or 9. 7. The optical recording medium according to any one of claims 3 to 6, wherein M is Ni. 8. The optical recording medium according to any one of claims 1 to 7, wherein the recording layer contains a resin. 9. The optical recording according to any one of claims 1 to 8, wherein the dye cation is a monomer, a polymer, or bonded to a resin. Medium. 10. The optical recording medium according to any one of claims 1 to 9, wherein the substrate has an underlayer on the recording layer supporting surface. 11. The optical recording medium according to any one of claims 1 to 10, which contains a dye in addition to the conjugate. 12. The optical recording medium according to any one of claims 1 to 11, in which writing and reading are performed from the base side. 13. The optical recording medium according to any one of claims 1 to 12, wherein a reflective layer is not laminated on the recording layer.