JPH0532231B2 - - 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.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. For example, a part of the medium is melted or removed using laser recording light to create small holes called pits. There is a pit-forming type in which writing is performed by forming a pit, recording information using the pit, and reading by detecting the pit 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 laser use, squalirium dye [JP-A No. 56-46221, VBJipson
and CRJones, J.Vac.Sci.Technol., 18 (1)105
(1981)] and metal phthalocyanine dyes (Unexamined Japanese Patent Publication No. 1983)
-82094, 57-82095), etc. There is also an example of using metal phthalocyanine elements 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 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, a vapor-deposited reflective film is used to increase the reflectance and S/N.
This is to improve the ratio, and by forming pits, the reflective film is exposed and the reflectance increases, or in some cases, the reflective film is removed and the reflectance is decreased. However, recording and playback cannot be performed through the substrate. Similarly, JP-A-55-161690 discloses a recording layer consisting of IR-132 dye (manufactured by Kodatsu) and polyvinyl acetate, and JP-A-57-74845 discloses 1,
A recording layer consisting of 1'-diethyl-2,2'-tricarbocyanine iodide and nitrocellulose, and furthermore, 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 surface 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 a slightly high reflectance [P. Kivits, etal.
Appl.Phys.Part A 26 (2)101 (1981) Japanese Patent Application Publication No. 1987-
No. 97033], but the writing sensitivity is low, probably due to the high sublimation temperature. In addition, cyanine dyes and merocyanine dyes such as thiozole 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. -112790, these dyes have low solubility in solvents, tend to crystallize, and are extremely unstable against readout light, causing them to quickly decolorize, especially when applied as a coating film. , cannot be put to practical use. 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). −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, −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. 168048/1986, etc.). ). However, a mixture of an indolenine cyanine dye and a quencher has a problem in moisture resistance due to the presence of unnecessary quencher countercations and dye counteranions. Therefore, in order to improve moisture resistance and shelf life, we are proposing a coating film using an equimolar ionic combination of an indolenine cyanine dye cation and a quencher anion of a transition metal compound. (Patent Application No. 59-019715) By the way, in an equimolar ionic combination of an indolenine cyanine dye cation and a fiber metal quencher anion, the ratio of cyanine dye is relatively small, and the amount of cyanine dye per unit weight of the coating film is small. Since it is diluted, its absorption rate and reflectance as an optical recording medium are somewhat low, and its writing sensitivity and reading S/N ratio may not be sufficient. Furthermore, equimolar ionic combinations of indolenine-based cyanine dye cations and fiber metal quencher anions generally have poor solubility and poor film-forming properties, which makes it difficult to obtain sufficiently high S/N ratios. There is a problem that cannot be resolved. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to have sufficient stability against readout light, have higher absorption rate, higher reflectance, and dissolve An object of the present invention is to provide an optical recording medium having a recording layer containing an indolenine cyanine dye with good properties. These objects are achieved by the invention described below. That is, the present invention provides an optical recording medium having a recording layer formed on a substrate, in which the recording layer contains an indolenine cyanine dye represented by the following general formula [] and an indolenine cyanine dye represented by the following general formula []. An optical recording medium characterized by containing a mixture of a cyanine dye cation and a quencher anion combination. 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, and R ₁ and R ₁ ' are each , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, X ^- represents an acid anion, m is 0 or 1 . } 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, and R ₁ and R ₁ ' are each , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and Q ^- represents a quencher anion. } 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 an indolenine cyanine dye. There are no particular restrictions on the indolenine cyanine dye, and various types can be used. However, among these various indolenine-based cyanine dyes, those having high writing sensitivity and high reading S/N ratio when incorporated in the recording layer are cyanine dyes 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, benzoindolenine ring, or dibenzoindolenine ring, and R ₁ and R ₁ ′ are, respectively, represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group; L represents a polymethine linking group for forming a cyanine dye; X ^- represents an acid anion; m is 0 or 1; In the above general formula [], Z and Z' represent an isdolenine ring to which a directional ring, for example 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. As the skeletal rings of these Φ ⁺ and Ψ, the following formulas [Φ] ~ [Φ] and [Ψ] ~ [Ψ]
It is preferable that it is shown in the following. In these various rings, the groups R ₁ and R' ₁ that engage with the nitrogen atom in the ring are substituted or unsubstituted alkyl, aryl, or alkenyl groups. A group R ₁ bonded to the nitrogen atom in such a ring,
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 predetermined positions in the ring represented by Φ ⁺ and Ψ. Such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamide group, alkalcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino group, carboxylic acid group,
Alkylsulfonyl group, arylsulfonyl group,
It may be a variety of substituents such as an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, and a nitro group. 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 condensed or non-condensed 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 [LI]
It is preferable that it is any one of ~[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 tilthio 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. Furthermore, X ^- is an ion, preferable examples of which are I ^- , Br ^- , ClO ₄ ^- , BF ₄ ^- ,

【formula】

[Formula] etc. can be mentioned. Note that m is 0 or 1, but when m is 0, R ₁ of Φ usually has a negative charge and becomes an inner salt. Next, specific examples of the indolenine cyanine dye of the present invention will be given, but the present invention is not limited to these.

【table】

【table】

[Table] Furthermore, these cyanine dyes can be easily synthesized according to the method described in books such as Dai Organic Kagaku (Asakura Shoten) Nitrogen-Containing Heterocyclic Compounds, page 432. That is, first, the corresponding Φ″−CH ₃ (Φ″ is the above Φ
represents the ring corresponding to . ) 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″ to form Φ−CH ₃ I ⁻
get. Next, this may be subjected to dehydration condensation with unsaturated dialdehyde, unsaturated hydroxyaldehyde, allyl pentadiene, isophorone, etc. using an alkali catalyst or acetic anhydride. These indolenine cyanine dyes are usually
It is contained in the recording layer in the form of a monomer, but it may be in the form of a polymer if necessary. In this case, the polymer has two or more molecules of cyanine dye, and may be a condensate of these cyanine 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 cyanine dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dyes. 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) sialates of titanium, zircon, aluminum, etc.). Furthermore, -OH group, -OCOR group, and -
One or more cyanine dyes having at least one COOR group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and other spacer components or other -COO through transesterification reaction with dye
Those bonded through a - group can also be used. 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 cyanine dye 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. Cyanine dyes are linked via a spacer component, etc., if necessary. In addition to such an indolenine-based cyanine dye, the recording layer of the optical recording medium of the present invention further contains a photostabilized cyanine dye consisting of a combination of an indolenine-based cyanine dye cation and a quencher anion. In this case, there is no restriction on the ionic valence of the indolenian 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, and R ₁ and R ₁ ' are each , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linkage for forming a cyanine dye, and Q ^- represents a quencher anion. } In the above general formula [], Z and Z' are 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 to complete the . The ring completed with 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. The skeletal rings of these Φ ⁺ and Ψ are the above-mentioned [Φ] ~ [Φ] and [Ψ] ~ [Ψ
] is preferable. The same applies to L as described above. Specific examples of the cyanine dye cation in the present invention are listed below.

[Table] As mentioned above, such indolenine cyanine dye cations include I ^- , Br ^- , ClO ₄ ^- ,
BF _4- ^,

【formula】

It is known as a conjugate with an acid anion such as [Formula]. In addition, as mentioned above, these indolenine-based cyanine dye cations and acid anions combine with nitrogen-containing heterocyclic compounds (Daikai Kagaku (Asakura Shoten)).
It can be easily synthesized according to the method described on page 432, etc. As mentioned above, these indolenine cyanine dye cations are usually in the form of monomers, but
If necessary, it may be in the form of a polymer. In this case, the polymer has two or more molecules of indolenine cyanine dye cations, as described above, 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, _-SO3H , etc., or dialcohols, There are cocondensation components such as dicarboxylic acids or their chlorides, diamines, di- and triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, diiminocarbonates, and cocondensation products with other dyes. Alternatively, the indolenine cyanine dye cation having the above functional group may be processed alone or together with a spacer component and other dyes with a metal crosslinking agent. 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, ketone alcohols, amino alcohols, enols) 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 these and other It is also possible to use a spacer component or another dye bound by a -COO- group by transesterification. 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. Indolenine cyanine dye cations are linked via a spacer component, etc., if necessary. On the other hand, Q ^- represents a quencher anion.
In this case, various quencher anions can be used as the quencher anion Q ^- constituting the conjugate, but in particular, the anion form of the quencher can be used to reduce regeneration deterioration and to have good compatibility with the dye-binding resin. For this reason, an anion of a transition metal chelate compound is preferable. In this case, the central metals include Ni, Co, Cu,
Mn, Pd, Pt, etc. are preferred, 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 such as a dimethylamino group or a diethylamino group, and M is Ni, Co, 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) Bisdiothi-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, φ' is 1,
The 2-phenylene group, benz, represents that adjacent groups on the ring are bonded to each other to form a fused benzene ring.

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

[expression] or

【formula】 represents.

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

[Formula] or represents CQ ² , 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】 \
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, 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 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 No Among the above quencher anions,
The phenylbisdiothiol 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 a photostabilized cyanine dye of the present invention is produced, for example, as follows. First, a cationic indolenine cyanine dye bonded to an anion is prepared. In this case, the anion (An ^- ) is I ^- ,
Br ^- , ClO ₄ ^- , BF ₄ ^- ,

【formula】

[Formula] etc. may be used, and it is synthesized as described above. 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 the cyanine dye and quencher are dissolved in a polar organic solvent. N,N-dimethylformamide or the like is preferably used as the polar organic solvent. Further, its concentration may be approximately 0.01 mol/. Thereafter, an aqueous solvent, particularly water, is added to this 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. This operation is then repeated as necessary. Then, both liquid phases are separated, filtered and dried,
A photostabilized cyanine dye can be obtained by recrystallizing with DMF-ethanol or the like. In addition to the above method, a neutral quencher cation intermediate may be dissolved in methylene chloride or the like, and an equimolar amount of cyanine dye may be added thereto, concentrated, and recrystallized. Alternatively, nickel may be oxidized to form an anionic salt while blowing air according to Japanese Patent Application No. 57-166832. Next, an example of synthesis of the photostabilized cyanine dye of the present invention will be given. Synthesis example 1 (S1 synthesis) 1,3,3,1',3',3'-hexamethylindolinotocaribocyanine iodide [manufactured by Japan Photosensitive Color Research Institute, NK-125, D ⁺ 1 iodide] (0.0005 mol, 025g) and bis(3,4,6-trichloro-1,2-diothiphenolate)nickel ()
Tetra-n-butylammonium [manufactured by Mitsui Toatsu Co., Ltd., PA-1006, tetrabutylammonium salt of Q ^- 1-8] (0.0005 mol, 0.39 g) was added to N,N'-
Dissolved in 20 ml of dimethylformamide, kept at 70℃ for 3 hours, poured into cold water, filtered the precipitate, washed with water and dried under reduced pressure to obtain 1,3,3,1′,3′,3′-
Hexamethylindolinotricarbocyanine bis(3,4,6-trichloro-1,2-diophenolate) nickel () [S1] was obtained. Yield: 0.40 g (yield: 88%) This was heated and dissolved again in 10 ml of DMF, and 30 ml of hot ethanol was added and allowed to stand for recrystallization. mp 206-208°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 S5) 1,3,3,1',3',3'-hexamethyl-4 ，
5,4',5'-dibenzoindotricarbocyanine perchlorate (0.00025 mol, 0.153 g) [E.
Kodak, HDITC-15073, D ⁺ 3 perchlorate] and PA-1006 (0.00025 mol, 0.197
g) [Tetrabutylammonium salt of Q ^- 8] was subjected to metathesis in the same manner as in Synthesis Example 1 to obtain photostabilized dye S5. Yield: 0.23 g (87% yield) Recrystallized from DMF-ethanol. mp 177-179℃ (gray-green) Ni content (%) Calculated value 5.56 Measured value 5.54 Calculated value as a mixture 4.2 Synthesis example 3 (Synthesis of S2) Iodide of D ⁺ 1 (NK- manufactured by Japan Photosensitive Color Research Institute)
125] and the tetrabutylammonium salt of Q ^- 1-12 [manufactured by Teikoku Kagaku Sangyo Co., Ltd., NIR C-2] in the same manner as in Synthesis Example 1 to obtain photostabilized dye S2. Yield 91% mp Gradual decomposition (black color) Ni content (%) Calculated value 7.04 Measured value 6.93 Synthesis example 4 (Synthesis of S3) Perchlorate of D ⁺ 2 (manufactured by Japan Photosensitive Color Research Institute, NK-2905) and Tetrabutylammonium salt of Q ^- 1-12 [manufactured by Teikoku Kagaku Sangyo Co., Ltd., NIR C-
2] in the same manner as in Synthesis Example 1 to obtain a photostabilized dye.
Got S3. Yield 80% mp 240℃ (decomposition) (black-green) Ni content (%) Calculated value 4.85 Measured value 4.77 Synthesis example 5 (Synthesis of S4) D ⁺ 1 iodide (NK- manufactured by Japan Photosensitive Color Research Institute)
125] and the tetrabutylammonium salt of Q ^- 1-3 [manufactured by Mitsui Toatsu Co., Ltd., PA-1005] in the same manner as in Synthesis Example 1 to obtain photostable dye S4. Yield 95% mp 219-220℃ (green) Ni content (%) Calculated value 6.63 Measured value 6.51 Synthesis example 6 (Synthesis of S6) Perchlorate of D ⁺ 3 [manufactured by E. Kodak, 15073]
The tetrabutylammonium salt of Q ^- 1-12 was used in the same manner as in Synthesis Example 1 to obtain photostabilized dye SD6. Yield 89% mp 210-212℃ (dark green) Ni content (%) Calculated value 6.28 Measured value 6.41 Synthesis example 7 (Synthesis of S7) Perchlorate of D ⁺ 4 [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 S7. Yield 75% mp 137-140℃ (black-green) Ni content (%) Calculated value 4.69 Measured value 4.10 Synthesis example 8 (Synthesis of S8) Perchlorate of D ⁺ 5 [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 S8. Yield 88% mp 73-75℃ (black-green) Ni content (%) Calculated value 3.83 Measured value 4.22 Synthesis example 9 (Synthesis of S9) Perchlorate of D ⁺ 6 [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 S9. Yield 100% mp 217-218℃ (reddish-purple) Ni content (%) Calculated value 4.70 Measured value 4.55 Synthesis example 10 (Synthesis of S10) Bromide of D ⁺ 7 [manufactured by Japan Photosensitive Color Research Institute, NK
-2902] and the tetrabutylammonium salt of Q ^- 1-8 in the same manner as in Synthesis Example 1 to produce a photostabilized dye.
Got S10. Yield 92% mp Gradual decomposition (dark green) Ni content (%) Calculated value 4.90 Measured value 4.88 Synthesis example 11 (Synthesis of S11) Bromide of D ⁺ 7 [manufactured by Japan Photosensitive Color Research Institute, NK
-2902] and the tetrabutylammonium salt of Q ^- 1-2 [manufactured by Teikoku Kagaku Sangyo Co., Ltd., NIR C-1] in the same manner as in Synthesis Example 1 to obtain photostabilized dye S11. Yield 97% mp 183-184℃ (black-green) Ni content (%) Calculated value 5.75 Measured value 5.88 Synthesis example 12 (Synthesis of S12) Perchlorate of D ⁺ 8 [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 S12. Yield 81% mp 193-194℃ (dark green) Ni content (%) Calculated value 4.62 Measured value 4.75 Synthesis example 13 (Synthesis of S13) Perchlorate of D ⁺ 9 [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 S13. Yield 88% mp 140℃ (decomposition) (black-green) Ni content (%) Calculated value 5.57 Measured value 5.48 Example 14 (Synthesis of S15) Perchlorate of D ⁺ 11 [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 S15. Yield Yield 96% mp 209℃ (bright orange) Ni content (%) Calculated value 6.28 Measured value 6.32 Synthesis example 15 (Synthesis of S16) D ⁺ 3 perchlorate [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 S16. Yield 71% mp 200-201℃ (green) Ni content (%) Calculated value 5.22 Measured value 5.21 The absorption spectrum λmax of each photostabilized dye in dichloroethane is almost the same as that of the raw cyanine dye. It was hot. The content of these conjugates is preferably 10 to 80 wt%, more preferably 30 to 60 wt%. If the amount of the bond exceeds 80 wt%, the absorbance and reflectance of the optical recording medium will decrease. Furthermore, compatibility deteriorates and film formability deteriorates, resulting in a decrease in the S/N ratio and the like, resulting in deterioration in sensitivity. When the amount of the conjugate is less than 10 wt%, the anion portion of the quencher decreases, resulting in regeneration deterioration. In addition, unnecessary anions exist in the recording medium, and this causes hydrolysis, which tends to produce acids, alkalis, etc., and deteriorates moisture resistance. 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. (i) Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc. (ii) Polyolefin copolymer For example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-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. (iii) 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-vinyl acetate copolymer with vinyl chloride graft polymerized, etc. In this case, the copolymerization ratio can be arbitrary. (iv) Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acronitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc. In this case, the copolymerization ratio can be arbitrary. (v) Polystyrene (vi) Styrene copolymer For example, styrene-acronitrile 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. (vii) Styrene type polymers, such as α-methylstyrene, p-methylstyrene, 2,5-dichlorostyrene, α,β-
Vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester. (viii) Coumarone-indene resin A copolymer of coumaron-indene-styrene. (ix) Terpene resin or picolite For example, terpene resin which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene. (x) 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 a hydrogen atom or a carbon atom number of 1 to 1.
4 is preferably a lower alkyl group, 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. (xi) Polyacrylonitrile (xii) Acrylonitrile copolymer For example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer polymer, 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 reacting acetone with 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, polyamides include nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 9, nylon 11, nylon
In addition to regular homonylon such as 12 and nylon 13,
Nylon 6/6-6/6-10, Nylon 6/6
-6/12, nylon 6/6-6/11, or modified nylon in some cases. () Polyester For example, oxalic acid, succinic acid, maleic acid,
Various dibasic acids such as aliphatic dibasic acids such as adipic acid and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, ethylene glycol, tetramethylene glycol,
Condensates and co-condensates with glycols such as hexamethylene glycol are suitable. Among these, condensates of aliphatic dichloric acids and glycols and co-condensates of glycols and aliphatic dibasic acids are particularly suitable. Furthermore, for example, daliptal resin, which is a condensate of phthalic anhydride and glycerin, can be used as a fatty acid,
Modified glyptal resins that are esterified with natural resins and the like are 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 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. (xi) 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. (xii) Cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose,
Various esters and ethers of cellulose, such as ethylhydroexyethylcellulose, and mixtures thereof. () Polycarbonate For example, various polycarbonates such as polydioxydiphenylmethane carbonate and dioxydiphenylpropane carbonate. (xi) 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 (i) 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 conjugate are usually
Layers are deposited in a wide range of weight ratios from 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, coating may generally be carried out according to a conventional method. The thickness of the recording layer is usually about 0.3 to 10 μm. 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 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 recording layer described above on one surface of such a substrate, or may have recording layers on both surfaces thereof. In addition, two recording layers are coated on one side of the substrate, 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 choose not to have one. 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 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, the absorbance as an optical recording medium increases and the reflectance increases. In addition, it has good solubility and film forming properties, so
An optical recording medium with good sensitivity such as S/N ratio can be obtained. In this case, in the present invention, an ionic combination of an indolenine cyanine dye cation and a quencher anion is mixed with the indolenine cyanine dye, and the mixture of the indolenine cyanine dye and the quencher is reproduced by the readout light. Because it has little deterioration and good light resistance, there is little characteristic deterioration when stored in a bright room. Furthermore, the absorbance is higher and the reflectance is higher than that of an ionic combination of an indolenine-based cyani dye cation and a quencher anion. Therefore, 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 the dyes and ionic binders shown in Table 1 below, they were dissolved in a predetermined solvent, coated with a titanium chelate compound [T-50 (manufactured by Nippon Soda Co., Ltd.)], and hydrolyzed to produce the following. Diameter 30cm with stratum (0.01μ)
A layer of 0.06 μm thick was coated on an acrylic disk substrate 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 K6703, and its content is 10wt%
It is. Separately, for comparison, a medium containing only a mixture of an indolenine cyanine dye and a quencher, a medium containing only an indolenine cyanine dye, and tetrabutylammonium salts of D10 and Q ^- 1-8, or D1 A medium containing a mixture of tetrabutylammonium salt and Q ^- 1-12 was prepared. Note that the dye used was the dye No. exemplified above. Writing was performed on each of the media thus produced from the back side of the substrate using a semiconductor laser (830 nm). In this case, the condensing section output was 10 mW. While changing the pulse width, the pulse width that gave an extinction ratio of 2.0 was determined, and the reciprocal of the pulse width was calculated to display the sensitivity. Next, write with a semiconductor laser,
830nm, condenser output: 1mW as readout light,
The reflected light through the substrate was detected and the C/N ratio was measured at a band width of 30 KHz using a spectrum analyzer manufactured by Hewlett Packard. In addition, the 1 mW laser readout light is 1 μsec wide.
After irradiating as a 3KHz pulse for 5 minutes in a static state (regeneration degradation) and at 40℃ and 88%RH,
After storage for 500 hours (storability), the change (%) in reflectance from the back side of the substrate was measured. These results are shown in Table 2.

【table】

[Table] From the results shown in Table 2, the effects of the present invention are clear. That is, samples Nos. 1 to 10 of the present invention exhibit significantly reduced regeneration deterioration compared to sample No. 11 containing only indolenine dye. Furthermore, compared to Sample Nos. 13 and 14 containing a mixture of indolenine dye and quencher, the C/N ratio is improved by 2 dB or more, and the storage stability is significantly improved. Furthermore, we see a significant improvement in the C/N ratio of over 3dB.

Claims (1)

[Claims] 1. An optical recording medium comprising a recording layer formed on a substrate, wherein the recording layer comprises an indolenine cyanine dye represented by the following general formula [] and the following general formula []
An optical recording medium comprising a combination of an indolenine cyanine dye cation and a quencher anion represented by: 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, and R ₁ and R ₁ ' are each , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, X ^- represents an acid anion, m is 0 or 1 . } 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, and R ₁ and R ₁ ' are each , represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and Q ^- represents a quencher anion. }