JPH0262281A - 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 pyrrocoline 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. pyrrocoline 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 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 denote alkyl, aryl or alkenyl, X<-> denotes an anion, G denotes a group for forming a five- or six-members 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] C. Industrial Application Field] The present invention relates to a heat mode optical information recording system that includes an organic dye thin film and records, reproduces, or erases information by causing a state change using a laser beam. Regarding the medium.

[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 has not been easy to achieve both the high reflectance necessary for reading and the high absorption rate necessary for recording at the same wavelength. The reflectance of these media is 2
It remained at about 0-30%. One of the reasons is
The reflectance of a dye film made of a single dye generally appears on the longer wavelength side than the absorption maximum wavelength of the dye film, so the wavelength of the laser light used for recording and reading must match the maximum wavelength of the dye film's reflectance. This is because, if the wavelength of the laser beam is adjusted to the maximum absorption wavelength of the dye film, the absorption rate of the dye film at that wavelength becomes low. 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.

[Means to solve the problem]

As a result of various studies, the present inventor surprisingly discovered 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 formation <ff) is supported on the same substrate,
This was achieved using an optical information recording medium for reproducing or erasing information.

-Formation (1) [However, 2+ 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. (, Q is N or C-Rh(R
'represents a hydrogen atom, an alkyl group or an aryl group), and R1, R2 and R3 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 the same as L. may be linked to form a ring; or represents a trivalent group formed by connecting seven methine groups or substituted methine groups to form a conjugated double bond] In the above-formation (1), Zl and 22 are connected to each other. A benzene ring, a naphthalene ring, a benzene ring with a substituent, or a naphthalene ring with a substituent formed by The 5- or 6-membered ring is preferably an imidazoquinoxaline ring, quinoline ring, benzothiazole ring, benzimidazole ring or imidazoquinoline ring.

-Formation (n) In the formula, R7 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryol group, or a benzene ring fused to a pyridine ring. R11 and R9 each represent a hydrogen atom, an alkyl group or an aryl group, and Z3 represents an atomic group having a nitrogen atom or an oxygen atom at the end necessary to complete a conjugated chain with the pyrocholine nucleus.

Among the compounds represented by the above general formula (I), preferred are compounds represented by the following formula (Ia).

General formula ([a): [In the formula, R', R'', R' and R%/ represent an alkyl 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 zSz
' represents an atomic group for completing an aromatic ring, and X- represents an anion. ] In the above-formation (I a) z, z'', L'%R4,
R5, R4/ and R5l may each further have a substituent.

Among the substituents of these groups, preferred ones are C0t(an
The hydrophobicity parameter, π, proposed by Sch et al.
, has a value in the range of -0,5 to 15. Note that the hydrophobicity parameter can be calculated according to the following literature.

1) C0 Hansch et al., J. Med, Che.
m, , vol. 16, p. 1207 (published in 197'3), 2) C, l1ansch et al., same magazine, vol. 20, 3
Page 04 (published in 1977) Preferred groups represented by R', R'', R' or RS1 are substituted or unsubstituted phenyl groups,
a substituted or unsubstituted lower alkyl group (having 1 to 8 carbon atoms) or a substituted or unsubstituted lower alkenyl group (having 2 to 8 carbon atoms);
The hydrophobicity parameter π proposed by Ansch et al. may have substituents with values ranging from -0.5 to 15.

Particularly preferred substituents in the case where R', R4', and R' also have the setting mM include L< and R'' are halogen atoms < F+ c 1 * Br, I), substituted or unsubstituted phenyl! (e.g., i , haphenyl, m-chlorophenyl, p-methylphenyl, etc.), alkylthio groups (e.g. methylthio, butylthio, etc.), substituted or unsubstituted phenylthio groups (e.g. phenylthio, p-methylphenyl, etc.),
chlorophenylthio, m-methylphenylthio, etc.).

Among the groups represented by R', R'', R' or RSL, particularly preferred are unsubstituted alkyl groups having 2 to 8 carbon atoms or unsubstituted alkenyl groups having 2 to 8 carbon atoms, among which R4R ”, R5 and Rs' 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 further R', R''
, R' and Rs' may have the substituents mentioned above.

When z and z'' have a substituent, particularly preferred substituents are halogen atoms (F, C1, Br, etc.).

I), substituted or unsubstituted phenyl group (e.g. phenyl, m-/)lorophenyl, p-methylphenyl, etc.)
, alkylthio groups (e.g. methylthio, butylthio, etc.), substituted (negative or unsubstituted phenylthio groups (e.g. phenylthio, p-chlorophenylthio, m-methylphenylthio, etc.), substituted or unsubstituted alkyl groups (e.g. methyl, trifluoro methyl, tert-amyl, etc.), cyano groups, alkoxycarbonyl groups (e.g. propoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl, decyloxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), alkyl or arylsulfonyl groups (e.g. butanesulfonyl) , phenylsulfonyl, octanesulfonyl, etc.).

Among the atomic groups represented by z and z'', particularly preferable ones 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+
Atom groups for forming a benzene ring substituted with halogen atoms such as C1, Br, and I are preferred.

The trivalent group represented by L' is a substituted or unsubstituted methine group, or 3,5. Alternatively, it represents a linking group formed by linking seven substituted or unsubstituted methine groups via a conjugated double bond, and those represented by -formation (a) to i) are particularly preferred.

-Formation (a) -C= General formula (b) ~CH= CH-C= CH-CH= General formula (e) General formula (f) General formula (d) General formula (g) -CH±C-CH =CH-CH= -Formation (h) -CH=CH-CH=C-CH=CH-C)l=General formula (i) -C)l = C-CH= -mFormula (a) or i ), 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 substituted or unsubstituted phenyl group, an aralkyl group such as a benzyl group, a methoxy group, etc. Lower alkoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidino groups, disubstituted amino groups such as ethoxycarbonylpiperazino groups, alkylcarbonyloxy groups such as acetoxy groups, alkylthio groups such as methylthio groups It is preferably a cyano group, a nitro group, or a halogen atom such as F, C1, or Br.

Among the linking groups represented by Ll, particularly preferred are those represented by (a), (b), (h), and (i).

The anion represented by X'' supplies the necessary number of negative charges to neutralize the charge of the cation moiety, and is a monovalent or divalent ion.

Examples of anions represented by X- include C1-Br-
, halogen ions such as I-, SO42-, HSO4-
.

Alkyl sulfate ions such as CIItOSOz-, sulfonate ions such as paratoluenesulfonate ion, naphthalene-1,5-disulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, octanesulfonate ion, acetate ion, p- Chlorobenzoate ion, trifluoroacetate ion, oxalate ion,
Carboxylic acid ions such as succinate ions, PFb-2B
F4-, CI Ot-, l04-.

Examples include heteropolyacid ions such as tungstate ion and tungstophosphate ion, and phenolate ions such as HzPO4-+NO3- and picrate ion.

Preferred anions represented by X- are Cj
l! -+ Br-, I-, C! (IOS(h-+
CzHsOSOff-, paratoluenesulfonate ion, p-chlorobenzenesulfonate ion, methanesulfonate ion, butanesulfonate ion, naphthalene-1
, 5-disulfonate ion, perfluorosulfonate ion such as trifluoromethanesulfonate ion, PF
b-, BF4-, C1O,-, etc., and particularly preferred are trifluoromethanesulfonic acid ion, PF
b-, ClO4-, and among these, trifluoromethanesulfonic acid ion and PF6- are safe from explosion.
is most preferable.

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.

[-3 ■ ■ HgCFs PF6- HzCF3 n-L; J+5 ■-10 ■ ■ ■-13 ■ -CJw (: It Oa- -U4Hw ■ ■-18 ■-15 ■-16 ■-20 Cj! Oρ ■ ■-22 ■-23 ! -26 1-L+411w rh i-CaHl ■-24 ! −4 ■-28 ■-29 Ox ■-30 ■-31 ■ ■-36 i-Ca)It Fb- i-C4H Shizuku ! -32 ■-33 ■-34 -CJIq CX　O,,- 1-CaH* ■-37 ■-38 i-C,lIg Pt'&- 4-C4 ■Drop ■ ■-43 ■-44 CHtCHzOClb Cm! 01 CIlxGHzOCR3 i-CaH* ! n-L;ally -CaHv ■-41 ■-42 ■-45 ■ C.O.

Cf 04. - 1-CJl* ■-47 C21'IS l0P C Description S The compound represented by the general formula (I) of the present invention can be prepared, for example, by the method described in the apparatus of Dai Organic Chemistry (Breakfast Shoten) Nitrogen-Containing Compounds ■, page 432. can be synthesized by referring to. That is, -formation (A) R' ) is a quaternary salt represented by 1,1,3゜3-tetramethoxypropane or dialdehyde such as glutaconaldehyde, or 1,7-diaza-1,7-diphenyl-
It can be synthesized by condensation with a polymethine source such as 1,3,5-hebutatoluene. In particular, dyes having an imidazo(4,5-b)quinoxaline skeleton can be synthesized with reference to the method described in US Pat. No. 3,431,111.

Preferred dyes having a pyrrocholine nucleus represented by the general formula (II) (hereinafter referred to as pyrrocholine dyes) used in the present invention are as follows - formation (al, ('b) or (C1
It is expressed as

In the formula, R), R', and R' have the same meanings as defined in general formula (n), Ll, Lm, and L:l represent an optionally substituted methine chain, and m is 1.2 Or represents 3. Q represents an atomic group necessary to form a 5- to 6-membered heterocycle.

In the formula, R7, Re, and R9 have the same meanings as defined in general formula (II), L'sL" represents an optionally substituted methine chain, and n represents 1.2 or 3. P is 5
~ Represents an atomic group necessary to form a 6-membered heterocycle.

Phi 7 In the ceremony, R? , Re and R4 have the same meanings as defined in general formula (II), Ll, Ll and L3 represent an optionally substituted methine chain, and! represents 1 or 2.

Rlo and RI + represent a hydrogen atom, an alkyl group, or an aryl group, and Xl represents an anion.

More specifically, in preferred compounds among the compounds represented by -formation (al, ('b) or tc+, R7
is a hydrogen atom, a halogen atom (e.g. chlorine atom, ) soo atom,) an alkyl group having 1 to 1 carbon atoms (e.g. methyl, ethyl, butyl), an alkoxy group having 1 to 10 carbon atoms (e.g. methoxy, ethoxy, butoxy, methoxyethoxy)
, an aryl group having 6 to 20 carbon atoms (e.g. phenyl, p-
) lyle, m-chloroethyl, p~methoxyphenyl),
Represents a benzene ring (for example, 5,6-benzo, 6,7-benzo, 7,8-benzo) condensed with a pyridine ring.

R11 and R9 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, ethyl, butyl, benzyl), an aryl group having 6 to 20 carbon atoms (e.g. phenyl, p-bromophenyl, p-acetylaminophenyl, p-methoxyphenyl, p-tolyl). Ll, L2, L3
represents methine which may be substituted, and the substituent is an alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl)
, phenyl group, halogen atom (for example, chlorine atom), etc. are preferable. Furthermore, a 5- to 6-membered ring may be formed by the substituents Ll, L2, and L3, where n and m are each 1.2.3
．． 2 takes an integer of 1.2. P is necessary to form a basic heterocycle (e.g. oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, indolenine, benzindolenine, imidazole, benzimidazole). Q represents an atomic group necessary to form a heterocycle serving as an acidic nucleus (eg, indandione, isoxacilone, pyrazolone, barbital acid, thiobarbital acid, hydroxypyridone, pyrocholine, etc.). RIG, R11 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g. methyl,
Ethyl, hexyl, 2-ethoxycarbonylethyl, 2
-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methanesulfonylaminoethyl), and may form a 5- to 6-membered ring (eg, morpholine, piperidine) with R1 and R9.

X and - represent anions, such as Cβ-1Br-1■
-1CH3CO(l, CH3SO4-1CF, CC)z
-110m-BF, -Fb-5O4-PF, -1Cβ-, etc. are preferred.

Next, specific examples of the dye represented by the general formula (If) used in the present invention will be given, but the present invention is not limited thereto.

It-4 I[-5 ■-10 ■-11 ■-12 ■-13 ■-16 ■-17 lh ShigHs ■ ■-15 ■-18 ■-19 Shiri U■ OOH ■-21 ■-25 Ul; th ■ ■-23 The compound represented by the general formula (II) used in the present invention is described in "1 (eterocyclic
Systems with BRIDGEHEAD N
lTR0GEN ATOMS Part one”
IntersciencePublishers 19
61 or U.S. Patent No. 2.409.612, 2.
No. 511,222, No. 2.57L775, No. 2.62
It can be easily synthesized by the method disclosed in No. 2.082, No. 2,706.193, etc.

Next, a synthesis example of the compound represented by the general formula (II) used in the present invention will be given.

Synthesis Example 1 (Compound ■-5) 2.1 g and 1.3 g of 2-phenyl-3-methylpyrocholine
．． 1.5 mff of 3-1-rimethoxypropene is mixed with 15 nl of ethanol and heated to 40°C to dissolve. 1.5 mJ of concentrated hydrochloric acid is added to this mixture and heated under reflux for 10 to 15 minutes. The reaction mixture was cooled to 0° C., the precipitated crystals were collected, washed with cold ethanol, and then dried to obtain 2.2 g of Compound I[-5. Melting point 201-203
℃.

Araax 655rv Synthesis Example 2 (Compound 1l-2) 2.5 g of 2-phenyl-3-methylpyrocholine and 1.7 g of toglutacon dialdehyde dianyl hydrochloride are added to 30 ml of methanol and stirred. After adding 3 nu of acetic anhydride dropwise to this mixture, the mixture was heated under reflux for about 30 minutes. Cool the mixture to 0°C and add 3 ml of perchloric acid aqueous solution with stirring.
One drop of In was added, and the precipitated crystals were collected, washed with methanol, and then dried to obtain 2.8 g of compound n-2. Melting point: 210 to 213°C λ --- 748 nm In the optical recording medium of the present invention, the ratio of the dye represented by the -In formula (1) and the dye represented by the general formula (II) is preferably 100 molar ratio. :1 to 1:10, more preferably 20:1 to 1:5, most preferably 10:
The ratio is 1 to 2:1. Even when each dye is used alone,
Two or more types may be used in combination, or they may be used in combination with a dye other than the dye of the present invention. It is also effective to use various antioxidants and singlet oxygen quenchers in combination to improve reading durability. 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 Nis Co, CuSPd,
PL etc.

An example of a new Encher is JP-A-62-1747.
The following general formula (I[[) or (IV) described in Publication No. 14
The following can be mentioned.

(In the formula, (Cat l) and (Catt) represent cations necessary to neutralize the complex, M+ and M2 represent nickel, copper, cobalt, palladium, or platinum. n is 1 or 2. ) the -formation (nI
) or (TV), in which (Ca
Among the cations represented by (t + ) or (Catz), inorganic cations include alkali metals (for example, Li, Na, K, etc.), alkaline earth metals (Mg
, Ca, Ba, etc.) or NH4''.

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

In the compound represented by -formation (III) or (IV), the preferred order of M+ or M2 is nickel, cobalt, copper, palladium, and platinum.

The metal complex of -I'G2 (II[) or (IV) has a steric structure with four planar coordinations. In the compound of Formation (III), it is not unambiguously determined whether the thioketone group is symmetrical or asymmetrical with respect to the central metal, but in the present invention, it is conveniently expressed as shown in the general formula (IV).

The compound represented by the above-mentioned -formation (I[[) or (rV) can be synthesized as follows.

-The compound of formation (I[I) (n=2) is disodium 1, obtained by reacting carbon disulfide and sodium.
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.

Moreover, the compound of -formation CI[[] (n=1) can be obtained by oxidizing the complex obtained above (n=2) 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, - formation (■) (n=1) is the complex obtained above (n=
2) is oxidized with a suitable oxidizing agent.

- 1,3-dithiol-2-thione-4,5, which is an intermediate for obtaining the compound of formation (IIF) or (■)
The dithiolate anion can be obtained not only by the reduction method using Na as described above but also by electrochemical reduction.

Preferred examples of the compounds represented by -formation [I[1] are as follows.

Shi-1111-J Shi, -m-,-J Shi-1111-J Other quenchers include JP-A-59-17829.
Examples include the following compounds described in No. 5.

(i) Bisdithio-α-diketone system R21 to R24 represent an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a cyano group, and M is 2
Represents a valent transition metal atom.

(ii) Bisphenyldithiol type (v) Bisphenylthiol type (vi) Thiocatechol chelate type (vi) Salicylaldehyde oxime type (vii)
Thiobisferrate chelate type (ix) Phosphonous acid chelate type (x) Benzoate type (xi) Hindered amine type (xii) Transition metal salt Aminium type or diimonium type compounds represented by other formulas can be mentioned, and specific examples include: Made by Nippon Kayaku Co., Ltd. 11? G-002, IRG-003, IRG
-022 and IRG-023.

+ RZS and RZ& represent an alkyl group, a cyano group or a halogen atom, and M represents a divalent transition metal atom.

(iit) Acetylacetonate chelate system (iv)
Dithiocarbamate chelate NR.

(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 a quencher anion 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 the quencher may be contained in separate layers from the recording layer. The optical recording medium of the present invention may further be provided with a subbing 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. Furthermore, a subbing layer such as a plastic binder, an inorganic oxide, an inorganic sulfide, etc. may be provided on the glass or plastic substrate. An undercoat layer having a lower thermal conductivity than the substrate is preferred. 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. The dye can also be used as a thin film by the so-called Langmuir-Prodgett method.

The recording layer in the present invention is one layer or 2N or more.

An antioxidant or anti-fading agent may be present in the recording layer or in a 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, forming bits (holes) in the recording layer.

Information is read out by irradiating a laser beam with a low output power below the recording darkness value and detecting changes in the amount of reflected light or transmitted light between the bit portion and the portion where no bit is 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 pinch, 750mm deep) 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 used in combination with the compound represented by general formula (I) (such as the dye represented by -formation (II)) and the dye represented by general formula (I) was 1:4.

Recording and reproducing conditions Laser wavelength Laser beam diameter Linear velocity Recording power Recording frequency Recording duty Reproducing power Semiconductor laser (GaAβ8S) 30 nm 1.6 μm 5 m/s 2 to 10 mW 2.5 MHz 50% 0.4 mW Table Compound A for Comparison of Performance of Recording Media [Effects of the Invention] The optical information recording medium of the present invention has a high reflectance for laser beams used for reading and recording information, and also has an absorbance high enough for recording. Shows 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 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^- 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.▼ [In the formula, R^7 is a hydrogen atom, a halogen atom, an alkyl group,
Represents a benzene ring fused to an alkoxy group, aryl group, or pyridine ring. R^8 and R^9 are each a hydrogen atom,
It represents an alkyl group or an aryl group, and Z^3 represents an atomic group having a nitrogen atom or an oxygen atom at the end necessary to complete a conjugated chain with the pyrocholine nucleus. ]