JPH0441064B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical recording media, particularly heat mode optical recording media. Prior Art Optical recording media have the characteristic that the recording medium does not deteriorate due to wear since the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out. Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom. This heat mode optical recording medium is an optical recording medium that uses recording light as heat, and as an example, a part of the medium of recording light such as a laser is melted or removed, and it is called a pit. Some devices perform writing by forming small holes, record information using the pits, and read out information by detecting the pits with a readout light. Examples of such pit-forming media include media in which a recording layer made of a light-absorbing dye is formed on a substrate and pits are formed by melting the dye, and media in which pits are formed by melting the dye, and self-oxidizing media such as nitrocellulose. A recording layer containing a thermoplastic resin and a light-absorbing dye is formed, and a recording layer that forms pits by decomposing nitrocellulose, etc. There are also known methods that form pits by melting. However, in such media, by preservation,
The dye migrates and mixes into the substrate, re-agglomerates, recrystallizes, or bleeds out, resulting in disadvantages such as a decrease in writing sensitivity and a decrease in read S/N ratio. especially,
If the data is stored at a high temperature after recording, pits are formed and the readout S/N ratio is greatly reduced. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to improve preservability,
In particular, it is an object of the present invention to provide an optical recording medium in which deterioration of the S/N ratio due to high temperature storage after recording is reduced. These objects are achieved by the invention described below. That is, the first invention provides an optical recording medium having a recording layer on a substrate that includes a resin component and a light-absorbing component, in which one or more resins having a functional group and an aromatic ring are condensed. Optical recording characterized by using a resin-light-absorbing component made by stirring together one or more cyanine dyes having good indole rings at both ends and having a functional group with a metal crosslinking agent. It is a medium. Further, a second invention provides an optical recording medium having a recording layer on a substrate that includes a resin component and a light-absorbing component, in which one or more resins having a functional group and an aromatic ring are condensed. A resin-light-absorbing component formed by crosslinking one or more cyanine dyes having good indole rings at both ends and having a functional group with a metal crosslinking agent, and a resin component and a light-absorbing component. This is an optical recording medium characterized in that it is used in combination with one or more of these. Furthermore, a third invention provides an optical recording medium having a recording layer on a substrate that includes a resin component, a light-absorbing component, and a quencher, in which an aromatic ring is condensed with one or more resins having a functional group. A resin formed by crosslinking with one or more cyanine dyes having an optional indole ring at both ends and a functional group using a metal crosslinking agent, or using this resin. - An optical recording medium characterized by using a light-absorbing component in combination with one or more of a resin component and a light-absorbing component. Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The recording layer in the present invention is composed of a resin-light absorbing component, and the resin-light absorbing component includes one or more resins having a functional group and one or more pigments having a functional group. A material crosslinked with a crosslinking agent is used. The resin and dye used may be any resin as long as it has a functional group that reacts with the metal crosslinking agent described below. In this case, the functional groups of the resin and the dye are preferably one or more of a hydroxyl group, a carboxy group, and a sulfone group. Note that these functional groups may be metal salts. The dye preferably has 1 to 4, particularly about 1 to 3, more preferably 2 functional groups. The dye used is a cyanine dye having an indole ring at both ends to which an aromatic ring may be fused. Among such cyanine dyes, those represented by the following formula are preferred. Formula Φ-L=Ψ (X ^- ) _n In the above formula, Ψ and Φ represent an indole ring to which an aromatic ring such as a benzene ring, naphthalene ring, or phenanthrene ring may be fused. These Φ and Ψ may be the same or different, but are usually the same, and various substituents may be bonded to these rings. In addition, Φ means that the nitrogen atom in the ring has a + charge,
In Ψ, the nitrogen atom in the ring is neutral. The skeleton rings of these Φ and Ψ are preferably those represented by the following formulas [Φ] to [Φ]. In addition, in the following, the structure is shown in the form of Φ. In these various rings, the group R ₁ bonded to the nitrogen atom in the ring is a substituted or unsubstituted alkyl group or aryl group. There is no particular restriction on the number of carbon atoms in the group R ₁ bonded to the nitrogen atom in such a ring. In addition, when this group further has a substituent, examples of the substituent include a sulfone group, a hydroxyl group,
Functional groups such as carboxy groups are substituted, but in addition,
It may be an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxyoxy group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a halogen atom, or the like. Note that when m, which will be described later, is 0, the group R ₁ bonded to the nitrogen atom in Φ is an aryl group as the substituted alkyl group, and has a negative charge. Note that R ₁ is an alkyl group substituted with a hydroxyl group, a carboxy group, or a sulfone group, and it is preferable that these functional groups are included in R ₁ . Further, two substituents R ₂ and R ₃ are preferably bonded to the 3-position of the indole ring to which an aromatic ring may be fused. In this case, the two substituents R ₂ and R ₃ bonded to the 3-position are preferably an alkyl group or an aryl group. Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred. On the other hand, another substituent R ₄ may be bonded to a predetermined position in the ring represented by Φ and Ψ. Examples of such substituents include functional groups such as carboxy groups, sulfone groups, and hydroxyl groups, as well as alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, alkylthio groups, alkyloxycarbonyl groups, and alkylcarbonyloxy groups. It may be a variety of substituents such as. The number (p, q) of these substituents is usually about 0 or about 1 to 4. In addition, p, q
is 2 or more, a plurality of R ₄ may be different from each other. On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye, and is particularly preferably one of formulas [L] to [L]. Formula [L] Formula [L] Formula [L] Formula [L] Formula [L] Formula [L] Formula [L] Formula [L] Here, Y represents a hydrogen atom or a monovalent table. 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, ethoxycarbonylpiperazine groups, etc. Preferable examples include a di-substituted amino group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a nitro group, and a halogen atom such as Br and Cl. In addition, in these formulas [L] to [L],
Tricarbocyanine linking group, especially formula [L], [L
] is preferred. Furthermore, X ⁻ is an anion, and preferable examples thereof include I ⁻ , Br ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , p-toluenesulfonyl anion, p-chlorobenzenesulfonyl anion, and the like. 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. Further, it is preferable that the functional group is bonded to the R ₁ . Next, specific examples of the dyes used in the present invention will be given, but the present invention is not limited to these.

[Table] Such cyanine dyes can be easily synthesized according to known methods. That is, first, the corresponding Φ′−CH ₃ (Φ′ is the above Φ
represents the indole ring corresponding to . ) in excess, for example, A-R ₁ -I (where R ₁ is an alkyl group or an aryl group, A is a sulfone group, a carboxy group,
hydroxyl group) to introduce AR ₁ into the nitrogen atom in Φ' to obtain Φ-CH ₃ I ^- . Next, this may be subjected to dehydration condensation using an unsaturated dialdehyde and an acid anhydride. Note that when A is OH, an acetylated product is obtained, so an ester conversion reaction with methanol or the like is performed to obtain free OH. The resin used is not particularly limited as long as it has one or more of the above functional groups. Those that can be particularly preferably used are listed below. (1) OH-containing resin nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose,
Cellulose esters or their derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvinylbutyral, polyvinyl formal, epoxy resin, phenolic resin, alkyd resin, polytyrosine, polyvinylhydroquinone, polyvinylbenzylhydroquinone , methylolated polyacrylamide, polyacrylhydroxyamide, polyvinylmethylol, poly(p-hydroxyethyl)styrene or copolymers thereof, and ester partial hydrolysates such as ethylene-vinyl acetate copolymer. (2) COOH-containing resin Homopolymers of acrylic acid, methacrylic acid, etc. or copolymers with other monomers, or partial hydrolysates of these esters, maleic anhydride, pyromellitic anhydride, trimellitic anhydride, etc., and acetic acid. Copolymers of ethyl and other monomers, etc. (3) SO ₃ H-containing resin polystyrene sulfonic acid, etc. The number of functional groups in the resin is about 0.05 to 4 per repeating unit. Moreover, there is no particular restriction on its molecular weight, etc. Such resin has a ratio of 5 to 50% compared to pigment + resin.
Approximately 50wt% is used. The resin-light absorbing component may be a crosslinked product of one or more of these resins and a pigment, usually one each, but it can also be a crosslinked product of one or more of these resins and one or more of these pigments, usually one each. and one or more, usually one, of the compounds having the above-mentioned functional groups. The compound to be used may be one having one or more of the above functional groups, but it is particularly preferable to use a spacer component that is a multifunctional compound and functions as a spacer between crosslinking agent residues and dye residues. . As the spacer component, the following are suitable. (1) Polyhydric alcohol ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
1,10-decanediol, 1,4-cyclohexanediol, p,p'-dihydroxy-2,2
-dicyclohexylpropane, bisphenol A, hydroquinone, p,p'-biphenol,
Dialcohols such as hydroquinone dihydroxyethyl ether and polyethylene glycol (n = 2 to 50), glycerin, sorbitol, etc., glucose, sucrose, and their derivatives, such as partial esters and ethers. (2) Polycarboxylic acids Dicarboxylic acids such as succinic acid, malonic acid, glutanoic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Polymellitic acid, ethylenediaminetetraacetic acid, etc. These resins + dyes and these compounds (spacer components) are usually used in a weight ratio of 1:0.01 to 1. One or more of such pigments and resins,
Usually one type and one type or two or more types of the above-mentioned compounds, usually one type, are crosslinked with a metal crosslinking agent. The metal crosslinking agent used is preferably an organic compound or chelate of titanium, zirconium, or aluminum. Among these, the following are particularly suitable. (1) Titanium alkoxide Tetra-i-propoxytitanium (TPT), Tetra-n-butoxytitanium (TBT), Tetrakis(2-ethylhexoxy)titanium, Tetrastearoxytitanium, TPT polymer (n=2-10), TBT polymer (n=2-10), tributoxystearoyl titanium polymer (n=2-10), etc. (2) Titanium chelates Di-i-propoxy-bis(acetylacetonato) titanate, di-n-butoxy-bis(triethanolaminate) titanate, dihydroxy-bis(lactate) titanate, (ethylene glycolate) titanium bis(dioctyl) titanium-i-propoxyoctylene glycolate, di-i-propoxy-bis(ethyl acetoacetate) titanate, etc. Ligands include β-diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic active compounds, etc. (3) Titanium acylate oxotitane bis(monoammonium oxalate), tri-n-butoxytitanium monostearate, i-propoxytitanium dimethacrylate-i
-stearate, i-propoxytitanium tris(4-aminobenzoate), i-propoxytitanium tris(dioctyl phosphate), etc. (4) Zircon alkoxide Tetraethoxyzirconate, Tetra-i-propoxyzirconate, Tetra-n-propoxyzirconate, Tetra-n-butoxyzirconate, Tetra-t-butoxyzirconate, Tetra-(2-methyl)butoxy zirconate, tetra-(3-methyl)pentoxyzirconate, tetra-n-heptyloxyzirconate, tetra-n-octyloxyzirconate, etc. (5) Zircon chelate β-diketone such as zirconium tetraacetylacetonate, such as 2,4-pentanedione, 2,4-heptanedione, etc. Keto esters, such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, etc. Hydroxycarboxylic acids or their esters and salts, such as methyl lactate, ethyl lactate, ammonium lactate, salicylic acid, methyl salicylate,
Ethyl salicylate, phenyl salicylate, malic acid, ethyl malate, tartaric acid, methyl tartrate, ethyl tartrate, etc. Keto alcohols For example, 4-hydroxy-4-methyl-2-
Pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-heptanone, etc. Amino alcohol For example, monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine , N-ethylmonoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, etc. Enolic active hydrogen compounds For example, diethyl malonate, methylolmelamine, methylolurea, methylol acrylamide, etc. Something to do. (6) Zircon soaps, such as zirconium-2-ethylhexoate, zirconium naphthenate, zirconium stearate, etc. (7) Zirconium acetate (8) Aluminum alkoxide Aluminum isopropylate Monosec-butoxyaluminum diisopropylate Aluminum sec-butyrate, etc. (9) Aluminum chelate Ethyl acetoacetate Aluminum diisopropylate, Aluminum tris(ethyl acetoacetate), Aluminum tris acetylacetonate, Aluminum mono-acetylacetonate bis(ethyl acetoacetate), Aluminum di-n-butoxide mono- Ethyl acetoacetate, aluminum di-i-propoxide mono-
Ethyl acetoacetate, aluminum oxide octoate, aluminum oxide stearate, etc., β
- Ligands include diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic activated compounds, and the like. The above-mentioned dye, resin, and, if necessary, one or more spacer components are crosslinked with these metal crosslinking agents. The crosslinking agent is used in an amount of about 0.01 to 20 wt%, particularly about 0.1 to 10 wt%, based on the total of the resin, dye, and spacer component. In order to obtain a crosslinked product, a dye, a resin, and, if necessary, a spacer component and a crosslinking agent may be dissolved in predetermined amounts in a solvent, and a reaction may be caused at a temperature of about room temperature to 50°C. Alternatively, as a more preferred embodiment,
After coating this to form a recording layer,
Preferably, crosslinking is carried out by heating. At this time, the desorbed alcohol, chelating agent, etc. can also be evaporated. Through such a crosslinking reaction, the dye, resin, and spacer component are bonded to Ti, Zr, and Al via -O-, -COO-, _-SO3- , and the like. And Ti,
Zr, Al atoms contain 2 or 4 M-O-C or M-O-(CO or SO ₂ )-C (M is Ti, Zr,
Al) bond will occur. A plurality of such bonding units exist. Although the recording layer of the medium of the present invention is made of such a crosslinked product, the recording layer can also contain other resin components and/or light-absorbing components separately. As the light-absorbing component, there are various dyes with or without the above-mentioned functional groups, especially the above-mentioned cyanine dyes. It may also be a condensate of these dyes. For example, dyes having one or more functional groups such as -OH, -COOH, -SO ₃ H, etc., especially single or co-condensates of the above cyanine dyes, or combinations thereof with dialcohols, dicarbonates, etc. There are cocondensates with cocondensation components such as acids or their chlorides, diamines, di- or triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates. Alternatively, the dye having the above-mentioned functional group, particularly the cyanine dye mentioned above, may be cross-linked alone or together with a spacer component using a metal-based cross-linking agent. This crosslinked product is a by-product when the above-mentioned crosslinking is performed in the coating film. Furthermore, as a resin component, the above-mentioned resin,
Alternatively, other resins may be contained. Resins that can be suitably used are thermoplastic, self-oxidizing or depolymerizable resins, such as those described in the patent application
There is one described in No. 58-15229, etc. Further, like the dye, it may be a condensate or a crosslinked product of a resin having a functional group as described above. The resin crosslinked product may be mixed as a by-product as described above. Note that these resin components and light-absorbing components are generally contained in an amount of 20 wt% or less based on the resin-light-absorbing component. Furthermore, as the second resin-light absorbing component, a condensate of a resin and a dye, a condensate of a resin, a dye, and a co-condensation component, etc. may be contained. Preferably, such a recording layer further contains a quencher. This reduces reproduction deterioration and improves light resistance. Various types of quenchers can be used, but in particular, when a dye is excited and singlet oxygen is generated, it undergoes electron transfer or energy transfer from the singlet oxygen and becomes excited, returns to the ground state by itself, and , is preferably a singlet oxygen quencher that converts singlet oxygen to the triplet state. Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dyes. In this case, the central metals are Ni,
Co, Cu, Mn, etc. are preferred, and the following compounds are particularly preferred. (1) Acetylacetonate chelate system Q1 Ni () Acetylacetonate Q2 Cu () Acetylacetonate Q3 Mn () Acetylacetonate Q4 Co () Acetylacetonate (2) Bisdithio-α-diketone system Here, R ⁽¹⁾ to ^{R (4)} represent a substituted or unsubstituted alkyl group or aryl group, and M is 2
Represents a valent transition metal atom. In this case, M has a negative charge and may form a salt with a quaternary ammonium ion or the like. Q5 Ni()diobenzyl Q6 Ni()diotibiacetyl (3) Bisphenyl dithiol type Here, R ⁽⁵⁾ and R ⁽⁶⁾ represent an alkyl group such as a methyl group or a halogen atom such as Cl, and M represents a divalent transition metal atom such as Ni. Furthermore, a and b are each 0 or an integer of 4 or less. Further, M in the above structure may have a negative charge and form a salt with an anion, and further, other ligands may be bonded above and below M. As such, the following are commercially available. Q10 PA-1001 (Product name: Mitsui Toatsu Fine Co., Ltd.) Q11 PA-1002 (Same as above) Q12 PA-1003 (Same as above) Q13 PA-1005 (Same as above) Q14 PA-1006 (Same as above) Q15 Co-Bis(Benzene- 1,2-dithiol)tetrabutyl ammonium salt Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium salt Q17 Ni-bis(benzene-1,2-dithiol)tetrabutyl ammonium salt Q18 Ni-bis(0-xylene-4,5-dithiol)tetrabutyl ammonium salt Q19 Ni-bis(5-chlorobenzene-1,2
-dithiol)tetrabutyl ammonium salt Q20 Ni-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutyl ammonium salt Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1 , 2 dithiol) tetrabutyl ammonium salt (4) dithiocarbamate chelate system Here, R ⁽⁷⁾ and R ⁽⁸⁾ represent an alkyl group. Moreover, M represents a divalent transition metal atom. Q22 Ni-bis(dibutyl dithiocarbamic acid) [Antigen NBC (manufactured by Sumitomo Chemical)] (5) Bisphenylthiol type Q23 Ni-bis(octyl phenyl) sulfide (6) Thiocatechol chelate type Here, M represents a divalent transition metal atom. Further, M has a negative charge and may form a salt with an anion, and the benzene ring may have a substituent. Q24 Ni-bis(thiocatechol)tetrabutyl ammonium salt (7) Salicylaldehyde oxime type Here, R ⁽⁹⁾ and R ⁽¹⁰⁾ represent an alkyl group, and M represents a divalent transition metal atom. Q25 Ni()0-(N-isopropylformimidoyl)phenol Q26 Ni()0-(N-dodecylformimidoyl)phenol Q27 Co()0-(N-dodecylformimidoyl)phenol Q28 Cu()0 -(N-dodecylformimidoyl)phenol Q29 Ni()2,2'-[ethylenebis(nitrilomethylidine)]-diphenol Q30 Co()2,2'-[ethylenebis(nitromethylidine)]-diphenol Q31 Ni()2,2'-[1.8-naphthylenebis(nitrilomethylidine)]diphenol Q32 Ni()-(N-phenylformimidoyl)phenol Q33 Co()-(N-phenylformimidoyl)phenol Q34 Cu()-(N-phenylformimidoyl)phenol Q35 Ni()salicylaldehyde phenylhydrazone Q36 Ni()salicylaldehyde oxime(8) Thiobisphenolate chelate system Here, M is the same as above, R ⁽¹¹⁾ and
R ⁽¹²⁾ represents an alkyl group. Moreover, M has a negative charge and may form a salt with an anion. Q37 Ni()n-butylamino[2,2'-thiobis(4-tert-octyl)-phenolate][Cyasorb-UV-1084 (American Cyanamide Co., Ltd.)] Q38 Co()n-butylamino[ 2,2'-thiobis(4-tert-octyl)-phenolate] Q39 Ni()-2,2'-thiobis(4-tert-octyl)phenolate (9) Phosphonous acid chelate system Here, M is the same as above, R ⁽¹³⁾ and
R ⁽¹⁴⁾ represents a substituent such as an alkyl group or a hydroxyl group. In addition, other quenchers include the following. (10) Benzoate Q51 Existing chemical substance 3-3040 [Tinuvin-120
(manufactured by Ciba Geigy)] (11) Hindered amine Q52 Existing chemical substance 5-3732 [SANOLIS-770
(manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such a quencher is synthesized according to a known method. These quenchers are generally contained in an amount of about 0.05 to 12 moles, particularly about 0.1 to 1.2 moles, per mole of the dye in the crosslinked product. Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used. As a result, reproduction deterioration becomes extremely small. In this case, the difference between the two is preferably 0 or 350 nm or less. In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method. The thickness of the recording layer is usually 0.03 to 100 μm.
It is considered to be a degree. In addition, such a recording layer contains other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, crosslinking agents, etc. It's okay. To deposit such a recording layer, on the substrate,
What is necessary is just to apply|coat using a predetermined solvent and to dry. In this case, when performing the crosslinking reaction in the coating film, it is preferable to perform heating. 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. Alternatively, an aromatic type such as toluene or xylene, a halogenated alkyl type such as dichloroethane, an alcohol type, etc. may be used. The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc. In addition, the shape varies depending on the purpose of use, such as tape,
It may be a disk, drum, belt, etc. Note that the base body usually has a tracking groove. Further, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc. Specific effects of the invention When the medium of the invention is running or rotating,
Recording light is irradiated in a pulsed manner. At this time, due to the heat generated by the dye in the crosslinked material in the recording layer, the crosslinked material is melted and pits are formed. The pits thus formed are read out by detecting the transmitted light, especially the reflected light, of the readout light while the medium is running or rotating. In this case, recording and reading are preferably performed from the base side, but may also be performed from the recording layer 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 first and second inventions of this application, even if the medium is stored for a long time, the writing sensitivity and S/
Deterioration of N ratio is extremely small. In particular, after recording and storing at a high temperature, the deterioration of the readout S/N ratio becomes extremely small. Furthermore, the read S/N ratio is extremely high. In addition, according to the third invention, reproduction deterioration is significantly reduced and light resistance is extremely high. The present inventors conducted various experiments to confirm the effects of the present invention. An example is shown below. Experimental Example 1 As shown in Table 1 below, the following dye, resin, spacer component, and crosslinking agent were mixed in a weight ratio of dye/resin/crosslinking agent = 60/38/2, (dye +
It was dissolved in dichloroethane in a quantitative ratio of resin)/spacer=3/1. This was coated on a polymethyl methacrylate substrate whose surface had been treated with a Ti chelate and heated to 40°C to obtain a recording layer with a thickness of 0.07 μm. As a result of IR measurement, it was confirmed that a crosslinked product was formed in each of these recording layers. In this case, in addition to the resin-dye crosslinked product, some samples also contained crosslinked resin-resin, dye-pigment, and other crosslinked products. Separately, for comparison, a recording layer consisting only of resin and dye was formed. The resin, spacer component, and crosslinking agent used are as follows. Crosslinking agent
Resin B Partial hydrolyzate of polymethyl methacrylate (number average molecular weight 30,000, hydrolysis rate 50%) Resin C Nitrocellulose (number average molecular weight 100,000) Resin D Partial hydrolyzate of ethylene vinyl acetate copolymer (number average molecular weight 30,000, hydrolysis rate 50%) Spacer component S Bisphenol A For each sample prepared in this way,
While rotating at 1800 rpm, a semiconductor laser (830 nm) is focused on a diameter of 1 μm (focusing section output 10 m).
W), writing was performed with a pulse width of 100 nsec. After this, a 1 mW semiconductor laser readout light is applied.
The C/N ratio was measured by emitting irradiation as a 3 KHz pulse with a width of 1 μsec and detecting the reflected light. Next, each sample was stored at 50°C and 90% relative humidity for 1000 hours, and then the deterioration of the C/N ratio was measured. Table 1 shows the deterioration rate (%) of the C/N ratio after storage.

[Table] From the results shown in Table 1, the effects of the first and second inventions are clear. Experimental Example 2 Sample No. 13 was obtained by adding 30% by weight of Quencher Q14 to the dye polymer in Sample No. 1 of Experimental Example 1. Table 2 shows the deterioration rate (%) of the C/N ratio when samples Nos. 1 and 13 were irradiated with readout light of 1 mW, 1 μs, and 3 KHz for 4 minutes.

[Table] From the results shown in Table 2, the effect of the third invention is clear.

Claims (1)

[Scope of Claims] 1. In an optical recording medium having a recording layer on a substrate that includes a resin component and a light-absorbing component, even if an aromatic ring is condensed with one or more resins having a functional group, A light characterized by using a resin-light absorbing component, which is formed by crosslinking one or more cyanine dyes having a good indole ring at both ends and a functional group with a metal crosslinking agent. recoding media. 2. The optical recording medium according to claim 1, wherein the metal crosslinking agent is an organic compound or chelate of titanium, zirconium, or aluminum. 3. The optical recording medium according to claim 1 or 2, wherein the functional group of the resin and the cyanine dye is at least one selected from the group consisting of hydroxyl group, carboxy group, and sulfone group. 4 Resin - The light absorption component is resin and cyanine dye,
Alternatively, the optical recording medium according to any one of claims 1 to 3, which is obtained by crosslinking a resin, a cyanine dye, and a spacer component. 5. In an optical recording medium having a recording layer containing a resin component and a light-absorbing component on a substrate, one or more resins having a functional group and an indole ring to which an aromatic ring may be fused are attached at both ends. and one or more cyanine dyes having a functional group, crosslinked with a metal crosslinking agent - a light-absorbing component, and one or more of the resin component and the light-absorbing component. An optical recording medium characterized in that it is used in combination with. 6. The optical recording medium according to claim 5, wherein the crosslinking agent is an organic compound or chelate of titanium, zirconium, or aluminum. 7. The optical recording medium according to claim 5 or 6, wherein the functional group of the resin and the cyanine dye is at least one selected from the group consisting of hydroxyl group, carboxy group, and sulfone group. 8 Resin - The light absorbing component is resin and cyanine dye,
Alternatively, the optical recording medium according to any one of claims 5 to 7, which is obtained by crosslinking a resin, a cyanine dye, and a spacer component. 9 Claims 5 to 8, wherein the resin component is a resin or a condensate or crosslinked product of a resin.
The optical recording medium according to any of paragraphs. 10. The optical recording medium according to any one of claims 5 to 9, wherein the light-absorbing component is a dye or a condensate or a crosslinked product of a dye. 11 In an optical recording medium having a recording layer on the medium containing a resin component, a light absorbing component, and a quencher, an indole ring to which an aromatic ring may be fused with one or more resins having a functional group is used. 1 of cyanine dyes having functional groups at both ends
A resin-light-absorbing component formed by crosslinking a species or two or more species with a metal-based crosslinking agent is used, or this resin-light-absorbing component and one or more of the resin component and the light-absorbing component are used. An optical recording medium characterized in that it is used in combination. 12. The optical recording medium according to claim 11, wherein the crosslinking agent is an organic compound or chelate of titanium, zirconium, or aluminum. 13. The optical recording medium according to claim 11 or 12, wherein the functional group of the resin and the cyanine dye is at least one selected from the group consisting of hydroxyl group, carboxy group, and sulfone group. 14. The optical recording medium according to any one of claims 11 to 13, wherein the resin-light absorbing component is formed by crosslinking a resin and a cyanine dye, or a resin, a cyanine dye, and a spacer component. 15. The optical recording medium according to any one of claims 11 to 14, wherein the resin component is a resin or a condensate or a crosslinked product of a resin. 16. The optical recording medium according to any one of claims 11 to 15, wherein the light-absorbing component is a dye or a condensate or a crosslinked product of a dye. 17. The optical recording medium according to any one of claims 11 to 16, wherein the quencher is a transition metal chelate compound.