JPH0262283A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To obtain a high absorption index and high reflectance being necessary for recording and reading by laser light, by compounding specified thiazolopyrimidine dyestuff into specified polymethine dyestuff and by making the compounded dyestuff borne on a substrate. CONSTITUTION:Dyestuff expressed by a formula (I) and dyestuff expressed by a formula (II) are borne on the same substrate. Concretely, the dyestuff expressed by the formula (II), e.g. thiazolopyrimidine dyestuff expressed by a formula (III), is compounded into polymethine dyestuff expressed by the formula (I), and a solution thereof is applied by spin-coating on a polycarbonate plate, so as to form a recording medium. In the formulas, Z<1> and Z<2> denote alkyl, aryl or alkenyl, Q denotes N or C-R<6> (R<6> denotes a hydrogen atom, alkyl or aryl), R<1> to R<3> denote alkyl, aryl or alkenyl, X1<-> denotes an anion, G denotes a group for forming a five- or six-membered ring in combination with N-R<3>, and L denotes a trivalent group formed of 1, 3, 5 or 7 methine groups or substituted methine groups being so combined as to form a conjugate double bond.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a heat mode optical information recording medium that has an organic dye thin film and performs recording, reproduction, or erasing by causing a state change with a laser beam. Regarding.

[Conventional technology]

2. Description of the Related Art A recording medium is known in which a recording layer is formed by supporting a substance that changes in quality when irradiated with a laser beam on a substrate, and the state of the change in quality of the recording layer is read as a change in the reflectance of the recording layer. In recent years, organic dyes have been used for such recording layers, but it is not easy to achieve the high reflectance required for reading and the high absorption required for recording at the same wavelength. Therefore, the reflectance of these media remained at about 20 to 30%. One of the reasons for this is that the reflectance of a dye film made of a single dye generally appears on the longer wavelength side than the maximum absorption wavelength of the dye film, so the wavelength of the laser light used for recording and reading is This is because if the wavelength of the laser beam is made to match the maximum wavelength of the reflectance, the absorption rate at that wavelength will be lowered, and conversely, if the wavelength of the laser beam is made to match the maximum absorption wavelength of the dye film, the reflectance of the dye film at that wavelength will be reduced. Another reason is that when a dye having a high reflectance at a certain wavelength is used in combination with a dye having a high absorbance at that wavelength, the reflectance often decreases. Therefore, there has been a need for an optical information recording medium that can set both reflectance and absorption to high values at the wavelength of the laser beam used for recording and reading information.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide an optical information recording medium having a novel structure that has a high reflectance for laser beams used for reading and recording information, and also has an absorption coefficient high enough for recording.

[Failure to solve the problem]

As a result of various studies, the inventor surprisingly found that the general formula (
The present invention was completed by discovering that the dye represented by I) can provide a dye thin film exhibiting sufficiently high reflectance even when mixed with other dyes.

That is, the object of the present invention is to combine at least one dye represented by the following general formula (I) and at least one dye represented by the following general formula (I).
Recording using a laser beam, characterized in that a dye represented by format (II) is supported on the same substrate,
This was achieved using an optical information recording medium for reproducing or erasing information.

General formula (1) [However, zl and Z2 represent an alkyl group, an aryl group, or an alkenyl group, and these may be the same or different from each other, or Zl and 22 may be linked to each other to form a ring. Often, Q is N or C-Rb (R
'represents a hydrogen atom, an alkyl group, or an aryl group), and R1, R2, and R3 represent an alkyl group or an alkenyl group, and may be the same or different from each other, or at least one of these groups is
(, X, - represents an anion; G represents a group for forming a 5- or 6-membered ring by connecting with N-R3; Represents a trivalent group formed by linking 3, 5 or 7 methine groups or substituted methine groups to form a conjugated double bond] -Format (II) AI and A'' are independently hydrogen atoms or a substituent, Z3 represents an atomic group necessary to form a 5-membered heterocycle, R7-R10 independently represent a hydrogen atom or a substituent, R11 represents a substituent, or together with Z3 A 6-membered heterocycle may be formed, n represents 0, 1 or 2, and X!- represents an anion.

In the above-format (I), zl and Z2 are a benzene ring, a naphthalene ring, a benzene ring having a substituent, or a naphthalene ring having a substituent, which are connected to each other, and Q is N or C-H It is preferable that the 5- or 6-membered ring formed by linking G with NR'' is an imidazoquinoxaline ring, a quinoline ring, a benzothiazole ring, a benzimidazole ring or an imidazoquinoline ring.

Among the compounds represented by the above-mentioned form CI), preferred are compounds represented by the following form (Ia).

General formula (Ia): (wherein R4, R4', Rs and R S / are 7) L/
Represents a kyl group, an alkenyl group, or an aryl group, which may be the same or different from each other, and Ll is 1, 3,
Represents a trivalent group formed by connecting 5 or 7 optionally substituted methine groups via a conjugated double bond, and z
, z' represents an atomic group to complete the aromatic ring, and X
l- represents an anion] In the above-format (Ia), z, z', Ll, R 4
, RS , R4 L , and R5 / may each further have a substituent.

Among the substituents of these groups, preferred are C. Hans
The hydrophobicity parameter, π, proposed by ch et al.
has a value in the range of -0.5 to 15. In addition,
Hydrophobicity parameters can be calculated according to the following literature:

1) C. Hansch et al., J. Med. Chem.
, Vol. 16, p. 1207 (published in 1973) 2) C. Hansch et al., Vol. 20, 304.
Page (published in 1977) Preferred groups for R', R'', RS, or R5' are substituted or unsubstituted phenyl groups, substituted or unsubstituted lower alkyl groups (having 1 to 8 carbon atoms). ) or a substituted or unsubstituted lower alkenyl group (
2 to 8 carbon atoms), and the above-mentioned C, Ha
The hydrophobicity parameter proposed by nsch et al.
π may have a substituent having a value in the range of −0.5 to 15.

When R4, R4', R5 or R5/ has a substituent, a particularly preferred substituent is a halogen atom (F
% ClBr, ■), substituted or unsubstituted phenyl groups (e.g. phenyl, m-chlorophenyl, p-methylphenyl, etc.), alkylthio groups (e.g. methylthio,
butylthio), substituted or unsubstituted phenylthio groups (e.g. phenylthio, p-chlorophenylthio, m
-methylphenyl, etc.).

Among the groups represented by R', R'', R' or RS', particularly preferred are unsubstituted alkyl groups having 2 to 8 carbon atoms or unsubstituted alkenyl groups having 2 to 8 carbon atoms, among which R4R41, R5 and RS l
are most preferably the same.

Examples of the atomic group represented by z and z' include atomic groups for completing benzene rings, naphthalene rings, and anthracene rings, and preferred are atomic groups for completing benzene rings and naphthalene rings.

and may further have the substituents described as substituents on R', R'', R' and R%J.

When z and z' have a substituent, particularly preferred substituents include a halogen atom (F, C1, Br, ■), a substituted or unsubstituted phenyl group (e.g., phenyl, m-chlorophenyl, p-methylphenyl, etc.). ), alkylthio groups (e.g. methylthio, butylthio, etc.), substituted or unsubstituted phenylthio groups (e.g. phenylthio, p
-chlorophenylthio, m-methylphenylthio, etc.)
, substituted or unsubstituted alkyl groups (e.g. methyl, trifluoromethyl, tert-amyl, etc.), cyano groups, alkoxycarbonyl groups (e.g. propoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl,
decyloxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), alkyl or arylsulfonyl groups (eg, butanesulfonyl, phenylsulfonyl, octanesulfonyl, etc.).

Particularly preferred among the atomic groups represented by z and z' are those that form a benzene ring having a substituent with a relatively weak electron donating property and having a Hammett sigma constant of -0.2 to +0.7. is a group of atoms, among which F, (
An atomic group for forming a benzene ring substituted with a halogen atom, such as 1, Br, and ■, is preferable.

The trivalent group represented by Ll represents a substituted or unsubstituted methine group, or a linking group formed by connecting 3.5 or 7 substituted or unsubstituted methine groups via a conjugated double bond, but especially - Those represented by formats (a) to 1) are preferred.

-Format (a) -C= General formula (b) -CI-1= CH-C-CH-CH=General formula (cl General formula fd) General formula fa) -Format (II General formula (gl -CH=C -CHfuCH-CH= general formula (hl -CH=CH-CH=C-CH=CH-CH= general formula (
1) % Formula % In general formulas fa) to 11, Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group includes a lower alkyl group such as a methyl group, a monosubstituted or unsubstituted phenyl group, an aralkyl group such as a benzyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methyl Disubstituted amino groups such as phenylamino group, morpholino group, imidazolidino group, ethoxyluponylpiverazino group, alkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylthio group, cyano group, nitro group, F, C1 , halogen atoms such as Br, etc. are preferable.

Among the linking groups represented by LL, particularly preferred are those represented by (Ill), (b), fh), and (1).

The anion represented by xl- is a monovalent or divalent ion that supplies the number of negative charges necessary to neutralize the charge of the cation moiety.

An example of an anion represented by X, - is C7! -B
y” Halogen ions such as I-, so, “-1H
Alkyl sulfate ions such as 3O, -1CHffOS Ch-, paratoluenesulfonic acid ions, naphthalene-1
, 5-disulfonic acid ion, methanesulfonic acid ion,
Sulfonate ions such as trifluoromethanesulfonate ion and octane sulfonate ion, acetate ion, p-
Carboxylate ions such as chlorobenzoate ion, trifluoroacetate ion, oxalate ion, and succinate ion,
PFh-B Fa\ CZO, -1■04-, heteropolyacid ions such as tungstate ion, tungstophosphate ion, H, PO4-, NO, -, phenolate ion such as picrate ion, etc. .

Preferred anions represented by X and - are C
7! -, Br-T-, CHsO3O3-Cz HsO
S O: l-, perfluorosulfonic acids such as paratoluenesulfonate ion, p-chlorobenzenesulfonate ion, methanesulfonate ion, butanesulfonate ion, naphthalene-1,5-disulfonate ion, trifluoromethanesulfonate ion ion, PF6-,
BFa-1CI104-, etc., and particularly preferred are trifluoromethanesulfonic acid ion, PFt, -
1C104-, and among these, trifluoromethanesulfonic acid ion and PF,- are the most preferred since there is no risk of explosion.

Next, specific examples of the dye represented by the general formula (1) of the present invention will be given, but the present invention is not limited to these.

The compound represented by the general formula N) of the present invention can be synthesized, for example, by referring to the method described at the bottom of Nitrogen-Containing Compounds, page 1432, published by Dai Organic Chemistry (Breakfast Shoten). That is, the general formula (A) (wherein Z', Z'', Q, R', R'' are the general formula (A)
It represents the same group as defined in I), and X'- represents an anion. ) A quaternary salt represented by 1,1,3,3-tetramethoxypropane or a dialdehyde such as glutaconaldehyde, or 1,7-diaza-1,7-diphenyl-1,3
, 5-hebutatoluene or the like by condensation with a polymethine source. Especially imidazo (
4,5-b) A dye having a quinoxaline skeleton can be synthesized with reference to the method described in US Pat. No. 3,431.111.

Among the compounds represented by the general formula (n) used in the present invention, particularly preferred compounds have the following format (Iff).
It is expressed as

General formula (I [I) In the formula, AI and A2 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a cyano group, a substituted or unsubstituted alkyl group represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group; Y is N RI 2 (RI2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, represents a substituted or unsubstituted aralkyl group), 0,
represents S-, Se, or Te, zS represents an atomic group necessary to form a 5-membered heterocycle, and R? , R11
, R9 and RIO represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a hydrogen atom; R'' is a substituted or unsubstituted alkyl group, a substituted or unsubstituted Aryl group, substituted or unsubstituted aralkyl group, or Z
Represents an atomic group necessary to form a 6-membered heterocycle by combining with S: n represents 0.1 or 2; x2- represents an anion. However, X is Rma, RII, R9, R10,
It may be bound to R1, RI2, zS, AI or A2 to form an inner salt.

The compound represented by general formula (III) will be explained in more detail.

Among the groups represented by A I and A Z, preferred are a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a C 6 to 2 alkyl group.
0 substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group having 7 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
These are a substituted or unsubstituted phenoxy group having 6 to 20 carbon atoms, or a monosubstituted or unsubstituted benzyloxy group having 7 to 20 carbon atoms, and preferred as these substituents are halogen atoms (F, C1゜Br, I)
, cyano group, alkoxy group, aryloxy group, ester group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, sulfonyl group, hydroxy group, sulfo group, or carboxyl group, which are further substituted. may have been done. Al5A!
Among the groups represented by, particularly preferred are hydrogen atoms,
A chlorine atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group.

Among the groups represented by Y, preferred are 0, S,
Se, Te, and N R having 1 to 20 carbon atoms
I 2 and RI2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and preferred substituents are A I , the group represented by A 2 The preferred substituents are the same as those mentioned above.

Of the groups represented by Y, particularly preferred are 0, S
, Se, Te, and NRI in which R12 is an alkyl group having 1 to 6 carbon atoms, phenyl, or benzyl group
It is Z.

Among the atomic groups represented by zS, preferred are the atomic groups necessary to form a benzo or naphthoazole ring or -←CH=CH→", which is AI, A2
The group represented by may be substituted with the groups mentioned above as preferred substituents. Among the atomic groups represented by Z5, particularly preferred are →CH=CH→r and a halogen atom (F, Cu2, Br, I), an alkyl group having 1 to 6 carbon atoms, a phenyl group, and 6 carbon atoms. Substituted phenyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted phenoxy group having 6 to 20 carbon atoms, carbonamide group having 1 to 20 carbon atoms, carbon amide group having 1 to 20 carbon atoms These are a sulfonamide group, a group substituted with a ureido group having 1 to 20 carbon atoms, or an atomic group that can be bonded to the R eyes to form a condensed pyrimidine ring.

Among the groups represented by R7, R@, R9 and RIG, preferred are a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, and a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms. 7 to 20 substituted or unsubstituted benzyl groups, or a hydrogen atom, and examples of the substituent include the groups mentioned above as preferred substituents for the group represented by AI and AI. Particularly preferred as the group represented by R9 are a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms.Particularly preferred as R8 is hydrogen. atoms, alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms, and particularly preferred as RIG are phenyl groups or substituted phenyl groups having 6 to 20 carbon atoms. .

Among the substituents represented by R1+, preferred are a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted phenyl group having 7 to 20 carbon atoms. It is a substituted or unsubstituted aralkyl group, or an atomic group necessary to form a condensed pyrimidine ring by linking with Z5. Preferred substituents are the same as those for the groups represented by AI and At.

Among the substituents represented by RI 1, particularly preferred are alkyl groups having 1 to 20 carbon atoms and 2 carbon atoms.
to 4 sulfoalkyl groups, phenyl groups, sulfophenyl groups, benzyl groups, sulfobenzyl groups, phenethyl groups, sulfophenethyl groups, or an atomic group (-CR'= CRB-
CR7=N-).

The preferred value of n is determined depending on the wavelength of light used for recording or reading information; for example, when using light of 700 to 900 nm, n is 2.600 to 850 nm, particularly 660 to 850 nm.
When using 800 nm light, n-1,500 to 65
When using light of 0 nm, especially 540 to 560 nm, it is preferable that n=o.

Preferred anions represented by X2- include halide ions, sulfate ions, monoalkyl sulfate ions, perchlorate ions, sulfonate ions, carbonate ions,
Nitrate ion, acetate ion, benzoate ion,
Examples include oxalate ion, phosphate ion, tetraphenylborate ion, and tetrafluorophosphate ion.

Particularly preferred anions represented by X2- are bromide ion, iodide ion, sulfate ion, monoalkyl sulfate ion, perchlorate ion, alkylsulfonate ion, and alkylsulfonate ion.

Specific examples of the compound represented by general formula (II) are listed below, but the present invention is not limited thereto.

rl-7 ■-5 ■-14 ■-13 ■-16 ■-20 ■-21 ■-19 ■-22 ■ - Synthesis of the compound represented by form (II) is, for example,
Report by G., G., Dyadyusha et al. (dyes and pigments)
Dyes and Pigments) Magazine, Volume 4, 1
79 to 194, published in 1983), and various derivatives can also be synthesized according to this method.

In the optical recording medium of the present invention, the usage ratio of the dye represented by -C formula (1) and the dye represented by general formula (n) is as follows:
Preferably, the molar ratio is 100:1 to 1:10, more preferably 20:1 to 1:5, most preferably 10:1 to
The ratio is 2:1. Each dye may be used alone or in combination of two or more types, or may be used in combination with dyes other than the dyes of the present invention, and various antioxidants and singlets may be used to improve reading durability. It is also effective to use an oxygen quencher. Moreover, various resins may be used in combination.

Alternatively, durability can be increased by adding transition metal ions to form a chelate.

Various quenchers can be used in the optical recording medium of the present invention. As such an encher, a transition metal complex is preferable because it reduces regeneration deterioration and has good compatibility with the dye. In this case, preferable central metals are Ni, C0% CLI, P
d, Pt, etc.

An example of a new Encher is JP-A-62-1747.
Examples include those represented by the following general formula (IV) or (V) described in Publication No. 41.

[ [ (In the formula, (Cat, ) and (Catz) represent the cations necessary to neutralize the complex, and M and M
2 represents nickel, copper, cobalt, palladium or platinum; n represents 1 or 2; ) In the compound represented by the above-format (EV) or (V), (Cat,)
Among the cations represented by (Catz), inorganic cations include alkali metals (for example, Lis N
as K), alkaline earth metals (Mg, Ca, etc.),
(Ba, etc.) or NH.

Examples of the organic cation include quaternary ammonium ions and quaternary phosphonium ions.

In the compound represented by the above-mentioned formula (IV) or (V), the preferred order of M or M2 is nickel, cobalt, copper, palladium, and platinum.

The metal complex of general formula (TV) or (V) has a three-dimensional planar structure. Note that in the compound of formula (V), it is not unambiguously determined whether the thioketone group is symmetrical or asymmetrical with respect to the central metal, but in the present invention, for convenience, general formula (V)
Expressed as follows.

The compound represented by the above formula (IV) or (V) can be synthesized as follows.

-71 The compound of formula (IV) (n=2) is disodium 1.
3-dithiol-2-thione-4,5-dithiolate is first converted into a zinc complex, and this is reacted with benzoyl chloride to form a bisbenzoylthio compound. It is obtained by decomposing this with an alkali and then reacting it with a metal salt.

Further, a compound of -form (rV) (n=1) can be obtained by oxidizing the complex (n=2) obtained above with a suitable oxidizing agent.

The compound of general formula (IV) (n=2) is prepared by first heating disodium 1,3-dithiol-2-thione-4°5-dithiolate obtained by reacting carbon disulfide and sodium to about 130°C. Disodium 1,2-
Isomerize to dithiol-3-thione-4°5-dithiolate. This is made into a zinc complex, and this is reacted with benzoyl chloride to form a bisbenzoylthio compound. It is obtained by decomposing this with an alkali and then reacting it with a metal salt.

Moreover, -form (V) (n=1) is the complex obtained above (n=
2) is oxidized with a suitable oxidizing agent.

-i The 1,3-dithiol-2-thione-4,5-dithiolate anion, which is an intermediate for obtaining the compound of formula (IV) or [V], can be produced by electrolysis in addition to the reduction method with Na as described above. It can also be obtained by chemical reduction.

Preferred examples of the compounds represented by the above-mentioned formula (IV) are as follows.

Other quenchers include JP-A-59-17829
Examples include the following compounds described in No. 5.

(i) Bisdithio-α-diketone system R"=R" represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a cyano group, and M represents a divalent transition metal atom.

(ii) Bisphenyl dithiol system and ≧ ≧ and R'', Roll represents an alkyl group, cyano group or halogen atom, and M represents a divalent transition metal atom.

(iii) Acetylacetonate chelate system (iv)
Dithiocarbamate chelate system (V) Bisphenylthiol system (vi) Thiocatechol chelate system (vi) Salicylaldehyde oxime system (vii) Thiobisferrate chelate system (ix) Phosphonous acid chelate system (x) Benzoate system (xi) Hindered amine type (xii) transition metal salts In addition, aminium type or diimonium type compounds represented by the formula are mentioned, and specific examples include IRG-002, IRG-003, IRQ-0 manufactured by Nippon Kayaku Co., Ltd.
22 and IRG-023.

fh (In the formula, R represents an alkyl group or an aryl group.) In the present invention, a combination of a cation of the dye and an anion of a quencher can also be used.

The quencher is generally 0.05 per mole of the dye.
~12 mol, preferably 0.1-1.2 mol is used.

The quencher is preferably contained in the dye thin film recording layer, but may be contained in a layer separate from the recording layer. The optical recording medium of the present invention may further include an undercoat layer on the substrate, a protective layer on the recording layer, and a reflective layer on the substrate or the recording layer, if necessary.

Any known substrate can be used as the substrate. Typical examples include glass or plastic; plastics include acrylic, polycarbonate,
Polysulfone, polyimide, amorphous polyolefin, epoxy resin, polyester, etc. are used. Its shape can be various, such as a disk, card, sheet, or roll film.

A guide groove may be formed on the glass or plastic substrate to facilitate tracking during recording. Further, a subbing layer such as a plastic binder, an inorganic oxide, an inorganic sulfide, etc. may be provided on the glass or plastic-based material, and an undercoating layer having a thermal conductivity lower than that of the substrate is preferable. It is also possible to have a so-called air sand inch structure in which two recording media are placed facing each other with their recording layers inside.

The recording layer in the present invention can be formed by, for example, using a dye and a quencher in an organic solvent (e.g., methanol, ethanol, isopropyl alcohol, fluorinated alcohols such as 2.2.3.3-tetrafluoropropanol, dichloromethane, dichloroethane, etc.). acetone, etc.) and, if necessary, a suitable binder (e.g. PVA, PV
P, polyvinyl butyral, polycarbonate, nitrocellulose, polyvinyl formal, methyl vinyl ether, chlorinated paraffin, maleic anhydride copolymer, styrene-butadiene copolymer, xylene resin) and apply this solution (e.g. with spin cord). This can be done by co-depositing a dye and a quencher, or by vacuum-depositing a dye and then applying a quencher. When a binder is used, the weight of the binder is preferably 0.01 to 2 times the weight of the dye, and the dye can also be used in the form of a thin film by the so-called Langmuir-Prodgett method.

In the present invention, the recording layer is IN or two or more layers are provided.

Record! An antioxidant or anti-fading agent may be present in the three layers or in the layer adjacent thereto to prevent deterioration of the dye.

The thickness of the recording layer is usually in the range of 0.01 μm to 2 μm, preferably 0.02 to 0.8 μm.

When a reflective layer is provided for a semiconductor laser or a He-Ne laser, the reflective layer is provided on the substrate and then a recording layer is provided on the reflective layer using the method described above, or the recording layer is placed on the substrate. There is a method of providing a reflective layer and then providing a reflective layer thereon.

The reflective layer can be made by the following methods, in addition to vapor deposition, sputtering, and ion blating.

For example, a solution containing a metal salt or a metal complex salt dissolved in a water-soluble resin (PVP, PVA, etc.) and a reducing agent added thereto is applied to the substrate, and the solution is applied at 50°C to 150°C, preferably from 60°C to
It is formed by heating and drying at 100°C.

The weight ratio of the metal salt or metal complex salt to the resin is 0.
1 to 10, preferably 0.5 to 1.5. In this case, the appropriate thickness of the recording layer is 0.01 to 0.1 .mu.m for the metal particle reflective layer and 0.01 to 1 .mu.m for the light absorption layer.

As the metal salt or metal complex salt, silver nitrate, potassium silver cyanide, potassium gold cyanide, silver ammine complex, silver cyanide complex, gold salt, or gold cyanide complex can be used. As the reducing agent, formalin, tartaric acid, tartrate, hypophosphite, sodium borohydride, dimethylamine borane, etc. can be used.

The reducing agent is 0.2 to 1 per mole of metal salt or metal complex salt.
It can be used in an amount of 0 mol, preferably 0.5 to 4 mol.

In the optical recording medium of the present invention, information is recorded by irradiating the recording layer with a spot-like high-energy beam from a laser (e.g., semiconductor laser, He-Ne laser, etc.) through the substrate or from the opposite side of the substrate. carried out,
The light absorbed by the recording layer is converted into heat, and a focus (hole) is formed in the recording layer.

Information is read out by irradiating a laser beam with a low output power below the recording dark value energy and detecting changes in the amount of reflected light or the amount of transmitted light in pit areas and areas where no pits are formed.

The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited to these.

Example 1 A 1% 2,2,3,3-tetrafluoropropanol solution of the compound shown in Table 1 was spin-coded onto an injection molded grooved polycarbonate plate (1.6μ pitch, 750 depth) and dried. . Recording and reproduction were performed on the thus prepared recording medium under the following conditions.

The results are shown in Table 1. From this table, it can be seen that the recording media of the present invention (sample numbers 10 to 23) exhibit high reflectance and high C/
It can be seen that N is given. The mixing ratio of the dye (such as the dye represented by general formula (II)) used together with the compound represented by formula (I) and the dye represented by general formula (I) was 1:4.

Recording and reproducing conditions Laser wavelength Beam diameter Linear velocity Recording power Recording frequency Recording duty Reproducing power Semiconductor laser (GaA IAs) 30 nm 1.6 μm 5 m/s 2 to 10 m-2, 5 MHz 50% 0.4 mW Comparative compound A [Effects of the Invention] The optical information recording medium of the present invention has a high reflectance with respect to the laser beam used for reading and recording information, and has a sufficiently high absorption rate for recording, so it exhibits a high C/N. .

Claims (1)

[Scope of Claims] A laser beam characterized in that at least one dye represented by the following general formula (I) and at least one dye represented by the following general formula (II) are supported on the same substrate. An optical information recording medium for recording, reproducing, or erasing using. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ^1 and Z^2 may be linked to each other to form a ring, and Q is N or C-R
^6 (R^6 is a hydrogen atom, an alkyl group, or an aryl group), and R^1, R^2, and R^3 represent an alkyl group, an aryl group, or an alkenyl group, and may be the same or different from each other. , or at least one of these groups may be linked to L to form a ring, X_1^- represents an anion, and G is linked to N-R^3 to form a 5- or 6-membered ring. and L represents a trivalent group formed by linking 1, 3, 5 or 7 methine groups or substituted methine groups to form a conjugated double bond] General formula [ II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [A^1 and A^2 independently represent a hydrogen atom or a substituent, and Z^3 represents an atomic group necessary to form a 5-membered heterocycle. , R^7~R^1^0 independently represent a hydrogen atom or a substituent, R^1^1 represents a substituent, or together with Z^3, 6
A membered heterocycle may be formed, n represents 0, 1 or 2, and X_2^- represents an anion. ]