JPH0448638B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical recording media, particularly heat mode optical recording media. Prior Art Optical recording media have the characteristic that the recording medium does not deteriorate due to wear since the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out. Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom. This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium, which is called a pit. Some types write by forming small holes, recording information using the pits, and detecting the pits with a readout light to read out information. 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 self-oxidizing media such as nitrocellulose. A recording layer containing a resin and a light-absorbing dye is formed, and a recording layer that forms pits by decomposing nitrocellulose or the like, or a recording layer consisting of a thermoplastic resin and a light-absorbing dye is coated.
Some are known that form pits by melting resin and pigment. 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. In particular, storage at high temperatures after recording causes the pits to deform, resulting in a significant drop in the readout S/N ratio. 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, one or more resins having a functional group and one kind of dye having a functional group. Alternatively, it is an optical recording medium characterized by using a resin-light absorbing component which is formed by crosslinking two or more kinds of light absorbing components with a metal crosslinking agent. 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, comprising one or more resins having a functional group and one kind of dye having a functional group. or an optical recording medium characterized in that a resin-light-absorbing component formed by crosslinking two or more of them with a metal-based crosslinking agent is used in combination with one or more of the resin component and the light-absorbing component. It is. Furthermore, a third invention provides an optical recording medium having a recording layer on a substrate that includes a resin component, a light absorption component, and a quencher, which comprises one or more resins having a functional group and a dye having a functional group. A resin-light-absorbing component formed by crosslinking one or more of them with a metal 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. This is an optical recording medium characterized in that it is used in combination with the following. 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. There are no particular restrictions on the types of resin and dye used, as long as they have 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, and more preferably 2 functional groups. The following dyes are particularly suitable as the dyes to be used. D1 Cyanine dye 2-thiazolyl, 2-(4,5-benzothiazolyl), 2-[naphtho(1,2-d)thiazolyl],
2[naphtho(3,4-d)thiazolyl], 2-[phenanthrino(9,10-d)thiazolyl], 2-
Heterocyclic residues such as benzoxazolyl, 2-selenazolyl, 2-quinolyl, 4-quinolyl, 2-benzimidazolyl are present at both ends, and these are substituted or unsubstituted 1,3,5,7-
Nonatetraenylidene, 1,3,5-heptatrienylidene, 3,5-dimethylene-1,3,5-
Heptatrienylidene, 2,4-neopentylene-1,3,5-heptatrienylidene, 2-methine-4-propenyl-5,6-benzopyrylium, 1,3-pentadienylidene, 2-butenylidene , 3,5-trimethylene-1,3,5-heptatrienylidene, etc. In addition, since one heterocyclic residue has a positive charge, the substituent of that heterocyclic residue may have a negative charge, or I, Br, ClO ₄ , BF ₄ ,
Salts may be formed with anions such as p-toluenesulfonyl and p-chlorobenzenesulfonyl. And in these cases, -OH, -COOH,
A functional group such as -SO ₃ H is bonded directly to the heterocyclic residue, more preferably to the N atom of the heterocyclic residue via an alkyl group or the like. For example, 3,3'-di(6-hydroxyhexyl)-11-
Diphenylamino-10,12-ethylene-5,6,
5',6'-dibenzothiatricarbocyanine perchlorate, 3,3'-di(2-hydroxyethyl)-11-diphenylamino-10,12-ethylene-5,6,
5',6'-dibenzothiatricarbocyanine perchlorate, 3,3'-di(4-carboxybutyl)-11-diphenylamino-10,12-ethylene-5,6,
5',6'-dibenzothiatricarbocyanine perchlorate, 3,3'-di(6-sulfohexyl)-11-diphenylamino-10,12-ethylene-5,6,5',
6'-dibenzothiatricarbocyanine perchlorate, 3,3'-di(6-hydroxyhexyl)-10,
12-trimethylene-pentatrienylidene-5,
6,5′,6′-dibenzothiatricarbocyanine
Perchlorate, 3,3'-di(2-carboxybutyl)-10,12
-trimethylene-pentatrienylidene-5,
6,5′,6′-dibenzothiatricarbocyanine
perchlorate, 1,1'-di(2-hydroxyethyl)-2,
2'-tricarbocyanine perchlorate, 1,1'-di(4-hydroxybutyl)-2,
4'-tricarbocyanine perchlorate, 1,1'-di(4-sulfobutyl)-4,4'-tricarbocyanine perchlorate, etc. D2 Phthalocyanine dye The benzene ring of the phthalocyanine dye contains -OH, -
Functional groups such as COOH, -SO ₃ H, etc. are directly connected, more preferably, suitable linking groups, such as -OCO-, -COO-,
-C0NH ₂ -, SO ₂ -, SO ₂ NH ₂ -, etc. bonded via an alkyl group, etc. As the central metal atom of the phthalocyanine, Pb, VO, Mn, Sn, Cu, etc. are particularly preferable. For example, 3,3'-di(6-hydroxyhexyloxycarbonyl)vanadyl phthalocyanine, 3,3'-di(6-carboxypentyloxycarbonyl)vanadyl phthalocyanine, and the like. D3 squalirium pigment What is shown in Here, A and B each represent an aromatic ring, and the following are particularly preferred. In this case, R ₁ and R ₂ represent substituents such as an alkyl group. In particular, the alkyl group is preferably -
Those to which functional groups such as OH, -COOH, and -CO ₃ H are bonded are preferable. For example, bis(2-hydroxy-4-dimethylaminophenyl) squarylium, 4-di(hydroxyethyl)aminophenyl-
4′-diethylaminonaphthyl squalirium, etc. D4 Choline or Corol The above functional groups −OH, −COOH, −
A combination of SO ₃ H. D5 Anthraquinone type Directly or via an alkyl group, -OH, -
A combination of functional groups such as COOH and -SO ₃ H. For example, 1,5-di(δ-hydroxybutylamino)anthraquinone, di(4-methyl-2-sulfophenylamino)
Anthraquinone, di(4-methyl-2-carboxyphenylamino)anthraquinone, etc. D6 Azo type In particular, bisazo type, trisazo type, azochrome type, etc., which have the above functional groups bonded to them. For example, azobenzoic acid, azo-2-hydroxynaphthalene-1'-hydroxybenzene, etc. These dyes can be easily synthesized according to known methods. 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 Cellulose esters or derivatives thereof such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, epoxy resin , phenolic resin, alkyd resin, polytyrosine, polyvinylhydroquinone, polyvinylbenzylhydroquinone, methylolated polyacrylamide, polyacrylhydroxyamide, polyvinylmethylol, poly-(p-hydroxyethyl)styrene or a copolymer thereof, furthermore, ethylene - Partial hydrolysates of esters such as vinyl acetate copolymers, etc. 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 ethyl acetate, etc. copolymers with 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 dye, usually one each, but it may also be a crosslinked product of one or more of these resins and one or more of these dyes, usually one each. , it may be a crosslinked product with 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, hydroquinone dihydroxyethyl ether, polyethylene glycol (n=2-50 ), glycerin, sorbitol, etc., glucose, sucrose, etc., 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, polymeric acid , ethylenediaminetetraacetic acid, etc. These resins + dyes and these compounds (spacer components) are usually used in a weight ratio of 1:0.01 to 1:1. 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 to 10), TBT polymer (n = 2-10), tributoxystearoyl titanium polymer (n
=2~10) etc. 2 Titanium chelate Di-i-propoxy-bis(acetylacetonato) titanate, di-n-butoxy-bis(triethanolaminate) titanate, (ethylene glycolate) titanium bis(dioctyl phosphate), titanium-i-propoxy Ligands include octylene glycolate, di-i-propoxy-bis(ethyl acetoacetate) titanate, β-diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic active compounds, etc. What to do. 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)butoxyzirconate , tetra-(3-methyl)pentoxyzirconate, tetra-n-heptyloxyzirconate, tetra-n-octyloxyzirconate, etc. 5 Zircon chelate β-diketones such as zirconium tetraacetylacetonate Ketoesters such as 2,4-pentanedione and 2,4-heptanedione For example, hydroxycarboxylic acids and their Esters and salts such as methyl lactate, ethyl lactate, ammonium lactate, salicylic acid, methyl salicylate, ethyl salicylate, phenyl salicylate, malic acid,
Keto alcohols such as ethyl malate, tartaric acid, methyl tartrate, ethyl tartrate, etc. For example, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-pentanone,
-Amino alcohols such as hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-heptanone, etc. For example, monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N,N -dimethylethanolamine, N,
Enolic active hydrogen compounds such as N-diethylethanolamine, for example those containing diethyl malonate, methylol melamine, methylol urea, methylol acrylamide, etc. as a ligand. 6 Zircon soap For example, 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 acetate acetate, aluminum di-i-propoxide mono-ethylacetoacetate, aluminum oxide octoate, aluminum oxide stearate, etc., β-
Ligands include diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic active compounds, etc. The above-mentioned dye, resin, and optionally 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, predetermined amounts of a dye, a resin, a crosslinking agent, and, if necessary, a spacer component may be dissolved in a solvent and allowed to react at a temperature of about room temperature to 50°C. Alternatively, as a more preferred embodiment, after coating this to form a recording layer, crosslinking is preferably 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 that may or may not have the above-mentioned functional groups. It may also be a condensate of these dyes. For example, single or co-condensates of one or more dyes having one or more functional groups such as -OH, -COOH, -SO ₃ H, etc., or dialcohols, dicarboxylic acids, or their chlorides together with these. , diamines, di- or triisocyanates, diepoxy compounds, acid anhydrides, dihydrazides, diiminocarbonates, and other cocondensation components. Alternatively, a dye having the above functional group alone,
Alternatively, it may be crosslinked together with a spacer component using a metal crosslinking 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, a condensate of a resin, a dye, and a co-condensed component may be contained as the second resin-light absorbing component. Preferably, such a recording layer further contains a quencher. This reduces reproduction deterioration of the S/N ratio due to repeated irradiation with readout light and improves light resistance. Various quenchers can be used as the quencher, but in particular, when the 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 substances can be used as singlet oxygen quenchers, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dye-binding resins. preferable. In this case, the central metal is preferably Ni, Co, Cu, Mn, etc., 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 represents a divalent 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()dithiobenzyl Q6 Ni()dithiobiacetyl 3 Bisphenyldithiol series 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. Examples of this include the following: Q10 PA-1001 (Product name: Mitsui Toatsu Fine Co., Ltd.) Q11 PA-1002 [Same as above Ni-bis(toluenedithiol)tetra(t-butyl) ammonium] Q12 PA-1003 (Same as above) Q13 PA-1005 [Same as above Ni -bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 PA-1006 [Same as above Ni-bis(trichlorobenzenedithiol)tetra(t-butyl)ammonium] Q15 Co-bis(benzene-1,2-dithiol)tetra Butylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17 Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18 Ni-bis(0-xylene-4 ,5-dithiol)tetrabutylammonium Q19 Ni-bis(5-chlorobenzene-1,2-
dithiol) tetrabutylammonium Q20 Ni-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol ) Tetrabutylammonium 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)tetrabutylammonium 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(nitrilomethylidine)]-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 [SANOLS-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 nitro 12 moles, particularly about 0.1 to 1.2 moles, per 1 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 about 0.03 to 10 μm. 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, heating is preferably performed when performing the crosslinking reaction in the coating film. Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carbitol acetate, and butyl carbitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. , aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, and alcohol systems. The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc. Further, the shape thereof may be a tape, a disk, a drum, a belt, etc. depending on the intended use. 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. 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. These substrates can also be coated with a primer to improve solvent resistance, wettability, surface tension, thermal conductivity, etc. As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, and the like can be used. Further, on the recording layer, a reflective layer that functions as a back surface when a transparent substrate is used, various uppermost protective layers, a half mirror layer, etc. can be provided as necessary. The medium of the present invention may have the above-mentioned recording layer on one surface of such a substrate, or may have recording layers on both surfaces thereof. Also,
Two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, and they are sealed to prevent dust and scratches. You can also do it like this. Specific effects of the invention When the medium of the invention is running or rotating,
A pulse of recording light is applied. At this time, the crosslinked material melts due to the heat generated by the dye in the crosslinked material in the recording layer.
A pit is formed. The pits thus formed are read out by detecting the reflected or transmitted light of the readout light, particularly the reflected light, while the medium is running or rotating. In this case, recording and reading may be performed from the base side or 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, the deterioration of the S/N ratio when read after recording and storage at a high temperature is 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 = 70/2/28, (dye +
It was dissolved in dichloroethane in a quantitative ratio of resin)/spacer=3/1. This was applied onto 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 dye, resin, spacer component, and crosslinking agent used are as follows. Crosslinking agent
-11-diphenylamino-10,12-ethylene-
5,6,5',6'-dibenzothiatricarbocyanine perchlorate dye B 1,1'-di(2-hydroxyethyl)-
2,2'-Tricarbocyanine perchlorate dye C 3,3'-di(6-hydroxyhexyloxycarbonyl)vanadyl phthalocyanine dye D 3,3'-di(6-carboxypentyloxycarbonyl) vanadyl phthalocyanine resin K Acetyl cellulose (approximately average molecular weight 10
Resin L Partial hydrolyzate of polymethyl methacrylate (approximately average molecular weight 30,000, hydrolysis rate 50%) Resin M Nitrocellulose (approximately average molecular weight 100,000) Resin N Hydrolyzate containing ethylene vinyl acetate copolymer (approximately average molecular weight 100,000) (molecular weight 30,000, hydrolysis rate 50%) Spacer component S Bisphenol A For each sample prepared in this way, a semiconductor laser (830 nm) was focused on a diameter of 1 μm while rotating at 1800 rpm (concentrating part output 10mW),
Writing was performed with a pulse width of 100nsec. After this, a 1mW 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 40% 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 sample 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 3, the effect of the third invention is clear.

Claims (1)

[Scope of Claims] 1. An optical recording medium having a recording layer on a substrate that includes a resin component and a light-absorbing component, which comprises one or more resins having a functional group and one kind of dye having a functional group. Or an optical recording medium characterized in that it uses a resin-light absorbing component formed by crosslinking two or more types with a metal crosslinking agent. 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. Claim 1, wherein the functional group of the resin and the dye is at least one selected from the group consisting of hydroxyl group, carboxy group, and sulfone group.
The optical recording medium according to item 1 or 2. 4. The optical recording medium according to any one of claims 1 to 3, wherein the resin-light absorbing component is formed by crosslinking a resin and a dye, or a resin, a 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 one or more dyes having a functional group are used. An optical recording medium characterized in that a resin-light absorbing component crosslinked with a metal crosslinking agent is used in combination with one or more of the resin component and the light absorbing component. 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. Claim 5, wherein the functional group of the resin and the dye is at least one selected from the group consisting of hydroxyl group, carboxy group, and sulfone group.
6. The optical recording medium according to item 6. 8. The optical recording medium according to any one of claims 5 to 7, wherein the resin-light absorbing component is formed by crosslinking a resin and a dye, or a resin, a 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 that has a recording layer on a substrate that includes a resin component, a light-absorbing component, and a quencher, one or more resins having a functional group and one or more dyes having a functional group. A resin-light-absorbing component formed by cross-linking with a metal cross-linking agent is used, or this resin-light-absorbing component is used in combination with one or more of the resin component and the light-absorbing component. An optical recording medium characterized by: 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 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 dye, or a resin, a 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.