JPS59188854A - Optical recording medium - Google Patents

Abstract

PURPOSE:To improve a shelf life at a high temp. after recording by providing a recording layer consisting of a resin having a specific structure and a quencher on a substrate. CONSTITUTION:A recording layer consists of a resin having a cyanine dye having an indole ring at the side chain and a quencher. The cyanine dye is expressed by the formula PHI-L=PSI(X<->)m, in which PSI and PHI denote an indole ring which may be condensated with an aromatic ring, for example, benzene ring, phenanthrene ring, etc., and PHI and PSI are usually the same. L denotes a connecting group for forming a mono-, di-, tri or tetracarbocyanine dye. X<-> is anion and m is 0 or 1. The resin is enumerated by an OH-contg. resin, COOH or acid chloride group-contg. resin and NH2-contg. resin. The resin and the dye are bound by direct condensation or condensation with the other connecting component. The quencher is particularly preferably a singlet oxygen quencher and is incorporated at generally 0.05-12mol, more particularly 0.1-1.2mol in 1mol the cyanine dye in the dye-bound resin. The thickness of the recording layer is made usually about 0.03-10mum.

Description

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

Prior art optical recording media have 71.
Since it is non-contact, the recording medium is characterized by no 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 image processing in a darkroom.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat, and one example is a laser or other recording light that melts or removes a part of the body to create a pit. There are some devices that perform writing by forming small holes, record information using these pits, and read out information by detecting the pits with readout light.

As an example of such a focus forming type medium,
A recording layer made of a light-absorbing dye is formed on the substrate to form a focus by melting the dye, or a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye is formed. However, there are also known methods that form pits by decomposing nitrocellulose, etc., and methods that form a focus by coating a recording layer made of thermoplastic resin and light-absorbing dye and melting the resin and dye. .

When a cyanine dye having an indole ring is used as the dye, it is stable and exhibits an extremely high reflectance, resulting in an extremely high readout S/N ratio.

However, in media using such cyanine dyes having indole rings, the dyes migrate during storage, may become mixed into the substrate, reagglomerate, recrystallize, or bleed out, resulting in a decrease in writing sensitivity. There are disadvantages in that the readout S/N ratio decreases.

In particular, the readout S/N ratio decreases significantly due to high temperature storage after recording.

II. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a cyanine dye having an indole ring that has improved storage stability, especially storage stability at high temperatures after recording. The purpose of the present invention is to provide an optical recording medium with a high quality.

Such objects are achieved by the invention described below.

That is, the first invention is an optical device characterized in that a recording layer made of a resin having in its side chain a cyanine dye having an indole ring at both ends to which an aromatic ring may be fused is provided on a substrate 42. It is a recording medium.

Further, the second invention is provided with a recording layer comprising a quencher and a resin having in its side chain a cyanine dye having an indole ring at both ends to which an aromatic ring may be condensed, and a quencher. 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 in the present invention is made of a resin having a cyanine dye having an indole ring in its side chain.

In this case, the dye-bound resin is one in which one or more of the cyanine dyes described below are bonded to the side chain directly or via a linking moiety.

Among the resins bound with such dyes, 1
One or two dyes having one or more functional groups
A condensate of a resin having a plurality of functional groups, or a condensate of a resin having one or more functional groups, or one or more dyes having one or more functional groups, and a resin having two or more functional groups. Preferably, it is a condensate of one or more connecting components and a resin having a plurality of functional groups.

In such a case, a condensation reaction can be carried out after coating and other handling is easy.

Condensation reactions to form such condensates include:
In particular, one or two of the following functional groups with a degree of condensation of 15:
A combination of more than one species is preferred.

That is, 1, the dye-binding resin in the present invention, θr, preferably, through a linking group obtained by one or more of the following reactions, or via the following linking group and a linking component residue described below, It is preferable that one or more indole cyanine dyes and a resin are combined.

In the following, A represents a dye, a resin, or a residue of a connecting component, R represents a hydrogen or hydrogen substituted or unsubstituted alkyl group or an aryl group, and X represents a halogen.

1) -COOH+ -0)1 → -co
o−+ H2o ↑2) −C:00H+ −
NHR--CONHR-+ H2,O↑→ -coo
-c-c-+ H20↑8) -Cocl)-N)
I2-”-fl:ONH+ H20t+ H20
↑ 11) -OH+~NCO→-0CCIN)l-1
2) “NH2+-NCO→-NHCONH-14
) -NH2+SO3H→-3O2NH-+ H2
0t→-N-C-'C(OH)- ■ C-C(0)1)- 0-, G-C:(OH)- 1B) -3O3)1 +-0)1 → -
5o3 − + )+2 0 1+8) −3
O2C,l+ -OH→ -3O3-+ HCI↑2
0) −3O2Cl+ −NH2→ −3O2N
H−+HCI ↑C−CGI − 23) −CHO + −NH2→ −C=
N-+H20+24) -0ctal +-Pi
)+ 2 → -0CONH-+ HCI↑25
) 2-NHCH20H+H2NGONH2→ −
M)IG)+2 9HCONHCH2N)l-2B)
-CONHNH2+ -GOCI → -CON
HNHC:O-28) x-A-x 10 K2 C0
3→-+AOC00 squares+2Kx↓ Therefore, the dye and co-condensation component used preferably have one or more of the functional groups listed in 1) to 28) above. .

In this case, especially the above 1), 2), and 3).

5), 6), 7), 8), 9), 10), +1).

+2) , 13) , +4) , 19)
, 20) are preferred.

The functional groups of the dyes, resins, and linking components used are, in particular, -OH, -NH2, and -COO).

The functional groups of one or more of -3O3H, especially the cyanine dye, are -OH, -CooH, -803H, and the functional groups of the resin are -08, -COOH, -5o3H, -Cocl.
.

-N)l　2 is preferred.

Note that the dye and the connecting component may be provided with two or more types of -L functional groups, but considering problems in their synthesis and ease of control of the condensation reaction, the functional groups of the dye and the connecting component may be added. It is preferable that the number of groups is one type, and in particular, it is preferable that the dye is 1-functional to 2-functional, especially 1-functional, and that the linking component is di-functional. However, the resin has multiple functional groups.

In the combination in which the condensation reactions of 1) to 28) above occur, a mono- or di-functional dye and a resin are usually used, or a mono- or di-functional dye and a resin are used.
- A bifunctional dye, a bifunctional linking component, and a resin are used.

The dye used is a cyanine dye having an indole ring at both ends to which an aromatic ring may be fused.

Among such cyanine dyes, those represented by the following formula CI) are preferred.

Formula (I) Φ−L=! (X) In the above formula CI), heavy and Φ represent an indole ring to which an aromatic ring, such as a benzene ring, naphthalene ring, or phenanthrene ring, may be fused.

These Φ and ψ may be the same or different, but are usually the same, and various substituents may be bonded to these rings.

Note that Φ means that the nitrogen atom in the ring has ten charges, and heavy means that the nitrogen atom in the ring is neutral.

These Φ and! The skeletal ring is preferably one represented by the 5F notation [Φ] to [Φ■].

In addition, in the following, the structure is shown in the form of Φ.

1 1 [Φ■] In these various eggs, the group R bonded to the nitrogen atom in the ring is a substituted or unsubstituted alkyl group or aryl group.

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

Moreover, it is preferable that this R1 group further has a substituent. In this case, the substituents for R1 are:
Preferably, a functional group such as a sulfone group, a hydroxyl group, or a carboxy group, which may be a metal salt, is substituted, but in addition, an alkylcarbonyl group, an alkylamide group, an alkylsulfonamide group, an alkoxyoxy group, an alkyl It may be an amino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a halogen atom, or the like.

In addition, when m described below is O, the group R bonded to the nitrogen atom in Φ is a substituted alkyl or aryl group,
and - has an electric charge.

The above functional group is preferably included in R1, and is particularly preferably an alkyl group to which a hydroxyl group, a carboxy group, or a sulfone group which may be a metal salt is bonded. When a carboxyl group or a sulfone group is bonded to R1, it is preferable that the -- group has a single charge and the group has a ■ function, since a linear resin can be obtained.

Furthermore, at the 3-position of the indole ring, two substituents R2,
Preferably, R3 is bonded.

In this case, two W substituents R2 attached to the 3-position.

R3 is preferably an alkyl group or an aryl group. And among these, the number of carbon atoms is 1
or 2, particularly 1, is preferably an unsubstituted alkyl group.

Another substituent R4 may be bonded to a predetermined position in the ring represented by -, Φ, and double.

Such substituents include functional groups such as carboxy groups, as well as various substituents such as alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, alkylthio groups, alkyloxycarbonyl groups, and alkylcarbonyloxy groups. It may be a base.

And the number of these substituents (p, q) is usually
0 or about 1 to 4. In addition, p and q are 2 or more.
When the number of R4s is two, the plurality of R4s may be different from each other.

On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye;
It is preferably any one of I) to (LVII[).

Formula (LI) CH= CH-CH= CH-C= C)l-C)l=
C)l-C)! Formula (LII) C)l=c)l-C
) l=c-CH=CH-cH formula [Lm) formula (LV) formula [L■) CH=CH-C=f:H-CI (formula (L
■) to)l-C'=CI(-C)lwhere, Y is
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, imitazolidine groups, ethoxycarbonylpiperazine groups, etc. Preferable examples include a di-substituted ami7 group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a sia/group, a nitro group, and a halogen atom such as Br and CI.

Among these formulas (LI) to [L■], tricarbocyanine linking groups, particularly formulas [Ln) and (Lm), are preferred.

Furthermore, X- is an anion, and preferable examples thereof include I-, Br-, Cl04-, B F4-
.

can be done.

Note that m is O or l, but when m is O, R1 of Φ usually has a - charge and becomes an inner salt.

Further, it is preferable that the functional group is bonded to R1.

Next, specific examples of the dyes used in the present invention will be given, but the present invention is not limited to these. - In the following, φ represents a phenyl group.

Color 1 (Un-covered-L-Car) Yu D 2
ΦI CH2CH20HttD 3
ΦI tt
ttD 4 ΦI
// 、
ttD 5 Φwork (CR2) 60Htt
D 6 ΦI CH2CH20H
ttD 7ΦI
tt.

D8' ΦII t
t.

D 9 ΦII, t
t, , /DIOΦm
tt 7゜Dll Φm tt
//D13 O
I[[(CH2)4 C0OH/ID14
Φ■／／
〃D l 5' Om
tt ttD 16
Φm tt
ttD17 ΦII
I tt,
//D18 Om CH2
CH20HttD19 Φm
tt //D2
0 Φ■l//l -BUKIN J-L Y X//
tt tt
ClO4/l ll
Nφ2 //” rV
Htt//■l1ll/ ll ■ Nφ2
tt/' m CH3/
/// II Nφ2
IItt //
Htt//ll
//'
/111 ll Nφ2
////tt
H-//ll
Nφ2 −tt
ffl H-”
Vl tt -
” VII t
t-tt tt
Nφ2 −//
// // cl Q
４／／■／／
//llI]Illll These cyanine dyes having an indole ring can be easily synthesized according to known methods.

On the other hand, the resin used is ``one insert of two functional groups.''
There is no particular restriction as long as it has a plurality of 2.

Those that can be particularly preferably used are listed below.

■) OH-containing resins Cellulose esters or their derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, epoxy Resins, phenolic resins, alkynd resins, polytyrosine, polyvinylhydroquinone, polyvinylbezidylhydroquinone, methylolated polyacrylamide, polyacrylhydroxyamide, polyvinylmethylol, poly(p-hydroxyethyl)styrene, etc.

2) C0OH or acid chloride group-containing resin Homopolymers of acrylic acid, methacrylic acid, etc. or copolymers with other monomers, maleic anhydride, pyromellitic anhydride, trimellitic anhydride, etc., and ethyl acetate, etc. copolymers with monomers, acid chlorides of these, etc.

3) 5O3H-containing resin polystyrene sulfonic acid etc.

4) NH2-containing resin poly-p-aminostyrene, polyvinylamine etc.

5) Other polyacrylic acid hydrazide, polymethacrylic acid hydrazide, polyvinylbenzaldehyde, copolymer of p-chloromethylated polystyrene and iminodiacetone trile, etc.

Note that the number of functional groups in the resin is 0 per repeating unit.
．． It is said to be around 05-4.

Moreover, there is no particular restriction on its molecular weight, etc.

Such a resin and a dye may be directly condensed and bonded, but they can also be condensed and bonded with another connecting component.

As the connected component, the following are suitable.

Jl Dialcohol ethylene glycol, ■, 3-propanediol, ■,
4-butanediol, ■, 5-bentanediol, 1.
6-hexanediol, 1.10-decanediol, ■
, 4-cyclohexanediol, p,p'-dihydroxy-2,2-dicyclohexylpropane, bisphenol A, hydroquinone, p.

p'-biphenol, hydroquinone dihydroxyethyl ether, polyethylene glycol (n-2 to 50), etc.

J2 Dicarboxylic acids and their acid chlorides, such as succinic acid, malonic acid, glutanoic acid, adipic acid, pimelic acid, superric acid, sepacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid.

Or these acid chlorides.

J3 Diamine 1,2-diaminoethane, 1,4-diaminobutane, hexamethylene diamine, diaminobenzyl, p, p'-
Diaminodiphenylmethane, diaminodiphenyl sulfide, diaminodiphenylsulfone, 3.3'-dichloro-4,4'-diaminodiphenylmethane, diaminodicyclohexylmethane, piperazine, 2,5-dimethylpiperazine, bisaminopropylbiperazine, 4.4'
-diaminodiphenyl ether, 3,3'-dimethyl-
4,4'-diaminodicyclohexylmethane, 4,4'
- Diaminodicyclohexylmethane, inphorondiamine, etc.

J4 Di- to triisocyanate 2.4-tolylene diisocyanate, 2゜6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, voluminous.

Tilene diisocyanate, adduct polyisocyanate, etc. Coronate) HL, Coronate AP, Coronate) 2030, manufactured by Nippon Polyurethane Co., Ltd. Demodur N, Demodur HL manufactured by Sumitomo Bayer Urethane Co., Ltd.
Various di- or triisocyanates such as DIION (manufactured by Takeda Pharmaceutical Co., Ltd.), LDI-100 (manufactured by Kyowa Hakko Co., Ltd.), and MS50 (manufactured by Japan Polyurethane Co., Ltd.).

J5 Jepoxy compound ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, trimethylolpropane diglycidyl ether, fatty acid diglycidyl ether, terephthalic acid diglycidyl ether, spiroglycol diglycidyl ether, and the like.

J6 Butyric anhydride pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, cyclohexanetetracarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,
Tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.

J7 Dihydrazide Sebacic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, etc.

J8 Diiminocarbonate N, N'-p-phenylenebis (ethyleneiminocarbonate), etc.

The cyanine dye having an indole ring and the resin, or the cyanine dye, the resin, and, if necessary, a connecting component, may be condensed separately in advance according to a conventional method, and then purified and used. Alternatively, they may be dissolved separately in a composition liquid for coating the recording layer, applied, and then heated to cause a condensation reaction.

It is also possible, if necessary, to condense a cyanine dye residue to a vinyl monomer via a chain component residue, without carrying out such condensation with the resin, and to radically polymerize this in accordance with a known method.

In addition, in the resin bound with the dye, the dye is 10 to 96w.
It is preferably contained in an amount of about 50 to 96 wt%, particularly about 50 to 96 wt%.

Although the recording layer of the medium of the present invention is made of a polymer of such a dye, the recording layer may contain other resins separately. At this time, coating properties are improved, and recording sensitivity, readout S/N ratio, etc. are improved.

Examples of such resins include, for example, Japanese Patent Application No. 58-152
Those described in No. 29 etc. are suitable.

The resin is contained in an amount of about 50% or less by weight based on the resin to which the dye is bonded.

Preferably, such a recording layer further contains a quencher.

This reduces reproduction deterioration and improves light resistance.

A variety of quenchers can be used, but especially when the dye is excited and singlet oxygen is produced,
- It is preferable that it is a singlet oxygen quencher that undergoes electron transfer or energy transfer from main term oxygen to become excited, returns to the ground state by itself, and - converts main term oxygen to a triplet state.

-A variety of substances can be used as a stacked oxygen quencher, but transition metal chelate compounds are particularly preferred because they reduce regeneration deterioration and have good compatibility with dye-binding resins. It is preferable that there be. In this case, the central metals include Ni, Co, C
u, Mn, etc. are preferred, and the following compounds are particularly preferred.

l) Acetylacetonate chelate QINi (It
) Acetylacetonate Q 2Cu(II) Acetylacetonate Q3 Mn(m) Acetylacetonate Q
4Co(II) acetylacetonate 2) Bisdithio-α-diketone system Here, R(IL) R(4) represents a substituted or unsubstituted alkyl group or aryl group, and M represents a divalent transition metal atom. .

In this case, 1M has a single charge and may form a salt with a quaternary ammonium ion or the like.

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl 7 N''(C4)19)4 3) Bisphenyldithiol system (5) (8) - Here, R and R are an alkyl group such as a methyl group, Alternatively, it represents a halogen atom such as CI, and M
represents a divalent transition metal atom such as Ni. Furthermore, a
and b are each 0 or an integer of 4 or less.

Further, M in the above structure has a single charge and may form a salt with an anion, and further, other ligands may be bonded above and below M.

Examples of such tools include the following.

QIO PA-1001 (product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (same as above Ni-bis(toluenedithiol)tetra(t-butyl)ammonium) Q12 PA-1003 (same as above) Q13 FA-1005 (same as above) Same as above Ni-bis(dichlorobenzene)tetra(butyl)ammonium] Q14 FA-1006 (same as above Ni-bis(trichlorobenzenedithiol) tetra(t-butyl)ammonium) Q15Co-bis(benzene-1,2- dithiol) tetrabutylammonium Q16Co-bis(O-xylene-4,5-dithiol)tetra(t-butyl) ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis(0-xylene -4,5-dithiol)tetrabutylammonium Q19Ni-bis(5-chlorobenzene-1,2-dithiol)tetrabutylammonium Q20Ni-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetra Butylammonium Q21Ni-bis(3,4,5,6-titrachlorobenzene-1.2dithiol)tetrabutylammonium 4) Dithiocarbamate chelate system (7) (8) Here, R and R represent an alkyl group. Moreover, M represents a divalent transition metal atom.

Q22Ni-bis(dibutyl dithiocarbamic acid) [
Antigen MBC (manufactured by Sumima Kagaku Co., Ltd.)] 5) Bisphenylthiol-based Q23Ni-bis(octylphenyl) sulfide 6) Thiocatechol superlate system Here, M represents a divalent transition metal atom. Also, M
has a single charge and may form a salt with an anion,
The benzene ring may have a substituent.

Q24Ni-bis(thiocatechol)tetrabutylammonium salt 7) Salicylaldehyde oxime system (9) (10) Here, R and R represent an alkyl group, and M represents a divalent transition metal atom.

Q25 N1(II)O-(N-isopropylformimidoyl)phenol Q26 Ni(II)O-(N-dodecylformimidoyl)phenol Q27 Co(II)O-(N-dodecylformimidoyl)phenol Q28 C 'u (II')0- (N-dodecylformimidoyl)phenol Q29 N1(II)2.2'-(trilomethylidine on ethylenebis)]-diphenol Q30 Co (1,I) 2 ,2'-( ethylene bis trilomethylidine)]-diphenol Q31 Ni (II)2.2' (1,
8-naphthylene bis trilomethylidine))-diphenol Q32 Ni (II) -(N-phenylformimidoyl)phenol Q33 Co(II)-(N-phenylformimidoyl)phenol Q 34 Cu (II) (N -7x =
(formimidoyl) phenol Q35 N1(II) salicylaldehyde phenylhydrazone Q36 N1(II) salicylaldehyde oxime 8) Thiobisferrate chelate system R(11) R(
12) (11) Here, M is the same as above, and R and R (12) represent an alkyl group. Further, M has one charge and may form a salt with an anion.

Q37 N1(II) n-butylamino[2゜2'-
Thiobis (4-tert-oct/l/) -7z/
L/-h) (Gyasorb-UV-108
4 (American Seanad Co., Ltd.) Q3
8 Co'(II) n-butylamino[2°2'-thiobis(4-tert-octyl)-ferulate] Q39 N1(II)-2,2'thiobis(4-te
rt-octyl)-ferulate 9) Phosphonous acid chelate system (13) Here, M is the same as above, and R and RHa) represent a substituent such as an alkyl group or a hydroxyl group.

40 In addition to this, other quenchers include the following.

10) Benzoate Q51 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Geigy)] 11) Hindered amine Q52 Existing chemical substances 5-3732 (SANOLLS
-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such an entcher is synthesized according to a known method.

The quencher is generally contained in an amount of about 5 to 12 moles, particularly about 0.1 to 1.2 moles of O, per mole of cyanine dye in the dye-binding resin.

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

As a result, ILF biodegradation becomes extremely small.

In this case, the difference between the two is preferably 0 or 35 Or+m or less.

In order to form such a recording layer, it is generally necessary to apply the coating according to a conventional method, and the thickness thereof is generally 0.03-100.
It is considered as gm.

The thickness of the recording layer is usually 0.03 to 10 pLm.
It is considered to be a degree.

In addition, such a recording layer may contain other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, crosslinking agents, etc. Good too.

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 systems such as ethyl acetate, carpitol acetate, butyl carpitol acetate-1, etc., methyl cellosolve,
An ether type such as ethyl cellosolve, an aromatic type such as toluene or cylene, a halogenated alkyl type such as dichloroethane, an alcohol type, etc. may be used.

The material of the substrate on which such a recording layer is provided is not particularly limited, and may be any of various resins, glass, ceramics, metals, etc.

In addition, the shape varies depending on the purpose of use, such as tape, disk,
It may be a drum, a belt, etc.

Note that the base body usually has a groove for trunking.
Further, if necessary, it may have a base layer such as a reflective layer, a heat storage layer, a light absorption layer, etc.

In addition, the resin materials used for the base include acrylic resin,
Non-grooved substrates such as epoxy resins, polycarbonate resins, polysulfone resins, polyethersulfones, methylpentene polymers are suitable.

These substrates can also be coated with a primer on the substrate to improve solvent resistance, wettability, surface tension, thermal conductivity, and the like.

As the primer, for example, titanium-based, silane-based, or aluminum-based coupling agents, various photosensitive resins, etc. can be used.

In addition, on the recording layer, if necessary, a reflective layer that functions as a back surface when using a transparent substrate, various uppermost protective layers, etc.
It is also possible to provide a single layer of half-mirror.

The medium of the present invention may have two recording layers on one side of such a substrate, or may have recording layers 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, which is then sealed tightly to prevent dust and scratches. You can also do it like this.

(2) Specific Effects of the Invention The medium of the present invention is irradiated with recording light in pulses while running or rotating. At this time, the dye-binding resin in the recording layer generates heat, melts it, and forms bits.

The focus formed in this way is also 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 preferably performed from the base side, but may also be performed from the recording R layer side.

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

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

(2) Specific Effects of the Invention According to the present invention, even if the medium is stored for a long period of time, there is very little deterioration in writing sensitivity or S/N ratio. In particular, the deterioration of the S/N ratio when read after recording and storage at a high temperature is extremely small.

Furthermore, since a sheacon dye having an indole ring is used, the reflectance is high and the readout S/N ratio is also extremely high.

In addition, according to the second invention, regeneration deterioration is significantly reduced,
Extremely high light resistance.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

Examples The above cyanine dyes Dl, D2, DIo, 0
12 and 018, the following connecting components A and B, and resin R
1, R2 was condensed according to a conventional method to synthesize a dye-binding resin.

As a result of IR and thin layer chromatography measurements, it was confirmed that the dye was bound to the resin in all of these ζ.
In this lip treatment, the amount of pigment in each pigment binding resin was about 70 wt%.

This dye-binding resin was dissolved in dichloroethane, and a recording layer was formed by dissolving the dye-binding resin in a thickness of 0.07 pLm on a polymethyl methacrylate acid substrate having trunking grooves.

Separately, for comparison, a recording layer was formed in which the above dye and resin were added in a weight ratio of 8:2.

The resins and connecting components used are as follows.

Connecting component A Adipic acid Connecting component B Hexamethylene diamine resin R1 Poly-
p-aminostyrene resin R2 acetylcellulose For each sample thus prepared, l 80
While rotating at 0 rpm, writing was performed from the back side of the substrate with a semiconductor laser (830 nm) focused on Igmφ with a condenser output of 10 mW) and a pulse ++ of 100 n see.

After this, 1 mW semiconductor laser readout light was applied for 1 ILs.
The C/N ratio was measured by irradiating the substrate with a pulse of EC width and 3 KHz from the back side, and detecting the reflected light.

Next, each sample was stored at 50°C and 90% relative humidity for 1000 hours, after which the deterioration of the C/N ratio was measured.

Table 1 shows the deterioration rate (%) of the C/N ratio after storage.

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

Examples Between the samples of Experimental Example 1 and 2, Sample 25 was obtained in which Quencher Q14 was added in a weight ratio of 50% to the dye polymer.

Between samples, 2 and 25, 1 mW, 1 p-se
Table 2 shows the reproduction deterioration rate (%) of the C/N ratio after irradiation with a 300 Hz readout laser beam for 4 minutes.

Table 2 Yang.

Quencher-Q14 C/N ratio deterioration rate (%) High temperature storage deterioration 11 Reproduction deterioration 35 2 From the results shown in Table 2, the effect of the second invention is clear.

Applicant: TDC Co., Ltd. Agent, Patent Attorney: Yo Ishii - Procedural proceedings (spontaneous) June 1988: 2F Date, 1982 Patent Application No. 63210 2, Title of invention Optical recording medium 3, Amendment Relationship with cases involving persons who apply for patents
13-1 Hiki Tachibana-chome, Chuo-ku, Tokyo
(306) Representative of TDC Co., Ltd.
Kan Otoshi 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
No. Yabe Building 1st floor Telephone: 988-168020
Correct as described below.

■) In the 1st q line of the 2nd ct page, lt'Ni, Co, C
u.

M n j is INi , Co , Cu , M
n.

Correct Pd and Ptj.

II) The descriptions from line 19 on page 4 to consultation line on page 40 are amended as follows.

11' 1) Acetylacetonate chelate system Q
INi(II) acetylacetonate Q2 (:'u
(II) Acetylacetonate Q3Mn (m) Acetylacetonate Q 4 'Co (II) 7 cetyl 7 setonate 2
) Hisdithio-α-diketone system Here, R(It (4) represents a substituted or device-substituted alkyl group or aryl group, M is Ni, Co
, represents a non-transfer metal atom such as Cu, Pd, or Pt.

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

Q5Ni(II) dithiobenzyl Q6Ni(II) dithiobiacetyl N''(C:,H9)4 3) Hisphenylinthiol system Here, R(5) and R(6) are alkyl groups such as methyl group , or represents a /\rogen atom such as C5L, and M is Nt or Co.

Represents a transition metal atom such as Cu, Pcl, or Pt. Furthermore, a and b are each O or an integer of 4 or less.

Further, M in the above structure may have a single charge and form a salt with a cation, and h'F of t±M may be bonded to another ligand and may be zero.

Examples of this type of car include the following:

QIOPA-1ool (Product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-'1002 (2 times) N1-Vice(toluenedithiol)tetra(butyl)ammonium] Q12 PA-1003 (2 times) Q13
PA-1005 (same as above Ni-bis(dichlorobenzene)tetra(t-butyl)ammonium] Q14 PA-1006 (same as above Ni-his(trichlorobenzenedithiol) tetra(t-butyl)ammonium) Q15 Co-bis(benzene) -1,2-dithiol)tetrabutylammonium Q)6Co-his(0-xylene-4,5-dithiol)tetra(t-butyl)ammonium Q17Ni-bis(benzene-1,2-dithiol)tetrabutylammonium QlB Ni -bis(0-xylene-4,5-dithiol)tetrabutylammonyram Q19 Ni-bis(5-chlorobenzene-1,2-
dithiol) tetrabutylammonium Q2ONi-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutylammonium Q21Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol)tetra Butylammonium 4) Dithiocarhemine-derived chelate system Here, R (7) and R represent an alkyl group (8). Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd or Pt.

Q22Ni-bis(dibutyl dithiocarbamic acid) [
Antigen NBC (manufactured by Sumitomo Chemical Co., Ltd.) 5) Bisphenylthiol-based Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate-based where M is Ni, Co, Cu, Pd.

Represents a transition metal atom such as Pt. Further, M has a single charge and may form a salt with a cation, and the benzene ring may have a substituent.

Q24Ni-bis(thiocatechol)butylammonium salt 7) Salicylaldehyde oxime system (8) (10) Here, R and R represent an alkyl group, and M is Ni, Co, Cu.

Represents a transition metal atom such as Pd or PL.

Q25 Ni (II)o -(N-isopropylformimidoyl)phenol Q26 Ni(IT)o -(N-dodecylformimidoyl)phenol Q27 Co(II)o -(N-dodecylformimidoyl)phenol Q28 Cu (II)'o -(N-dodecylformimidoyl)phenol Q29 N1(11)2.2' (nitrilomethylidine on ethylene his)] -diphenol Q30 Co(II)2.2'-Cx tyrene bis[nitrilomethylidine] lysine)]-diphenol Q31 N1(II)2.2'-(1,8-naphthylenebis-nitrilomethylidine)]-diphenol Q32 N1(II) (N-phenylformimidoyl)phenol Q 33 Go ( II ) −(N −7, =
Jl/ho Jl/muimitoyl) phenol Q34 Cu (II) -(N-7,-1-ruho J
L/ Muimidoyl) Phenol Q35 N1 (II) Salicylaldehyde Phenylhydralane Q36 N1 (II) Salicylaldehyde oxime 8) Thiobisferrate chelate-1 system R (11) R
(12) (11) Here, M is the same as above, and R, (12) and R represent an alkyl group. Further, M has a single charge and may form a salt with a cation.

Q37 N1(II) n-butylamino[2゜2'-
Thiobis(4-tart-octyl)-2ert)
(CyaSorb-UV-1084 (American Cyanamide Co., Ltd.)) Q38
C0(II), n-butylamino [2゜2'-thiobis(4-tert-octyl)-phenolate] Q39 N1(II)-2,2'-thiobis(4-t
ert-octyl)-phenolate 9) Phosphonous acid chelate system (13) Here, M is the same as above, and R and R (14) represent a substituent such as an alkyl group or a hydroxyl group.

40 In addition to this, other quenchers include the following.

10) Benzoate Q41 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Gaiki Co., Ltd.)] 11) Hindered amine Q42 Existing chemical substance 5-3732 (5ANOLL)
s-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]j 31

Claims (1)

[Claims] l. A light source comprising a recording layer formed of a resin having a cyanine dye in its side chain, which has an indole ring at both ends to which an aromatic ring may be fused, on a substrate. recoding media. 2. Optical recording characterized in that a recording layer comprising a quencher and a tree +11i having a cyanine dye as a side chain having an indole ring at both ends to which an aromatic ring may be fused is deposited on a substrate. Medium.