JPS6116894A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve a bright chamber preservation property by containing a sulfonic acid group coupled to a dolenian system cyanine pigment frame work, the reaction products between a carboxilic acid group, a sulfonic acid basic group, or a carboxilic acid basic group and a transition metallic salt in an indolenine system cyanine pigment. CONSTITUTION:A sulfonic acid group coupled to a dolenine system cyanine pigment frame work, the reaction products between a carboxilic acid group, sulfonic acid basic group or a carboxilic acid basic group and a transition metallic salt are contained in the indolenine system cyanine pigment. There are Na salt, K salt and the like as a sulfonic acid basic group or carboxilic acid basic group, and the numbers of the sulfonic acid group, the carboxilic acid group, and the sulfonic acid basic group in a molecule are 1-6, preferably a quencher is also contained in a recording layer. Thereby, a reproduction deterioration of S/N ratio due to a repeated irradiation of a read out is reduced and a light resistance property owing to a bright chamber reservation is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION I. BACKGROUND OF THE INVENTION Technical Field The present invention relates to optical recording media, particularly heat mode optical recording media.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require development in a dark room.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. There is a pit-forming type in which writing is performed by forming small holes, information is recorded using the pits, and reading is performed by detecting the pits with a readout light.

Until now, most of these pit-forming type media, especially those using a semiconductor laser as a light source that can make the device smaller, have a recording layer made of a material mainly composed of Te.

However, in recent years, due to the fact that Te-based materials are harmful and the need for higher sensitivity and lower manufacturing costs, organic materials based on one dye have been used instead of Te-based materials. For example, for He-Ne lasers, there are an increasing number of proposals and reports on media using recording layers such as squarylium dye [JP-A-58-413221 V.

B.Jipson and C.R.Jones
, J., Vac., Sci.

Technol, 18 (1) 105 (198
1) ) and metal phthalocyanine dyes (JP-A-57-8
No. 2094, No. 57-82095), etc.

There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-Open No. 5Ei-887115).

All of these have a recording layer formed into a thin film by vapor deposition of a dye, and there is no major difference from the Te type in terms of medium production.

However, the reflectance of a dye-deposited film to a laser is generally small, and the current conventional method of obtaining a readout signal by changing (reducing) the amount of reflected light due to pits cannot obtain a large S/N ratio.

Further, the transparent substrate supporting the recording layer was integrated with the recording layer facing each other. Using a medium with a so-called air sandwich structure and writing and reading through the substrate is advantageous in that the recording layer can be protected without reducing the writing sensitivity and the recording density can also be increased. This method is also impossible with dye-deposited films.

This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate).
In addition, the reflectance of one surface is relatively high (4%), and the reflectance through the substrate of the recording layer is about 60% or less for polymethyl methacrylate, for example, so it is difficult to detect a recording layer that shows only a low reflectance. Because you can't.

In order to improve the readout S/N ratio of a recording layer made of a dye-deposited film, AM is usually added between the substrate and the recording layer.
A vapor-deposited reflective film such as the following is interposed.

In this case, the vapor-deposited reflective film is intended to increase the reflectance and improve the S/N ratio, and the reflective film may be exposed due to pit formation and the reflectance may increase, or in some cases, the reflective film may be removed. It removes the reflectance and reduces the reflectance.
Naturally, recording and reproduction cannot be performed through the substrate.

Similarly, in JP-A-55-161890, IR-13
A recording layer consisting of two dyes (manufactured by Kodak) and polyvinyl acetate;
- a recording layer consisting of diethyl-2,2'-trivalent lupocyanine iodide and nitrocellulose;
, Law, et al., Appl., Phys.

Lett, 3El (9) 718 (11381)
discloses a medium in which a recording layer made of a dye and a resin is formed by a coating method, such as a recording layer made of 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate.

However, these cases also have the same drawback as the dye-deposited film in that a reflective film is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the back side of the substrate.

In this way, recording and reproduction through the substrate is possible,
In order to realize a medium having a recording layer made of an organic material that is compatible with a medium having a recording layer made of a Te-based material, the organic material itself needs to exhibit a high reflectance.

However, conventionally, there are very few examples of a single layer of organic material exhibiting high reflectance without laminating a reflective layer.

It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits slightly high reflectance (P, KivitS, etal, Ap
pl, Phys, Part A 2B (2) 1
01 (IHI), JP-A-55-97033), but the writing sensitivity is low, probably due to the high sublimation temperature.

In addition, cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes have been reported [Yamaki et al., Proceedings of the 27th Japan Society of Applied Physics, 1p-P-9 (1980)].
A proposal based on this was made in JP-A No. 58-112790, but these dyes have low solubility in solvents, are easily crystallized, and are more sensitive to readout light, especially when applied as a coating film. It is extremely unstable and immediately discolors, making it unsuitable for practical use.

In view of these circumstances, the present inventors first developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It is proposed to be used as a single layer film (patent application filed in 1973).
No. 7-134387, No. 57-134170).

Furthermore, in other cyanine dyes such as indolenine, thiazole, quinoline, and selenazole, long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization. (Patent Application No. 57-182588, Patent Application No. 57-177776, etc.)
.

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a quencher to cyanine dyes in order to prevent regeneration and deterioration (Japanese Patent Application No. 57-1).
No. 88832, No. 57-188048, etc.).

However, even those having a recording layer formed of a coating film of these indolenine cyanine dyes have problems in storage stability in a bright room.

II. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium having a recording layer containing an indolenine cyanine dye that has high storage stability in a bright room. It is in.

Such objects are achieved by the invention described below.

That is, the first invention provides an optical recording medium having a recording layer formed of an indolenine cyanine dye or a composition of indolenine cyanine dyes on a substrate, in which the indolenine cyanine dye is attached to the indolenine cyanine dye skeleton. attached sulfonic acid group,
The present invention is an optical recording medium characterized by containing a carboxylic acid group, a sulfonic acid group, or a reaction product of a carboxylic acid group and a transition metal salt.

Further, a second invention provides an optical recording medium having a recording layer on a substrate made of a composition of an indolenine cyanine dye, wherein the indolenine cyanine dye has a sulfonic acid group bonded to the indolenine cyanine dye skeleton; The optical recording medium is characterized in that it contains a carboxylic acid group, a sulfonic acid group, or a reaction product of a carboxylic acid group and a transition metal salt, and the recording layer further contains a quencher.

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

The indolenine cyanine dye used in the present invention is
A substance having a sulfonic acid group, a carboxylic acid group, a sulfonic acid group, or a carboxylic acid group on the indolenine cyanine dye skeleton directly or through an appropriate linking group (reactive indolenine cyanine dye) and a transition metal salt. It is a reaction product.

In this case, the sulfonic acid group or carboxylic acid group includes Na salt, K salt, etc.

In addition, there is no particular restriction on the number of sulfonic acid groups, carboxylic acid groups, sulfonic acid groups, or carboxylic acid groups in the molecule, but 1 to 6, particularly 2 to 4, are preferred. When two or more of these are included, One of these may form an inner salt with quaternary nitrogen.

Furthermore, as a linking group, an alkylene group, an arylene group, or a combination thereof, and a combination thereof with an imino group, an oxy group, a sulfonyl group, a carbonyl group, etc.
There are groups in which more than one species is bonded.

The site to which the sulfonic acid group, carboxylic acid group, sulfonic acid group, or carboxylic acid group is bonded to the indolenine cyanine dye skeleton directly or through an appropriate linking group is either the aromatic ring of the skeleton or the nitrogen in the ring. But that's fine.

However, from the viewpoint of ease of synthesis, it is preferable that the bonding site is a ring nitrogen and is introduced into the ring nitrogen in the form of -(CH2)cross-A or (CI(2)JloA).

In this case, the value is an integer, and 1 to 4 is particularly preferred. A represents the above-mentioned sulfonic acid group or the like.

The skeleton of the reactive indolenine cyanine dye in the present invention is not particularly limited, and various types can be used.

However, when incorporated into the recording layer as various indolenine cyanine dyes, the writing sensitivity is high;
A cyanine dye having a high reading S/N ratio is represented by the following general formula (I).

General formula (I) (In the above general formula (I), Z and 2' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring, or dibenzoindolenine ring.

R1 and R1' each represent a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, X- represents an acid anion, m is 0 or 1. ) In the above general formula (I), Z and Z' represent an indolenine ring to which an aromatic ring such as a benzene ring or a naphthalene ring may be fused, particularly an indolenine ring, a benzindolenine ring or a dibenzoindo ring. Represents the atomic group necessary to complete the renin ring.

These rings completed by Z (hereinafter referred to as Φ◆) and rings completed by Z' (hereinafter referred to as '%P) may be the same or different, but are usually the same. Various substituents are attached.

The skeletal rings of these Φ1 and ψ are expressed by the following formula [Φ■
]~(Φ■) and [!work]~[!■] are preferable.

(R4') q [ψIII) (R4') In various rings such as q1, the groups R1 and R'l bonded to the nitrogen atom in the ring are substituted or unsubstituted alkyl groups, aryl groups, and alkenyl groups. It is.

Group R1* 11 bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of carbon atoms in '.

In addition, if this group further has a substituent,
Examples of substituents include sulfonic acid groups, alkylcarbonyloxy groups, alkylamido groups, alkylsulfonamide groups, alkoxycarbonyl groups, alkylamino groups, alkylcarbamoyl groups, alkylsulfamoyl groups, hydroxyl groups, carboxy groups, halogen atoms, etc. It may be.

However, as described above, it is particularly preferable that R1 contains a sulfonic acid group, a carboxylic acid group, a sulfonic acid group, or a carboxylic acid group as a substituent.

Furthermore, at the 3-position of the indolenine ring, two substituents R2
, R3, R2', and R3' are preferably bonded.

In this case, the two substituents R2, R3, R
2'#R3' is preferably an alkyl group or an aryl group.

Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

On the other hand, other substituents R4 and R4' may be bonded to predetermined positions in the ring represented by Φ+ and . Such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbinyl groups, and aryloxycarbonyl groups. group, alkyl group, arylcarbonyloxy group, alkylamido group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group,
Various substituents may be used, such as an arylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, and a nitro group.

However, as described above, R4 and R4' may contain a sulfonic acid, a carboxylic acid, a sulfonic acid group, or a carboxylic acid group.

and the number of these substituents (p, q, r.

s, t) is 1, usually 0 or about 1 to 4. Note that when p+ q+ r + S + L is 2 or more, the plurality of R4s and R4' may be different from each other.

On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetracarbocyanine dye, and is particularly preferably one of formulas (LI) to (LXI).

Formula (LI) Here, Y represents a hydrogen atom or a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamine groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxycarbonylpiperazine groups. Preferred examples include a di-substituted amino group such as Nato, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyan group, a nitro group, and a halogen atom such as Br and Cl.

Furthermore, R8 and R9 each represent a hydrogen atom or a lower alkyl group such as a methyl group.

And the value is 0 or 1.

Furthermore, X- is an anion, preferably CH303
03-, C-cross 0S03-, etc.

Note that m is 0 or 1, but when m is 0, R1 and L of Φ usually have one charge and form one inner salt.

Next, specific examples of the indolenine cyanine dye of the present invention will be given, but the present invention is not limited to these.

匡υ I+II+IoI EE cel E bacterium c) EE:! :-J-
J -J -J -no -no -no -no -Jri a+alalalcdalalalalcd222
ta χ χ book χ χ book□ one no -no -no
-ノ 1v1+7v Roro%-
J% - 10 mouth:i::l: Figure:e:I::l: Work Field Work ω ■ 1”) IM Fl g'l Fl)
l”l Fl 1”) l”l
ω:e:! ::! : Flash :! :
Taira Dai Sen Sen To Q υ υ υ
0 υ ω 0 υ alalcd#alalalalal χ χ χ χ χ 2 χ 2 χ cQ of 0 0 of V of
ooooooooo.

V2 ψ 〃 〃 η 〃 η η
〃NNNCtIC'JNNNN:! ::! ： MI 工 工 工 み Ｇ Ｇ Ｑ
ω υ Q υ υ υ ω −ノ −ノ ζノ
ζNoyo order -++ ee-e***ee, e Korororororororororo As described above, the reactive indolenine cyanine dye forms a reaction product with the transition metal salt.

The transition metals used include Ni, Co, Cu, Mn, and P.
b, Pt, etc., such as chloride, bromide, etc., and NiCl2, NiBr2, etc. are particularly suitable.

Then, these reactive indolenine cyanine dyes are dissolved in a predetermined solvent, such as ethylene glycol or a mixture of ethylene glycol and an alcohol, ketone, aromatic solvent, etc., and dissolved in a transition metal salt with an equivalent amount of NiCl2. By carrying out a heating reaction and isolating, an indolenine cyanine dye having a quencher function part is obtained as a reaction product.

The reaction product forms a complex with Ni2+ etc. depending on the number of sulfonic acid groups etc. in the reacted indolenine cyanine dye.

For example, when two sulfonic acid groups etc. are present in the reactive dye, and if the reactive dye having two -5o3- groups is D2-, then ((D2-) 3 ・Ni 2 2+ )
2 - or convert it into ethylene glycol EG2
- and ((D2-)2.Ni2''(EG2-))2-.And it is produced as a mixture of these.

These syntheses were presented at the 44th Autumn Annual Meeting of the Chemical Society of Japan 3M.
24 Proceedings P628 (19B, 47th Spring Annual Meeting 4038 Proceedings PI421 (1983)).

The reaction product can usually be isolated by distilling off the solvent.

Alternatively, it may be precipitated by adding alcohol or water.

Specific examples of reactive indolenine cyanine dyes are listed below.

DI-L D'3 NiC12EGD
I-2D' 4 NiCl2 EG+methanol DI-3D' 13 NiCl2 EGD
I-4D' 15 NiCl2 EGDl-5D'
5 NiCl2 EGDI-6D' 7
NiCl2 EG, DI-7D' 8
NiCl2 EGDi-8D' 11 NIC
12EGDi-9D' 12 NiCl2
EGDi-10D' 18 NiCl2 EGThe visible and ultraviolet absorption spectrum of the reaction product of the reactive indolenine cyanine dye and Ni salt is almost the same as the absorption spectrum of the reactive indolenine cyanine dye itself. The presence of Nf was confirmed in the material.

In addition to the dye as a reaction product with such a transition metal salt, other dyes may be contained in the recording layer.

Such dyes include the above-mentioned indolenine cyanine dyes, stilbene dyes, styryl dyes, isidigo dyes, azo and bisazo dyes, di and triphenylmethane dyes, anthraquinone dyes, merocyanine dyes, pyrazolone dyes, thiazole dyes, and azine dyes. , pyridine and quinoline dyes, benzophenone, benzophenone and naphthoquinone dyes, acridine dyes, thiazine dyes, oxazine dyes, nitro and nitroso dyes, quinoanyl, insiphenol, indoaniline and indamine dyes, and the like.

Among these, indolenine cyanine dyes are particularly preferred.

The indolenine cyanine dye is preferably the same as the above-mentioned reactive indolenine cyanine dye, and may or may not contain a sulfonic acid group.

Specific examples of indolenine cyanine dyes are listed below.

Goshu μ Menyo j Shakutama a j
Ll work 1 main 11D2 (Φm) CH3CH3
D2-2(Φm) CH3CH3D2-3(
Φm) C2H40HCH3D2-4
(:411) , Suzume Sakuji,.

CH3I)2-5(Φm) CH3c)
(3D2-8(Φm), (c old) = wife 8; 2,.

. Old D2-7 (Φm) CH2CH20H
CH3D2-8(Φm) (CH2)20CO
CH3CH3D2-f3(ΦIII) (CH
2) 20COCH3CH3D2-10 (Φm)
CH3CH3D2-11 (Φm)
CH3CH3D2-12 (Φ■) C
l8H3□ CH3D2-13
(Φm) C4H9CH3D2-14 (
Φm) C3H160COCH5CH3D2-15
(Φm) C7H14CH20HCH3LtL
--Eeeee difference -X--(LII)
HI - (LII) HC standing 04- (
Lm) HBr-(LII)
H- -(LII) HC Mi04- (
LII) H--(LII)
HC standing 04- (Lll)
HBr(Lm) -N(C6H5)2 0
0 sentence 04- (LII) H
C view 04 (Lm) -N (C6H5)2 0
C look 04- (Lll)
HI-(LII) HC standing 04-
(Lm) -N(Cal(5)2 0
C view 04- (LII) HI
Yamaguchi L-1-' Beni-IhD2-Iff
(Φ■] C8H17CH3-H2-17 (Φ■)
C8H17CH3-H2-19 (Φ■) C7H1
4COOC2H5CH3-H2-20(Φm) C
, H8CH3-H2-21(ΦII[) Cl8H
37CH3-H2-22(Φm) Ca Hs
CH3-H2-23(ΦI) C
HCOOCH3CH3-H2-24(ΦI) CH
OCOCH3CH3-H2-25 (ΦI) C8
H17C2Hs -H2-26(ΦI) C7H
15C2H5-H2-27 (ΦII) CHCO
OCH3CH3-H2-28 [ΦII) Ca H
16CH20COCH3CH3-H2-29 (ΦII)
Ct7H+s CH3-L
Y and ” Shikuku L I
I) HC Emperor 04 (L II)
H-(LII) HBF
4 (Lm) -N(C8H5)2 0 C look 0
4(L II ) HCL; LOa(L
II) HC Mi04 (L II)
H1 (Lm) -N (C8H5) 2 0
I (LH) HI (L II) H1 (L II) HC 04J (G) Begging Anal anus' Beni-O Beni D2-30 (ΦII
) CHCOOCH3C2H5-02-31(Φ■
] C7H14CH20HCH3-H2-32 (Φm
) c7t+1. an2ococ2u5CH3,-
H2-33(Φ■]C17H34COOC2H5CH3
-H2-34(Φ■]C17H35CH3-D2-35
(Φm) C7H15C2Hs -H2-3
8 (4'IV) CH3, CH3-H2-37 (Φ
IV) CH3CH3-H2-38 (Φ■)
C4H9CH3-H2-39CΦIV) (CH2
)20COCHa CH3-H2-40(ΦI)
CHCHOCOCH3CH3H2-41 (ΦI)
CHCH20HCI(3-H2-42(Φm)
CH3CH3-H2-43 (Φ engineering) C2H
5CH35-C, H2O2-44 (ΦI) C2H
5CH35-C6H3L Y
Kiln ”L (LII) HC-view 04 (LII) HC-view 04 (LII) H' (Lm) -N (C6H5)2 0 I (L
yt) l(OI (L II) HI (LH) HI (L II) HC Mi04 (LII)
HC view 04 (L II) HI (L II) HC cross 04 (LII)
, HBr (LVI) Br CJIO
aSO2(LVI) Br l
lSO2(L [[) C standing I
C Sentence 04 Meal 1 μ Sorry j 1 above,”b-′
Danl-111D2-48 (ΦI)
C2H5CH3D2-47 (ΦI) C
2H5CH3D2-48 (ΦI) C2
H5CH3D2L49 (ΦI) C2H5
CH3D2-50 (ΦI) C2H5CH
3D2-51 (ΦI) CH3CH3D
2-52 (ΦI) CH30H3D2-
53 (ΦI) n-C489CH3D2-
54 (ΦI) n-C (I H13CH3D2
-55 (()I) (EC old(:Wish03.-.
CH3D2-58 (ΦI) C2H5C
H3D2-57 (ΦI) CH3CH3D
2-58 (ΦI) C2H50H3D2
-59 (ΦI) C2H5CH3D2-
110 (ΦI) C2H5H3-l1
l--eee again -su5-
C6Hs SO2(LI[I) Cl 0C
H3C6) I4S035-Ca H6S02 (
LV[) C1I BFa5-CaB6
SO2 (LVI) Cl l
Cl045-Ca H5SO2 (LVI)
Cl0■5-C6H5SO2 (LVI)
C100H3C8H4SO35-Ca H530
2 (LVI) 0 sentences OCl045-
06H5SO2(L■) C1OH5-Co
H5302 (LVI) C1I Cl0
45-Ca H5SO2(LVI) Cl
I Cl045-Ca H5SO2
(LVI) Cl l −
5-C6H5SO2 (LVI) N-Yumiji C-CN
1-5-Ca H5SO2(LV
I) N″″-C謔C-(JM l
-■ 5-C6H5Co (LII[) C
l I H5-C6H5C0(Ln
[) Br l H5
-C6H5Co (LH) CJL
I ClO 4-color Kokyuki Senshu j
1-JLL' DanUD2-1111
(ΦI) C2H6CH3D2-82
(ΦI) C2H5CH3D2-83 (Φ
I) C2H5CH3D2-84 (ΦI
) C2H6CH3D2-85 (ΦI)
CH3CH3D2-Bill (ΦI)
CH3CH3D2-87 (ΦI)
c2 H40COCH3CH3 once t
1- 1- Ei I5-C6H5C
0(LI[I) C1I CH3C3H,5
035-Ca Hr, Co (LVI)
Cl I Cl045-C, H5Co
(LVI) Cl I I'5-
C8H5Co (LVI) C1OCH3C3
H4S035-CHa Co (LII)
HC1o45-CHaCO(Lll) HH
5-CH3CO(LII)HI Note that these dyes are contained in an amount of about 60% or less by weight of the dye as a reaction product with the transition metal salt.

By adding these dyes, writing sensitivity and reading S/N ratio are improved.

As described above, in the present invention, the dye as a reaction product with the transition metal salt and a normal dye are contained as necessary, but the recording layer may further contain a quencher. It is preferable that

As a result, the S/N due to repeated irradiation of readout light is
The reproduction deterioration of the ratio is reduced.

In addition, light resistance is improved by storage in a bright room.

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

Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce reproducibility deterioration and have good compatibility with dyes. Preferably, in this case, the central metal is Ni, Co, Cu, Mn, Pd, Pt.
etc., and the compounds described in Japanese Patent Application No. 59-62387 are particularly preferred.

Specific examples of quenchers are listed below.

1) Acetylacetonate chelate Ql-IN
i (II) Acetylacetonate Ql-2Cu (I
I) Acetylacetonate Ql-3Mn (m) Acetylacetonate Ql-4Co (II) Acetylacetonate 2) Bisdithio-α-diketone system represented by the following formula, where R-R is substituted or unsubstituted alkyl group or aryl group, M is Ni
, represents a transition metal atom such as Co, Cu, Pd, PL, etc.

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

In addition, in the following description, ph is a phenyl group, and φ is 1
．． 4-phenylene group, φ'4ft, 2-phenylene group,
benz is a symbol indicating that adjacent groups on the ring are bonded to each other to form a condensed benzene ring.

R1R2R3RM Q2-1 ph ph ph
ph N1Q2-2 CH3CO
CH3COCH3COCH3CON1Q2-3 1(C
2H5)2ph φN(C2H5)2ph
N1Q2-4 φN(cH3)2ph φNC
CH3)2ph N1Q2-5 ph
ph ph ph Ni
ut K・(C4H8)4 3) Bisphenyldithiol cough represented by the following formula, where R to R8 are hydrogen or an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C11, or a dimethylamino group or diethylamino group. M represents a transition metal atom such as Nf, Co, Cu, Pd or Pt.

Furthermore, M in the above structure has a single charge and may form a salt with a cation (Cat) such as a quaternary ammonium ion.

Furthermore, other ligands may be bound.

Examples of this include the following.

Q3-I HHHHNi Q 3-2 HCH3HHN 1 Q3-3 H0 sentence 0 sentence ) (N1Q3-
4 CH3HHCH3N1 Q3-5 CH3CH3CH3CH3N1Q3-6
HCI HHN1 Q3-7 0 sentences C standing C standing C looking
N1Q3-8HC sentence C-view C-view N1Q
3-9 HHHHC.

Q3-10 HCH3CH3HC0at N" (C2Hs) a N" (n-C4Hg) 4 N" (n-C4Hg) 4 N+ (0H3)3°1BH33 N" (n-Ca H9)a N" (n-C4Hg) 4 N÷ (n-CnH2)a N" (n-Ca H9) a N" (n-C4H9) a N" (n C4H9)4 Q3-11 HCH3CH3HN1Q3-12
HCH3CH3HN1Q3-100 sentence CfL
CI CI N 1Q3-14
HCI C-view C-stand N1Q3-15
HN(CH3)2 HHN1Q3-18
HN(CH3)2 N(CH3)2 HN1Q3-
17 HN(CH3)2 CH3HN1Q3-1
8 HN(CH3)2 HHN1Q3-19
HN(Oh)2CI HN1Q3-20
HN(CH3)2 HHNiat N” (n-Ca H9)a N” (CH3)3°IEiH33 N・ (CH3)3C18H33 N+ (CH3)3016H33 N” (n-C4H9) a N÷ (n-C7H15)4 N+ (C8H17) (C2H5)3 N÷ (n-C4H9) a N+ (C8H8) (CH3)3 In addition, JP-A No. 50-45027 and Patent Application No. 58-16
Such as those described in No. 3080.

4) Dithiocarbamic acid chelate system represented by the following formula S Here, R9 and R10 represent an alkyl group.

Further, 1M represents a transition metal such as N[, Go, Cu, Pd, or Pt.

5) What is shown by the following formula Here, M represents a transition metal atom.

Ql is and Cat represents a cation.

Mouse-7c a t Q5-I N i Ql2 2CI
N” (CH3)3Q 52 N i Q
122C (C4Hs) 4”Q 5-3 COQ
12 2C(C4H8)4N+Q 5-4 C
u Q 122(E(CaHs)4”Q 5-5
P d Q 12 2C (C2H8), N
÷In addition, those described in Japanese Patent Application No. 58-125654.

6) What is shown by the following formula Here, M represents a transition gold atom.

R11 and R12 are CN and C0R1!, respectively. c.
o OR14:c ON R'qR16 or 5O2R
17, R13 to R17 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, Q2 represents an atomic group necessary to form a 5- or 6-membered ring, and Cat is It represents a cation, and n is 1 or 2.

In addition, those described in Japanese Patent Application No. 58-127074.

7) Compound represented by the following formula Here, M represents a transition metal atom, Cat represents a cation; n is 1 or 2.

M Cat Q 7- I N i 2 ((n-c4
HB) 3N) Q 7-2 N i 2 (
nc, 8H33(OH3)3)l) In addition, those described in Japanese Patent Application No. 58-127075.

8) Bisphenylthiol system QB-I Ni-bis(octylphenyl) sulfide 9) Thiocatechol chelate system represented by the following formula, where M represents a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc. .

Further, M has a single charge and may form a salt with a cation (Cat), and the benzene ring may have a substituent.

M Cat Q9-I Ni N” (C4H9)
410) Compound represented by the following formula, where R18 represents a monovalent group, θ~6, M represents a transition metal atom, and Cat represents a cation.

Q 10-I N i HON (n-C, H8)
4Q 10-2 N i CH31N(n-C
4H8).

Those described in Japanese Patent Application No. 58-143531 11) Compounds represented by the following formulas: In the above formulas, R, R, R and R23 each represent a hydrogen atom or a monovalent group, and 24 25 2B R, R, R and R27 represent a hydrogen atom or a monovalent group, but 24 25 25 2B R and R, R and R, R26 and R27 combine with each other to form a 6-membered ring. Good too.

Moreover, M represents a transition metal atom.

One dog RRRR-- Qll-1CI) n-CH48Hn-C4H3HQ1
1-2 [Engineering] C2H5C00C2H5C00C2H5C
00C2H5C00HHHHNi HHHHNi In addition, those described in Japanese Patent Application No. 58-145294.

12) A compound represented by the following formula, where M represents Pt, Ni or Pd, xl,
X 21 X 3 and X 4 are each O or S
represents.

M
SS In addition, those described in Japanese Patent Application No. 145295/1982.

! 3) Compound represented by the following formula, where R31 is a substituted or unsubstituted alkyl group or aryl group.

R, R, R and R35 represent a hydrogen atom or a monovalent group, R32 and R33, R and R,
R and R may be combined with each other to form a 6-membered ring.

Moreover, M represents a transition metal atom.

31 32 R33R34R35MR Q 131 nC4H9HHHHN+HCHH old Q13-2C6■5 H25 Q13-3 nC4H8HHbenz Ni In addition, those described in Japanese Patent Application No. 151928-1982.

10 Compounds R, R, R and R44 shown in both formulas below each represent a hydrogen atom or a monovalent group, but R41 and R42, R42 and R43, R43 and R44t±
, may be combined with each other to form a 6-membered ring.

Further, R and R46 represent a hydrogen atom or a monovalent group.

Furthermore, 1M represents a transition metal atom.

R41R42R43R44R45R48MQ14-IH
HHHH-N1 Q14-2 HHC4■7000 HH-Old and others described in Japanese Patent Application No. 151929/1983.

15) Compound represented by the following formula ,,51 Here, R, R, R, R, R.

R, R, and R58 are each a hydrogen atom or 1
It represents the base of valence.

R and R, R and R, R and R, R and R, R and R, and R57 and R58 may be bonded to each other to form a 6-membered ring.

Or it represents halogen.

M represents a transition metal atom.

RR54R55R58 R51R5253 Q 15-I Hn C4Hs HHHHQ1
5-2 HHnC4H90COHHHE11 ・R
58R59x M HHHCjLNi HHHCjLNi In addition, those described in Japanese Patent Application No. 58-153392.

te) Salicylaldehyde oxime system represented by the following formula, 81 Here, R and R81 represent an alkyl group, and M
are Ni, Co, Cu, and Pd.

Represents a transition metal atom such as Pt.

Reo, Nose 1.

Q l 6-1 1-C3R71-C3H7N iQ
l 6-2 ((:H) (:H(CH2)1, C
N3N i916-3 (CH) CHCCH2)
1□CH3COQ16-4 (CI) CI
(CH2)11CH3C.

Q16-5 C6R5C6R5N1 Q16-6 C6R5C6R5C.

Q16-7 C6R5C6R5CuQ l 6-
8 NHCa Hr, NHCa R5N
1Q16-111 0HOHN1 17) Thiobisferrate chelate system represented by the following formula, where M is the same as above, R85 and R66 represent an alkyl group, M has one charge, and a cation ( Cat) may form a salt.

RRM (:at -１－－Riyo■騨■−■■−■■■――■■Open■■−騨一■−■−■■■■■−■■■■■■■■− ------
■――■１－－■■－－關－－－－Q l 7-1
t-C3H1□ N i N”N3(C,H,)Q
l 7-2 t-CHCON+H3(C4H9)Q1
7-3t-CHNi-18) Phosphonous acid chelate system represented by the following formula, where M is the same as above, and R71 and R72 represent a substituent such as an alkyl group or a hydroxyl group.

R-12R-1111-------￥ Q 18-1 3-t-C4H,, 5-t-C,H,
, 6-OHNi19) Compounds represented by the following formulas where R, R, R and R84 are hydrogen atoms or 1
Although it represents a valent group, R and R, R and R, and R and R may be bonded to each other to form a 6-membered ring.

R and R88 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

R88 represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group or aryl group.

R87 represents a substituted or unsubstituted alkyl group or aryl group.

Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring.

M represents a transition metal atom.

R8182838485 RRRR Qllll-I HOHHHnc5HIHQ19
-2 HOHtCaH9Hnc9 Hz+Q19
-2゛ tCaH90HHOHCHaB RZM (H-Ni g H-Ni OH-Ni In addition, those described in Japanese Patent Application No. 58-153393.

20) Compound represented by the following formula, where R and R82 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N
- represents an alkylcarbamoyl group, an N-7 arylcarbamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and M represents a transition metal atom.

81R82 Q10-1 nC4Hg CH3N 1Q20-
2 CR3CH30-φ-NHCO, Ni and others,
What is described in Japanese Patent Application No. 155359/1983.

In addition, other quenchers include the following.

21) Benzoate type Q 21-1 Existing chemical substance 3-3040 (Tinuvin-120 (manufactured by Ciba Gaiki)) 22) Hindered amine type Q 22-1 Existing chemical substance 5-3732 (SANO
LIS-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.) Among these, bilphenyldithiol is particularly preferred.

Quencher is 20 to 60 mol% based on the total amount of pigment components.
Contains to some extent.

Furthermore, the quencher may form an ionic bond with the dye.

As a conjugate, Japanese Patent Application No. 59-089841, No. 59
Those described in No. 090748 and No. 59-091567 are preferred.

Among these, a combination of an indolenine cyanine dye cation and the various quencher anions described above is desirable, and a combination of an indolenine cyanine dye cation and a bisphenyldithiol quencher anion is particularly preferred.

Specific examples are given below.

In addition, in the following, the dye cation is the above-mentioned dye No.
, and the quencher number 7 is indicated by adding a minus sign to the quencher number.

p+ Q knee-5I
D+ 2-I Q-3-8S
2 D+ 2-I Q-3-15
S3 D+ 2-2
Q-3-15S4 D+ 2-I
Q-3-3S5 D
” 2-3 Q'-3-8SS
D+ 2-3 Q-3-1
537D+ 2-4 Q-3-8S8
D+ 2-5 Q-3-8S
9 0÷ 2-6 Q-
3-83100÷ 2-7 9-3-8st
t n÷ 2-7 Q
-3-2512D ÷ 2-8 Q-3-
15Sla D ◆ 2-9
Q-3-15314D ÷ 2-10
Q-3-15315D ÷ 2-11
Q-3-15Sle D ÷ 2-
3 Q-3-7S17
D ◆ 2-12 Q-3-12S18
D ÷ 2-13 Q-
3-18S19 D ◆ 2-14
Q-3-1?320
D” 2-15 Q-3-1?521
D” 2-18 Q-3-12
S22 D ÷ 2-17
Q-3-15S23D”
2-17 9- 3-13S24
D+ 2-18 Q-3-1B
S25 D+ 2-111
Q-3-17S28 0”
2-I Q-3-IS2?
D” 2-I Q-3-2S28
D ÷ 2-I Q
-3-16S29 D ÷ 2-I
Q"'3-1?330
D+ 2-19 Q-3-85310
÷ 2-20 Q-3-8332D+2-2
0 Q-3-15S33
D+ 2-2I Q-3-8S34
D" 2 -21 Q-3
-15S35 D+ 2-2I
Q-3-73380" 2-19
Q-3-15337D" 2-3
Q-3-7S38 D+ 2
-9 9- 3-8S39
D ÷ 2-9 Q-3-7340D
+ 2-9 Q-3-2S41
D+ 2-9 Q-3-16S4
2 D ÷ 2-22
Q-3-8S43 D ÷ 2-2
2 l3-15S44
D+ 2-11 Q-3-8545D÷
2-11 Q-3-2348D+ 2-
11 Q-3-7S47 D+
2-11 Q-3-1O548D" 2
-23 Q-3-8S49
D+2-24 Q'″ 3-2S50
D+2-I Q″″ 3-
3351 0+ 2-3
Q"' 5-IS52 D+
2-2 Q-2-IS53
D+ 2-4 Q-17-l554
D” 2-6 Q-1
O-IS55 D+ 2-5
9- 7-2S58 D+
2-7 Q-9-l557
D÷ 2-8 Q-10-IS5
8 D+ 2-9
Q-6-IS59 0÷ 2-11
Q-3-3 Such a photostabilized cyanine dye of the present invention is produced, for example, as follows.

First, a cationic indolenine cyanine dye bonded to an anion is prepared.

In this case, the anion (An-) is:

I-, 13r-, ClO4-, BF4-.

It may be CH30SO3, C0S03-, etc., and is synthesized as described above.

On the other hand, an anionic quencher bonded to a cation is prepared.

In this case, the cation (Cat◆) is especially N÷(
Tetraalkylammoniums such as CH3)a, N''(C4l9)a, etc. are preferred.

In addition, these quenchers are
B32, Japanese Patent Application No. 58-183080, etc.

Next, equimolar amounts of the cyanine dye and quencher are dissolved in a polar organic solvent.

As the polar organic solvent used, N,N-dimethylformamide and the like are suitable.

Further, its concentration may be approximately 0.01 mol/cross.

Thereafter, an aqueous solvent, particularly water, is added to this to cause double decomposition and to obtain a precipitate. The amount of water added may be in excess of 10 times or more.

In addition, the reaction temperature is preferably about room temperature to 90°C.

This operation is then repeated as necessary. .

Next, the two liquid phases are separated, filtered and dried, and recrystallized from DMF-ethanol or the like to obtain a photostabilized cyanine dye.

In addition to the above method, a neutral quencher cation intermediate may be dissolved in methylene chloride or the like, and an equimolar amount of cyanine dye may be added thereto, concentrated, and recrystallized.

Alternatively, nickel may be oxidized to form an anionic salt while blowing air according to Japanese Patent Application No. 57-11118832.

The ionic binder is contained in an amount of about 40 mol % or less based on the total amount of pigment components.

Note that, if necessary, two or more types of dyes, dyes, quencher, and conjugates may be contained as reaction products.

In addition, resin may be included. As the resin material, those described in Japanese Patent Application No. 513-0823117 are suitable.

Specific examples are given below.

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

ii) Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene -maleic anhydride copolymer,
such as ethylene propylene terpolymer (EPT).

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

1ii) Vinyl chloride copolymer, for example, vinyl acetate-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride copolymer, acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer,
Ethylene or propylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer with vinyl chloride graft polymerized, etc.

In this case, the copolymerization ratio can be arbitrary.

ii) 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.

m) Polystyrene m) Styrene copolymer For example, styrene-acrylonitrile copolymer (As resin), styrene-acrylonitrile-butadiene copolymer (ABS resin).

Styrene-maleic anhydride copolymer (SMA resin), styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer (SBR), styrene-vinylidene chloride copolymer, styrene-methyl methacrylate copolymer Such.

In this case, the copolymerization ratio can be arbitrary.

ii) Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2
, 5-dichlorostyrene, α.

β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester.

m1ii) Coumarone-indene resin Coumarone-indene-styrene copolymer.

ix) Terpene resin or picolite For example, terpene resin which is a polymer of limonene obtained from α-pinene, or picolite obtained from β-pinene.

Tomi) Acrylic resin Particularly preferred are those containing an atomic group represented by the following formula.

Formula R - CH-C- -OR In the above formula, R represents a hydrogen atom or an alkyl group, and R represents a substituted or unsubstituted alkyl group.
In this case, in the above formula, R is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

Further, R may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R is a substituted alkyl group, the alkyl group The substituent to be substituted is preferably a hydroxyl group, a halogen atom, or an amino group (particularly a dialkylamino group).

The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one type of atomic group represented by the above formula is used. Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer, for example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer , acrylonitrile-methyl methacrylate copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

xiii) Diacetone acrylamide polymer A diacetone acrylamide polymer obtained by reacting acetone with acrylonitrile.

x+M) Polyvinyl acetate

The copolymerization ratio may be arbitrary.

xii) Polyvinyl ethers such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc.

xiii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-1O, nylon 6-12. In addition to regular homonylons such as nylon 9, nylon 11, nylon 12, and nylon 13, nylon 676-676-1
0, nylon 67 low 6712, nylon 6/6-67
Polymers such as No. 11 or modified nylon may be used as the case may be.

! 1ii) Polyester For example, various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid, and ethylene Condensates and co-condensates with glycols such as glycol, tetramethylene glycol and hexamethylene glycol are suitable.

Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable.

Furthermore, for example, a modified glybutal resin obtained by esterifying and modifying glybutal resin, which is a condensation product of phthalic anhydride and glycerin, with a fatty acid, a natural resin, etc., is also suitably used. ′! Polyvinyl acetal resins Polyvinyl formals and polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol are both preferably used.

In this case, the degree of acetalization of the polyvinyl acetal resin can be arbitrary.

! polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

Particularly suitable are polyurethane resins obtained by condensation of glycols and diisocyanates, particularly polyurethane resins obtained by condensation of alkylene glycol and alkylene diisocyanate.

! ! i) Polyether styrene formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc.

xxii) Cellulose derivatives For example, various esters and ethers of cellulose, such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, and mixtures thereof.

xxiii) polycarbonates such as polydioxydiphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylpropane carbonate.

xxi) Ionomer Na such as methacrylic ugliness and acrylic acid.

Li, Zn, Mg salts, etc.

! ! m) Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde.

i) Xylene resin, for example, a condensate of m-xylene or mesitylene with formalin, or a modified product thereof.

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

xxiii) A blend of two or more of the above i) to iii), or a blend with other thermoplastic resins.

In addition, the molecular weight etc. of resin may be various.

Such a resin and the above-mentioned dye are usually mixed in a weight ratio of 1 l.
Layers are deposited in a wide range of ratios from 91 to 100.

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method.

The thickness of the recording layer is usually 0.03 to 1101L.
It is considered to be a degree.

In addition, such a recording layer may contain other dyes, other polymers or oligomers, 8M plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and antioxidants. , a crosslinking agent, etc. may be contained.

To form such a recording layer, it may be applied onto the substrate using a predetermined solvent and dried.

Examples of solvents used for coating include ketones such as methyl ethyl ketone, methyl imbutyl ketone, and cyclohexanone, esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, and ethers such as methyl cellosolve and ethyl cellosolve. or aromatic systems such as toluene and xylene, halogenated alkyl systems such as dichloroethane, alcohol systems, etc. may be used.

The material of the substrate on which such a recording layer is provided is not particularly limited as long as it is substantially transparent to writing light and reading light, and may be any of various resins, glass, etc.

Further, its shape may be a tape, a drum, a belt, etc. depending on the intended use.

Note that the base body usually has a groove for tracking.

Further, as the resin material for the substrate, a substrate without grooves, such as polymethyl methacrylate, acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyether sulfone, methylpentene polymer, etc., is suitable.

In order to improve solvent resistance 1, wettability 1, surface tension, thermal conductivity, etc., it is preferable to form a base layer on these bases. The material of the base layer is Si, Ti, etc.
, All, Zr, In, Ni, Ta, or other organic complex compounds or organic polyfunctional compounds are preferably applied and dried by heating.

In addition, various photosensitive resins can also be used as the base layer.

In addition, on the recording layer, various uppermost protective layers,
It is also possible to provide a single layer of half-mirror. however,
It is preferable that the recording layer is a single layer film and that one reflective layer is not laminated above or below the recording layer.

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.

In addition, two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, which is then sealed tightly to prevent dust and scratches. You can also do it like this.

(2) Specific Effects of the Invention The medium of the present invention irradiates recording light in a pulsed manner while running or rotating. At this time, due to the heat generated by the cyanine dye in the recording layer, the cyanine dye melts and pits are formed.

The pits formed in this manner 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 through the substrate from the substrate side.

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

Note that a semiconductor laser, He--Ne laser, Ar laser, He--Cd laser, etc. can be used as the recording or reading light.

■Specific effects of the invention According to the first invention, storage stability in a bright room is significantly improved.

Furthermore, according to the second aspect of the invention, storage stability in a bright room is improved and reproduction deterioration is significantly reduced.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Examples The dyes shown in Table 1 below, indolenine cyanine dyes (hereinafter referred to as reaction products) as reaction products with transition metal salts, and quenchers (although they may form ionic bonds with one dye) ) is dissolved in a specified solvent, and a silica colloid dispersion [Colcoat ■ (
Full Coat Co., Ltd.)] was applied and hydrolyzed to form a base layer (0,
Various media were obtained by coating layers of 0.061 LII on injection molded acrylic disk substrates with a diameter of 30 cm provided with OIILm).

Note that the reaction product with Ni salt was synthesized as follows.

The dye (0.01 mol) and twice the mol (equal mol if the dye forms an inner salt) of NiCu2 were dissolved in 80 mL of ethylene glycol, and reacted at about 80° C. for 2 hours. Then, pour it into water, filter the precipitate,
After washing and drying, a crude reaction product was obtained.

This was recrystallized from alcohol or a dichloroethane-alcohol mixture.

The selected reaction product showed almost the same absorption spectrum as the original dye, confirming the presence of Ni.

Separately, for comparison, a medium containing no reaction product, ie, a medium containing only a dye or a dye and a quencher, was prepared.

Each medium produced in this way was heated using a semiconductor laser (8
30 nm), writing was performed from the back side of the substrate.

In this case, the light converging unit output was 10 mW.

While changing the pulse width, the pulse width at which a contrast of 0.5 was obtained was determined, and the reciprocal of the pulse width was calculated to display the sensitivity.

Next, writing was performed using a semiconductor laser, and 830n
Using a semiconductor laser with a condenser output of 1 mW as the readout light, the reflected light through the substrate was detected, and the C/N ratio was measured at a band width of 30 KHz using a spectrum analyzer manufactured by Hewlett Paracard. .

Also, 111%ll laser reading light is l#Lae
After being irradiated for 5 minutes in a stationary state as a pulse of c width and 3 KHz (regeneration deterioration), and after being irradiated with light cut below 520 nm with a filter of a 100 W high-pressure Hg lamp from a distance of lOCm for 20 hours (in a bright room). The change (%) in reflectance from the back surface side of the substrate was measured.

These results are shown in Table 2.

From the results shown in Table 2, the effects of the present invention are clear.

Namely, 1 samples No. 1 to 3 of the present invention and No.
, 6 to 8 have significantly improved storage stability in a light room compared to samples No. 4 and No. 5, which do not contain the reaction product (Dl''-NI).

Applicant: TDC Co., Ltd.

Claims (2)

[Claims] (1) In an optical recording medium having a recording layer formed of an indolenine cyanine dye or a composition of an indolenine cyanine dye on a substrate, the indolenine cyanine dye has a sulfonic acid group bonded to the indolenine cyanine dye skeleton. , a carboxylic acid group, a sulfonic acid group, or a reaction product of a carboxylic acid group and a transition metal salt. (2) In an optical recording medium having a recording layer made of a composition of an indolenine cyanine dye on a substrate, the indolenine cyanine dye contains a sulfonic acid group, a carboxylic acid group, a sulfone group bonded to the indolenine cyanine dye skeleton. An optical recording medium comprising a reaction product of an acid base or a carboxylic acid base and a transition metal salt, and further comprising a recording layer containing a quencher.