JPS61213193A - Optical recording medium - Google Patents

Abstract

PURPOSE:To enhance solubility and prevent crystallization from occurring in a coated film, by providing a recording layer containing a photo-stabilized cyanine coloring matters consisting of a combination of an indolenine coloring matter cation and a bisphenyldithiol-transition metal complex anion. CONSTITUTION:A recording layer containing at least two photo-stabilized cyanine coloring matters each of which consists of a combination of an indolenine cyanine coloring matter cation and a bisphenyldithol-transition metal complex anion such that the complex anions are isomers of each other is provided on a base. Alternatively, a recording layer comprising at least two such complex anions which are isomers of each other and an indolenine cyanine coloring matter is provided on a base.

Description

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

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading 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. For example, a part of the medium is melted or removed using recording light such as a laser, and it is called a bit. There is a two-peat type in which writing is performed by forming a small hole, information is recorded using this bit, and reading is performed by detecting this bit 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. There are an increasing number of proposals and reports on media using recording layers.

For example, for He-Ne lasers, squarylium dye [JP-A-513-48221 V] is used.

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. 88795/1983).

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 the dye-deposited film to the laser is generally small, and a readout signal is obtained by a change (reduction) in the amount of reflected light due to the pits. A large S/N ratio cannot be obtained with the conventional methods currently in use.

In addition, if a transparent substrate supporting a recording layer is integrated with the recording layers facing each other in a so-called air sandwich structure medium, and writing and reading are performed through the substrate, the recording layer can be layered without reducing the writing sensitivity. However, such a recording/reproducing method is also not possible with a dye-deposited film.

This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate) and a relatively high surface reflectance (4% for polymethyl methacrylate), so that it is possible to This is because, for example, the reflectance of polymethyl methacrylate is about 60% or less, and therefore it cannot be detected with a recording layer that exhibits only a low reflectance.

In order to improve the readout S/N ratio of a recording layer made of a dye-deposited film, An 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, one 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-55-181890, IR-13
A recording layer consisting of two dyes (manufactured by Kodak) and polyvinyl acetate;
- a recording layer consisting of diethyl-2,2''-1 lycarpocyanine iodide and nitrocellulose;
, Law, at al, , Appl, Phys.

Lett, 31 (9) 71B (1981) describes a coating method for forming a recording layer composed of a dye and a resin, such as a recording layer composed of 3,3'-diethyl-12-7cetylthiatetracarpocyanine and polyvinyl acetate. A layered medium is disclosed.

However, these cases also require a reflective film between the substrate and the recording layer, and have the same drawbacks as the single-dye vapor deposited film in that 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, in the past, there have been very few examples of exhibiting high reflectance with a single layer of organic material without laminating a reflective layer.

It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance (P, Kivits et al.
Appl, Phys, Part A 2Ei
(2) 101 (1981), JP-A-55-9703
No. 3], 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. 7-134397, 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. (Japanese Patent Application No. 57-1825H, Patent Application No. 57-177778, etc.).

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a transition metal complex quencher such as nickel bisphenyl geotere to indolenine-based cyanine dyes to prevent regeneration and deterioration (regeneration deterioration).
(Japanese Patent Application No. 188048/1983, etc.)

However, indolenine cyanine dyes and quenchers
In the case of a mixture of , there is a problem in moisture resistance due to the presence of an unnecessary countercation of the encher and a counteranion of the dye.

Therefore, in order to improve moisture resistance and improve storage stability,
We are proposing a coating film containing a photostabilized cyanine dye consisting of an equimolar ionic combination of an indolenine cyanine dye cation and a bisphenyldithiol transition metal complex quencher anion such as nickel bisphenyldithiol (patent application). (Sho 59-19715).

However, compounds of indolenine-based cyanine dye cations and bisphenyl dithiothyl-based transition metal complex quencher anions generally have poor solubility, precipitate crystals, and often have poor film-forming properties, resulting in poor S/N There is also the problem that sufficiently large values cannot be obtained for ratios, etc.

Therefore, in the case of having a recording layer containing a combination of an indolenine-based cyanine dye cation and a bisphenyldithiol transition metal complex-based quencher anion, the recording layer components have a high solubility in a solvent and can be applied to a substrate as a coating film. There is a need for an optical recording medium having a recording layer in which crystals do not precipitate when deposited on the recording layer.

■Object of the Invention The object of the present invention is to improve solubility when using a recording layer containing a photostabilized cyanine dye consisting of a combination of an indolenine dye cation and a bisphenyldithiol transition metal complex quencher anion. It is an object of the present invention to provide an optical recording medium having a recording layer having a good quality and in which crystals do not precipitate in the coating film.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the first invention is a photostabilized cyanine dye consisting of a combination of an indolenine cyanine dye cation and a bisphenyldithiol transition metal complex anion, the complex anions of which are isomers of each other. An optical recording medium is characterized in that it has a recording layer containing on a substrate.

* 4- @ 9 rrs n FIZ
l-) No -/L' I+
-+/IS/V-+/At least two types of photostabilized cyanine dyes consisting of a combination of a dye cation and a bisphenyldithiol transition metal complex anion, in which the complex anions are isomers of each other. This is an optical recording medium characterized in that the substrate E has a recording layer containing an indolenine cyanine dye.

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

The recording layer of the optical recording medium of the present invention contains a photostabilized cyanine dye consisting of a combination of an indolenine cyanine dye cation and a quencher anion, in this case, an indolenine cyanine dye cation and bisphenyldithiol. There is no restriction on the ionic valence of the metal complex quencher anion, and various combinations are possible.
Usually both are monovalent.

That is, the indolenine cyanine dye cation is D+
, bisphenyldithiol-based metal complex quencher -7 When the anion is Q-, the conjugate is usually D+/Q-.

Various cations D+ of the indolenine cyanine dye constituting the ionic bond in the present invention can be used, and the following general formula % formula % general formula (I) (in the above general formula (I)).

Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R1 and R1' are
Each represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, and L represents a polymethine linking group for forming a cyanine dye.) In the above general formula (I), Z and Z' are aromatic family,
For example, it represents an atomic group necessary to complete an indolenine ring to which a benzene ring, a naphthalene ring, etc. may be fused, particularly an indolenine ring, a benzindolenine ring, or a hashihendiindolenine ring.

The rings completed by Z (hereinafter referred to as Φ+) and the rings completed by Z′ (hereinafter referred to as middle) may be the same or different, but are usually the same, and these rings have various substitutions. Groups may be bonded.

And these Φ1 and! The following skeletal rings are [Φwork] ~ [Φ■] and [ψwork] ~ [! (2) It is preferable to use the one shown in [2].

j4. - In these various rings, the group Rj, R'' bonded to the nitrogen atom in the ring is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group.

Groups R1, R' 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.

Among these, unsubstituted alkyl groups or alkyl groups substituted with an alkylcarbonyloxy group, a hydroxyl group, or the like are particularly preferred.

Furthermore, at the 3rd position of the indolenine ring, there are two W-valent D
-D a Q -' R-s ' Iso (strange Δ+
It is preferable that

In this case, the two substituents R2, R3, R
2' and R3' are 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, Φ+ and ! Further, other substituents R4 and R4' may be bonded to a predetermined position in the ring represented by. Examples of such substituents include an alkyl group, an aryl group, and a heterocyclic residue.

Halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamide group , alkylcarbamoyl group, arylcarbamoyl group, alkylamino 7 group, arylamino group,
Various substituents may be used, such as a carboxylic acid group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, an argylsulfamoyl group, an arylsulfamoyl group, a cyan group, and a nitro group.

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

s, t) are usually O or about 1 to 4. When p, q, r, s, and t are 2 or more, multiple R
4 and R4' may be different from each other.

The cyanine dye cation has a condensed or non-condensed indolenine ring, has excellent solubility, coating properties, and stability, and exhibits extremely high reflectance.

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 (LIX).

Formula (LI) CH=CH-CH=CH-C=CH-CH=CH-CH
↓ Here, 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 lower alkoxy group such as a methoxy group, a dimethylamino group, and a diphenylamino group. , methylphenylamino group, morpholino group, imidazolidine group, disubstituted amine group such as ethoxycarbonylpiperazine group, fulkylcarbonyloxy group such as acetoxy group, furkylthio group such as methylthio group, cyano group, nitro group, Br, C1 It is preferable that it is a halogen atom such as.

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.

In addition, among these formulas (LI) to (LIX), the tricarbocyanine linking group, especially the formula %) Immune-LL Presentation-&LL "D"
1 ΦI CH3CH3'l'ID"2
ΦI C2H5CH35-CH3SO2'l
'ID'3 ΦIII CH3CH3'l'
[[ID”4 ΦIII C8H17CH3-fold■
D”5 ΦII[Cl8H37CH3?mD”6
ΦIII CH3CH3'PH-! ■ D”7 Φm 0H2CH20(:0CH3CH
3-! ■ D+8 ΦIII 0H2CH20COCH3CH
3D”9 ΦII [CH3CH3 Weight D+ 10
ΦIII CH3c) I3'! 'ID+1
1 ΦII CH3CH3'i'IID+ 1
2 Φmc4Hg CH3'PmD+
13 ΦI CHCHOHCH triple ID”14
Φm CH(:HOHCH3ψ■D”
15 0111 C4H9CH3'PIIID
+16 ΦI (:H2CH2OC0CH5CH3
ψID+ 17 ΦI CH3CH3? ID+
18 Φm CH3CH3ψ■D+19
ΦlCH3CH3-! 1 once 2' and m=&
LL' L Y-also CH3CH3LII
H- C2H5CH35-CH3SO2LIIr N(C
6H5) 21CH3CH3LII H- C8H17CH3LHH- C18H37CH3LII H- CH3CH3Lm N(C:8H5) 210H2
(:H2OC0CH5CH3L II H--L[
N(C6H5) 21 CH2CH20COCH3CH3 CH3CH3LVI Br lCH3
CH3LII H- CH3CH3L II H- C4Hg CH3LII H-(1:
HC: HOHCH3LII H-CHCHO)l
CH3LII H-Ca H9CH
3L m N (CeHs) 210820H20
GOCI3CH3L II H-CH3CH3LV
Ir H- CH3CH3LVI[H- CH3CH3LI[IN(CH) 1 Sat-
LL Dan L-1111 Satju RD
+ 20 ΦI CH3CH3'PI C
HD÷ 21 ΦI CH3CH3OI
CHD◆ 22 ΦIII CH3CH3-Weight CHD”23 OI CH3CH3
OI [I CHD+ 24 ΦlCH3CH3
Heavy [CHD+ 25 ΦI CH3CH3'!
'r CH2H5 D+ 26 ΦI CH3CH35-CfL
'i'I CHD ÷ 27 ΦI
CH3CH35,8-(11'l'I CH
D"2'8 ΦI CH3CH35-HC2
H5'l'I, CHD+ 28 ΦI C
H3CH35-CHCONH'l'I CHs D+ 30 ΦI CH3CH35,7-0 sentence OI (, HD"31 ΦI C
H3CH35,7-C,, H3O0C'%'I'I
CHD÷32 ΦI CH3CH35,7-CH
302S Heavy I CHD÷ 33 ΦI
CH3CH35,3-CH3'PI CHD+
34 ΦI CH3CH35,7-CI3CO
NH'! 'I CHD+ 35 ΦI C
H3CH3B-CI3CONH'i'I CHD+
36 ΦI CH3C2H55-C:H3O
2S 'l'I c,.

D+ 37 ΦI CH3CH35-CHOO
C heavy I CH3S L' and 2, ``b' and L' l, Y- to 3
CH3-LVIBr 1(Ra
=R9=H) 3 CH3-LII C1-3CH
3-LIIC Interchange - 3CH3-Lm H- 3C) (3Lm N(C6H5) 213
CH3, LIIH- 2H5 3CH35-C1LIIH- 3CH35,8-0 sentence LII H-3CH
35-0C2H5LII H-3CH35-CH
CON)I LII H-3CH35,7-
Cl LII H-3CH35,7-C2H
5000L II H-3G) (35,7-(:)
1302S LHH-3CH35,3-CH3Lll
H-3CH35,7-CH3C0NHL II
H-3CH38-CH5CONHLHH- Hs CH35-CHs O2S L II
N(C8H5)213CH35-(:2H500G
LHH-Such indolenine cyanine dye cations include I"-, Br-, CuO4, BF4"',
These are known as conjugates with acid anions such as CH3<>SO3- and CfL<>SO3-.

In addition, these combinations of indolenine-based cyanine dye cations and acid anions can be easily synthesized according to the method described in books such as Dai Organic Chemistry (Breakfast Shoten) Nitrogen-Containing Heterocyclic Compound Engineering, page 432. be able to.

That is, first, the corresponding Φ'-CH3 (Φ' represents the ring corresponding to the above Φ) is heated with excess RI I (Rt is an alkyl group or an aryl group) to form R1
is introduced into the nitrogen atom in Φ' to obtain Φ-CH5I-.

Alternatively, the conventional method by Fisher or Haral
The method of d et al. (S7nthesis, 958, 198
According to method 1), an indolenine derivative is obtained from acetylene alcohol.

Next, this may be dehydrated and condensed with unsaturated dialdehyde or unsaturated hydroxyaldehyde using an alkali catalyst, or pyridine is cleaved according to the ZINGK reaction to obtain glutaconaldehyde, which is combined with a quaternary indolenine derivative. Tricarbocyanine can be obtained by reacting with salt.

These indolenine cyanine dye cations are usually:
In monomeric form, as required.

It may also be in the form of a polymer.

In this case, one polymer has two or more molecules of indolenine cyanine dye cations, and may be a condensate of these indolenine cyanine dye cations.

For example, the above-mentioned indolenine cyanine dye cations having one or more functional groups such as -OH, -COOH, -3O3H, etc. alone or co-condensates, or together with dialcohols, dicarboxylic molecules, etc. There are also cocondensation components such as or chlorides thereof, diamines, di- or triisocyanates, jepoxy compounds, acid anhydrides, dihydrazides, diiminocarbonates, and cocondensates with other dyes.

Alternatively, the indolenine cyanine dye cation having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dyes.

In this case, the metal crosslinking agents include alkoxides of titanium, zircon, aluminum, etc., chelates of titanium, zircon, aluminum, etc. (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and their esters, ketoalcohols, aminoalcohols, enols) those with active hydrogen compounds, etc. as ligands)
, titanium, zircon, aluminum, and other 7 sylates.

Sarani is -OH group, -0COR group Oyobi -COOR
one or more indolenine-based siacone dye cations having at least one of the groups (wherein R is a substituted or unsubstituted alkyl group or aryl group), or together with this; It is also possible to use a compound in which other spacer components or other dyes are bonded through a -〇〇〇- group through a transesterification reaction.

In this case, the transesterification reaction is preferably carried out using an alkoxide such as titanium, zircon, or aluminum as a catalyst.

In addition, the above-mentioned indolenine cyanine dye cation may be bound to a resin.

In such cases, a resin having a specified group is used, and the side chain of the resin is added to the side chain by condensation reaction, transesterification reaction, crosslinking, etc., as in the case of the polymer described above. Indolenine cyanine dye cations are linked via a spacer component, etc., depending on the conditions.

On the other hand, as the quencher anion Q- constituting the conjugate, two or more isomers of bisphenyldithiol transition metal complex anions are used.

The binuphenyldithiol transition metal complex anion is represented by the following formula (II).

Formula (II) where R1 is a monovalent substituent, preferably a methyl group,
Alkyl groups such as ethyl groups, halogen atoms such as CU,
Or 7 such as dimethylamino group, diethyl 7mino group, etc.
k is an integer from 1 to 4, and when k is 2 or more, multiple R1s may be the same or different; however, when the mouse is 4, the four R1s are not the same, Two or more isomers always exist.

M represents a transition metal atom such as Ni, Co, Cu, Pd, Pt, and more preferably Ni.

Further, M in the above structure has one charge.

Furthermore, other ligands may be bonded above and below M.

Therefore, the conjugate used in the present invention is isomers of the quencher portion of the compound represented by the following formula (m).

Formula (IIIl[) In the present invention, at least two or more isomers of the bond represented by the general formula (m) must be contained in the recording layer.

In this way, it is possible to prevent crystals of the composition components of the recording layer from precipitating in the coating film, and the film formability is good, the sensitivity such as the S/N ratio is good, and there is little reproduction deterioration due to readout light. , an optical recording medium with extremely high light resistance can be obtained.

Next, a specific example of the quencher anion Q- will be shown.

R1k M Q-I CI (31NiQ'-2C sentence
2 NiQ′″ 3
CH32NfQ-4C
I NiQ′″ 5 C
Sentence 3 N1Q-6CH
32C0 Q-7CH32N1 Q-8NCCH3)2 1 N1Q
-9N(CH3)2 2 NiQ″
″ 10 N(CH3)2, (:R32N
1Q-11N(CH3)2, 8fL2
Ni Preferred photostabilized cyanine dyes used in the present invention are isomers of the following specific examples.

Dゝ-Uni31 D+I Q-5SZ
D◆2 Q-5 S3 D+3 Q-5S4
D+4 Q-5SS D◆5
Q-5 S6 D+6 Q-5S7
D÷7 Q-5 Sg D-9 Q-5 59D”ll Q-5 510D÷17 Q-5 Sll D÷19 Q-5S12
D◆20 Q'''5513 D”21
Q-5514D+22 Q″″5 515 D+23 Q″″5516
D◆26 Q-5S17 D+3
0 Q-5S 18 0”37
Q-53190”38 Q
-5 S20 D"I Q-8
S21 D”2 Q-8
S22 D”I Q-23
23D÷ 3 Q-8 S24 D+7 Q-IS
25 D”8 Q-832
60”9 Q-8 S27 D ÷ 10 Q-
8S28 D"ll Q-8
S29 D”12 Q-85
30D+13 Q-9 S31 D" 14 Q-1
0S32 D+15 Q-1
1S33 D+16 Q-''
9S34 D”17 Q-
″ 8535 D+18 Q
-8536D+I Q-1 337D+I Q-9 338D"I Q-10 S39 D÷ 20 Q-3S4
0 D+2I Q-8541D+
19 Q-8 S42 D"9 Q"" l5
43 D”9 Q-9S44
D"22 Q"" 8S45
D"ll Q-1346D'> 1
1 Q-7347DelIQ
-9 348D+I Q-2 349D"ll Q-2 Such a photostabilized cyanine dye of the present invention is produced, for example, as follows.

First, a cationic cyanine dye combined with an anion is prepared.

In this case, as the 7-ion (An-).

I-, Br-, ClO4-, BFa-.

CH34j:>503-, C10SO4-, etc. may be used.

Such cyanine dyes are known and synthesized according to conventional methods. That is, for example, the method described in Nitrogen-Containing Heterocyclic Compound Engineering, Dai Organic Chemistry (Breakfast Shoten), page 432, or the method of Harald et al. and ZINCK may be followed.

On the other hand, an anionic quencher bonded to a cation and used in the present invention is prepared.

In this case, the cation (Cat'') is particularly N.
” Tetraalkylammoniums such as (CH3)4.N◆ (C4H9)4 are preferred.

In addition, these quenchers are patent application No. 57-1f! 88
No. 32, 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.

Moreover, its concentration is 0.01 mol/9. It is sufficient to set the degree.

Thereafter, an aqueous solvent, particularly water, is added to the mixture 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.

In addition, cyanine dyes such as p-)luenesulfonate and p-
In the case of highly soluble dyes such as chlorobenzene sulfonate, if the dye is dissolved in methanol or the like and mixed, the desired stabilized dye will precipitate.

Next, the two liquid phases are separated, filtered and dried, and recrystallized with DMF-ethanol or the like, thereby converting the light-stabilized cyanine dye into a light-stabilized 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, according to Japanese Patent Application No. 57-188832, nickel may be oxidized while blowing air to form an anionic salt.

Next, an example of synthesis of the photostabilized cyanine dye of the present invention will be given.

Synthesis Example 1 (Synthesis of Sl isomers) 1.3,3.1',3',3''-hexamethyl-indorinotricarpocyanine iodide [Nippon Kanko Shiki Kenkyushin NK-125D''l iodide )(0,0
005 mol, 0.25 g) and (3,4,8-trichloro-1,2-dithiophenolate)nickel (n)
Tetra-n-butylammonium, the tetrabutylammonium salt of Q-5 (o,ooos mol, 0.39 g) was dissolved in 20 mfL of N,N'-dimethylformamide, kept at 70 °C for 3 hours, and then poured into cold water. Pour, filter the precipitate, wash with water, dry under reduced pressure, 1.3, 3.1',
3',3'-hexamethylindolinotricarbocyanine bis(3,4,8-trichloro-1,2-dithiophenolate) nickel (II) [S1] was obtained.

The isomers were synthesized in the same manner as above, except that the starting materials were changed. The same applies below.

Yield: 0.40g (yield: 88%) This was heated and dissolved again in DMFlomJl.

30 ml of hot ethanol was added and left to stand for recrystallization.

mp 206-208℃ (reddish brown) The content of Ni was determined by atomic absorption spectrometry, and the following results were obtained.

Ni content (%) Calculated value 6.15 Measured value 6.
07 Dye stabilizer 1:1 Calculated value as a mixture 4.43 Synthesis example 2 (S3
1.3,3.1'',3',3''-hexamethyl-4,5°4'',5''-dibenzoindotricarbocyanine perchlorate (0,00025 mol, 0,
153 g) (E, Kodak MDITC
0.00025 mol, 0.197 g of the tetrabutylammonium salt of Q-5 of Synthesis Example 1 was metathesized in the same manner as in Synthesis Example 1, and the isomer of photostabilized dye S3 was obtained. I got it.

Yield o, 23g (yield 87%) Recrystallized from DMF-ethanol.

mp 177-179°C (gray-green) Ni content (%) Calculated value 5.56 Measured value 5.
54 Calculated value as a mixture 4.2 Synthesis Example 3 (Synthesis of 320 isomer) Of the iodide of D+ 1 and the isomer of Q-8, bis(
4-dimethylamino-1,2-dithioferrate) nickel (■) tetrabutylammonium salt was used in the same manner as in Synthesis Example 1.

An isomer of photostabilized dye 520 was obtained.

Yield 91% mp Gradual decomposition (black color) Ni content (%) Calculated value 7.04 Measured value 6.
93 Synthesis Example 4 (Synthesis of isomer of 521) Barchlorate of D”2 [Nippon Kanko Shiki Kenkyushin NK
-2905) and the tetrabutylammonium salt of the isomer of Q-8 in Synthesis Example 3 were used in the same manner as in Synthesis Example 1 to obtain the isomer of photostabilized dye 521.

Yield 80% mp240℃ (decomposition) (black edge color) Ni content (%) Calculated value 4.85 Measured value 4.
77 Synthesis Example 5 (Synthesis of isomer of 323) D÷3 barchlorate (E, Kodak 1507
3) and the tetrabutylammonium salt of Q-8 of Synthesis Example 3 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye 323.

Yield 89% mp 210-212°C (dark green) Ni content (%) Calculated value 6.28 Measured value 6.
41 Synthesis Example 6 (Synthesis of S4 isomer) Barchlorate of D+4 (Nippon Kanko Shiki Kenkyushin Co., Ltd., NK
-2865) and the tetrabutylammonium salt of isomer Q-5 in the same manner as in Synthesis Example 1.
The isomer was obtained.

Yield 75% mp 137-140°C (black edge color) Ni content (%) Calculated value 4.69 Measured value 4.
10 Synthesis Example 7 (Synthesis of S5 isomer) Barchlorate of D4″5 [Nippon Kanko Shiki Kenkyushin Co., Ltd., N
K-2868) and the tetrabutylammonium salt of Q-5 of Synthesis Example 1 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye S5.

Yield 88% mp 73-75°C (black edge color) Ni content (%) Calculated value 3.83 Measured value 4.
22 Synthesis Example 8 (Synthesis of S6 isomer) Barchlorate of D+6 (Nippon Kanko Shiki Kenkyushin NK
-2873) and the tetrabutylammonium salt of Q''''5 of Synthesis Example 1 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye S6.

Yield 100% mp 217-218°C (magenta) Ni content (%) Calculated value 4.70 Measured value 4.
55 Synthesis Example 9 (Synthesis of S7 isomer) D+7 bromide (Nippon Kanko Shiki Kenkyushin NK-290
2) and the tetrabutylammonium salt of Q-5 of Synthesis Example 1 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye S7.

Yield 92% mp Gradual decomposition (dark green) Ni content (%) Calculated value 4.90 Measured value 4.
88 Synthesis Example 10 (Synthesis of isomer of S25) Barchlorate of Dl et al. [Nippon Kanko Shiki Kenkyushin Co., Ltd., NK
-2910) and the tetrabutylammonium salt of Q-8 of Synthesis Example 3 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye S25.

Yield 81% mp 193-194°C (dark green) N1 content (%) Calculated value 4.62 Measured value 4.
75 Synthesis Example 11 (Synthesis of isomer of 326) Barchlorate of D”9 (Nippon Kanko Shiki Kenkyushin Co., Ltd., NK
-2921) and the tetrabutylammonium salt of Q''''8 of Synthesis Example 3 were used in the same manner as in Synthesis Example 1 to obtain an isomer of photostabilized dye S26.

Yield 88% mP 140°C (decomposed) (black border color) Ni content (%) Calculated value 5.57 Measured value 5.
48 Synthesis Example 12 (Synthesis of S2B isomer) Barchlorate of D◆11 [Nippon Kanko Shiki Kenkyushin Co., Ltd., N
K-2880) and the tetrabutylammonium salt of Q-8 of Synthesis Example 3 were used in the same manner as in Formation Example 1 to obtain an isomer of photostabilized dye 528.

Yield Yield 96% mp 209°C (bright orange) Ni content (%) Calculated value 6.28° Measured value 6
．． 32 The absorption spectrum of each photostabilized dye in dichloroethane was almost the same as that of the raw material cyanine dye.

These photostabilized cyanine dyes represented by the general formula [■] may be used in combination of two or more in any desired combination.

When two types are used in combination, the weight ratio is l: 0.1 to 1:
When three or more kinds are used in combination, the weight ratio is about 1:0.1 to 1:10.

In addition, Dl of 2-3 types of compounds used together may be the same or different.

Furthermore, in addition to at least two or more isomers of the photostabilized cyanine dye composed of such a conjugate, an indolenine cyanine dye may be contained.

In this case, among the various indolenine cyanine dyes, those having high writing sensitivity and high reading S/N ratio when incorporated in the recording layer are expressed by the following general formula (I
V) is a cyanine dye.

General formula (ff) In the above general formula (ff), Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R1 and R1' are , each represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and X- represents an acid anion.

In the above general formula (17), Z and Z' are an indolenine ring to which an aromatic ring such as a benzene ring or a naphthalene ring may be condensed, particularly an indolenine ring or a benzindolenine ring * Tal * Dibenzo Represents the atomic group necessary to complete the indolenine ring.

The ring completed by Z (hereinafter referred to as Φ4'') and the ring completed by Z' (hereinafter referred to as Φ4'') may be the same or different, but they are usually the same, and these rings may have various substitutions. Groups may be bonded.

The skeleton rings of these Φ÷ and ψ are represented by the following formula [ΦI
] ~ [Φ■] and [! ■〕～〔! (2) It is preferable to use the one shown in [2].

In these various rings, the groups R1 and R'1 bonded to the nitrogen atom in the ring are substituted or unsubstituted furkyl, aryl, or alkenyl groups.

Groups R1, R"l 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.

Among these, unsubstituted alkyl groups or alkyl groups substituted with alkylcarbonyloxy groups, hydroxyl groups, etc. are particularly preferred.

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' and R3' are preferably an alkyl group or an aryl group.

Among these, the number of carbon atoms is 1 or 2. In particular, one unsubstituted alkyl group is 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, hetero ring residue.

Halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamide group , alkylcarbamoyl group, arylcarbamoyl group, alkylamino group, arylamino group,
It may be one of various substituents such as a carboxylic acid group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, and a nitro group.

And the number of these substituents (P*qr*s,
t) is usually 0 or about 1 to 4. In addition,
When p, q, r, s, and t are 2 or more, a plurality of 14
, R4' may be different from each other.

The cyanine dye cation has a condensed or non-condensed indolenine ring, has excellent solubility, coating properties, and stability, and exhibits extremely high reflectance.

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 (LIX).

Formula (LI) Formula (L l1l) CH-C=CH↓ Formula (LAX) C ↓ Here, Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group is a methyl group, etc. lower alkyl groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, ethoxycarbonylpiperazine groups, etc. Preferred examples include alkylthio groups such as a fulkylcarbonyloxy group and a methylthio group, a cyano group, a nitro group, and a halogen atom such as Br and CJL.

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

And, or 0 or l.

Furthermore, x″″ is an anion, and a preferable example thereof is:

I-, Br″″, Cl0a-, BFa-.

CH3-C>SOs-, C10303-, etc. can be mentioned.

Note that 1m is 0 or l, but when 1m is 0, R1 of Φ usually has one charge.

It becomes an inner salt.

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

m immun-v 1L-1 top k211
且11 [Φm) CH3CH3-2(Φ
m) CH3CH3' -3 [Φm)
C2H4OHCH3-5 [Φ■) CH3CH3
- 7 [Φm] CH2CH20HCH3-8 [Φm
) (CH2)20COCH3' CH3-
9 [ΦIII) (CH2)20COCH3CH3
-10 (□m) CH3CH3- 11 (Φm) CH3CH3- 12 (Φm) Cl8H37CH3-13 (Φm
) C4Hg CH
3-14 [Φm) Ca Ha; 0COC
H5CH3-15 [Φm) C7HB4CH2
0HCH3-L Y
I 2 0
C9,0a(LII) HCICl0a(L-N(CsHs)20
Cl0a (LH) HI (Ln) HCICl 04 (L' -N (C6H5)2 0
Cl0a[LH] l(I Grave lshi Earthwork 'l'LL Work 1 top 1L1
11 and 116 [Φm] Ca II7
CH3-17 (Φm)
CaH hill CH3-19 (Φ
m) C7II4 COOC2H5CH3-20
(Φm) C4H9CH3-21 [Φm]
Cl8H37CH3-22 [ΦIII) C4
H9CH3-23 [Φm) C17H34CO
OCH3CH3-24 [Φm] ca HI6
0COCH3CH3-25 [Φm] C8H17
C2H5-26 [Φm] C7H15C2H5-
27 [ΦII) C17H34COOCH3C
H3-28 [ΦII) Ca H+s CH2
0COCH3CH3-29 [ΦIl) c,,)
(17CH3-L Y
IX [LH]
HCfLOa [LH) H- (Ln) HBF4 (Lm) -N (C6Hs) 2 0
CJLOa (Ln) HC104 (L II ) HCI O4 (L I
I) HI (Lm) -N (Ca Hs) 2
0 I[:L II) HI (L II) HI (LII) HCiO4 fish 11 soil, -! K1-JLL presentation-
JLL030 (ΦII) Cy H14
COOCH3C2 [6D 31 (em)
C7HB4 CH20HCH3.

D32 [ΦIII] C7 HucHz 0
COCz Hs CH3D33 [9m]
Cl7H MinohCOOC2H5c) I3D34 [9
m) C17H35CH3D35 (eII
I) Cy H15C2H5D36 [Φf
f) CH3CHsD37 ・(ΦIV)
CH3CH3D38 [Φff] C4H
9CH3D39 (ΦN) (CH2)20CO
CH3CH3D40 [ΦI] CH2CH2
0COCHs CHs041 (ΦI)
CH・・2 CH20HCH3D42 (9m)
CH3CH3D43 [ΦI) C
2H5CHa 5-CD44 (ΦI)
C2H5CHa 5-CD45 [ΦI]
C2H5CH35-C1 Soil L
Y see X-(Ln)
HClO4-(Ln) HClO4-(L
n) HI (Lm) -N(C6H5)2 0 I
-(LIT) HOI -(Lll) HI -(Ln) HI -(Lll) HCJlO4-(LII)
HC1o4- (L■]HI (Lll) HC1o4- (Lll) HBr-(L
vI) Br CJ
LO4aHssO2(L[) Br
I H6H5SO2 (Lm)
C1I CILO48H6SO2(L
m) C1OI fish 11 earthwork j K1
-JLL DanL-L1L and 1D46
(ΦI) C2Hs C
H35-C6H5:D47 [ΦI) C2H
s CH35-C6H5:D4B
[ΦI) C2H5CH35-C81 (5 pieces D
49 (ΦI) C2H5CH35-C6H5
Poor D50 [ΦI) C2H5CH,5-C,
I (5 deficiency D51 (ΦI) CH3CH35
-CaB6 Deficient D52 (ΦI) CH3
CH35-CsHs poor D53 [ΦI]
n-C4Hg CH35-C6H53D
54 (ΦI) n-C6H13CH35-C
6H5EH5 deficiency D56 [ΦI) C2H5CH35-C6
H53D57 [ΦI] CH3CH35-C
aB6 Poor D58 (ΦI) C2H5CH
35-Cs H5 (D59 (ΦI) C2
H5CHa 5-Ca Hs (D60
(ΦI) C2Hs CH3
5-Ca H5(LY
I X'+02 (Lm) Cl
OCH3C6H45O3i02 (
LVI) C1l BF4102'
(L■) Cl I Cl0
a:02 (LVI) CI Ol1
0z (LVI) CI OCH
3C6H45O3i02 (LIII) C1O
Cl04102 (LVI) Cl
0 engineering: 02 (LVI) Cl
l Cl04.02 [L■] C5L
I CIL04:02 [L■]
C9,l-,02(LVI)N-
Shizuyumi (:N l -102 (LVI)
N --(knee C-(:N 1-:0
(LII[)Ci l I:
O(Lm)Br l I:O
(Lm) C1l C1()s color 11
East-v7 upper LL engineering 1e once Sat 061
(ΦI) C2H5CH35-CoH
Electric D62 [ΦI) C2Hs
CH35-C6HHD63 [ΦI]
C2I(5c)I3 Ri-ca H.

D64 [ΦI] C2H5cI (3ri-co
H.

D65 [ΦI] CH3CH3CH3C0D
66 [ΦI) CH3CHs CH
3C0D67 [ΦI] C2H40COC
H3CH3CH3C0D68 [ΦI) C
Ha CH35-C look D69
[ΦI) CH3, CH35-CH5D70
(ΦI) CH3CH35-C2HpiLYI
X , Co (Lm) C1l CH3C
aH4SO3, Co (L■) C! L
I C104ico (LVI)
C1l I, Co (LV
I) C1OCH3CaH4SO3(Ln)
HCl0a (Ln) HI [Ln) HI [Ln) HCl0a (LII) HCl0a, COO (LII) HCIL04 also. These cyanine dyes can be easily synthesized according to the method described in books such as Dai Organic Chemistry (Breakfast Shoten) Nitrogen-Containing Heterocyclic Compound Engineering, page 432.

That is, first, the corresponding Φ~-〇H3 (Φ~ represents a ring corresponding to the above Φ) is converted into the excess RI I (Rt
is an alkyl group or an aryl group) to form R
1 is introduced into the voiceme atom in Φ- to obtain Φ-CH5I-.

Next, this may be subjected to dehydration condensation with an unsaturated dialcohol, unsaturated hydroxyaldehyde, allyl pentadiene, isophorone, etc. using an alkali catalyst or acetic anhydride.

These indolenine cyanine dyes are usually contained in the recording layer in the form of a monomer, but may be in the form of a polymer if necessary.

In this case, the polymer has two or more molecules of cyanine dye, and may be a condensate of these cyanine dyes. For example, one or more functional groups such as -OH, -COOH, -303H, etc. A single or co-condensate of the above dyes having one or more of the following.

Or these together with dialcohols, dicarboxylic acids or their chlorides, diamines, di- or triisocyanates,
There are cocondensation components such as jepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other dyes.

Alternatively, the cyanine dye having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a spacer component or other dye.

In this case, the metal crosslinking agent is Alkoxides of titanium, zircon, aluminum, etc.

Chelates of titanium, zircon, aluminum, etc. (e.g. those with β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, ketoalcohols, 7-minoalcohols, enolic active hydrogen compounds, etc. as ligands)
, shearates of titanium, zircon, aluminum, etc.

Furthermore, -OH group, -0COR group, and -COOR
One or more cyanine dyes having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and other spacer components or other dyes It is also possible to use a compound in which these are bonded through a -COO- group through a transesterification reaction.

In this case, the transesterification reaction is preferably carried out using a flukoxide such as titanium, zircon, or aluminum as a catalyst.

In addition, the cyanine dye described above may be bound to a resin.

In such cases, a resin having a specified group is used, and the side chains of the resin are added as necessary by condensation reaction, transesterification reaction, or crosslinking, as in the case of the polymer described above. Cyanine dyes are linked via a spacer component, etc., as appropriate.

When containing these dyes in addition to the conjugate, the content of the conjugate is 10 to 80 wt%, more preferably 30 to 60 wt%.
It is preferable to set it as wt%.

When the amount of the bond exceeds 80 wt%, the absorbance and reflectance of the optical recording medium decrease. Furthermore, compatibility deteriorates and film formability deteriorates, resulting in a decrease in SZN ratio, etc., and deterioration in sensitivity.

If the amount of the conjugate is less than 10 wt%, the 7-ion portion of the quencher decreases, resulting in regeneration deterioration. Further, unnecessary anions are present in the recording layer, which causes hydrolysis and tends to generate acids, alkalis, etc., resulting in poor moisture resistance.

The recording layer may contain a resin if necessary.

The resin used is preferably a self-oxidizing, depolymerizable or thermoplastic resin.

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

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

ii) Polyolefin copolymer For example, ethylene-vinyl acetate copolymer.

Ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-maleic anhydride copolymer, ethylene-mpropylene terpolymer ( EP
T) etc.

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

fii) 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 set arbitrarily.

m) Polystyrene m) Styrene copolymer such as 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, etc.

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.

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

acrylic resin Particularly preferred are those containing an atomic group represented by the following formula.

2 R10 CH-C- -0R20 In the above formula, R10 represents a hydrogen atom or an alkyl group, and R20 represents a substituted or unsubstituted alkyl group. In this case, in the above formula 2, R10 is a hydrogen atom Alternatively, it is preferably a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

Further, R20 may be a substituted or unsubstituted alkyl group, but the number of carbon atoms in the furkyl group is preferably 1 to 8, and when R20 is a substituted alkyl group, the alkyl The substituent for the group 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, 7-acrylonitrile monobutyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

xiii) Dia7ton Acrylamide Polymer 7 Dia7ton acrylamide polymer obtained by reacting a7ton with acrylonitrile.

xii) Polyvinyl acetate (polyvinyl acetate) copolymers such as copolymers with acrylic esters, vinyl ethers, ethylene, vinyl chloride, etc.

The copolymerization ratio may be arbitrary.

Tomi i) Polyvinyl ether, such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl butyl ether, etc.

! iii) Polyamide In this case, the polyamide includes nylon 6, nylon 6-6, nylon 6-10. Nylon 6-12. Nylon9. Nylon ll, nylon 12. In addition to normal homonylon such as nylon 13, nylon 6/6-6/6-1
O, nylon 67 low 6712. Nylon 6/6-6/
Polymers such as No. 11 or modified nylon may be used as the case may be.

! 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, Condensates and co-condensates with glycols such as ethylene glycol, tetramethylene glycol and hexamethylene glycol are suitable.

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

Particularly suitable.

Furthermore, for example, a modified gliptal resin, which is a condensation product of phthalic anhydride and glycerin, is esterified and modified with a fatty acid, a natural resin, etc., and the like.

xix) Polyvinyl acetal resin Both polyvinyl formal and polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol are preferably used.

In this case, the degree of 7-cetalization 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 fullylene diisocyanate.

xxi) 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 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.

xxii) Ionomer Na such as methacrylic acid and acrylic acid.

Li, Zn, Mg salts, etc.

Violet! 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.

xxiii) Petroleum resins C5 type, C9 type, C5-c9 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof.

! ! M1ii) Above i)~! ! xxiii Blends of two or more types, or blends with other thermoplastic resins.

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

Such a resin and the above-mentioned combined body are usually layered in a wide range of weight ratio of 1:1 to 0.1 to 100.

In addition, other quenchers may be separately included in such a recording layer.
1. For example, those described in Japanese Patent Application No. 58-181388 may be included.

In order to form such a recording layer, coating may generally be performed according to a conventional method.

The thickness of the recording layer is usually about 0.3 to 10 m.

It may contain a plasticizer, a surfactant, an antistatic agent, a lubricant, a flame retardant, a stabilizer, a dispersant, an anti-corrosion agent, a crosslinking agent, and the like.

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

The solvent used for coating is, for example, 1.

Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and esters such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate.

Ethers such as methyl cellosolve and ethyl cellosolve,
Alternatively, an aromatic type such as toluene or xylene, a halogenated alkyl type such as dichloroethane, an alcohol type, 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.

Also, the shape of the tape depends on the intended use.

It may be a drum, a belt, etc.

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.

These substrates have solvent resistance 1. In order to improve wettability, surface tension, thermal conductivity, etc., it is preferable to form a base layer on the substrate. The material of the base layer includes Si, Tf, etc.
, Al, Zr.

It is preferable to use an oxide formed by applying an organic complex compound or an organic polyfunctional compound such as In, Ni, Ta, etc. and drying it by heating.

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

In addition, on the recording layer, various uppermost layer protectors: aM
, a single layer of half-mirror, etc. can also be provided.

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, one dye is melted by the heat generated by the dye in the recording layer, and a bit is formed.

The bits formed in this manner are read out by detecting the reflected light, the transmitted light, and especially the reflected light of the read 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 bits once formed in the recording layer with light or heat and rewrite them.

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

(2) Specific Effects of the Invention According to the present invention, the composition of the recording layer of the present invention has good solubility, and crystals of the composition do not precipitate when it is coated on a substrate.

Therefore, an optical recording medium with good film formability and high sensitivity such as S/N ratio can be obtained.

(1) Specific Examples of the Invention One specific example of the present invention will be shown below and explained in more detail.

Example 1 A photostabilized cyanine dye consisting of a combination of an indolenine cyanine dye cation and a bisphenyldithiol transition metal complex anion shown in Table 1 below was used, or an indolenine cyanine dye was added thereto. These are dissolved in a prescribed solvent using
Various test specimens were obtained by coating a layer of 10 g, m on a 5 cm square acrylic resin substrate provided with 10 g, m). After the coating, the presence or absence of precipitation of crystals of the constituents in the coating was confirmed using a reflection microscope.

The results are shown in Table 1.

In Table 1, the number after the hyphen, such as 1, for example, 5l-1, indicates that the quencher anion is as follows.

” Shimata From the results in Table 1, the effects of the present invention are clear.

Applicant TDC Co., Ltd., Tij
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Claims (2)

[Claims] (1) A recording layer containing at least two kinds of photostabilized cyanine dyes consisting of a combination of an indolenine cyanine dye cation and a bisphenyldithiol transition metal complex anion, the complex anions of which are isomers of each other. An optical recording medium characterized in that it has on a substrate. (2) A photostabilized cyanine dye consisting of a combination of an indolenine cyanine dye cation and a bisphenyldithiol transition metal complex anion, in which at least two complex anions are isomers of each other, and an indolenine dye. 1. An optical recording medium comprising, on a substrate, a recording layer containing a cyanine dye.