JPS60205841A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve sensitivity and light resistance by providing a recording layer contg. >=2 kinds of cyanine dyes one of which is an indolenine dye and has absorption max. near writing light and the dye having reflection max. near reading-out light in combination. CONSTITUTION:An optical recording layer contg. >=2 kinds of cyanine dyes, >=1 kinds of which are more particularly preferably the dye expressed by the formula (Z, Z' are the atom group necessary for completing an indolenine ring, benzoindolenine ring or dibenzoindolenine ring, R1, R'1 are (substd.) alkyl, aryl or alkenyl, X<-> is an acidic anion, m is 0 or 1) in such combinations that the absorption max. wavelength of >=1 kinds thereof is -40nm-+70nm of writing light and the reflection max. wavelength of >=1 kinds thereof is -40nm- +70nm of reading-out light is formed. A quencher is further incorporated into the recoding layer and the recording medium which permits writing and reading out from the substrate side, is not laminated with a reflecting layer on the recording layer, permits writing and reading out with high sensitivity and has excellent light resistance is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Background of the Invention Field of the Invention The present invention relates to optical recording media, particularly heat mode optical recording media.

First I T technology light record #i1. The medium is Of type and writing or reading 1
Since the optical recording medium is non-contact, the recording medium does not deteriorate due to wear and tear, 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 Mort optical recording medium is an optical recording medium that uses recording light as an optical recording medium. Then, a part of the medium is melted or removed using recording light such as a laser, forming a small hole called a pit, and writing is written on it. Information is recorded through this pit, and this pit is read out using light. There is a pit-forming type that performs detection and reading.

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

However, in 2013, because the T'e thread material was harmful, and it was necessary to make it more sensitive and to lower the manufacturing cost, the dye was changed to a Te-based one, and the dye was changed to T. An increasing number of proposals and reports are being made about media using recording layers made of organic materials.
ipson and C, R, Jones, J, Vac.
, Sci.

Technol,, +8 (1) 105 ('19
B+) ] and metal phthalocyanine dyes (JP-A-57-
82094, No. 57-82085).

An example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-open No. 88785/1983) is also discussed.

All of these are based on a thin recording layer formed by cutting a dye, and are not much different from the production system of IIIjm.

However, the reflectance of the (g-element deposited film) to the 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 has a large S/N ratio. I can't.

In addition, if a transparent substrate with a recording layer is integrated with the recording layer facing each other in a so-called Air Santoy/Sochi structure, and writing and reading are performed through the substrate, the writing sensitivity will be reduced. Although it is advantageous in that the recording layer can be protected without scratching and the recording density can be increased, such a recording and reproducing method is also not possible with dye cutting IIQ.

This is because 1. Normal transparent horizontal resin substrates have a certain refractive index (1.5 for polymethyl methacrylate).
In addition, the surface reflectance is somewhat high (4%), and the reflectance through the substrate of the recording layer is about 60% or less in polymethyl methacrylate, for example, so recording with only a low reflectance2. This is because it cannot be detected in the layers.

In order to improve the readout S/N ratio of a recording layer made of a dye layer, a M blue reflection such as an A pattern is usually interposed between the substrate and the recording layer.

In this case, each of the IM reflections 11 has a higher reflectance and the S/
The purpose is to improve the N ratio, and the reflective film is exposed due to the formation of bints, increasing the number of misfires, or in some cases, the reflective film is removed to reduce the anti-Qt m. Because of the nature of the material, recording and reproducing through the substrate is not possible.

Similarly, in No. 55-181890, IR-13
A recording layer consisting of two dyes (manufactured by Kota νRI Co., Ltd.) and polyvinyl acetate, and 1.1
'-diethyl-2.2'-tricarbocyanine iotide and nitrocellulose;
s.

Lett, 39 (9) 71B (1981) describes a method in which a recording layer consisting of one dye and a resin, such as a recording layer consisting of 3,3'-diethyl-12-acetylthiatetrasulfocyanine and polyvinyl acetate, is formed by a coating method. The layered media is disclosed.

However, even in these cases, a reflective layer is required between the substrate and the recording layer, making it impossible to record and reproduce data from the back side of the substrate, which has the same drawback as the case of dye M 119. In this way, in order to realize a medium having a recording layer made of an organic material, which is capable of recording and reproducing through the substrate and has compatibility with a medium having a recording layer made of a Te-based material, it is necessary to The organic material itself needs to exhibit high reflectance.

However, 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 vanadyl phthalocyanine 11@ exhibits slightly high reflectance (P, Kivits, etal,...
'App1. Phys, Part A 2B (2
) 101 (11181), JP-A-55-11703
3], but it is probably Noboru! This is probably due to the high temperature 1@, but the writing sensitivity is low.

It has also been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes exhibit high reflectance [Yamaki et al., 27th Japan Society of Applied Physics (f4'J ITI-P
-9 (1980)) Saleseo'J,: Shinitoto〈Although this proposal was made in JP-A No. 58-1127H, these dyes are the most soluble in solvents, especially when they are applied as a coating. It is small, easily crystallized, and is extremely unstable against readout light, resulting in immediate bleaching.

It doesn't work in practical terms.

In view of these circumstances, the inventors first developed an indolenine-based cyanine pigment that has high solubility in solvents, little crystallization, is thermally stable, and has a high reflectance. is proposed as a single layer 119 (#
Intercondylar No. 57-134387, Intercondylar 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. 57-182589, Patent Application No. 57-17777111, 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.
(Japanese Patent Application No. 57-188832, No. 57-168048, etc.)

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

II. OBJECTS OF THE INVENTION The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium having a recording layer containing an indolenine-based cyanine dye, which has further improved writing sensitivity. It's about doing.

Such objects are achieved by the invention described below.

That is, the present invention provides an optical recording medium having a recording layer made of a dye or a composition of dyes on a substrate, wherein the dye consists of two or more types of cyanine dyes, and at least one of the dyes is an indolenine-based cyanine dye. pigment, and at least 1
The maximum absorption wavelength of the two dyes is 40n, which is one wavelength of the writing light.
■~+70ns, and the reflection maximum wavelength of at least one dye is one wavelength of the readout light, 40n~+7On.
This is an optical recording medium characterized by being a phoenix.

■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 two or more types of cyanine dyes.

Among the two or more types of cyanine dyes in the present invention, at least one of them is an indolenine cyanine dye.

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 readout S/N ratio is represented by the following general formula CI).

General formula CI) (In the above general formula (I), Z and Z' are each an indolenine ring.

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

These rings completed by Z (hereinafter referred to as Φ+) and rings completed by Z' (hereinafter referred to as q?) may be the same or different, but are usually the same, and these rings have various Substituents are attached to these Φ and ψ as the skeletal rings below.

Notation [ΦI] ~ [Φ■] and [! ■〕〜〔ψIV）
It is preferable that it be as shown in 1゛Φ1ll)
f'RA)q ■ R+'i'RII"I Q 1':'PIII) (Ra')++R+'1\/' In these various layers, + is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group.

A certain R + -, R' bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of + carbon atoms.

Also, if this vote further has the position @X,
Examples of substituents include sulfonic acid group, alkylcarbonyloxy group, alkylamide group, alkylsulfonamide group, alkoxycarbonylhemoyl group, alkylsulfamoyl group, Suikoku J, (,
It may be a carboxy group, a halogen atom, or the like.

Among these, particularly preferred are non-MAI alkyl groups, alkylcarbonyloxy groups, and alkyl groups substituted with water S Ac s.

Furthermore, at the 3-position of the indolenine ring, two substituents u.
、． In cases where it is preferred that R3, R2', R3' be bonded, the two substituents R2, R3,...
R2' and R3' are preferably an alkyl group or an aryl group, and among these, carbon atoms *i or 2. It is preferable that @ be an unsubstituted alkyl group, while Φ+ and ! Further, another substituent RA or Ra' may be bonded to a predetermined position in the group represented by . Examples of such substituents include alkyl groups, aryl groups, atomic ring residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, and aryloxycarbonyl groups. Carbonyl group, alkylcarbonyloxylsulfonyloxy group, alkylamido group, aryl-furamide group, alkylcarbamoyllylcarbamoyl group Alkylamino group, arylamino group Carboxylic acid group, alkylsulfonylsulfonamide group, arylsulfonamide K IAc Alkyl sulfur moyl group, arylsulf 7 moyl group,
Various substituted nors may be used, such as cyano, 21 and 21 groups.

And the number of these permutations (p.q.r.

s. t) is usually 0 or 1 to 411I8:. In addition, p. Q. r. S. When t is 2 or more, the plurality of R4 and R11' may be different from each other.The cyanine dye cation has a condensed or non-condensed indolenine apex, and its solubility and size vary. 1? It has excellent flexibility and stability, and exhibits extremely high reflexivity.

On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetracarbocyanine dye, but especially in the formula % formula % formula (LI) CH=CH-CH=CH-C= CH-CH=CH-CH
Formula C L II ) CH=CH-CH=C-CH=C
H-CH formula (LIX) C ■ Here, Y' represents a hydrogen atom or a monovalent atom.
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, a diphenylamino group, a methylphenylamino group,
Morpholino group, imitasilidine group, alkylcarbonyloxy group such as ethoxycarbonylpiperazine group, alkylthio group such as methylthio group, cyano group, nitronol, Br. 9. Preferably, J and R9 each represent a halogen atom such as Cl, or a waterwheel atom or a lower alkyl group such as a methyl group. is 0 or l.

Furthermore, X- is an anion, preferably CH3-Q
-303-, CfL-eJ5 303-, etc., m is O or l, but m is 0>, g
Usually, R1 of Φ has a single charge and becomes an inner salt.Next, we will give examples of uninvented indolenine-like cyanine dyes. Naitsu 9 (g) I'm sorry 'P R+. R+ Crab” giant Dl [Φ
I) CH3 CH3 O2 ((RII) CH3 CH2 O 3 (O I ) C2 H40H CH3O4
(OI) ((CH2)3SO3- CH3(CH!
)3 SO3 - Na'' D5 (tDll) CH3 CH3 O6 C ΦIII) , ('CH2) 3 503
2 CH3 (CH2 )3 303 Na1D7 (ΦIll) CH2 CH2 0H CH3O
8 (Oll) (CH2 )2 0COCH3 C
H3O9 (ΦLL[) (CH2)20COCH3
CH3DIG ['OLII) CH3 CH3DIl
(OILI) CH3 ,, CH3O12 [ΦI
) c18H37 CH3013 (ΦI) CAHq
CH3 old 4 [Φ engineering] c8H16ococH5cH3015
((!II) C7H,4CH,, O.H CH3Ra
L' Y fl X.

- (Lll) HI (L+ri 'H Cloll - '(Llll) H Br - (L II) H - CLII) H CIOs - (Lll) H - (Lll) H C9. Oa − (Lll) H Br (LLL+) −N (Co Hh) 2 0 cl
Oa- (Lll) H CQOa- (Llll) -N(C6HR)2 0 CJ10
4- (Lll) H 1 (L II ) H' C I O a (Lllll)
-N (C6H5)2 0 ClO2- (Lll)
' H I L personμ <1, 9 R + engineering 1 uLLll IB
(ΦII) C8H, 7CH3037 (ΦIII) C
8H, □ CH3037 (ΦIII) CHC00CH
CH371425 D20 [ΦIII] C4H8CH3037 [Φha
) c 1s ii a 7c H3D22 (ΦI
II) C2H8CH3037 037 [Φ engineering] C3H160COCH3CH3037
[Φwork] C8H17C2Hh D26 [ΦI] C7H15C2H5D27 [Φ
II) CI. H34C00CH3CH3D28 (Φ
II) CA H-+a CH20COCH3CH3D
28 [ΦII) C+p to H1 CH3 and soil L
Y-also -in- -(Lll) HC sentence OL+ -(L'll) H- -(LI[) HBFi (Lllll) -N (Co Hh)2 0 C intersection 04
- (Lll,) HC 04 - (Lll) HCQOA - (LII) HI (LIII) -N (Ce Hh) 20 I-[LX
I) H knee (Lll) Hr - (Lll) HC exchange OII Ikio Hitoshi Menko presentation R1 work 1 work Lm work 11030 CΦ
Old C7H1, C00CH3C2Hl.

031' (ΦIII) C7H1, CH20HCH3
037 [Φ111) C7H1, CH20COC2)
15CH3D33 [Φ111] CHCOOC2H5
CH3734 D34 [Φ■] C17H35CH3037 [ΦII
I) C7H15C2HP.

D3B (ΦIV) CH3CH3 037 (OIV') CH3CH3 037 (ΦIV) CA MQ CH3038 (OIV
] (CH2)2 0COCI(3CH3037(Φ1
) CHCHOCOCH3CH32 D41 [ΦI) CH2CH20HCH3037 [Φ
1 Old CHa CH3 D43 [ΦI] CqHh CH35-CD44 [
ΦI) C2HFI CH35-CD45 [ΦI)
C2Hli CH35-CRa L1E1-(Lll) HCl06-(Lll) HC-04-(Lll), HI-(Lllll)-N(CeHs)20, 1-(
LIV) HOI -(Lll) H1 -(Lll) H1 -(Lll) H0 Sen04 -CL II) HC9,OLl -(Lll) H1 -(Lll) HC04 - (Lll) HBr -(LVI) Br Cl0s sH5sO2 (LVI) Br l Ie H5502
(LIII) Cl l Cl04s Hh SO2(
Lll[) 0 sentences OI1 Yin +, V R+, R+ Red Koan -Le D46 [ΦI) C2HF, CH35
-Cs H530X047 (OI) C2H5CH3
5-C6HRSo:D48 [ΦI) C2Hh C
1(35-Co Hh SO:D49 (OI) C2
Hs CH35-Co H55oXD50 (ΦI)
C2Hs CH35-Cs Hs So:D51 [
ΦI) CH3CH35Cue HFI 50sD5
2 [ΦI) CH3CH35-Cs H5SO:D5
3 [ΦI) n-C11HQ CH35-C6HF
I 5OHD54 [ΦI) n-C6H13CH35-
Cs HF, So:D55 [ΦI) (+, 'CH2
) a 503 CH35-Ce HFI 30: (CH
2) a 503 H 2SO [OI) C2Hh CH35-Cr, Hh S
O:D57 [ΦI] CH3CH35-Ce Hs
So: D58 [ΦI) C2HF, CH35~C6
HRC0D59 [ΦI] C2H5CH35-C6H
F, C0DEIO ((DI) C2HF, H35-C
o H6C0L Y-To -Niichi (LIII) C Stand OC83C6) 1,5O3 (LV
I) C1l BF4 (LVI) C1l Cl0a ・(LVI) Cl OI ・[LvI)C! LOCH3C6H4S03・ (LV
I) Cl OCuba ・ (LVI) Cl OCuba ・ (LV[) 0 sentences I C9,041 (LVI)
C1I CuO2, (LVI) C1-1 [LVI) N-=C=C;-CMl-1 (LI TV
-C-C-C: N l - (Llll) C111I (Llll) Br l l (Lm) C1I C9,0a Colored Man Menyo f R+, R+, Lm211 - Presentation D
61 [ΦI) C2Hf1 CH35-C6H et al.
D62 [ΦI) C2HRCH35-Co Hh C
D63 [ΦI) C2) [5' CH35-CeHh
CD64 [ΦI) C2Hh CH35-C6HR (
D65 [ΦI) ct-t3 CH3CH3C0D6
B [ΦI] CH3CH3CH3C0D67 [ΦI
) C2Ha OCOCH3CH3CH3C0 1
- Also X O(LIII) 0 sentences t CH3C6)+4So30
(LVI) CQ I CJJO40 (LVI) C
gL I I O [Lv ■] C9, OC ■ 3C6H9S03 (Lll)
HCQOa (Lll)' HI (Lll) H' I Two or more of these indolenine-based cyanine dyes may be used or may be used in combination with other cyanine dyes. There are no particular restrictions on dyes,
Various types can be used.

However, the cyanine dye 17 is preferably one represented by general formula (I) or (II).

General formula (I) Φ1-L, = l'CX-).

General formula 1: II) Φ=L−ψ (X−) □ In the general formulas CI) and (11), Φ is a thiazole ring, an oxazole point, and selenazole to which an aromatic ring may be fused, respectively. ff+ represents imidazole IC or a 172-valent residue of a pyridine ring, and ψ represents thiazole I to which an aromatic ring may be fused, respectively.
I1. Divalent to monovalent oxazole former, selenazole ring, imidazole ring, pyridine II or indolenine ring
L represents a polymethine linking group for forming a cyanine dye, Q- represents an acid anion, and m is O or l.

In the isomerized structures represented by general formulas (I) and CII), Φ is a thiazole ring or an oxazole ring to which an aromatic ring, such as a benzene ring, naphthalene ring, phenanthrene ring, or quinoxaline ring, may be fused. , selenazole ring, imidazole 10, monovalent to divalent JIj;, represents a group of pyridine 10.

Also,! is a divalent to monovalent ring such as a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, a pyridine ring, an indolenine ring to which an aromatic ring such as benzene 1a, naphthalene ring, phenanthrene ring, quinoxaline ring, etc. may be condensed. represents the residue of

These Φ and! may be the same ring or different rings.

Nao, Φ10 and! ◆, the poisonous atom in the ring has a + charge! and Φ are those in which the air atoms in the ring are neutral.

These Φ and! The skeletal ring of the following formula [Φ′
It is preferable that they are those shown by (2) to [Φ'K] and [ψ'I) to [ψ' double].

In addition, in the do-ki, Φ and ! The structure of is represented by the general formula ['I
) in the form of Φ0− and weight=.

1 (Φ'IV) (RA)q (RA) q 1 R1'(y'B) (Ra '') q R+' (Raiq) a group R, R (R
R') is a substituted position or 11 1bi 11 is an unsubstituted alkyl group, aryl group, alkenyl group, especially an alkyl group. There are no particular restrictions on atomic mosquitoes.

In addition, when this group further has a substituent #l) group, examples of the substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamido group, an alkylsulfonamidorphonyl group, an alkylamino group, an alkylcarbonyloxy group, and an alkylcarbonyloxy group. Moyl group, alkylsulfamoyl jA. It may be any of a hydroxyl group, a carboxy group, a halogen atom, etc.

moreover,! When the ring of (ψ10) is a fused or non-fused indolenine ring (formula [ψ″ engineering] to [ψ′IV)], the same two substitutions '&R2' as above are present at the 3rd position, R
It is preferable that 3' be bonded.

On the other hand, Φ and! At a given position in the ring represented by
Furthermore, the other substituents Ra and Rd' described above may be bonded.

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

s, t) are usually O or about 1 to 4. In addition, when ptq, r, s, and t are 2 or more, multiple R
a, R4' are X even if they are very different.

On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetoxy-y□p rubocyanine dye, but especially those of the formulas (Ll) to (LIX)
It is preferable that it is either.

Here, Y represents a hydrogen atom or a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamine groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxyl groups. Preferred examples include a di-substituted amine group such as a biverazine group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as methylthiol, a cyano group, a nitro group, and a halogen atom such as Br and CQ.

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.

Further, X- is an anion as above, m is O or l, and m is 0.

Specific examples are given below.

餉l　L"　Gen-" ``工　Gen-'' is shi.

D'l (%I/'V) 02 HF, -4-C
H:D' 2 C'? 'V) CH3-4-CH:D
' 3 C9' Vl) C2R5--〇' 4 ('
P'Vl) C2Hs = 5-CID' 5 ('i
"VI] C2HF, -5-QCD' 6 (?'
Vl) C2HFI-5-oC:D' 7 ('P'
VI) C2HF, -D'8 (!'Vl) CH
-- 5 D'9 1. :! 'V[) C,, R5--D'lO(
'! "Vl) CR 25-- D'll ('P'VI) C2H3--D'12 [
ψ'l C2H5-- D' +3 ('i/' Vl) C2R5-D'14
('?'■) (CH) OCOCH3--3 D'15 ('l/'Vl) CH2CH20H-5-
CID' +8 C%F'■) C2H5--L Y-
To -X- 1(Lll) H1 1(Lll) 'HI (Lll) HBr (Lllll) -N(C6'H5)2 0 Br(3(
Ill) HC)13C61(4SO3(3(Lll)
H'Br (Lll) HBr (LI) HBr (Lll) CH3Br (LV) HI Br (LV), HOBr (Lll)' N, (C6R5) 2. 0 08
3C, H2SO4(L II ) H”C) I3C:
, H, 5O3 (Lll) HBr Risa Kuchi Suke-'' Engineering Beni-Anal Beni D'17 ('P'lX) C21 (5--D'18
fJ"IX) C2H5'--D'lEl(%F'
lX) C2H5--D'20 (%F'X) C2H
5--D'21[:ψ'X[) CH2CH20H-D
'22(ψ'Xl['I C,, H5-D'23(ψ'
)G[)(CH2)30COCH3--D'24 (
! ) 02H5- D'25 (ψ') CH2CH2CH2So3H---
D'26 (to ψ') C2H5- D'2? Cψ' store) C,, H5- D'2B [ψ' double] C2H5- D' 29 C%ir' Vl) C8H17-4-C
'HD'30 (%ir' Vl) Cl8H3゜-D
'31 (ψ'vl'3C8H17--↓-"=
Yu upper (Lll) 'HBr (Lllll) &. . . 21-t5. CfLO+(
LIII) OCH31I (L II ) HI (L[[) HBr (L [1) I(1 (L II ) = 0゜0OC2H!1 ” Cross 06 (
L II ) H' (LII[) N (', Ce H5)2 0 C intersection 0
4(Llll) -N(C6HF,)2 0 I(Ll
() HBr (Lll) H, Br + [Lll) H■ (Lllll) -N(CsHh)20 Br(L II
) HC exchange C) + Susashi] Phantom-"Eng 7-" Yue D'321"Vl) 08H, 7-5-(ID'33(
%P'VI) C,8H37-5-CID' 34 (
! 'Vl) C,,HI3-,. 5-OCI-QC
I D'35(ψ' V[) C8H,? -5-OCID'
3B1J"Vl) C8H,?-5-CD'37 ('
P' Vl) C,8H3□-5-CD'38(!'V
l) C8H,7--D' 39 (%P' Vl)
C8H,7-D'40(ψ'vr) Cl8H37'
-5-CD'41(ψ'Vl) C,, H37-5-C
D'42 C'f' Vl) C8H17-D' 43
[ψ′V[) CRHI3. -D' 44 ('P'
Vl) C3H1゜-D'45Cψ'■) C3H1□
.

0'4B(v' ■) 018H3゜ -Rainbow Engineering and
Engineering: (Llll) -N'(Cs H5)2 0 Cview041(L II ) H' (3(Lll) H1 3 (3(LIV)-〇1 1 (Lu[) -N(C6HF,)2 0 Br11
j (Lllll) -N (COH5)2 0 Br(
Lll) H1 sentence (L II) H0H3C6H, SO3 look (L
ll) H, G view C6) 1,5o3 (LV) HOI [:LVl[) -' (LVl[) HBr (L II ) HC) 13C6) + 45O3 ri(t)
``Suke-''Kou Kamimi''Yu Beni D'4? ('l”
■] C13H2□ -D'48 ('P' Vll)
C13H2□ -D'48 ('P' ■) C3H
1゜ --D'50 (ψ'■) C8H17- D' 51 ('!'' ■] Cl8H37-D'52
[ψ′■] C3H1゜ −D' 53 ('l”
■) Cl8H3゜ -D'54(ψ'k) C8H1
7- D'55 (ψ' cutting) C3H1゜ - D' 58 ('P' cutting) Cgl (I7 -ri, '5
7 (ψ'■] C13H2□ -5-C sentence '58 [ju' cut) C8H,. -D'58 ('l' cut) Cl8
H3゜ --D' 80 1" cave) C3H1? --
D' + 31C double) C8H, □ --L "bifurcated" L (Lll) ) i' Br (Lll) HBr (Lllll) OCH31 (L +111) H'0H3C6H4SO3 (L
II') HCH3C6H,5O3(Lll+) −
N (C6H5) 2 0 0H308H4SO3(L
ll) HBr (L II ) H1 (L 11 ) HI (Lug) -N (C6H5)2 0 l1r(Lu
l) -N(CaH2)20Br[LvII)HB
r (L■) HBr Iiōtsugu Menkobo Hitoshi-Ju Gen-"YuD'82Cju' V) C3H1□ -D' 63 (
'P' ■) C3H1-7-D'64 (ψ' store) C
3H1゜ - CH2=CHCH2 D'86 (ψ' Isao) CH2=CHCH2-D'87
(Shige' Isao) CH2=CH (:H2-D'881゛ψ
' Circumference) CH2=CHCH2-D' 68 (ψ' Reservoir) CH2=CHCH2-D' 70 [! ′ Kaoru)
CH2=CHCH2-D' 72, (ψ' history) C
6H5-D' 73 (ψ' Isao) C2H,0CR3-
D′? 4 (ψ' circumference) CH2=CHCH2-D'?
5 ('I' Ru) C2HaOCH3-Red Length Y
See Knee (LVII) HBr (LVII) HBr -]'L■) HBr -C6HRCo-V' I (L■) HC)13C6
H,,SO3-(L Vllll) Hc)13c6)1
, 5o35-0 sentence [L■) HCH3c 6 H4S
o 35-C6H5302 (L ■) Hctt3c6t
+, 5o35-C6Hs Co (L HC3LOs
(5-NO2(LVI[) HcH3c6H4so36
-C 5-C6H,, S02 (L■) HC intersection 04-NO2 5-Ce H2SO4 (L■) Hco3c6H,5o
35-NO2LL■) H[J3C6H4SO35-N
O2' (:L■) HCD, 0s-5-Ce H2S
O4 (L ■〕HCH3C6H4S03 color〕(Mukao,'
i' R+, R+ Group 1 = Civil D' 7B ('P'
Jun) C2Ha OCH3-D'? ? (ψ′) C
H2CHCH2-[ψ'HON]ψ' Quotient-(CH2)4
503 -R4L Y-Also -X- b-Cs HFI 'SO2CL ■) HC Standing OI1MC
1,' (LVII) HCl0s5-C6H,,S0
2-'i'' In addition, these cyanine dyes can be easily synthesized according to the method described in Nitrogen-Containing Heterocyclic Compounds I432 Pegoji et al., published by Dai Organic Chemistry ('Kyokusho Shoten).

That is, first, the corresponding Φ"-CH3, (Φ" is 111
represents a ring corresponding to the notation Φ. ) with an excess of R,I (R
, is an alkyl group or an aryl group),
R1 is introduced into the nitrogen atom in Φ" to obtain Φ-CH3I-. Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or 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 condensate of these cyanine dyes.

For example, single or co-condensates of the above dyes having one or more functional groups such as -OH, -COOH, -3O3H, etc., or with these, 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 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, amine alcohols, enols) those with active hydrogen compounds, etc. as ligands)
, titanium, zircon, aluminum, etc. Furthermore, -0HX, -0COR groups, 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 O
It is capable of r.

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 cyanine dye may be combined with m llll'l.

In such cases, a resin having a specified group is used, and the side chains of the resin are added with the necessary components by condensation reaction, transesterification reaction, or crosslinking, similar to the case of φ coalescence described above. Cyanine dyes are linked via a spacer component, etc., depending on the situation.

Cyanine dyes used in combination of two or more of these are:
The absorption maximum wavelength of at least one of the cyanine dyes is between V-40 and W+ with respect to the wavelength of the writing light.
70 nm.

In addition, at least one of the other cyanine dyes has a maximum reflection wavelength in the wavelength range P-40 to λ+++70 nm with respect to the wavelength P of the read light (usually the same as the write light).

The input R and input V are usually between 830 nm and 78 nm.
Semiconductor laser beams of 0 nm and 750 nm are used.

Therefore, for example, when input p = input w = 830 nm, the reflection maximum wavelength is input -40 to input P + 70 nm. The indolenine-based cyanine pigments included in Group B include the following.

Group A 01.02. D3. D4. D9. Dll.

D12. D13. D14. D15. D18゜020,D
23. D25. D26. D45°D49. 050.0
51, D58. D59.

D60. D64. D65. , D66, D67 equal group D5. D6. D7. D8. D9. Dlo.

Dll, D14. D16. D17. D18°D19. D
20. D21. D22. D24°D27. D28. D2
9. D30. D31.

D32. D33. D34. D35. D36°D37. D
38. D39. D43. D44°D47. D48. D5
3. D54. D55°D56. D57. D61, D6
2. For other cyanine series such as D63, the following is true.

A group D' 1. D'2. D'12. D'13°D'
15. D' 18. D'20.0'25°D' 26
．． D'29. D'31.0'32°D' 33.
D' 3.7. D', 45. D'75°D'76.
0' 77 Pier B group D"3.0'4.D'5.D'6.D'7゜D'8.D'9.D' lo, D'11゜D"
14.0'16.0'17.0'18°0' 1
9. D'22. D'23. D'24°D' 27. D'
28. D'30.0'31°0' 33. D'34
．． D'35. D'36°D'38. D'39. D'
40.0'41.

D'42. D'43. D'44. D'46°D'
47. D'48. D'49. D'53゜D' 5
5. D'56. D' 57. D' 5g.

D'59, etc. On the other hand, as a cyanine dye whose reflection maximum wavelength is ρ-40 to λρ+7Or+a+ when input ρ=input w=780na, the above-mentioned group B is good, and the maximum reflection wavelength is 40
As the indolenine cyanine dye having a wavelength of +70 nm, Group C is preferable.

Group 0 D40. D41. D42 etc. For cyanine dyes, it is as described above.

0 group D' 21, D'44.0' 50, D' 51
.

D'54. D'60, D'61, D'62
゜D' 63. D' 64. D' 65. D'66°D' 67, D'68.0' 69. D' 70°D
'71, D'72. D'' 73, D'74゜D'78.0' 79, etc. Regarding the cyanine dyes used in 11F, one of the cyanine dyes meets the above conditions only at the reflection maximum wavelength, and the other only the maximum reflection wavelength meets the above conditions. It may match.

Alternatively, both of them meet the above conditions for both maximum reflection wavelength and maximum absorption wavelength, and one of them meets the above conditions for both maximum reflection wavelength and maximum absorption wavelength. It may be.

In either case, sensitivity is improved.

Furthermore, at least one of the cyanine dyes may be an indolenine dye, and its maximum wavelength may meet the above conditions even if either reflection or absorption meets the above conditions.

Each of these dyes may be used in combination of two or more or any number of types.

In addition, the ratio is: absorption maximum wave input - -40 ~ input, +7
Total amount of dyes of 0ni and reflection thick wavelength input R-4 to input ρ+
The total amount of the 70 nm dye may be about 8:2 to 2:8 in terms of molar ratio.

Two or more of these cyanine dyes may be combined with other dyes to form the recording layer within a range that does not impair the effects of the present invention.

The recording layer may contain resin if necessary.

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

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

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

11) Examples of polyolefin copolymers include ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-prohylene copolymer, enalene-butene-1 copolymer , ethylene-maleic anhydride copolymer, ethylene propylene terpolymer (EPT), etc.

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

111) 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 miniaturized vinyl copolymer, acrylonitrile-vinyl chloride copolymer, vinyl chloride ether copolymer,
Ethylene or propylene-vinyl chloride copolymer, or ethylene-vinyl acetate copolymer with vinyl chloride graft polymerized.

In this case, the copolymerization ratio can be arbitrary.

1v) Vinyritine filtrate copolymer 71 Vinylidene chloride-vinyl chloride copolymer, hnyritene chloride-vinyl chloride-acrylonitrile copolymer, and vinylidene-vinylidene-vinylidene-halogenide copolymer.

In this case, the copolymerization ratio can be set arbitrarily.

V) Polystyrene vi) Styrene copolymers, such as styrene-acrylonitrile copolymers (A S
resin), styrene-acrylonitrile-butadiene copolymer (AB Sm IIM), 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 set arbitrarily.

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.

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

ix) Terpene tree 11 or picolite analogy is α-
Terpene resin, which is a polymer of limonene obtained from pinene, and picolite obtained from β-pinene.

X) Acrylic resin In particular, those containing an atomic group represented by the -t notation are preferred.

C-0R2I1 1 In the above formula, RIn represents a hydrogen atom or an alkyl group, and l(n represents a substituted or unsubstituted alkyl group. In this case, in the above formula, RIn represents a hydrogen atom or a carbon atom It is preferably a lower alkyl group of 1 to 4, particularly a hydrogen atom or a methyl group.

Further, Rη may be a substituted or unsubstituted alkyl group, but it is preferable that the number of atoms per atom of the alkyl group is 1 to 8, and when R is a substituted alkyl group, Substituents for alkyl groups include hydroxyl group, )\
It is preferably a rogene atom or an amino group (particularly a dialkylamino group).

Such an atomic group represented by the formula "-" may form a copolymer with other repeating atomic groups to form various acrylic trees 11h, or it is usually used in the above formula. The acrylic resin is formed by forming a homopolymer or copolymer having one or more of the atomic groups shown as repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer Examples include acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-hynyritene chloride copolymer, acrylonitrile-vinylpyridine copolymer acrylonitrile-butyl methacrylate copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be adjusted as desired.

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

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

The copolymerization ratio may be arbitrary.

xvi) Polyvinyl ethers, such as polyvinyl methyl ether, polyvinyl methyl ether, polyvinyl methyl ether.

X My ii) Polyamide In this case, the polyamides include nylon 6, nylon 6-6, nylon 6-1O, nylon 6-12, nylon 9, nylon 11, nylon 12. In addition to normal homonylon such as nylon 13, nylon 6/6-6/6-1
0, nylon 6/6-6/12, nylon 6/6-6/
It may also be a polymer such as 11 or modified nylon in some cases.

X-Ma 111) Polyesters For example, IIM rib group 2188 acids such as oxalic acid, succinic acid, maleic acid, adipic acid, sehestenic acid, or various dioxylic acids such as diaromatic diamic acid such as isophthalic acid and terephthalic acid. Condensates and co-condensates of basic acids and 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, glyptal resin, which is a condensate of phthalic anhydride and glycerin, is esterified with a fatty acid, a natural resin, etc., and a single-modified glyptal resin is preferably used.

xIx) Polyvinyl acetal resin Polyvinyl formal obtained by acetalizing polyvinyl alcohol and polyvinyl acetal resin are both preferably used. In this case, the acetalization of the polyvinyl acetal resin may be arbitrary. I can do it.

! polyurethane resin Thermal U with urethane bond (plastic polyurethane 4Mll1
．． i.

In particular, polyurethane resins obtained by the condensation of glycols and diisocyanates, especially polyurethane 4I obtained by the condensation of alkylene glycols and alkylene diisocyanates! 4 fats are preferred.

xxl) Polyether styrene formalin tree 11M, ring-opening polymer of i-type acetal, polyphelene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc.

xxii) Cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose.

Hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, various cellulose esters, ethers, or mixtures thereof.

xxii1) Polycarbonates such as polycyoxycyphenylmethane carbonate,
Various polycarbonates such as dioxydiphenylproban carbonate.

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

Li, Zn, Mg salts, etc.

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

(ii) Xylene resin, for example, a condensate of m-xylene or mesitylene and formalin, or a modified product thereof.

xxv'ii) Petroleum resin C5 type, CQ type, CRCQ copolymer type, dicyclopentadiene type, or copolymers or modified products thereof, etc. πxviii) Above i) ~! Blends of two or more of XMa11) or blends with other thermal IJ plastic resins.

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

Such a resin and the above-mentioned dye are usually used in a weight ratio of 1
The layers are deposited in a wide range of ratios from 0.1 to 100.

Preferably, such a recording layer contains a quencher.

As a result, the readout light repeats 1! S due to q morphism
/N ratio reproduction deterioration is reduced.

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

Various types of quennaya can be used, but in particular, when a dye is excited and a singlet atom is produced,
-fM term Oxygen undergoes 17 energy transfer without electron transfer, becomes an excited state, returns to the ground state by itself, and
- It is preferably a singlet oxygen quencher that converts stacked oxygen to the z-state.

Various singlet oxygen quenchers can be used, but transition metal chelate compounds are particularly preferred because they reduce acidic deterioration and have good compatibility with dyes. . In this case, the central metals include Ni, Co, Cu, Mn, Pd, P
t and the like are preferred, and compounds of group F are particularly preferred.

l) Acetylacetonate chelate Ql-I N1
(II) Acetylacetonate Ql-2Cu (11) Acetyl 1=t+-t Ql-3Mn (III) Acetylacetonate Ql-4Co (II) Acetylacetonate 2) Bisdithio-α converted into 2 by the above formula -diketone system Here, R-R4 represents a substituted or unsubstituted alkyl group or aryl group, and 1M is Ni
, represents a transition metal atom such as Co, Cu, Pd, Pt, etc.

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

In addition, in the following description, ph is a phenyl group, and φ is!
, 4-7 enylene group, φ′tt1.2-phenylene group,
benz represents that adjacent groups on the ring are bonded to each other to form a condensed benzene ring.

σ C1d (ICI 3) Bisphenyldithiol system represented by the above formula, where H to R8 are hydrogen or an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C1, or a dimethylamino group, a diethylamine group, etc. represents a 7-mino group such as Ni, Co, Cu, Pd, Pt, etc.
Represents a transfer metal atom.

In addition, M in the above structure has a single charge and may form a river with a cation (Cat) such as a quaternary ammonium ion, and furthermore, another ligand may be bonded to the upper part of M. good.

Examples of this include those mentioned above.

doldol ci α σ σ σ σQICI d
01 0101 σ σ σ σOthers, JP-A-1973
-45027 and those described in Japanese Patent Application No. 58-163080.

4) Dithiocar/hyumic acid chelate system S l゛・0.・'\+R1I) 2 N-CM C-NCR”) 2\/
\/S Here, RlI and R10 are alkyl.

Also, M is N i , Co , Cu , P d
, P L represents 2% transition metal.

R 9 R 10 M Q4-” C4HQ Ni 5) What is 7F in the above formula Here, M represents a transition metal atom.

Ql is.

1C=O(Qll) -C-CN ('Q12)1
1 or 11 represents C=O-C-CN, and Cat represents a cation.

L bale - Cat 9 51 N I Q 12 20 H 'N" (
CH3) 36 33 Q 5-2 N i Q 1220(C4H8)4N”
Q 5-3 C O 9 12 20 (C4) 18),
N”Q 5-4 Cu Q 12 2C, (C4H8
), N”Q 5-5 P d Q 12 20 (C2)
18), N"Others, Special IF] Those described in No. 125654/1982 6) Those expressed in the formula G. Here, M represents a crystal-transferred gold atom, and A represents S.C. (or C Q2 represents, 12 R11 and R each represent CN.COR"'2 cooR'!cosR'SER1B or L±SO2R, R13 to R each represent one hydrogen atom or L± substituted or unsubstituted represents an ajlekyl group or a ±71 nor group, Q2 represents a 1q+ group necessary to form a 5-membered or 60-membered ring, 'Cat represents a cation, and n represents 1 or It is 2.

Ha, χ Z A ('JN ni Szzzz 1N l”) Dimension Q II　I　II　I Coco Co COW C.

O' σ σ pi σ σ In addition, those described in #Condyle 58-127074.

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

M, Cat −1−■−−−□ Q 7 1 − N i2 (Cn-cans)3”)
Q 7-2 N i 2 (n-Ci, 6H3311:
)I3)3N) In addition, those described in Japanese Patent Application No. 58-127075.

8) Bisphenylthiol system Q8- I Ni-bis(octylphenyl) sulfide 9) Thiocatechol chelate system represented by the above formula, where M is a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc. represents.

Further, 1M has a single charge and may form a filling with a cation (Cat), and the benzene ring may have a substituent.

M Cat Q9-I Ni N" (C4Hq) 510) Compound represented by the above formula, where R18 represents a monovalent group, the intersection is θ to 6, M represents a transition metal atom, .

Cat represents a cation.

8 M RI Cat Q 101 N i HON (n-C4Hg)aQ 1
0-2 N iCH31N(n-cnua)a@-Sho5
8-143531.

11) - Compound represented by the formula (G) Here, in E, 20 21 22 R, R, R and R23 each represent a hydrogen atom or a monovalent group, and R24, R25, R2O and R27 represents a hydrogen atom or a monovalent group, 24 25 25 2B ' 211 2? R and R, R
and R, and R and R may be bonded to each other to form a 6-membered ring.

Moreover, M represents a transition metal atom.

Σ1 ; ; Flash 1 Tech Knee 1 Tech Technique 10: Knee I Technique σ σ In addition to these, those described in @Condylar 58-145294 12) A compound represented by the following formula, where M is Pt , represents Ni or Pd, and X+
, X2, X3, and X4 each represent 0 or S.

Sex – People and Madness ■■ Q12-I Ni O000 Q12-2 Ni S S S S In addition, those described in #Kokusho 58-145295.

+3) A compound represented by the following formula, where RJI is a substituted or unsubstituted 7-alkyl group or aryl group, and 32 33 34 R, R, R and R35 are hydrogen atoms or monovalent groups. However, R32 and R33, R33 and R34, and n34 and R35 may be combined with q to form 60JO.

Moreover, 1M represents a transition metal atom.

, 31. 32. 33. 34. 35.

Q13-1nCHHHHHNi 9 Q13-2 0HHHC2H3H-Ni5 Q13-3 nCHHHbenz Ni8 In addition, those described in Japanese Patent Application No. 58-151928.

+4) Compounds represented by the following formulas 41 41 43 R, R, R and R44 are each Represents a hydrogen atom or a monovalent group, 41 42 42 43 43 44 R and R, R and R, R and R.

may be combined to form a 6-membered ring, N645 4
6 Furthermore, R and R represent a hydrogen atom or a t±1-valent group.

Furthermore, M represents a transition metal atom.

13 RRR44R45R48M 41 42 43 Qt4-+=HHHN H-N1 Q14-2 8)l CHOCOHH-Ni7 In addition, those described in #Condylar No. 58-151929.

15) Compound 51 represented by the above formula, where R51, R52, R53, R54, R55゜H5O, R57, and R58 each represent a hydrogen atom or a monovalent group, and R51, R52, R52, R53, R53 and R54, R
55 and H5O, R5B and R57 and R51 and R58r
It can also be combined with O light to form a 6@ ring (N.

Or it represents halogen.

M represents a transition metal atom.

σ　σ In addition, those described in #58-153392 Gin between condyles.

1fl) Salicylaldehyde oxime system I represented by the above formula, where Rho and RB l represent an alkyl substitute, and M is Ni, Co, qu, Pd.

Represents a transition metal atom such as Pt.

R61 - 60 Q l 6-1 1-C3H71-C3H7N iQ
l 6-2 ((J)OH(CH,,),,CH3
N i211 3 916-3 CCH) OHCC:N2)1f; H2O
.

211 3 Q l 6-4 (CI() (i)I (12),,
0H3C02113 Ql 6-5 C6HF, Cs H et al. N1Ql 6
-8 C6'H5C6Hr; C.

Q16-? C6Hs Cs H5CuQl 6-8
NHO2H5NHO2H5N 1Q16-8 0HOH
Ni 17) Thiobisferrate chelate system represented by the following formula, where M is the same as above, and R65 and R68 represent an alkyl group. Further, M may have one charge and form a river with a cation (Cat).

Q 17-1 t-CHN i N”R314)18)
81? Q l 7-2 t-CHCO,N”H3(C4H8)
17 Q l 7-3 t-C3H, □ Ni1B) Phosphonous acid chelate system represented by the following formula, where 1M is the same as above, and R71 and R72 represent a substituent such as an alkyl group or a hydroxyl group.

R? l, R72M Q +8-1 3-t-CH, 5-t-C4H,, fl
-OHNi8 18) Compounds represented by the above formulas 787 81 82, R83 and R84r±, water here, R,
R represents an elementary atom or a monovalent group, but may be bonded to R81 and R82, R82 and R83, R83 and R84t to form a 6@ring.

RB5 and R8B each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

R86 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, or arylnoS.

R8? represents a substituted or unsubstituted alkyl group or aryl group.

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

M represents a transition metal atom.

α　σ　σ In addition, those described in Japanese Patent Application No. 58-153393.

20) Compound represented by the formula 1 Here, R and R92 each represent one hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acyl group, an N-alkylcarbamoyl group, an N-arylcarhemoyl group, N-furkylsulfamoyl &, N-
It represents an arylsulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and M represents a transition metal atom.

R91R92M Q20-1 nCa H! ! 'CH3N 1Q20
-2 CR3CH30-φ-N) ICONiOthers, s
- What is described in No. 155359/1983. ``Other quenchers include those mentioned above.

21) Benzate Q21-1 Existing chemical substance 3-3040 (tinuvin-
120 (manufactured by Chipakaiki)] 22) Hindered amine Q22-1 Existing chemical substance 5-3732 (,5ANOL
IS-770 (manufactured by Tenshi Pharmaceutical Co., Ltd.)] Each of these quenchers has a concentration of 0.01 to 1 mole of dye.
The content is about 12 moles, especially about 0.05 to 1.2 moles.

Note that the maximum absorption wavelength of the quencher is preferably greater than or equal to the maximum absorption wavelength of the dye used).

This results in extremely low regeneration and deterioration.

In this case, it is preferable that the difference between the two is O or 350 nm or less.

In order to miniaturize the device, it is preferable to use 750.780.830 as a light source for writing and reading.
nm semiconductor laser or 633 nm cr) He-
Since it is preferable to use an NE laser etc., the maximum absorption wavelength of the Toho oxygen quencher is 680 nm or more,
Particularly 680 to 1500, more preferably 800
~1500 nm).

Further, when the dye used (the effective value when two or more types are used) and the fractional coefficient of the stacked oxygen quencher at the wavelength of the readout light are εD and εQ, respectively, εD/εQ is preferably 3 or more. In addition, when using two or more types of one dye in combination, the absorption maximum wavelength and εD of the dye are arithmetic mean effective values depending on the concentration of injection.

With such a value, the excitation of the reencher during irradiation with the readout light becomes extremely small, and the deterioration of reproduction due to -main term oxygen becomes extremely small.

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

A quencher having such absorption characteristics is appropriately selected and used depending on the light source and dye used.

To form such a recording layer, generally follow the conventional method.
! Just set J.

The thickness of the recording layer is usually about 0.03 to 2 μm. Alternatively, if the recording layer is formed using only a dye and a quencher, it may be formed by sputtering, etc. The thickness of the recording layer should be 0.04 to 0.12 pm, preferably 0.05 to 0.08 gm. If it is less than 0.04 gm, especially 0.03 gm, both the absorption amount and the reflection amount are small, and neither the writing sensitivity nor the reproduction sensitivity can be made large.

If it is 0.12 μm or more, the pre-group will be buried, making it difficult to obtain a tracking signal. Also,
It is not easy to form pits, and writing sensitivity decreases.

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

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

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

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

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

Note that the base body usually has grooves for torso-soking.

In addition, the resin materials for the base include polymethyl methacrylate, acrylic resin, epoxy resin 11, and polycarbonate 14111! , polysulfone resins, polyethersulfones, methylpentene polymers, etc. are suitable.

It is preferable to form a base layer on these bases in order to improve solvent resistance, wettability, surface tension, thermal conductivity, etc. Materials for the base layer include Si, Ti, etc.
, AM, Zr.

Preferably, the material is a p4 cloth made of a complex compound such as In, Ni, or Ta, or an organic polyfunctional compound, or a liquor formed by heating and drying.

In addition, various photosensitive resins and the like can be used as the underlayer, and on the recording layer, if necessary, various uppermost protective layers, etc.
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 a reflective layer is not laminated above or below the recording layer.

The medium of the present invention has the above inscriptions on one side of such a substrate.
It may have a recording layer on both sides.

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, and they are sealed tightly to prevent dust and kisses from getting on them. You can also do it like this.

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

The thus formed peaks are read out by detecting the reflected or transmitted light of the readout light, especially the reflected light, while the medium is running or rotating.

In this case, recording and reading are performed through the substrate from the substrate side.

Then, the bits formed in the recording layer can be erased with light or heat and rewritten.The recording or reading light may be a semiconductor laser, He-NeLy laser, Ar laser, He- Cd
A laser or the like can be used.

V. Specific effects of the invention According to the invention, writing sensitivity is significantly improved.

IV Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown to explain the present invention in further 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 Shotasha)).
Hydrolyzed to form a base layer t'0. diameter 3 with olu, )
Various media were obtained by coating a layer of 0.06 Bm on a 0 cm acrylic paint substrate.

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

Also, (input V=input R)-40=790 nm.

(Enter=Enter R)+70=890111.

0 2 795 865 D Io 835 905 D 5' 840 910 DI3 790 860 D' 31 815 860 In this case, in Table 1, NC has a nitrogen content of 11.5 to
12.2%, viscous u 8 based on JIS K 8703
0s nitrocellulose, its content is 10w
t%, and was added in an amount of 0.2 fr based on the total amount of one dye.

While rotating each medium thus produced at 900 rpm, a semiconductor laser (830 nm) or H
Writing was performed from the back side of the substrate using an e-Ne laser.

Sensitivity was measured at a condensing unit output of 10+sW.

The sensitivity is determined by the minimum pulse width (' n
is the reciprocal of s ).

On the other hand, writing was performed with the condensing section output at lomW and the wave number at 2 MH2.

Next, a semiconductor laser (830n+i, condensing part output: 1 mW) was used as the readout light, and the reflected light through the substrate was detected, and a spectrum analyzer manufactured by Hewlett Par 7 Card Co., Ltd. was used to measure band III 30 KH'z. The C/N ratio was measured.

Further, with a laser readout beam of 1 mW, the reflectance from the substrate≠[ω side was set to 1111.

These results are shown in Table 1.

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

Application submitted T.D.K Co., Ltd. Agent Patent attorney: Yo Ishii - Continued from page 1 @ Inventor: Takahashi - Husband @ Inventor: Akihiko Kuroiwa] T.D.K. Stock: Inside the company 1-1, Nihonbashi, Chuo-ku, Kyoto TDC Co., Ltd. Inside the company

Claims (1)

[Scope of Claims] (1) An optical recording medium having a recording layer made of a dye or a composition of dyes on a substrate, wherein the dye is made of two or more cyanine dyes, and at least one of the dyes is an indica dye. It is a renin-based cyanine dye, and the absorption maximum wavelength of at least one dye is from 140 nm to +70 nm of the writing light wavelength, and the reflection maximum wavelength of at least one dye is 40 nm to +70 nm of the reading light wavelength.
An optical recording medium characterized by having a +70n layer. (2) The optical recording medium according to claim 1, wherein the indolenine dye has a structure represented by the following general formula CI). General formula CI) In (the above general formula CI), Z and Z' each represent an atomic group necessary to complete an indolenine ring, a pensointrenine ring, or a 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, X- represents an acid anion, m is 0 or 1, and be. (3) A recording medium as claimed in the claims, wherein the recording layer is made of a dye composition, and the dye composition contains a quencher. (5) The optical recording medium according to any one of claims 1 to 4, wherein the recording layer is made of a dye composition, and the dye composition contains a resin. (6): Writing and reading from the back (2) side of the X body 1
An optical recording medium according to any one of claims 1 to 5, which performs the following. (7) The optical recording medium according to any one of claims 1 to 6, in which a reflective layer is not laminated on the recording layer.