JPH0441062B2 - - 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 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., or a recording layer consisting of a thermoplastic resin and a light-absorbing dye is coated, and a recording layer containing a thermoplastic resin and a light-absorbing dye is formed. 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,
When stored at high temperatures after recording, the pits become deformed and the readout S/N ratio decreases significantly. 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 present invention provides an optical recording medium having a recording layer made of a light absorber or a composition of light absorbers on a substrate, in which one or more kinds of dyes having a functional group and a functional group are used as the light absorber. This optical recording medium is characterized in that it uses one or more compounds having the following properties, which are crosslinked with a metal crosslinking agent. 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 made of a light absorber,
The light absorber used is one formed by crosslinking one or more dyes having a functional group with one or more compounds having a functional group using a metal crosslinking agent. There are no particular restrictions on the type of dye used, as long as it has a functional group that reacts with the metal crosslinking agent described below. In this case, the functional group is 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 about 1 to 4, more preferably 2, of these 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-[Fennatrino(9,10-d)thiazolyl], 2-benzoxazolyl, 2-selenazolyl, 2-quinolyl, 4-quinolyl, 2-benzimidazolyl and other heterocyclic residues at both ends; , respectively 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, C10 ₄ ,
Salts may be formed with anions such as BF ₄ , p-toluenesulfonyl, and p-chlorobenzenesulfonyl. And in these cases -OH, -
A functional group such as COOH or -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-hydroxyl)-10,12-
trimethylene-pentatrienylidene-5,
6,5′,6′-dibezothiatricarbocyanine
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'-
Tricarbocyanin perchlorate etc. D2 Phthalocyanine dye The benzene ring of the phthalocyanine dye contains −OH,
A functional group such as -COOH, -SO ₃ H, etc. is directly connected, more preferably a suitable linking group, such as -OCO-, -
Bonded via an alkyl group bonded to COO-, _-CONH2- , _-SO2- , _{-SO2NH2- ,} 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 a substituent 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) squalirium, 4-di(hydroxyethyl)aminophenyl-4'-diethylaminonaphthyl squalirium, and the like. D4 Choline or Corol The above functional groups -OH, -COOH are added to the choline or corol proposed in Japanese Patent Application No. 57-80487.
−, −SO ₃ H bonded. D5 Anthraquinone type Directly or through an alkyl group, -OH-, -
A substance bonded with a functional group such as COOH or -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 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-propadiol, 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, dialcohols such as polyethylene glycol (n = 2 to 50), glycerin, sorbitol, etc., glucose, sucrose, etc., and their derivatives, such as partial esters and ethers. Such. (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 dyes and these compounds (spacer components) are usually used in a weight ratio of 1:0.01 to 1:1. One or more such dyes, usually one
~2 types and one or more types of the above compounds,
Usually one or two types 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. B1 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 (n2-10), etc. B2 Titanium chelates Di-i-propoxy-bis(acetylacetonato) titanate, di-n-butoxy-bis(triethanolaminate) titanate, dihydroxy-bis(lactate) titanate, (ethylene glycolate) titanium bis(dioctyl phosph) ate), titanium-i-propoxyoctylene glycolate, di-i-propoxy-bis(ethyl acetoacetate) titanate, β-diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enols Ligands for sexually active compounds, etc. B3 Titanium acylate Oxotitanium bis(monoammonium oxalate), tri-n-butoxytitanium monostearate, i-propoxytitanium dimethacrylate-i
-stearate, i-propoxytitanium tris(4-aminobenzoate), i-propoxytitanium tris(dioctyl phosphate), etc. B4 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. B5 Zirkoxylate β-diketones such as zirconium tetraacetylacetonate, e.g. 2,4-pentanedione, 2,4-
Heptanedione, etc. Ketoesters For example, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, etc. Hydroxycarboxylic acids or their esters and salts For example, 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-heptano, etc. Amino alcohol For example, monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine , N-ethylmonoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, etc. Enolic active hydrogen compounds such as diethyl malonate, methylolmelamine, methylolurea, methylol acrylamide, etc. as ligands That is. B6 Zircon soap For example, zirconium-2-ethylhexoate, zirconium naphthenate, zirconium stearate, etc. B7 Zirconium acetate B8 Aluminum alkoxide Aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, etc. B9 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-
Ethyl acetoacetate, aluminum oxide octoate, aluminum oxide stearate, etc., β
-Those having diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic active compounds, etc. as ligands. One or two of each of the above dyes and compounds
More than one species is crosslinked by these metal crosslinking agents. The crosslinking agent is generally used in a molar ratio of about 0.1 to 2 to 1 in total of the dye and the compound. In order to obtain a crosslinked product, predetermined amounts of a dye, a compound, and a crosslinking agent may be dissolved in a solvent, and a reaction may be caused at a temperature of about room temperature to 50°C. Alternatively, after coating this to form a recording layer, crosslinking may be performed, preferably by applying heat. At this time, it is preferable to evaporate the desorbed alcohol, chelating agent, and the like. Through such _a crosslinking reaction, dyes and compounds can be bonded to Ti,
Combines with Zr and Al. And Ti, Zr, Al atoms have 2 or 4 M-O-C or M-O-
A (CO or SO ₂ )-C (M is Ti, Zi, Al) bond will be formed. In this case, if the dye or compound has two or more functionalities, a crosslinked product having a plurality of such bonding units will be produced. Note that a dye-compound bond may also occur. Although the recording layer of the medium of the present invention is made of such a crosslinked product, the recording layer may also contain other resins separately. At this time, the coating properties and coating properties are improved, and the recording sensitivity, readout S/N ratio, etc. are improved. The resin used is preferably a self-oxidizing resin or a thermoplastic resin. The self-oxidizing resin contained in the recording layer undergoes oxidative decomposition when the temperature rises.
Among these, nitrocellulose is particularly suitable. In addition, thermoplastic resins soften due to the temperature rise of the dye in the crosslinked material that absorbs recording light.
Various known thermoplastic resins can be used as the thermoplastic resin. Among these, thermoplastic resins that can be particularly preferably used include the following. () Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc. () Polyolefin copolymer For example, ethylene-vinyl acetate copolymer, ethylene-acrylate acid 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. () 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. () Vinylidene chloride copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc. In this case, the copolymerization ratio can be arbitrary. () Polystyrene () Styrene copolymer For example, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-
Butadiene copolymer (ABS resin), styrene-
Maleic anhydride copolymer (SMA resin), styrene-acrylic ester-acrylamide copolymer, styrene-butadiene copolymer (SBR),
Styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc. In this case, the copolymerization ratio can be arbitrary. () Styrene type polymers For example, 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. () Coumarone-indene resin A copolymer of coumaron-indene-styrene. () Terpene resin or picolite For example, terpene resin, which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene. () Acrylic resin Particularly preferred is one containing an atomic group represented by the following formula. formula In the above formula, R ₁₀ represents a hydrogen atom or an alkyl group, and R ₂₀ represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R ₁₀ is 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. Furthermore, R ₂₀ may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 4 carbon atoms, and when R ₂₀ is a substituted alkyl group, the alkyl group preferably has 1 to 4 carbon atoms. The substituent substituting the group is preferably a hydroxyl group, a halogen atom, or an amino group (particularly a dialkylamino group). Such an 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, 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, the polyamides include nylon 6, nylon 66, nylon 610, nylon 612,
In addition to regular homonylons such as nylon 9, nylon 11, nylon 12, and nylon 13, polymers such as nylon 6/66/610, nylon 6/66/12, nylon 6/66/11, and in some cases may be modified nylon. () 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 dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable. Furthermore, for example, a modified gliptal resin, which is a condensation product of phthalic anhydride and glycerin, is esterified and modified with a fatty acid, a natural resin, etc., and the like can also be suitably used. () Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used. In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary. () Polyurethane resin Thermoplastic polyurethane resin with urethane bonds. Particularly suitable are polyurethane resins obtained by condensation products of glycols and diisocyanates, particularly polyurethane resins obtained by condensation products of alkylene glycols and alkylene diisocyanates. () Polyether Styrene-formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc. () Cellulose derivatives For example, various organic acid esters of cellulose, ethers, or mixtures thereof, such as acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylhydroxyethylcellulose. () Polycarbonate For example, various polycarbonates such as polydioxydiphenylmethane carbonate and polydioxydiphenylpropane 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 C ₅ series, C ₉ series, C ₅ -C ₉ copolymers, dicyclopentadiene series, or copolymers or modified products thereof. () A blend of two or more of the above () to (), or a blend with other thermoplastic resins. The molecular weight of self-oxidizing or thermoplastic resins may vary. The weight ratio of such self-oxidizing or thermoplastic resin and the above-mentioned crosslinked product is usually 1:0.1.
Layers are laid in a wide range of quantity ratios from ~100. 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 Cl () 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 single charge and may form a salt with a quaternary ammonium ion or the like. Q5 Ni() dithiobenzyl Q6 Ni() diothibiacetyl (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 less than or equal to 4. Further, M in the above structure may have a single 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)tetrabutylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17 Ni-bis(benzene-1,2-dithiol) -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-1,2-dithiol)tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1, 2 dithiol) 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(octylphenyl) sulfide (6) Thiocatechol chelate type Here, M represents a divalent transition metal atom.
Further, M has a single 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(nitromethylidine)]-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-phenylformimide yl)phenol Q34 Cu()-(N-phenylformimidoyl)phenol Q35 Ni()salicylaldehyde phenyldrazone Q36 Ni()salicylaldehyde oxime(8) Thiobisphenolate chelate system Here, M is the same as above, R ⁽¹¹⁾ and
R ⁽¹²⁾ represents an alkyl group. Further, M has one 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-actyl)-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 [SANOLLS-770
(manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such a quencher is synthesized according to a known method. These quenchers are generally used in an amount of 0.05 to 12 mol per mol of dye in the crosslinked product.
In particular, it is contained in a range of about 0.1 to 1.2 moles. 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 10 nm.
It is considered to be a degree. In addition, such a recording layer may contain other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, heat retardants, stabilizers, dispersants, and crosslinking agents. It may also contain agents. Further, a crosslinked product of a dye alone or a crosslinked product of a spacer component alone 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. In this case, the crosslinking reaction can also be carried out at the time of application,
In this case, heating is usually performed after coating. 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, the reflective layer etc. may have a base 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,
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 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 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. V. Specific Effects of the Invention According to the present invention, even if the medium is stored for a long time,
There is very little deterioration in writing sensitivity or S/N ratio. 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. Specific Examples of the Invention The present invention will now be described in more detail with reference to Examples. Example 1 As shown in Table 1 below, the following dye, spacer component, and crosslinking agent were mixed in a dye:spacer component weight ratio = 3:1, (dye + spacer component):crosslinking agent molar ratio = 4:1 This was applied onto a polymethyl methacrylate substrate 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 these all formed a crosslinked product containing a dye and a spacer component. Separately, for comparison, a recording layer consisting only of a dye was formed as shown in Table 1 below. The dyes and crosslinking agents 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 spacer component J 1 ,6-hexanediol Spacer component K Bisphenol A Spacer component L Terephthalic acid Spacer component M Leic acid 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 present invention are clear. Example 2 A sample in which 30% by weight of resin was added to the crosslinked product in Samples No. 1 and 4 of Example 1.
I got No.12 and 42. The resins used were coumaron-indene resin (number average molecular weight 800) and polyα-methylstyrene (number average molecular weight 80,000). These results are shown in Table 2.

[Table] From the results shown in Table 2, the effect of the second invention is clear. Example 3 Sample No. 13 was obtained by adding 40% by weight of quencher Q14 to the dye in the crosslinked product in Sample No. 1 of Example 1. Table 3 shows the C/N deterioration rate (%) when sample Nos. 1 and 31 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 present invention when containing a quencher is clear.

Claims (1)

[Scope of Claims] 1. In an optical recording medium having a recording layer made of a light absorber or a composition of light absorbers on a substrate, one or two kinds of dyes having a functional group are used as the light absorber.
and one or more compounds having a functional group.
An optical recording medium characterized in that it uses an optical recording medium obtained by crosslinking at least one species 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. The optical recording medium according to claim 1 or 2, wherein the functional group is at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, and a sulfone group. 4. The optical recording medium according to any one of claims 1 to 3, wherein the recording layer is made of a light absorber. 5. The optical recording medium according to any one of claims 1 to 3, wherein the recording layer is made of a composition of a light absorber, and the composition contains a resin. 6. The optical recording medium according to any one of claims 1, 2, 3, and 5, wherein the recording layer is made of a composition of a light absorber, and the composition contains a quencher.