JPS618384A - Optical recording medium - Google Patents

Abstract

PURPOSE:To contrive enhancement of writing sensitivity and S/N in reading, by providing a recording layer which comprises a coloring matter and an ion combination of a coloring matter cation and a quencher anion, in which at least one is an indolenine cyanine coloring matter or a cation thereof, at least one of the coloring matter and the ion combination consists of two kinds of members, and absorption and reflection maximum wavelengths are specified. CONSTITUTION:The recording layer comprises a coloring matter and an ion combination of a coloring matter cation and a quencher anion. At least one of the coloring matter and the coloring matter cation is an indolenine cyanine coloring matter or a cation thereof. At least one of the coloring matter and the ion combination consists of two kinds of members, in which at least one coloring matter or ion combination has an absorption maximum wavelength in the range of -40-+70nm relative to the wavelength of writing light. At least one of the other coloring matters or ion combinations has a reflection maximum wavelength in the range of -40-+70nm relative to the wavelength of reading light.

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, two types of optical recording media are being developed and researched.

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 row rabbit forming type in which information is recorded by forming a small hole, and this bit is detected by a read light and read out.

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-58-48221-V] is used.

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

Ding echno1. ．． +8 (1) 105 (198
1) ) and metal phthalocyanine dyes (JP-A-57-8
No. 2094, No. 57-82095), etc.

In addition, examples of using metal phthalocyanine dyes for semiconductor lasers (Japanese Unexamined Patent Publication No. 58-813795) are all cases in which the dye is formed into a thin recording layer by vapor deposition, and there is no major difference from the Te-based medium in terms of media 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.

In addition, if a transparent substrate carrying a recording layer is integrated with the recording layers facing each other, which is a so-called air sand weasel structure, and writing and reading are performed through the substrate, it is possible to record without reducing the writing sensitivity. Although it is advantageous in that the layer can be protected and the recording density can be increased, such a recording/reproducing method is also not possible with a dye-deposited film.

This is 1. Normally, a 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, an anode 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 bit formation and the reflectance may increase, or in some cases, the reflective film may This method reduces reflectance by removing
Naturally, recording and reproduction cannot be performed through the substrate.

Similarly, IR-132
A recording layer consisting of a dye (manufactured by Kodak) and polyvinyl acetate, and 1.1'-
A recording layer comprising diethyl-2,2'-)lycarpocyanine iodide and nitrocellulose, further comprising Y,
La, W, et al, Appl, Phys.

Lett, 39 (13) 718 (1981) discloses that a recording layer composed of a dye and a resin, such as a recording layer composed of 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate, is formed by a coating method. Layered media is disclosed 2. has been done.

However, these cases also require a reflective film between the substrate and the recording layer, and have the same drawbacks as the dye-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,
It is compatible with media having recording layers made of Te-based materials. In order to realize a medium having a recording layer made of an organic 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 high reflectance in Wasca (P, Kivits, etal,
Appl, Phys, Part A 2B (2)
101 (1981), Japanese Patent Publication No. 55-97033]
However, the writing sensitivity is low, probably due to the high sublimation temperature.

In addition, it has been reported that cyanine dyes and merocyanine dyes such as thiazole, lye, and quinoline dyes also exhibit high reflectance [
Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics +p-P-9
(1!380) ), and a proposal based on this is published in JP-A-58-1127130, but these dyes have low solubility in solvents, especially when applied as a coating film. It easily crystallizes, and furthermore, it is extremely unstable and immediately bleaches when exposed to readout light, 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 selenacyl dyes, long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization. (Japanese Patent Application No. 57-182589, Patent Application No. 57-177778, etc.).

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a transition metal compound quencher to cyanine dyes to prevent regeneration and deterioration.
Patent Application No. 57-188832, No. 57-18f1048
No. etc.).

Furthermore, by forming a recording layer consisting of an ionic combination of an indolenine-based cyanine dye cation and a quencher anion, it is possible to increase photostability and improve storage stability and durability (Japanese Patent Application No. 111715/1982). .

Furthermore, we have proposed a recording layer made of a mixture of an indolenine cyanine dye and the above-mentioned ionic binder, and are working to improve the read S/N ratio and write sensitivity (
Patent Application No. 511-11151117).

However, even when these indolenine-based cyanine dyes are used, further improvement in sensitivity is desired.

■ Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a record containing an indolenine-based cyanine dye, which has further improved writing sensitivity and reading S/N ratio. An object of the present invention is to provide an optical recording medium having layers.

Such objects are achieved by the invention described below.

That is, the present invention provides an optical recording medium having a recording layer on a substrate containing an ionic combination of a dye, a dye cation, and a quencher 7 anion, wherein at least one of the dye and the dye cation is an indolenine cyanine. A dye or a cation thereof, and at least one of the dye and the ionic binder contains 21I or more, and at least 1
The absorption maximum wavelength of at least one dye or ionic conjugate is between 140 nm and +70 nm of the writing light wavelength, and the reflection maximum wavelength of at least one dye or ion conjugate is between 140 nm and +70 nm of the reading light wavelength. This is an optical recording medium characterized by:

■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 dye and an ionic combination of a dye cation and a quencher anion.

and at least one of a dye and a dye cation.
The species is an indolenine cyanine dye or its cation.

In this case, both the dye and the dye cation are preferably indolenine cyanine dyes or their cations.

At this time, writing sensitivity increases, reflectance increases, and reading S/N ratio improves.

There are no particular restrictions on the indolenine cyanine dye, 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 general formula (I), Z and 2' each represent an atomic group 7 necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R , 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 anion resistance, m is O or l.) In the general formula (I) of 1-2, Z and Z' are an indolenine ring to which an aromatic ring, such as a benzene ring or a naphthalene ring, may be fused, especially an indolenine ring. Ring, benzindolenine s t *represents the atomic group necessary to complete the dibenzoindolenine ring.

The ring completed by Z (hereinafter referred to as Φ+) and the ring completed by Z' (hereinafter referred to as 'q/) may be the same or different, but they are usually the same, and there are various may be bonded with a substituent.

These Φ hands and the inner skeletal ring are represented by the following formula [ΦI
] ~ [Φ■] and [! ■〕～〔! (2) It is preferable to use the one shown in [2].

[Φm)'(R4)Q(R4')Q('I'm')(R4') qIn such various eggs, the nitrogen atom groups R1, R
', is a substituted or unsubstituted alkyl group, aryl group, alkenyl group] A group R'1 bonded to the nitrogen atom in the ring;
There is no particular restriction on the number of carbon atoms in this group, but the substituent may include a sulfonic acid group, an arecarbonyloxy group, an alkylamitokylsulfonamide group, and an alkoxycarboxylic acid group. group, alkylamine group, alkylamine group, alkylsulfamoyl group,
It may be any of a hydroxyl carboxy group, a halogen atom, etc.

Among these, unsubstituted alkyl groups, alkyl group, hydroxyl group, etc. are particularly preferred.

In sea urchin, there are two molecules at the 3rd position of the indolenine ring, R2 and 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, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

-・way, 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, a heterocyclic residue, and a halogen atom. , alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamido group, alkyl Carbamoyl group, arylcarbamoyl group, alkylamide 7 group,
Various substituents such as arylamide 7 group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, cyano group, nitro group, etc. It's good.

And the number of these substituents (P * 'Q + r
! s, t) are 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.

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 5 such as a mono-, di-, tri- or tetracarbocyanine dye, and in particular, it may be any one of formulas (LI) to (LX[). preferable.

Formula (LI) Formula (LAX) C 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, dimethylamino 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 cyano group, a nitro group, and a halogen atom such as Br and C1.

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

And the sentence is O or 1.

Furthermore, X- is an anion, preferable examples of which are I, Br, CfLO4, BF4.

CH3<)S03-, C-stand0S03-, etc. can be mentioned.

Note that when m is 0 or l but 1m is O, R1 and L of Φ usually have a single charge and become an inner salt.

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

CC Color” Niyo Shou-ichi! Foundation-JLL
Danri m-W1 RJ-Dl (
ΦI) CH3CH3-D2 (Φ
I) CH3CH3-1)3 (Φ
I) C2H4OHCH3-D4
(ΦI) (CH2)3 503-
CH3-' (CH2)3 S03- Na'' D5 (ΦII) CH3CH3
-06(Φm) (CH2)3 503-
CH3-' (CH2) 3303- Na
÷ D7 (Φm) CH2CH20H
CH3-D8 (Φm) (CH2)2
0COCH3CH3-D9 (ΦI[I)
(CH2)20COCH3CH3-Dlo
[Φm] CH3CH3-Dll [Φ
m) CH3CH3-Dl2 [Φ■]01
8H3? CH3-Dl3 [ΦI]
'C4H9CH3-D14 [Φwork]
C3H160COCH5CH3-Dl5 (Φ
I), C7H14CH20HCH3-■--Two-sentence -X- (LII) HI (L II) HCΩ04 (Lnl)
HBr (LII) H-(LII)
H0 sentence 04 (L II)
H-(LII) H0 sentence 04(L
ll) HBr (Lm) -N(C8H!+)2 0 0
Sentence 04 (LII) HCΩ04 (Lm
) −N (Cs Hb )2 0
0 sentence 04 ['LII) HI (LH] HC, QO4 (Lm)
-N (C8H5)2 0 C look 07
1 (Lll) HI Jinjin ~ Men-'P LLLLL
LLLll ShakutDie (ΦII) C8
1 (17CH3, -Dl7 [Φm) C3H1□
CH3-Dl9 (Φ■)
CHC00C2H5CH3-D20 [Φm] C
2H8CH3-D21 (OH) C,8)H3
7CH3-D22 [ΦIII) C4H9CH3
--D23 [ΦI) C,? ) f34COOC
H3CH3-D24 [ΦI] C3H160COC
H3CH3-D25 [ΦI) C8H17C2H
5-D26 [ΦI] C7H15C2H5-D2
7 [ΦII) C, □H34C00CH3CH3
-D28 [ΦIl] C8II6 CH20
COCH3CH3-D29 [ΦII) C+
7Hzs CH3-L
Y-Mata -X-(Lll)
'H0 sentence 04 (L II)
H-(Lll)
HBF4(Lm) -N(C6H5)2
O0 sentence 04 (L 1!)
HC Mi04 (LII) HC
Ω04(L II ) HI(L
m) -N (C6H5)2 0
I (LrI), HI (L II
) HI(LII)
HCIO 4 Mijin Selection Ignore J Watai-J Engineering'
C'yu and ID30 [ΦII]
C7H14CO, OCH3C2Hs -D3
1 (Om) C7H,,C,H20HCH3-
D32 [Φm]c7H14cH2ococ2H5cH
3-D33 (em) CHCOOC2H5CH
3-D34 (Om) C,7H”35C,H3
' -D35 (ci'm) C7H15
C2H5'-D3El (OIV)
CH3CH3-D37 (OIV) CH3CH
3-D38 (OIV) C4) (9CH3-D
39 (OrV) (CH2)20COCH3C
H3-D40 (OI) CH2CH20COC
H3CH3-D41 (Or) CH2CH20
HCH3-D42 (Om) CH3CH3-D
43 (c)I) C2H5CH35-C6H5
5O2D44 ((11) C2Hs
CH35-C6Hs 302D45 (4)
I) C2Hs CH35-
C6Hs 302L Y-text -X
-(Lll) HCl04 (LH) H(110°(L II ) H'
I(Lm) -N (C8Hs)2 0
r (LIT) HOI [LII) HI (LII) HI (Lll) HCl0a (Lll) HClO4 [L■] H Engineering (Lll) HC104 (Lll) HBr (LVI) Br Cl
04 (LVI) B r I
I (Lm) C1I C
l0a(LI[I) c sentence OI
I'm sorry! K1-1' Dan1--
11-1 Sat D4B [ΦI) C
2Hs CH35-C6Hs
5D47 [ΦI] C2Hs
CH35-C8Hs 5D48
[ΦI) C2Hs
CH35-Ca Hs 5D43 [ΦI]
C2Hs CH35-Ca
Hs 5D50 [ΦI] C2H
s CH35-Ca Hs
5051 (Φ-I) CH3CH35
-C6Hs 5D52 [ΦI] CH3C
H35-C6Hs 5D53 [ΦI]
ll-C4H9CH35-Ca Hs 5D54
[ΦI) n-Ce H13CHs5 Co
H5SD55 [ΦI) ((CH2)4303-
CH35-CaHs5(CH2)4SO3
H D56 [ΦI] C2Is
CH35-Cs Hs 5D57 [Φ
I) CI(3CH35-C6Hs 5D58
[ΦI) C2Hs
CH35-Ca Hs CD59 [ΦI]
C2Is CH35-Co
Hs CL Y again
-X-o2, (Lm) c intersection 0
CH3C6H4S0302 (LVI) C
5L I BF4o2 (LVI
) 0 sentences l C 0402
(LVI) Cl 0I02
(LVI) 0 sentences 0CH3C6H4S0
3o2 (LVI) 0 sentences oc sentence 0402 (LVI) 0 sentences
0I02 (LVI) 0 sentences
I 0 sentence 0402 (LVI)
, 0 sentences l C intersection 0402
(LVI) C look l -
02 (LVI) N-=C=ll knee CN
1 -o2 (LVI) N-=C=
C-CN 1-0 (Lm)
C1I IO(LIII)
Br I I color”
(U Little-one! Presentation-One skin L
Kariichi-11D61 [ΦI] C2H5C
H3D82 [ΦI) C2H5'
CH3D63 [ΦI]
C2H5CH3D64 [ΦI')
C2H5CH3D65 [ΦI) CH
3CH3D66 [ΦI] CH3CH3
D67 [ΦI] C2H40COCH3C
H3D68 [ΦI] CH3CH3D69
(ΦI) CH3CH3D70 [
ΦI) CH2C6H5CH3D71 (
Φm) CH3CH3D72 [ΦI)
CH3CHaD73 [Φm] CH
3CH3-1 branch L Y-mata -Eiichi 5-Ca H5Co (Lm)
C110H3C6H4SO35-Cs Hs C
o (L■) 0 sentences I
C sentence 045-C6H5Co (LVI)
C1l l5-C6H5Co (L
VI) 0 sentences 0 0H3C6H4SO35
-CH3Co (LII) HC view 0
45-CH3Co (LII) Hl
5-CH3Co (LH) Hl5-
0 sentences (LX)
--(LX)
-5-0 sentences [LX]
--(LX)
--(LII)
--(LX[)
- Furthermore, these cyanine dyes can be easily synthesized according to the method described in the number column of Nitrogen-Containing Heterocyclic Compound Engineering, page 432 of Dai Organic Chemistry (Breakfast Shoten).

That is, first, the corresponding Φ--CH3 (Φ'' represents a ring corresponding to the above-mentioned Φ) is converted into an excess R+ I (,-
R+ is an alkyl group or an aryl group) to introduce R1 into the nitrogen atom in Φ″ to form Φ-CH3I-
get. Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst.

These cyanine dyes are usually contained in the recording layer in the form of monomers, but may be in the form of polymers if necessary.

In this case, the polymer has two or more molecules of cyanine dye, and may be a condensation product of these cyanine dyes. For example, the polymer has functional groups such as -OH, -COOH, -503H, etc. Single or co-condensate of the above dyes having one or more of them.

Or these together with dialcohols, dicarbonyl alcohols 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, as a metal crosslinking agent.

Alkoxides of titanium, zircon, aluminum, etc.; chelates of titanium, zircon, aluminum, etc. (e.g., β-diketones, ketoesters, hydroxycarboxylic acids or their esters, ketoalcohols, aminoalcohols, enolic active hydrogen compounds, etc., with ligands) (things to do)
, shearates of titanium, zircon, aluminum, etc.

In addition, -OH group, -0COR group, and -COO
One or more cyanine dyes having at least one R group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and other spacer components or other It is also possible to use one in which the pigment is bonded to the dye through a -〇〇〇- 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.

The recording layer of the optical recording medium of the present invention contains, in addition to the above-mentioned preferably indolenine cyanine dye, a combination of a dye cation and a quencher anion.
The conjugate is particularly preferably a conjugate of an indolenine cyanine dye cation represented by the following general formula (n) and a quencher anion.

General Formula (II) D+.Q In the above general formula (II), D+ is an indolenine cyanine dye cation represented by, and Q- is a quencher anion.

Z, Z', R+, R+'' are represented by the general formula (i
It is similar to

These indolenine-based cyanine dye cations CD+) are not particularly limited, and various cations may be used as long as they do not have the above-mentioned acid anion X-.

Specific examples of the cyanine dye cation in the present invention are listed below.

Immunity-RL K1-1 Current I LL “D
"l ΦlCH3CH3-'!'ID"2
ΦI C2H5CH35-CH3SO2'i'I
D◆ 3 ΦmcH3CH3-'PII[D”4
ΦmCHCH3,-'Pm8 1? D◆5 Φm C, 8H37CH3-'PmD+6
ΦmCH3CH3-'PHD"7 Φm
C82CH20COCH3CH3-'f mD+8
Φm CH2CH20COCH3C1 (3-'!
'mD"9 Φm CH3CH3-'!mD+
10 ΦmcH3CH3-! ID"ll
ΦII CH3CH3-'PIID◆ 12
Φm C4H9CH3-heavy■D”13 ΦI
From CH2CH20HCH3-f ” 14 O
m CH2CH20HCH3'l'm-l1'
Knee, ordinary 4"LL', j ヱ
Also CH3CH3Lll H- C2Hs CH35-CH3SO2Lm
N((:CH5) 21CH3CH3, Lll
H- 817CH3LII H- CH- C18H37CH3LII H- CH3CH3Lm N(Ill:6H5) 21C
H2C:H,,0COIJ3CH3L II H-
CH2CH20COCH3CH3Lm N(CaB
6) 21CH3CH3LVI Br
IC1(3CH3LHH- CH3CH3LHH- C4H9CH3LII H- CH2CH20HCH3L II H-CH2CH
20HCH3LIIH- Menichi and s-1L21M! D”15 9
m C4H9CH3-'I'mD++8 ΦI
C82CH20COCH3CH3-9ID+17
ΦlCH3CH3-'PID"18 ΦmcH
3CH3-'I'mD◆ 19 ΦI CH
+20 ΦI CH3C from 3'CH3-ψ
+21 ΦlCH3CH3-'P from H3-%P
ID+22 ΦmcH3CH3-'I'mD"23
Or CH3CH3-'PUID◆24
ΦlCH3CH3-'I'm once above'u nie lv
'jLL' L Y-mata Ca H9CH
3Lm N(C6H5) 21C)12CH20C
OCH3CH3-Lll H-CH3CH3LVI
[H- CH3CH3-LW[H- CHa CH3Lm N(C6H5) 2
1CH3CH3LVI Br ICH3C
H3L II C-C: H3CH3
L II Cl 'CH3CH3Lll
H- CH3CH3LLTI N(CH) 1 These indolenine cyanine dye cations, as already mentioned for the indolenine cyanine dyes, 1 usually take the form of a -monomer, but if necessary, they can be in the form of a polymer. There may be.

The polymer may be a single polymer or a copolymer, or may be crosslinked with a metal crosslinking agent or ester bonded with another compound, just as in the case of indolenine cyanine dyes. .

Furthermore, these dye cations may be bonded to a resin, as in the case of dyes.

On the other hand, Q- represents the quencher 7 anion. In this case, the quencher anion Q- that constitutes the conjugate is
Although various anionic forms of quenchers can be used, in particular, the transition metal quencher 7 is used because it reduces regeneration deterioration and has good compatibility with dye-binding resins. Preferably, it is a nion.

Cu, Mn, Pd, PL, etc. are preferred, especially.

The following compounds are preferred.

l) A bisphenyldithiol system represented by the following formula, where R1 to R4 represent hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as CI, or a 7-mino group such as a dimethylamino group or a diethylamino group. In the formula, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt.

Furthermore, other ligands may be bonded above and below 1M.

Examples of this include the following:

l-K-l-已 L Q”'1-I HHHHN1 Q-1-2H(, R3HHN1 Q-1-, a HC sentence 0 sentence H
NiQ'-1-4CH3HHCH3Ni Q"'1-5 CH3CH3CH3CH3N1Q
-1-8'H0 sentence HHN1 Q-I-7CI CJI CI CI
N1Q-1-8HCI CI CI
N 1Q-1-9HHHHC.

q-t-to H(R3CH3HC.

Q-1-11H" CR3CH3HN iQ"' 1
-12 HN(CH3)2HHN iQ-1-13
HN(OH3)2N(OH3)2HN iQ -1-1
4HN(083)2 C83HN tQ-1-15HN
(CH) C1' HNiQ ”-1-18HN
(C2H5) 2 HHN i2) Bisdithio-α-dika represented by the following formula, where R5 to R represent a substituted or unsubstituted alkyl group or aryl group, and M
represents a metal atom such as Ni, Co, Cu, Pd, Pt, etc.

In the following description, ph represents a phenyl group, φ
represents a 1,4-phenylene group, φ' represents a 1,2-phenylene group, and benz represents that adjacent groups on the ring bond to each other to form a condensed benzene ring.

R5R6R7R8M Q-2-1φN(CH3)2ph φN(CH3)2
ph N 1Q-2-2ph pb
ph ph NiQ"-2-3φN(C)R3
)2ph #N(CH3)2ph N i3) represented by the following formula, where M represents a transition metal atom, and Q] is.

represents.

M ship- Q-3-I Ni Q32Q-3-2
Ni Q12 Q-3-3 (OQ32 Q-3-4CuQ12 Q-3-5Pd Q22 4) Here, it is represented by the following formula.

M represents a transition gold atom.

R and R12 are cN, coR'', respectively; 14
15 1BCOOR, C0
Represents NR, R or 5O2R17.

n13 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.

M A Q-4-I Ni 5Q-4
-2Ni S Q-4-4N i C(CN)2Q-
4-5N i C(CN)25) Those represented by the following formula Q-5-I Ni In addition, those described in Japanese Patent Application No. 58-127075.

6) In the thiocatechol chelate coconium represented by the following formula, M represents a transition metal atom such as Ni, Co, Cu, Pd, or Pt.

Further, the benzene ring may have a substituent.

7) Those represented by the following formula, where R18 represents a monovalent group, and the text is θ to 6.

M represents a transition metal atom.

Mouse-R1- Q-7-I Ni H0 Q-7-2Ni CH31 8) Thiobisferrate chelate system represented by the following formula, where M is the same as above, and R65 and R66 represent an alkyl group .

RRM Q-8-1t-C3H17N i Q-8-2t-C3H17CO Note that among the above quencher anions, the above l)
Most preferred are phenylbisdithiol-based ones,
This is because reproduction deterioration due to read light is further reduced and light resistance is extremely high.

Next, specific examples of the photostabilized cyanine dye that is the conjugate used in the present invention will be given.

p+ Q Uni 51
0”I Q-1-8
S2 D"I
Q-1-12S3 D”
2 Q-1-12S 4
D+ l Q-1-
3S5 D+3
Q-1-8S6 D+ 3
Q-1-1257D"4
Q-1-8380+5 Q
-1-839D+6 Q-1-8S
IOD+ 7 Q-1-8Sll
D+ 7 Q-1-2
S 12 0+ 8
Q-1-12S13 D+ 9
Q-112S14
D+ 10 Q-1-12S15
D+ 11 Q
-1-12S18 D+ 3
Q-1-7SIT D+
12 Q-1-12518~
D+ 13 Q-1-13S
19 D◆ 14
Q-1-14520D+ 15
Q-1-15313210" 16
Q-1-1B S+322,
D"l? Q"'l 1
7 S+323 D”
17 Q-1-17S+324
D” 18 Q-1-185
1325D + 18, , Q-11
85IS28 0"l
Q”-1-I S+S27
D+I Q-1-25r
528 D"I
Q-1-135IS2111D”
l Q-1-1451530D”
19 Q-1-85!531
D”20 Q-
1-85! S32 D”20
Q-1-125 beg S33
D”21 Q-1-835334
D÷ 2I Q-1-125533
5D÷2I Q-1-75553
8D◆ 11 Q-1-1235S3
? D◆ 3
Q-1-735S38 D◆ 9Q
-1-855+o D”9
Q-1-211D" 9
Q-1-13120"22 Q
-1-813D ÷ 22 Q'-1
-12140”ll Q-1-81
5D now 11 Q-1~2 [6D ◆ 11
．． Q-1-7170+ 11
Q-1-13180"23
Q-1-819D Ordinance 24/Q-1
-2i0 D"I
Q-1-3 if D÷ 3
Q-3-1i2
D”2 Q-2-1130”4
Q-814D+ 6
Q-7-150”5 Q-5-2 6D÷7 Cl6-1?
D"8 Q-7-18D◆ 9
Q-4-1S80
D'40 Q-1-83811)"
41 Q-1-8382D' 42
Q-1-12 Such a photostabilized cyanine dye which is a conjugate 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 7-ion (An-) is 1-, Br
-, ClO4-, BF4-.

It may be CH3<>S03, Cl(>S03-, 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 particularly N"
(CH3)4,N''(CaH9)4, etc.notetraalkylammoniums are preferred.

5 These quenchers are based on patent application No. 57-IH83.
No. 2, Japanese Patent Application No. 58-183080, etc.

Next, equimolar amounts of the cyanine element and the 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.

The reaction temperature is preferably room temperature to about 90''C.

This operation is then repeated as necessary.

Then, both liquid phases were separated and filtered and dried.

By recrystallizing with DMF-ethanol or the like, the photostabilized cyanine dye can be changed.

In addition to the method described above, 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. 57-1118832.

A specific example of synthesis of the photostabilized cyanine dye which is the conjugate of the present invention is shown in Japanese Patent Application No. 19715/1983.

These preferably indolenine cyanine dyes form a conjugate with these preferably indolenine cyanine dyes. On may be the same dye or may be different.

The amount ratio of the ionic binder to the dye is the dye weight/ratio,
10 to 80 wt%, preferably 20 to 60 wt%
It is.

The optical recording medium of the present invention contains two or more types of at least one of dyes and ionic binders.

The absorption maximum wavelength of at least one of the dyes and/or binders used in combination of two or more of these is between w-40 and w+7 on with respect to the wavelength of the writing light. It's in the intestines.

Further, the maximum reflection wavelength of at least one of the other dyes or conjugates is in the range of input R-40 to 8B+7on+w with respect to the wavelength λk of the reading light (usually the same as the writing light).

8R and input V are usually 830nm to 78nm.
A semiconductor laser beam of 0n and 750n is used.

Therefore, 1. For example, when λ = λw = 830 am, indolenine cyanine dyes or conjugates with a maximum reflection wavelength of λv-40 to 8R+70 nm are used as group A, and a maximum absorption wavelength of λv-40 to 830 am. , +70 ns indolenine-based cyanine dyes or conjugates of Group B include the following.

Group A DI, D2. D3. D4. D9. Dll.

DI2. DI3. DI4. DI5. DI8°D20,
D23, D25, D26, D45.

D49, D50.051, D58, D59.

D60. D64. D65. D66, D67 etc. SL, 32
．． S3. S4, 35. S6゜S7,513,515,3
17,518°S19,320,324,525,32
6°S27, 328, 329. S31. 332°32
7, S38, 339, 340, 341°S44. 34
5. 346. 347, S48.

S50. S51, S52. S53. S58°359
Etc. Group B D5. D6. D7. D8. D9. D.I.O.

Dll, DI4,016,017. DlB.

DI9. D20. D21. D22. D24°D27. D
28. D29. D30. D31.

D32, D33, D34, D35, D3
6.

D37. D38. D39. D43. D44°D47. D
48. D53, D54. D55°D56. D57.
D61. D62. D63 grade S8. S9, 310, 311
, 312° 513.314, 515, 321, 322° 323.324, 325, 330, 331.

S32,533. S34. S35. S36°338, S
39. S40, 341, 342°343. 344
, S45. 346, S47.

348, S49, 354. S55. S56°357, S
58, 359, etc. On the other hand, as an indolenine cyanine dye with a maximum reflection wavelength of λR - 40 to λB + 70 nm when R; λw = 78 On, the above group B is preferable, and As the indolenine cyanine dye of 40 to λ1+70n, the following group C is preferable.

0 group D40, 041.042 etc. S60. S61. Regarding the dyes or conjugates used in combination, such as S62, one may meet the above conditions only at the maximum reflection wavelength, and the other may meet the above conditions only at the maximum absorption wavelength.

Alternatively, both the maximum reflection wavelength and the maximum absorption wavelength may satisfy the above conditions.

Furthermore, under the condition that one reflection maximum wavelength meets the above conditions and the other absorption maximum wavelength meets the above conditions, either one of the reflection maximum wavelength and absorption maximum wavelength meet the above conditions. It may be a match.

In either case, the writing sensitivity and reading S/N ratio are improved.

Two or more of these dyes or conjugates may be used in combination.

Moreover, the ratio is the maximum absorption wavelength λw −40 to λw
The molar ratio of the total amount of dyes or conjugates with +70 nm and the total amount of dyes or conjugates with maximum reflection wavelengths of R-4 to B+70 nm may be about 8=2 to 2:8.

Such two or more types of dyes or conjugates are:

The recording layer may be formed in combination with other dyes as long as the effects of the present invention are not impaired.

The recording layer may contain 4# fat if necessary.

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

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

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

ii) Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, engineered 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.

l) 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 inide. copolymers with vinyl chloride, acrylonitrile-vinyl chloride copolymers, vinyl chloride ether copolymers, ethylene or propylene-hinyl chloride copolymers, ethylene-vinyl acetate copolymers grafted with vinyl chloride, etc.

In this case, the copolymerization ratio can be arbitrary.

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.

V) Polystyrene polymer 1) Styrene copolymer, for example, styrene-acrylonitrile copolymer (As resin), styrene-acrylonitrile-butadiene copolymer (ABS resin).

Styrene-maleic anhydride copolymer (SMAmm), 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.

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.

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

In the above formula, I'lto represents a hydrogen atom or an alkyl group, and R20 represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R10 is
A hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group, is preferred.

Further, R20 may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R20 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, the atomic group represented by the above formula An acrylic resin is formed by forming a homopolymer or copolymer having 11 or 2 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.

xii) Polyvinyl acetate x ma) Vinyl acetate copolymers, such as copolymers with acrylic esters, vinyl ethers, ethylene, vinyl chloride, etc.

The copolymerization ratio may be arbitrary.

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

xvii) 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 ll, nylon 12, and nylon 13, nylon 6/6-6/6-1
O, Nairo y 6/6-6/12, Nai 6
It may also be a polymer such as /6-6/11 or modified nylon in some cases.

Sumima 1ii) Polyester For example, with various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipine acid, and sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid. , condensates and cocondensates with glycols such as ethylene 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 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 can also be suitably used.

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

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

x-ri 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.

! Item X) Cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,
Various esters and ethers of cellulose, such as methylcellulose and ethylhydroxyethylcellulose, or mixtures thereof.

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

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

Li, Zn, Mg salts, etc.

1x Ma) Ketone resin For example, a condensate of a cyclic ketone such as cyclohexanone or acetophenone and formaldehyde.

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

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

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

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

The weight ratio of such resin and the above-mentioned dye is usually 1.
The layers are deposited in a wide range of quantity ratios of 0.1-100.

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 about 0.03 to 2 μm.

The thickness of the recording layer is 0.04 to 0.12 #Lm.

In particular, it is preferably 0.05 to 0.08 #Lm.

Absorption/reflection q at 0.04uLm, especially below 0.03pm
Both are small, and it is not possible to obtain high write sensitivity and playback sensitivity.

If it is 0.12 gm or more, the pre-group will be buried, making it difficult to obtain a tracking signal. Also,
Bit not easy to form.

Writing sensitivity decreases.

In addition, such a recording layer may contain other additives, such as other pigments, rheolibomers without other polymers, various materials, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and oxidizing agents. An inhibitor and a crosslinking agent may also be included.

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 isobutyl ketone, and cyclohexanone, and butyl acetate.

Ester types such as vinegar butyethyl, carpitol acetate, butyl carpitol acetate, ether types such as methyl cellosolve and ethyl cellosolve, and aromatic types such as toluene and xylene.

Alkyl halides such as dichloroethane, alcohols, 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.

It may be made of 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 groove-free substrate without grooves such as polymethyl methacrylate, acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyether sulfone, methylpentene polymer, etc. is suitable.

It is preferable to form a base layer on these bases in order to improve solvent resistance 1, wettability, surface tension, thermal conductivity, etc. Materials for the base layer include St, Ti, etc.
, Ai, 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 below or below the recording layer.

The medium of the present invention may have a recording layer as described in -1- on one surface of such a substrate, or may have a recording layer on both sides. - using two coated recording layers, and facing them with a predetermined gap, with the recording layers facing each other;
You can also seal it tightly to prevent dust and scratches.

(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, the dye and the like in the recording layer melt due to heat generation, 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 usually performed through the substrate from the substrate side.

Then, the pits formed in the --t4 recording layer can be erased with light or heat, and rewriting can be performed.

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 present invention, writing sensitivity is significantly improved.

In addition, the reflectance is improved and the readout S/N is significantly improved.

(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 pigmentation and quencher Q shown in Table 1 below are shown in Table 1.
Dissolve this in a predetermined solvent and apply a titanium chelate compound (T-50 (manufactured by Nippon Soda Co., Ltd.)).
Diameter 30 with a base layer (0, O1#L) after hydrolysis
Various media were obtained by coating a 0.06 JL layer on an acrylic disk substrate (c).

In this case, the absorption maximum wavelength and reflection maximum wavelength of each dye are as follows.

Also, (entering = entering R) -40 = 790 nm.

(λ0−R)+70=890 nm.

D2 795
865D Io 8,35
905D 5 8
40 9 l OD I3
790 860 While rotating each medium thus prepared at 900 rp+++, a semiconductor laser (830 nm) or He
Writing was performed from the back side of the substrate using a -Ne laser.

Sensitivity was measured using the light-condensing layer.

Sensitivity is the minimum pulse width (ns) that can change the erasure ratio to 1.4.
is the reciprocal of

On the other hand, writing was performed at a condensing unit output of 10 mW and a frequency of 2 MHz.

Next, the reflected light from the semiconductor laser (830 Dm) was detected at the condensing part, and the C/N ratio was measured at a band width of 30 KHz using a spectrum analyzer manufactured by Hewlett-Paracard.

Further, the reflectance from the back side of the substrate was measured using a laser readout beam of 1 mW.

These results are shown in Table 1.

be· hand]

Claims (1)

[Claims] (1) An optical recording medium having a recording layer containing a dye and an ionic combination of a dye cation and a quencher anion on a substrate, wherein at least one of the dye and the dye cation is an indolenine cyanine dye, or its cation, and contains two or more types of at least one of the dye and the ionic bond, and the maximum absorption wavelength of at least one of the dye or the ionic bond is -40 nm to +70 nm of the wavelength of the writing light. An optical recording medium characterized in that the maximum reflection wavelength of at least one dye or ionic binder is -40 nm to +70 nm of the wavelength of readout light.