JPS59198191A - Optical recording medium - Google Patents

Abstract

PURPOSE:To provide a heat-mode optical recording medium improved in preservability, particularly in deterioration of S/N ratio due to preservation at high temperature, wherein a light-absorbing substance obtained by cross-linking a dye having a functional group with a compound having a functional group by a metal cross-linking agent is used. CONSTITUTION:In an optical recording medium wherein a recording layer composed of a light-absorbing body or a composition thereof is provided on a base, a material obtained by cross-linking at least one dye having a functional group (e.g., OH, COOH or SO3H), e.g., 3,3'-di(6-hydroxyhexyl)-11-diphenylamino-10,12- ethylene-5,6,5',6'-dibenzothiatricarbocyanine perchlorate, and at least one compound having a functional group, e.g., ethylene glycol or succinic acid, by a metal cross-linking agent, e.g., an organic compound or chelated compound of Ti, Zr or Al, is used as the light-absorbing substance.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an optical recording medium, particularly a heat mode optical recording medium.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading spatula F are not in contact with each other, and for this reason, research and development efforts are being conducted to develop optical recording media of the gods.

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 for example, a part of the medium is completely melted or removed using recording light such as a laser, and it is called a bit. There is a device in which writing is performed by forming small holes (1), information is recorded using the pits, and information is detected and read using the biratra readout light.

As an example of such pit-forming media,
A recording layer consisting of a light-absorbing dye is formed on the substrate (7 to 1 dye is melted to form a layer), or a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye. There are those that form pits by forming layers and decomposing nitrocellulose, etc., and those that form pits by coating a recording layer made of thermoplastic resin and light-absorbing dye and melting the resin and dye. It has been known.

However, with storage of such media, dyes may migrate and become mixed into the substrate, re-agglomerate, recrystallize, or bleed out, resulting in a decrease in writing sensitivity (-) or readout. There is an inconvenience that the S/N ratio decreases.

In particular, storage at high temperatures after recording deforms the bits and significantly reduces the read S/N ratio.

■ Purpose of the Invention The present invention was developed in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium with improved storage stability and, in particular, with reduced deterioration of the S/N ratio due to high-temperature storage after recording. The goal is to provide a medium.

Such objects are achieved by the invention described below.

That is, the present invention.

In an optical recording medium having a recording layer made of a light absorber or a composition of a light absorber on a substrate, one or more kinds of dyes having a functional group and one kind of a compound having a functional group are used as the light absorber. Seedma f is an optical recording medium characterized by using a material obtained by crosslinking 24 or more layers with a metal crosslinking agent.

nl Specific configuration of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The recording layer in the present invention is made of a light absorber.

The light absorber used is one obtained by crosslinking one or more of 1N or 2 or more elements having a functional group with one or more kinds of fossilized adjuncts with a metal crosslinking agent.

The type of dye to be used is not particularly limited to ft111, as long as it has a functional group that reacts with the metal crosslinking agent described below.

In the case of nitride, the functional group is preferably 1s or two 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.

DI cyanine dye 2-thiazolyl, 2-(4,5-benzothiazolyl),
2-[nando(1,2-d)thiazolyl], 2-(naphthoC3,4-d)thiazolyl], 2-[phenanthrino(9,1O-d)thiazolyl L2-benzoxasilyl, 2-selenazolyl, 2 -quinolyl, 4-quinolyl,
It has heterocyclic residues such as 2-benzimidazolyl at both ends, and these are substituted or unsubstituted 1.3.5°7-nonatitraenylidene and 1,3.5-hezotatrienylidene. ,3
．． 5-dimethylene-1,3,5-hezotatrienylidene, 2,4-neopentylene-1,3,5-hebutatrienylidene, 2-methine-4-propenyl-5,6--Z
Those linked with nzobyrylium, 1,3-pentadixnylidene, 2-butenylidene, 3,5-trimethylene-1,3,5-heptatrienylidene, etc.

In addition, because one of the heterocyclic pigeons has ten charges,
The substituents of the heterocyclic residue may have a single charge, or I, Br, 010410F41 p
Anionic salts such as -toluenesulfonyl and p-chlorobenzenesulfonyl may be formed.

In these cases, -011, -000H.

A functional group such as -803H 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-diphenylaminol 10.12-ethylene-51615'
l 6'-dipenzothiatricarbocyanine, verchlorate.

3.3'-di(2-and droxyethyl)-11-diphenylamino-10,12-ethylene-5,6,5',6
'-dipenzothiatricarbocyanine verchlorate, 3.3'-di(4-cardixybutyl)-11-diphenylamino-10,12-ethylene-5,6,5',
6'-dipenzothiatricarbocyanine verchlorate, 3,3'-di(6-sulfohexyl)-11-diphenylamino-10,12-ethylene-5,6,5',6'
-Dipenzothiatricardocyanine chirochlorate, 3,3'-di(6-hydroxyhexyl)-10,12
-) Rimethylene-pentatrienylidene-5,6,5'
, 6'-dipenzothiatricaldecyanine verchlorate, 3.3'-di(2-carboxybutyl)-10,12-
) Rimethylene-pentatrienylidene-5,6,5'
, 6'-dipenzothiatricarbocyanine verchlorate.

1.1'-di(2-hydroxyethyl)-2,2'-)
Licarbocyanin verchlorate, 1,1'-di(4
-Hydroxybutyl)-2,4'-) Rical d? Cyanine nog-chlorate, 1,11-di(4-sulfobutyl)-4,4'-trical cyanine verchlorate, and the like.

D2 Phthalocyanine dye -OH in the benzene ring of the phthalocyanine dye.

A functional group such as -0OOH, -8o3H is directly connected, more preferably an appropriate linking group 5 such as -000-, -000,
Bonded via an alkyl group bonded to 0ONH2, -8og, -802NH2-, etc.

As the central metal atom of phthalocyanine, in particular, Pb,
VO, Mn, 8n, Ou, etc. are preferred.

For example, 3,3'-di(6-hydroxyhexyloxycarbonylphthalocyanine), 3,3'-di(6-hydroxybentyloxycarbonyl)nonadyl phthalocyanine.

D3 squarylium pigment - What is shown by. Here, each of the five members and B is an aromatic ring, and the following are particularly preferred.

0″″ In this case, i ″1 + ″2 represents a conversion fund such as an alkyl group.

And in %, the alkyl group is preferably -On,
Those to which functional groups such as -000H and -Do3)-1 are bonded are suitable.

For example, bis(2-hydroxy-4-diethylaminonaphthyl squarylium, 4-di(hydroxyethyl)aminophenyl-4'-diethylaminonaphthyl squarylium, etc.).

D4 Choline or Corol Corin ti proposed in Japanese Patent Application No. 80487/1987 has the above-mentioned functional group -OT-T in Corol.

A combination of -0OOH and -803H.

D5 Anthraquinone series -OH, -000H via Alkyl Foundation for direct calls.

A substance to which a functional group such as -8o3H is bonded.

For example, 1,5-di(δ-hydroxybutylamino)anthraquinone, di(4-methyl-2-sulfophenylamino)anthraquinone, di(4-methyl-2-calcexyphenylamino)anthraquinone, and the like.

D6 Azo-based, bisazo-based, trisazo-based, azochrome-based, etc., to which the above functional groups are bonded.

for example.

Azobenzoic acid, azo-2- and droxynaphthalene-1'-hydroxybenzenato.

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 in particular a spacer component that is a multifunctional adduct and functions as a spacer between crosslinking agent residues or dye residues may be used. I like it. As the spacer component, the following are suitable.

1) Polyhydric alcohol ethylene glycol, 1.3-propanediol, 1.
4-butanediol, 1,5-bentanediol, 1,
6-hexanediol, 1.10-decanediol, 1
．． 4-cyclohexane 2ol, p, p'-dihydroxy-2, 2-dicyclohexylpropane, bisphenol A1 hydroquinone h p* p'-biphenol, hydroquinone dihydroxyethyl ether, polyethylene crico/l/ (n=2-50), etc. dialcohols, glycerin, sorbitol, etc., glucose, sucrose, etc., and their derivatives,
For example, partial esters, ethers, etc.

2] Polycarboxylic acids succinic acid, malonic acid, glutanoic acid, adipic acid, pimelic acid, speric acid, henananosic acid.

Dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid, trimellitic acid, polymellitic acid, and ethylenediaminetetraacetic acid.

These dyes and these compounds (spacer components) are usually used in a ratio of 1 to 01 to 1 by M company.

One or more kinds of such dyes, usually one or two kinds, and one or two or more kinds, usually one or two kinds, of the above-mentioned adducts can be crosslinked with a metal-based crosslinking agent.

The metal crosslinking agent used is titanium, zirconium 1
It is preferable to use an organic compound or chelate of aluminum.

Konera Riuchi, '4! Examples of suitable materials for j include the following.

B1 titanium alkoxide tetra-1-zoloboxytitanium ('r'P'l'), tetra-n-butoxytitanium (T B i'), trakis(2-ethylhexoxy)titanium.

Detaster Logistic Titanium.

'r' PT polymer (n=2~101゜TBT polymer (n~2~io), tributoxystearoyl titanium polymer (n2~10), etc. B2 Titanium chelate di1-10 boxy bis(acetylacetonate) ) Titanate.

di-n-butoxy-bis(triethanolaminate)
Titanate.

Dihydro j1-sebis(raftate) titanate.

(Ethylene glycolate) -1'tambis(dioctyl phosphate), titanium-1-propoxyoctylene glycolate.

Ligands such as Jimmy propoxy-bis(ethyl acetoacetate) titanate, β-diketones, keto esters, hydroxycarboxylic acid esters and salts, keto alcohols, amino alcohols, enolic active compounds, etc.

B3 Titanium acylate oxotitanium bis(monoammonium oxalate octo-n-butoxytitanium monostearate, !-propoxytitanium dimethacrylate-1-stearate.

i-Propoxytitanium tris(4-aminobenzoate).

1-propoxy titanium tris (dioctyl phosphate), etc.

B4 Zircon alkoxide Tetraethoxyzirconate.

Tetra-1-propoxyzirconate, tetra-rhopropoxyzirconate.

-7”) two-1-butoxyzirconate, tetra-1
-Butoxyzirconate.

Tetra-(2-methyl)butoxyzirconate.

Tetra-(3-methylhupentoxyzirconate, Tetra-n-hebutyloxyzirconate.

Tetra-n-octyloxyzirconate and the like.

B5 Zircon chelate Zirconium tetraacetylacetonate, β-diketones, such as 2,4-pentanedione, 2,4-hebutanedione, etc. Ketoesters, such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, etc. Hydroxycarboxylic acids or Its esters and salts, such as methyl lactate, ethyl lactate, ammonium lactate, salicylic acid, methyl salicylate, ethyl salicylate,
Keto alcohols such as phenyl salicylate, malic acid, ethyl malate, tartaric acid, methyl tartrate, ethyl tartrate, etc. td, 4-hydroxy-4-methyl-2-pentanone% 4-hydroxy-2-pentanone, 4-hydroxy-2-to Sitanone, 4-hydroxy-4-methyl-2
- amino alcohols such as heptanone, e.g. monoethanolamine, jetanolamine,
Triethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, etc.Enol erogenous hydrogenation @product Nl,t? f, diethyl malonate, methylol melamine, methylol urea, methylol acrylamide, etc., all having a J configuration.

B6 Zircon soap For example, Marba.

Zirconium-2-ethylhexoate, zirconium naphthene, zirconium natostearate.

B7 Zirconium acetate B8 Aluminum alkoxide aluminum isopropylate, mono 5ec-butysia aluminum diisozolopyrate, aluminum 5ec-butyrate, etc.

B9 Aluminum chelate ethyl acetoacetate aluminum diinzolobile
Aluminum tris (ethyl acetoacetate).

Aluminum) IJ suacetylacetonate, aluminum mono-acetylacetonatobis(ethylacetoacetate), aluminum di-n-butoxide-mono-ethylacetoacetate, aluminum di-me propoxide-mono-ethyl 1cetoacetate, aluminum Oxide octoate, aluminum oxide stearate, etc.

Ligands include β-diketones, ketoesters, hydroxycarboxylic acids or their esters, 5-ketoalcohols, aminoalcohols, enolic active compounds, etc.

One or more of the above dyes and compounds are crosslinked with these metal crosslinking agents.

The crosslinking agent is 1 part of the total of the dye and the compound.

Generally, 0.1 to 2 culms are used at a molar ratio of 0.1 to 2.

In order to obtain a crosslinked product, it is sufficient to dissolve the two-color adduct and the crosslinking agent in a total solvent and allow the reaction to occur at a temperature of room temperature to about 50°C. Alternatively, after the entire coating is applied and a layer is formed as a recording layer, crosslinking may be effected by heating for a certain period of time. At this time, it is preferable to evaporate the desorbed alcohol, chelating agent, etc.

Such a crosslinking reaction results in the formation of dye 1 and compound 1.
, -0-, -000-, -803-, etc. All valves 1. ．．
Ti, Zr.

Combine with AI. And Ti, Zr, AI atoms have 2 or 4 M-0-0- or M-o-(co
Or 802) 0 (M is Ti, Zr, Nl) payment will occur.

If the monofunctional dye or compound is made to have two or more functionalities, a crosslinked product having a plurality of such bonding units will be produced.

Note that binding of one dye-conjugate may also occur.

The recording layer of the medium of the present invention is made of such a crosslinked material, but the recording layer contains a separate material.

It may also contain other resins.

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 is not raised;
Particularly suitable is nitrocellulose.

'1: The thermal r11 plastic resin is softened by the temperature increase of the dye in the tea caddy that has absorbed the recording light, and various known thermoplastic resins can be used as the thermoplastic resin.

Among these, thermoplastic resins that can be particularly preferably used include the following.

1) Polyolefin polyethylene, polypropylene, poly4-methylpentene-1, etc.

11) Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylate acid copolymer, ethylene-acrylic acid copolymer, ethylene-globylene copolymer, ethylene-butene-
t cote, ethylene-maleic anhydride copolymer, ethylene propylene terpolymer (EPT), etc.

In this case, the polymerization ratio of the comonomers can be arbitrary.

111) Enriched vinyl copolymer such as 1r[vinyl acid-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer M8, acrylic ester or methacrylic acid] Copolymers of ester and vinyl chloride, acrylonitrile-vinyl chloride copolymers, vinyl chloride ether copolymers, ethylene or propylene-vinyl chloride copolymers, and ethylene-vinyl acetate copolymers with vinyl chloride graft polymerized. things etc.

In this case, the copolymerization ratio can be arbitrary7
, IV) 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 Vi) Styrene copolymer such as styrene-acrylonitrile copolymer (A8 resin), styrene-acrylonitrile-butadiene copolymer (AB8 resin), styrene-maleic anhydride copolymer (8MA resin)% Styrene-acrylic ester-acrylic acid copolymer, styrene-butadiene copolymer (8
BR), styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be set to +-j.

vID Styrene type polymers, e.g. α-methylstyrene, p-methylstyrene
2 e 54 Chlorstyrene, α, β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or their co-1 (combined, e.g.,
Copolymer of α-methylstyrene and methacrylic acid ester.

Vllll) Coumarone-indene resin A copolymer of coumaron-indene-styrene.

1x) Terpene resin or picolite Examples include terpene resin, which is a polymer of limonene obtained from α-pinene, and picolite, obtained from β-pinene.

X-acrylic resin In particular, books containing atomic groups represented by the following formulas are preferred.

〒10 0H-0- 0-0R2゜I In the above formula, % R1 (1 represents a hydrogen atom or an alkyl group, and the corner 0 represents a substituted or unsubstituted alkyl group. In this case, in the above formula, J6 is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

ago may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 4 carbon atoms, and when FL and o are substituted alkyl groups, the alkyl group is substituted. The substituent is preferably a hydroxyl group, a halogen atom, or an amine group (particularly a dialkylamino group).

The atomic group represented by the above formula may be used to form a complete copolymer with other repeating atomic groups to form various acrylic resins, but usually, the atomic group represented by the above formula is Acrylic resins can be produced by forming homopolymers or copolymers containing one or more of these as repeating units.

×1) Polyacrylonitrile ×11) Acrylonitrile copolymer (e.g., acrylonitrile) IJ-vinyl acetate co-i4ton@
l) vinyl chloride conjugate, acrylonitrile-styrene copolymer b acrylonitrile-
Vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer.

Acrylonitrile-methacrylic and methyl copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butyl acrylate copolymers, etc.

In this case, the +41 combination ratio can be arbitrary.

× River) Dia Seventon Acrylamide Polymer Dia Seventon Acrylamide Polymer made by reacting acrylonitrile with acetone.

XMJ Polyvinyl acetate

The copolymerization ratio may be arbitrary.

XVI) Polyvinyl ethers such as polyvinyl methyl ether, polyvinylethyl ether, polyvinyl alcohol, etc.

11) Polyamide In this case, the polyamides include nylon 6, nylon 66, +ylon 61o1 nylon 612. nylon 9,
Nylon 11. Ordinary homonylon 3, such as nylon 12 and nylon 13, nylon 6/66/610. Polymers such as nylon 6/66/12, nylon 6/66/11 and 1. Depending on the I4 type, modified nylon may be used.

xviiD Polyester For example, oxalic acid, succinate, maleic acid.

Aliphatic dibasic acids such as adipic acid and heptanostenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and ethylene glycol, tetramethylene glycol, hexamethylene glycol, etc. Complementation and cocondensation products with glycols are preferred.

Among these, condensates of aliphatic dibasic acids and glycols and co-combinations of glycols and aliphatic dibasic acids are particularly suitable.

Furthermore, for example, a modified glycital resin, which is obtained by esterifying Glyptal J@KET, which is a combination of phthalic anhydride and glycerin, with a fatty acid, a natural resin, etc., is also preferably used.

, xix) 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 ribinyl acetal resin can be arbitrary).

××] Polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

Particularly suitable are polyurethane resins obtained from condensates of glycols and diisocyanates, particularly polyurethane resins obtained by mixing alkylene glycols and alkylene diisocyanates.

xx1) Polyether styrene formalin-resistant layer, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide co-t8, polyphenylene oxide, etc.

xxii) Examples of cellulose derivatives include acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose,
Hydroquinslobilcellulose, methylcellulose, ethylhydroxyethylcellulosenato, cellulose organic acid esters, ethers, or mixtures thereof.

xx+ii) polycarbonates such as polydioxydiphenylmethanecarbonate,
Various pressed polycarbonates such as polydioxydiphenylpropanecarnate.

XXIV) Ionomer Na, Li such as methacrylic acid and acrylic acid.

Zn, Mg, salt, etc.

xXv Ketone resin For example, a condensate of a cyclic ketone such as cyclohegisanone or acetophenone and formaldehyde.

XXVI) Xylene resin such as 1 m-xylene or a condensate of mesitylene and formalin, or a modified product thereof.

xxvii> Petroleum resins C5 type, C9 type, 05-C9 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof.

XXVI++) A blend of two or more of the above 1) to XXVH).

Also, blended with other thermoplastic resins.

For example, the molecular level of the thermoplastic resin may be O for the self-rendering property 1.

Such self-oxidizing or thermoplastic resin and the above-mentioned crosslinker are usually layered at a weight ratio of 1:0.1 to 100 over a wide range.

Preferably, such a recording layer further contains a quencher! Yes.

and n, SLN due to repeated irradiation with readout light
The reproduction deterioration of the ratio is reduced, and the light resistance is (b) improved.

Various quenchers can be used, but especially when the color patch is excited and singlet oxygen is generated,
- It is preferable that the quencher is a singlet oxygen quencher that undergoes electron transfer or energy transfer from oxygen to become excited, returns to the ground state by itself, and converts oxygen into a triplet state.

Although a variety of singlet oxygen quenchers can be used, transition wire mesh chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dye-binding resins. I like certain things.
In this case, the central metal is h N Ir COT O
u H to 4n etc. are preferred, and the following compounds are particularly preferred.

1) Acetylacetonate chelate Q I Nt
(II) Acetylacetonate Q 2 Ou (IT
J acetylacetonate Q3 'Mn Tsukud) acetylacetonate Q4 Co(TI) acetylacetonate 2) bisdithio-α-diketone system, where R(') to R(4) are substituted or unsubstituted alkyl groups or It represents an aryl group, and 1M represents a divalent transition metal atom.

In this case, 1M has a single charge and may form a salt with a quaternary ammonium ion or the like.

Q5Ni (dithiobenzyl Q 6 NI (It) dithiopiacetyl 7 Q8 9 Ni (0489) 4 3) bisphenyldithia J--/l/ system where,
R (5) and 1(, (″) represent an alkyl group such as a methyl group, or a halogen atom such as C1,
Represents a divalent transition metal atom such as M ij N i . Furthermore, a and b are each n10 or an integer of 4 or less.

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:

QIOPA-1001 (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 [same as above Ni-bis(toluenedithiol)tetra(t-butyl) ammonium] Q12 PA-1003 (same as above) Q13 PA-1005 [same as above] Top Ni-bis(
dichlorobenzene)tetra(t-butyl)ammonium] Q14 pA-xo06 [same as above Ni-bis(
trichlorobenzenedithiol)tetra(1-butyl)
Ammonium] Q150n-bis(benzene-1,2-17 naol)
Tetrazotylammonium Q150o -bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q]7Ni -bis(benzene-1,2-dithiol)tetrazotylammonium Q18Ni -bis(0-xylene) -4,5-dithiol)tetrabutylammonium Q19Ni -bis(5-chlorobenzene-1,2-dithiol)tetrazotylammonium Q2QNi -bis(3,4,5,6-titramethylbenzene-1.2/thiol) Tetrabutylammonium Q21 Ni -bis(3,4,5,6-tetrachlorobenzene-1,2dithiol)tetrabutylammonium 4) Dithiocar/samic acid chelate system Here, 几(7
) and R(8) represent an alkyl group, and 1M represents a divalent transition metal atom.

Q22Ni -bis(dibutyl dithiocarnocarnomic acid) [Antigen NBO (manufactured by Jushu Gakusha)] 5) Bisphenylthiol type Q23Ni -bis(octylphenyl) sulfide 6) Thiocatechol chelate type where 5M is a divalent transition If all metal atoms are represented by 1-0, M has one charge of gold, and anion and g = 9 may be formed, and benzene Bit is 11. J-substituent: r may be present.

q24iNi -bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime type salt (1(M) In particular, R(9) and R- represent an alkyl group and 5
M represents a divalent transition metal atom.

Q25 Ni (11)O(N-isozolobylformimidoyl)phenol Q26 Ni (JT)O-(N-dodecylformimidoyl)phenol Q27 Co (■)O-rN-dodecylformimidoyl)phenol Q28 Cu (II) O-(N-dodecylformimidoyl)phenol Q29 Ni (If)2.2' -C ethylene bis to trilomethylidine)]-diphenol Q30 Co (J[)2.2' -(ethylene bis to trilomethylidine) )]-Diphenol Q31 Ni(II)2.2'-(1,8-
Naphthylenebis to trilomethylidine>3-Dinenol Q32 Ni (U)-(N-phenylformimidoyl)phenol Q33 0o (1)-(''-phenylformimidoyl)phenol Q34 (3u (IT)-(N-phenylformimidoyl) Il) Phenol Q35 Nr cTI) Salicylaldehyde Phenylhydrazone Q36 Nr Nl) Salicylaldehyde oxime 8) Thi,t bisphenol-tochelate system where 1M is the same as above R, (u) and R (+, +)
represents an alkyl group. Further, M has one charge and may form a salt with an anion.

Q37 Ni(H)n-butylamino(2,2'
-Thiobis(4-tert-octyl)-phenolate:] (r+yasr>rb -U V -108
4 (American cyanamide Oo -T L' d): ] Q38 Co (1) n-butylamino (2,2'
-thiobis(4-tert-octyl)-phenolate] Q 39 Ni (H) -2+ 2' Thiobis(4-tert-octyl)-phenolate 9) Phosphonous acid chelate system where M is the same as in section M B (+3) and n, (I') irJ: represents a substituent such as an alkyl group or a hydroxyl group.

40 Other quench yards include the following.

IO) Benzoate Q, 5] Existing chemical substance -3040 [Tinuvin-120 (manufactured by Ciba Geigy)] 11) Hindered amine Q52 Existing chemical substance 5-3732 [5ANOT.

L8-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such a cuffenture is synthesized according to a known method.
Ru.

The quencher of Kohori et al. is generally 0.05 to 12 mol, particularly 0.1 to
It contains about 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.

Cracks, scratches, and regeneration deterioration are extremely small.

In this case, the difference between the two is preferably 0 or 350 nm or less.

To form such a recording layer, it is generally best to apply it by coating according to a conventional method.

The thickness of the recording layer is usually about 0.03 to 10 nm.

In addition, such a recording layer may contain other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and crosslinking agents. etc. may be included,'! In addition, a crosslinked product of a dye alone or a crosslinked product of a spacer component alone may be contained.

To form such a recording layer, it is sufficient to apply it onto the substrate using a predetermined solvent and dry it. In this case, the crosslinking reaction can be carried out at the time of coating, and at this time [Vi, heating is usually carried out after coating.

Furthermore, f/? Examples of solvents used for cloth include methyl ethyl ketone and methyl isodity ketone.

Ketones such as cyclohexanone, butyl acetate.

Ester systems such as ethyl acetate, carpitol acetate, and butyl carpitol acetate, ether systems such as methyl cellosol, ethyl cellosol, and aromatic systems such as toluene and xylene.

Alkyl halides such as dichloroethane, alcohols, etc. may be used.

There is no particular restriction on the material of the substrate on which such records are laid, and various resins, glass, ceramics, metals, etc.
It may be.

It was. The shape of the tape depends on the intended use.

It may be a disk, drum, belt, etc.

Note that the base body usually has a groove for tracking.
However, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc.

In addition, as the resin material for the base material, it is preferable to use a base material that does not have any stains, such as polymethyl methacrylate, acrylic resin, epoxy resin, polycarnate resin, polysulfon jugeji, polyether sulfon, or methylpentene polymer. be.

and t'15, etc., may be coated with Zolaimer in order to improve solvent resistance, toughness, surface tension, thermal conductivity, etc.

As the Zolaimer, for example, titanium-based, silane thread, aluminum-based coupling agents, and various photosensitive resins can be used.

In addition, on the recording layer, if necessary, there is a reflective layer that functions as a back surface when a transparent substrate is used.

Various uppermost protective layers, a single half-mirror layer, etc. can also be provided.

The medium of the present invention may have the recording layer described above on one surface of such a substrate, or may have recording layers on both surfaces thereof.

It's a good idea to use two substrates with a recording layer coated on one side, and make them face each other with a predetermined gap between them, with the recording layers facing each other. It can also be used to prevent scratches.

(2) Specific Effects of the Invention The medium according to the present invention irradiates recording light in a pulsed manner while running or rotating. 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 bits are formed.

The bits formed in this way are read out by detecting the reflected or transmitted light of the readout light, especially the reflected light, while the medium is running or rotating.In this case, recording and reading are performed from the substrate side. Although this is preferred, it may also be performed from the recording layer side.

It is also possible to erase the bits once formed in the recording layer with light or heat and rewrite the entire bit.

Note that the recording or reading light may be a semiconductor laser, a He-Ne laser, or an Ar laser.

IIe-Cd laser etc. can be used.

V. Specific effects of the invention One advantage of the present invention is that the medium can be stored for a long time.

There is very little deterioration in writing sensitivity or S/N ratio. In particular, the S/N of reading after being stored at high temperature after recording
The deterioration of the ratio becomes extremely small.

Also, the readout 8/N ratio is extremely high.

■Specific embodiments of the invention Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 In the coating shown in Table 1 below, the following dye, spacer component, and crosslinking agent were added at a dye coating spacer component weight ratio of 3:1.
, (dye + spacer component):crosslinking agent molar ratio = 4:1, and this ? It was coated on a substrate made of remethyl methacrylate 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
-Propylate crosslinking agent 2 Zirconium tetraacetylacetonate elA 3.3' -di(6-hydroxyhexyl)-11-diphenylamino-10°12-ethylene-
5,6,5',6'-Shihenzothiato IJ Calcisyanin Verchlorate Dye B 1,1'-di(2-hydroxyethyl)-
2,2'-tricarycyanine verchlorate dye 0 3,3'-di(6-hydroxyhexyloxycarbunyl)vanadyl phthalocyanine dye D 3,3'-di(6-cardixybentyloxycarbonyl)vanadyl Phthalocyanine spacer component J 1,6-hexanediol spacer component K Bisphenol A spacer component L Terephthalic acid spacer component M Maleic acid For each sample prepared in this way.

While rotating at 1800 rpm, a semiconductor laser (
830nm) e1μm Focusing part output IQm to focus on φ
W), writing was performed with a pulse width of 100 nsec.

After this, 4 cows of 1mW are read out and the capital is 1μse.
irradiated as a 3KHz pulse.

The reflected light was detected and the %C/N ratio was measured.

Next, each sample was stored for 1000 hours at a relative humidity of 501:90%, and then the deterioration of the C/N ratio was checked.

Table 1 shows the poor C/N ratio (%) after storage.

From the results shown in Table 1, two effects of the present invention are clear.

Execution 13i'I12 In sample storms 1 and 4 of Example 1, 5
Sunsol & 12 with 30% resin added by weight
I got 42.

The resins Vi, coumaron-indene resin (number average molecular weight: 5OO), and polyα-methylstyrene (number average molecular weight: 80,000) were used.

The results are shown in Table 2.

Table 2 Sample 12 42 Island Resin PMMA Polyα-methylstyrene 0/N ratio 51 50 Deterioration rate ■ 78 From the results shown in Table 2, the effects of the present invention are clear.

Example 3 In Sample Melon 1 of Example 1, Sample Melon 13 was obtained by adding Quencher Q14 at a weight ratio of 40% to the pigment in the crosslinked product.

1 mW, 1 μs for sample A 1 e 13.

Table 3 shows the deterioration rate (%) of the 07N ratio when irradiated with 3 KHz read light for 4 minutes.

Table 3 Sample A 1 13 Quencher-Q14 0/N ratio deterioration rate High temperature storage deterioration % 32 Reflectance deterioration rate Reproduction deterioration % 36 2 From the results shown in Table 3, it can be seen that the results of the present invention when containing a quencher The effect is obvious.

Applicant: TDC Co., Ltd. Agent Patent attorney: Yo Ishii - Procedural amendment signed) June 2r, 1982 Patent Application No. 72584 2, Name of invention: Optical recording medium 3, Person making the amendment Relationship to the incident Patent applicant Location
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
No. Yabe Building 1st Floor Telephone 988-1680 The description in Column 6 of Detailed Description of the Invention of the Specification, F3 of F3 of Details of Amendment-7, and Column of ``Detailed Description of Invention'' in the specification will be amended as shown in C.

■) In the first row of page 33, fNi, Co, Cu.

Mnj means fNi, Co, Cu, Mn.

Correct as Pd and Ptj.

fl) Acetylacetonate chelate QINi (
II) Acetylacetonate Q2Cu(II) Acetylacetonate Q3 Mn(m) Acetylacetonate Q4Co(II) Acetylacetonate 2) Bisdithio-α-diketone system where R(11, R(4) is substituted or Represents an unsubstituted alkyl group or aryl group, M is Ni, C
o, represents a transition metal atom such as Cu, Pd, or Pt.

In this case, 1M has a single charge and may form a salt with a cation such as a quaternary ammonium ion.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl 7 Q9 N”(C4)19) 4 3) hisphenyldithiol system (5) (6) where R and R are alkyl groups such as methyl, ( , or a halogen atom such as C1, and M is Ni or Co.

Represents a transition metal atom such as Cu, Pd, or Pt. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with a cation, and further, other ligands may be bonded above and below M.

Examples of this include the following:

QIOPA-1001 (Product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Ql l PA-1002 (Ni-bis(toluenedithiol)tetra(t-butyl)ammonium) Q12 PA-1003 (Ni) Q13
FA-1005 (same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 FA-1006(same as above Ni-bis(trichlorobenzenedithiol) tetra(t-butyl)ammonium) Q15Co-bis(benzene) y-1,2-dithiol)tetrabutylammonium Q16 Co-bis(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni- Bis(0-xyL/7-4.5-dithiol)tetrabutylammonium Q19Ni-bis(5-chlorobenzene-1,2-dithiol)tetrabutylammonium Q2ONi-bis(3,4,5,6-tetramethylbenzene -1,2 dithiol) tetrabutylammonium Q21Ni-bis(3,4,5,6-tetrachlorobenzene-1,2 dithiol) tetrabutylammonium 4) dithiocarbamate chelate system (?) (8) where R and R represents an alkyl group. Also, M is Ni, CO+ Cu +P
d, represents a transition metal atom such as Pt.

Q22Ni-bis(dibutyl dithiocarhemic acid) [
Antigen NBC (manufactured by Sumima Kagaku Co., Ltd.)] 5) Bisphenylthiol-based Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate-based Here, M is Ni, Go, Cu, Pd.

Represents a transition metal atom such as PL. Furthermore, M may have a single charge and form a salt with a cation, and the benzene ring may have a substituent such as 1 or X.

Q24Ni-bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime system where R and R(lO) represent an alkyl (9) group, and M is Nt, Co, Cu.

Represents a transition metal atom such as Pd or Pt.

Q25 Ni (TI) o -(N-isopropylformimidoyl) phenol Q26 Ni (TI) o - (N-dodecylformimidoyl) phenol Q27 Co (II) o - (N-dodecylformimidoyl) phenol Q28 Cu (II) o -(N-dodecylformimidoyl)phenol Q29 Nt(IT)2.2'-(trilomethylidine on ethylene bis)]-diphenol Q30 Co (II)2.2'-(trilomethylidine on ethylene bis) ]-diphenol Q31 Ni (II)2.2'-(1,8
-naphthylene bis trilomethylidine)] -diphenol Q32 Ni (II) -(N-phenylformimidoyl)phenol Q33 Co (11) -(N-phenylformimidoyl)phenol Q34 Cu (II) (N7 x
Nylformimidoyl) phenol Q35 N1 (IT) salicylaldehyde phenyl, dracin Q36 N1 (II) salicylaldehyde oxime 8) Thiobisferrate chelate system (11) where 1M is the same as above, and R (12 ) and R represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 N1(II) n-butylamino [2゜2'-
Thiobis(4-tert-octyl)-ferulate)
(Cyasorb-UV-LO84 (7merican Cyanamide Co,, Ltd.)) Q38
Co(II) n-butylamino [2゜2゛-thiobis(4-jerk-octyl)-ferulate] Q39 Ni (If)-2,2'-thiobis(4
-tert-octyl)-ferulate 9) Phosphonous acid chelate system Here, M is the same as above, and R(13), (14) and R represent a substituent such as an alkyl group or a hydroxyl group.

2 In addition to this, other quenchers include the following.

10) Benzoate Q41 Existing chemical substance 3-3040 (:Chikubin-
120 (manufactured by Ciba Geigy)] 11) Hindered amine Q42 Existing chemical substance 5-3732 (5ANOLL
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]j 3

Claims (1)

[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 more kinds of dyes having a functional group and one or more kinds of dyes having a functional group are used as the light absorber. 1. An optical recording medium which is formed by crosslinking one or more compounds having a functional group 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 calxoxy 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 one composition contains a resin. 6. Claims 1, 2, and 3 in which the recording layer is made of a composition of a light absorber, and the composition contains a quencher.
The optical recording medium according to any one of Items 1 and 5.