JPS59232896A - Photo-recording medium - Google Patents

Abstract

PURPOSE:To improve durability and prevent deterioration of S/N after high- temperature storage after recording, by forming a recording layer with a colouring matter-resin components connected with a special connecting group. CONSTITUTION:A substrate is provided upon it with a recording layer composed of coloring material-resin components, at least one kind of cyanine dye having on its both ends indole ring that may be formed by condensation of aromatic ring, resin with a connecting group consisting of -COO- group or that of valence higher than 2 including more than two -COO- groups. On the end of connection for the connecting group of valences of 2 or higher than 3 or of between 2 and 3 and up, COO or OCO is located. This kind of photo-recording medium shows insignificant deterioration of filling-in sensitivity and S/N. Especially, deterioration of the S/N of reading-out after a high-temperature storage after recording becomes exceedingly insignificant. Further, as the cyanine dye having the indole ring is used, a reflecting coefficient is high and S/N of reading-out is extremely high.

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 there is no contact between the medium and the recording head or the reading head.For this reason, research and development of optical recording media is 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. For example, a part of the medium is melted or removed using recording light such as a laser, and it is called a bit. There is a method in which writing is performed by forming a small hole, information is recorded using this bit, and reading is performed by detecting this bit with a readout light.

As an example of such bit-forming media,
A recording layer consisting of a light-absorbing dye is formed on the substrate, and the dye is melted to form a bit, or a recording layer containing a self-oxidizing resin such as nitrocellulose and a light-absorbing dye is formed. However, there are those that form bits by decomposing nitrocellulose, etc., and those that form bits by coating a recording layer consisting of a thermoplastic resin and a light-absorbing dye, and melting the resin and the dye.1. Jin is known.

As a dye, a cyanine dye having an indole ring exhibits an extremely high reflectance and can provide an extremely high readout S/N ratio.

However, in media using cyanine dyes having such indole rings, although the cyanine dyes are stable, storage may cause the dyes to migrate and become mixed into the substrate, or to re-agglomerate or recrystallize. This may cause bleed-out, lower write sensitivity, and read S/
There is an inconvenience that the N ratio decreases. In particular, the readout S/N ratio decreases significantly due to high temperature storage after recording.

■ Purpose of the Invention The present invention was developed in view of the above-mentioned circumstances, and its main purpose is to further improve storage stability and, in particular, to reduce deterioration of the S/N ratio due to high temperature storage after recording. An object of the present invention is to provide an optical recording medium using a cyanine dye having an indole ring.

Such objects are achieved by the invention described below.

In other words, the first invention provides an aromatic ring having an indole ring at both ends to which an aromatic ring may be fused.
-CO
Optical recording characterized by having, on a substrate, a recording layer consisting of a dye-resin component consisting of an O- group or connected by a divalent or higher linking group containing two or more -Cα)- groups. It is a medium.

Further, the second invention is characterized in that at least one cyanine dye having an indole ring to which an aromatic ring may be condensed and an aliphatic compound comprising a -COO- group or two -COO- groups. The present invention is an optical recording medium characterized in that it has a recording layer on a substrate, which includes a dye-resin component connected by a divalent or higher-valent linking group, and a quencher.

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

The recording layer according to the present invention contains one or more types of dyes.
It consists of a pigment component in which more than one molecule is linked to a resin via a predetermined linking group.

The linking group in the present invention is a -COO- group or a divalent or higher group containing two or more -〇〇- groups.

In the case of the latter 21i11i or a trivalent or higher valent linking group, C0C) or OCO is placed at the 16th-position at the 2 to 3 or more bond ends.

As such a group, those of the following formula are preferable.

Formula (B -)-(-L- 几Here, L represents OCO or COO, n is an integer of 2 or more, and B is 2iIl[I or a trivalent or higher residue (especially a substituted or An unsubstituted chain or cyclic hydrocarbon residue, a heterocyclic residue, or an imino group, or a combination of these, if necessary, through a group such as -0-1-S-1-CO- It is preferable to conclude.

In addition, two or more ``5'' are usually the same, but may be different from each other.

Furthermore, one or more types of linking groups represented by the above formula may be combined in a complex manner.

With such a linking group, usually one dye polymer is linked to the resin to form a dye-resin component.

In order to link the dye and the lipid with such a linking group,
It is preferable to follow the following.

This makes synthesis extremely easy. In addition, there are no side reactions, the purity is high, no purification is required, and the stability is high.

First, a lifting dye (usually one molecule) with a 1000- group as a linking group is used, and an R'oco- group and/or
or uLJltj' having a ttcoo- group (usually any of these), transesterification is performed between the RC(XJ- group and the Ice(JCO- group), and RCOO1'
J is eliminated, thereby linking the resin and the dye with -COO-.

In this case, R and lce each represent a substituted or unsubstituted alkyl group or an alkyl group.

In this case, ft is preferably a lower alkyl group, especially an unsubstituted or halogen-substituted alkyl group having 1 to 2 carbon atoms. , number of carbon atoms 1~
4 is preferably an unsubstituted alkyl group or an alkyl group substituted with halogen or the like.

When R and R' are such lower alkyl groups, the resulting ester becomes volatile and the reaction becomes easy.

Alternatively, one or more dyes having 1 or 2 or more (usually 1 to 4) 7000- groups (■ C is the same as above) and/or HO- groups (usually either one) (
Usually 1 type) and HO- group and/or lceOC〇-
using a resin having a group (usually either one), t+
Transesterification is performed between the oco- group and the 1-10- group, and 1
By removing 4401-1 and converting to -COO- group, 4M
The fat and the pigment may be linked.

In addition, 1 of the dyes having one or more of at least one of the RC■- group, +OCO group, and 1-IQ- group
species or two or more species, f(COO- group and 1('OC
The dye and the resin can also be linked by transesterification between the 〇- group and between the It'0CO- group and the HO- group.

Next, as mentioned above, two -COO- groups can be used as a divalent or higher linking group, but in this case, among the above-mentioned RCOO- group, 140CO- group and HO- group, One or more types (usually 1 type) of one or more types (usually 1 type) of pigments having 1 or 2 or more (usually 1 to 4) types
species) and RCOO- group, 11? Coo- group and HO
- a resin having one or more types (usually about 1) of the groups and one or more types of predetermined linking components (usually I Km )
Transesterification is carried out between TE, RCOO-g, OCO-%, and/or teaco- group and 1-10- group.

In this case, the linking component may be a combination such as Cete, RCOO-
It has two or more of one or more of the following: a group, an rr oco- group, an HO- group, and a HO- group.

That is, the connected components are (B) (A) corresponding to the above formula.
It has n-formation.

In this case, 13 is the same as above and A- is FLCOO
- group, R40CO- group or l-10- group, and n is the same as above.

Two or more A's may be the same or different.

However, if there are many A's, the reaction becomes complicated, so usually 2
~ Let the three A's be different.

This one type of connecting component, RCOO- group, R? 1 type of dye having 1 to 4 of 1 type of 0CO- group and HO- group, and 1 OO- group, it' 0CO- group and H
It is preferable to use a resin having one type of O-group in a combination in which transesterification occurs.

In addition, as B, unsubstituted or substituted chain hydrocarbons, alicyclic hydrocarbons, aryl rings (especially be/zene rings), petero rings, divalent to hexavalent groups such as imino groups, etc. , especially residues 2 to 3fIIi, or combinations of two or more of these, and furthermore, two or more of these, -0-1-
A combination with 5-1-C〇- or the like is preferred.

Moreover, in such a second aspect, (B++L-)n linking group and (B-1).

In addition to the repeat form of , a -COO- group may also be present as a linking group.

Furthermore, one dye may be linked to the resin side chain via a linking group, or a plurality of dyes may be further linked to this dye via linking groups.

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

Among such cylindrical dyes, those represented by the following formula are preferred.

Formula % Formula % () In the above formula, 1 and Φ represent an aromatic ring, such as an indole ring to which a Hensen ring, a Natstaleno ring, a phenanthrene ring, etc. may be fused.

These and V may be the same or different,
Usually they are the same, and in this (7) 3'fJ,
Various substituents may be bonded.

In addition, in Φ, the nitrogen atom in the ring has ten charges, and in F, the nitrogen atom in the ring is neutral.

The skeletal ring of choleranoΦOyobiV is represented by the following formula [ΦI]
It is preferable that it is represented by ~[Φ■].

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

(1'L・).

R. [Φ■] (1N・).

In these various rings, the group R□ bonded to the hydrogen 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 R bonded to the nitrogen atom in such a ring.

In addition, if this group further has a substituent,
As the substituent, the above-mentioned groups are substituted, but in addition to these, an alkylamide group, an alkylsulfonamide group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a halogen atom, etc. may be used.

In addition, when m described below is 0, the group R bonded to the nitrogen atom in Φ is a substituted alkyl or aryl group,
and - has an electric charge.

Nao, R□ is an alkyl group substituted with the above group,
It is preferable that the above group is included in I (U).

Further, two substituents, R, and It3, are preferably bonded to the 3-position of the indole ring to which an aromatic ring may be fused. In this case, the two substituents lt attached to the 3-position
2. R3 is preferably an alkyl group or an aryl group. Among these, unsubstituted argyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

On the other hand, at a predetermined position in the ring filled with Φ and W,
Furthermore, another substituent R4 may be bonded. In addition to the above-mentioned groups, such substituents include alkyl groups, -aryl groups, heterocyclic residues, halogen atoms, alkoxy groups,
It may be an individual substituent such as an argylthio group.

The number (p, q) of these substituents is usually about 0 or about 1 to 4. Note that when p and q are 2 or more, the plural It's may be different from each other.

On the other hand, L represents a linking group for forming a mono-, di-, tri- or tetracarbocyanine dye, especially one of the formula [L
It is preferably any one of I] to [L■].

Formula [LI:] CH=CH-CH=CH-C=CH-CH
Formula [L ■ ':l C1(=CH-CH=C
-CH=CH-CH formula [L■] Formula [LM:] Formula [L■] Needle 1 = cH-C-CH-CH formula [L■]
C1-1-C=Ct1-CH 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 ethoxycarbonylpiperazines. Preferred examples include a di-substituted amine group such as 7 groups, 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.

Among these formulas CLI) to [L■], tricarbocyanine linking groups, particularly formulas [LI[] and [LIII), are preferred.

, Furthermore, X- is an anion, and preferable examples thereof include I, Br, CzO,, BP,.

p-Toluenesulfonyl anion, p-chlorobenzenesulfonyl anion, etc. are produced.

Note that m is O or 1, but when m is 0, R□ of Φ usually has one charge and becomes an inner salt.

Further, it is preferable that the 'bifunctional group is bonded to the R0.

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

Pigment layer Φ, W R
II2. l(,.

Dl Φ Knee (CH2)201+CH3CH1)
2n tt
//D3 〃
〃 “D 4
// −(CH2), OH〃D5
//-(CI-12), C(X, IcH3//D6
ΦI[-(CI-12)20COCR3/IQ 7
ttu
II1) 8tt
tt ttD
9 〃 〃
〃D], 0 // −
(CH2)201-(〃1)11 ΦIIt
-(CI-12), 0(X)CI-j,
ttD12 // −(CH2
)60t(/.

Dl3〃-(CI,),0COCH,II1
) 14 tt tt
II1) 15
tt tt
II1) 1 6
// −(CI-1,),
,C(JOCH5//I)17 〃
〃 〃1
) l 3 // tt
ttl) ] 9
/l −(C1-12), (Jαhi H
,〃D20/l
tt ttHII
HCtO 〃 ■ −〃“
I Nφ2
//〃 ■ 〃
〃〃 ■
〃 〃u
l l(u〃
■ −〃〃
n t1 φ2
〃〃 ■
H//// VI
Nφ2〃〃l
l-1tt l/ II Nφ2
〃” ■Ht
tl ■ 〃
〃／／ ■
Nφ2〃t
l I-1〃//
'IIX //
////M
Nφ2 〃tt
H)l ttl ■
Nφ2 Such cyanine dyes can be easily synthesized according to known methods.

That is, first, the corresponding '-CH5 (ψ' represents the indole ring corresponding to Φ) is added to an excess of, for example, A.
-R□-I (here, II is an alkyl group or aryl group, A is RCOO- group, IseOC〇- group, HO- group)
ARo is introduced into the nitrogen atom in Φ' to obtain Φ-CH5i-. Next, this may be subjected to dehydration condensation using an unsaturated dialdehyde and an acid anhydride.

In addition, when A is OH, since it is converted into an acetylated form, an ester conversion reaction with methanol or the like is performed to form free OH.

The resin to be used is not particularly limited as long as it has a plurality of one or more of the above groups (A).

Those that can be particularly preferably used are listed below.

1) HO-group-containing resins Cellulose esters or their derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyethylcellulose, human o*Schiff-0-bill cellulose, methylcellulose, ethylhydroxyethylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl Butyral, polyvinyl formal, epoxy resin, phenolic resin, alkyd resin, polytyrosine, polyvinylhydroquinone, polyvinylbenzylhydroquinone, methylolated polyacrylic, amide, polyacrylhydroxyamide, polyvinylmethylol, 17-(p-hydroxyethyl)styrene or These copolymers, as well as partial hydrolysates of esters such as ethylene-vinyl acetate copolymers.

2) R′0CO- group-containing resins Homopolymers of acrylic esters, methacrylic esters, etc. or copolymers with other monomers, or partial hydrolysates thereof, maleic anhydride, bilomeriz anhydride 1[, trianhydride Esterified copolymers of mellitic acid and other monomers such as ethyl acetate.

3) f(coo-group-containing resins Cellulose acetate, acetyl butyl cellulose, etc., formalized products or butyralized products of polyvinyl acetate and partial hydrolysates of polyvinyl acetate, etc.).

The number of the above-mentioned groups in the resin is about 0.05 to 4 per repeating unit.

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

Such resin has a content of 5 to 50 wt% based on the color gradation + resin.
Used to some extent.

On the other hand, the following are suitable as the connected component.

1) 84-0H)n ethylene glycol, 1,3-propanediol, 1,
4-butanediol, 1゜5-bentanediol, 1,
6-hexanediol, 1,10-decanediol, 1
Dialcohols such as 4-cyclohexa/diol, p,p'-dihydroxy-2,2-dicyclohexylpropane, bisphenol A1 hydroquinone, p,p'-biphenol, hydroquinone dihydroxyethyl ether, polyethylene glycol (n=2-50) , glycerin, nruby], guruuse, sucrose, etc.
For example, ether.

2) Lower (methyl, ethyl, etc.) ester of polyhydric alcohol of E3-11-OCOI () 111).

3) B+COO1t') n Terephthalic acid ester, trimellitic acid ester, polymellitic acid ester, dimethyl malonate, dimethyl succinate, dimethyl methylmalonate, dimethyl glutarate, ethylenediami/tetraacetic acid L ester (EDTA ester 0 partial ester) ), hydroxyethylene diamide/tlJ vinegar 9 ester (t-i b v
polyhydric acid esters such as diethylene triamine/pentaacetate (D T I A ester), triethylenetetramine hexaacetate (T T HA ester);

4) 13(-OH)n, +0COI()n2 Esdelya curconate, partial ester of 1), etc.

5) t3-e-OCOR)n2(-COOR'),
Methyl 3-bisacetyl dimethylol propionate, ethyl acetyl milk, dimethyl acetyl malate, trimethyl acetyl citrate, dimethyl bis-acetyl tartrate, etc.

6) B, +C00R1)n3. fOH)n□Methyl dimethylolpropionate, fi! Ethyl, dimethyl malate, trimethyl citrate, dimethyl tartrate, etc.

These connecting components are usually used in an amount of 0.1 to 1 mole of dye.
It is used in an amount of 2 moles, usually an equimole amount, and is contained in the color formation resin component in such an amount ratio.

Various methods can be used for transesterification in forming such a dye-resin component.

However, it is preferable to use an alkoxide of titanium, zirconium or aluminum as a catalyst from the viewpoint of ease of production, fewer side reactions, and easy removal of impurities.

Among these, the following are particularly suitable.

B1 Titanium alkoxide tetra-i-propoxytitanium (1'P'l'), tetra-n-butoxytitanium (TBi''), tetrakis (2
-enalhexyloxy) titanium, tetrastearoxytitanium, TPTpoly-v-(n: 2-10), T
B T poly? -(n=2-10'), tributoxystearoyl titanium polymer Cn=2-10), di-i-globoxy bis(acetylacetonato) titanate, di-n-butoxy-bis(triethanolaminate)
Titanate, dihydroxy-bis(raftate) titanate, (ethylene glycolate) titanium bis(dioctyl phosphate), titanium-1-proboxyoctylene glycolate, di-1-globoxybis(ethyl acetoacetate) titanate, ToQ-n -butoxytitanium monostearate, i-propoxytitanium dimethacrylate-1-stearate.

i-propoxy titanium tris (4-aminobenzoate), i-propoxy titanium tris (dioctyl phosphate), etc.

B2 Zircon alkoxide tetraethoxyzirconate, tetra-1-propoxyzirconate, tetra-n-propoxyzirconate, tetra-n-butoxyzirconate, tetra-1-butoxyzirconate, tetra-(2-methyl)butoxyzirconate , tetra-(3-methyl)pentoxyzirconate, tetra-n-heptyloxyzirconate, tetra-n-octyloxyzirconate, etc.

B3 Aluminum alkoxide aluminum isoglobilate, mono-5ec-butygyl aluminum-11 diisopropylate, aluminum 5ec-butyrate, etc.

These catalysts have a 0.1 to 5
It is sufficient to use about wt%.

Transesterification using such a catalyst is usually carried out at an electric temperature to
Carry out the reaction at a temperature of about 60°C. At this time, the reaction is preferably carried out under reduced pressure while removing the produced lower ester. Then, if necessary, the pigment-resin component may be separated and purified.

Although the recording layer of the medium of the present invention is made of such a dye-resin component, the recording layer may also contain other resins separately.

Resins that can be suitably used are thermoplastic, self-oxidizing or depolymerizing resins, such as those described in Japanese Patent Application No. 58-1522.
There are some items listed in No. 9, etc.

Preferably, such a recording layer further contains a quencher.

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

As the quencher, various things can be used, but especially when the dye is excited and singlet oxygen is generated,
It is preferable that it is a singlet oxygen acid/char which undergoes electron transfer or energy transfer from -i-term oxygen to become excited, returns to the ground state by itself, and converts -singlet acid accumulation into a triplet state.

- As the heavyt oxygen chloride/char, it is possible to use a unique one, but in particular, it reduces regeneration deterioration and has good compatibility with the dye-tree ii and y components. , a transition metal chelate compound is preferred.

In this case, the central metals are Ni and Co.

Cu, Mn, etc. are preferred, and the following compounds are particularly preferred.

1) Acetylacetonate chelate Q I Ni (1) Acetylacetonate Q2
Cu(It) acetylacetonate Q3 Mn(Il
l) 7cetylacetoner 1.Q4 Co(II) acetylacetonate 2) Bisdithio-α-diketone system Here, ■4'l~I\4) is a substituted or unsubstituted alkyl group or a11- 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.

Q5 N1(n) dithiobenzyl Q6 N1(n) dithiobiacetyl 7 N+(C4H9)4 3) Hisphenyldithyl rule system where [51 and l(!G) are an alkyl group such as a methyl group, or Ct represents a halogen atom, etc., and M represents a Ni@0 divalent transition metal atom. Further, a and b are each 0 or a number of 4 or less.

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

Examples of this include the following:

QIO PA-1001 (Product name manufactured by Mitsui Toatsu Fine Co., Ltd.) Qlll'A-1002 [I same Ni-bis (
Toluene dithiol) tetra(1-butyl) ammonium] Q12 PA-1003 (same as above) Q13 PA
-1005 [Same as above Ni-bis(dichlorobenzene)
Tetra(1-butyl)ammonium] Q14 PA-1006 [Ni-bis(trichlorobenzenedithiol)tetra(t-butyl)ammonium] Q15Co-bis(benon-1,2-dithiol)tetrabutylammonium Q16Co-bis(0 -xylene-4,5-dithiol)tetra(t-butyl)ammonium Q171'Ji-bis(benzene-1,2-cinnaol)tetrabutylammonium Q18Ni-bis(0-xylene-4,5-dithiol)tetrabutylammonium Q191'Ji-bis(5-chlorobenzene-1,2-
dithiol) Tetrabutylammonium C20Ni-bis(3,,4,5,6-titramethylbenzene-],2dithiol) Tetrabutylammonium C21Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) Tetrabutylammonium 4) Dithiocarbamate chelate system Here, 1 (('71 and 1481 represent an alkyl group. M represents a divalent transition metal atom.

C22Ni-bis(dibutyl dithiocarbamate)
[A/Chigen NBC (manufactured by Sumitomo Chemical Co., Ltd.)] 5) Bisphenylthiol type C23Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate type Here, M represents a divalent transition metal atom. Also, M
has a constant charge and may form a salt with a cation,
Benzene Buoy may have a substituent.

C24Ni-bis(thiocatechol)tetrabutylammonium salt 7) Zalinaldehyde oxime system where R(91 and 1(lω represents an alkyl group and M represents a divalent transition metal atom.

C25N1(II) 0-(N-Inglobilformimidoyl)phenol C26N1(TI) O-(N-Dodecylformimidoyl)phenol C27C0(II) 0-(N-Dodecylformimidoyl)phenol C28Cu(11) 0-(N-dodecylformimidoyl)phenol C29N1(l[)2,2'-[trilomethylidine in ethylene bis)]-diphenol Q3o Co(TI)2,2'-C trilomethylidine in ethylene bis)]-di Phenol C31N1(II) 2 ,2'-II 1 ,8-
trilomethylidine on naphthylene bis)] - ginenol C32N1 (II) - (N-phenylformimidoyl) phenol C33Co (1) - (N-phenylformimidoyl) phenol C34Cu (■) - (N-phenylformimidoyl)
Phenol C35N1 (l [) salicylaldehyde phenyl hydrazone C36N1 (It) salicylaldehyde oxime 8) Thiobisferrate chelate system 1 (HR”) where M is the same as above and 1 ((lυ and R
Qa represents an alkyl group. Moreover, It1 has a single weight and may form a salt with a cation.

Q37 N1(If) n-butyl7'mino[2,2
'-thiobis(4-tert-octyl) 7/L/-[Cyasorb -UV-
1084 (American Cyanamide Co, Ltcl, )] Q38 Co(It) n-butylamino[2,2'
-thiobis(4-tcrt-octyl) -ferulate] Q39 N1(f[) -2,2'thiobis(4-t
ert-octyl)-ferulate 9) Phosphonous acid chelate system where M is the same as above, [((L31 and 1
< represents 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-12
(+ (manufactured by Ciba Geigy)] 11) Hifdartoamine Q52 Existing chemical substance 5-3732 [SANσ and L
S-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)] Such an entcher is synthesized according to a known method.

These quenchers are generally contained in an amount of about 0.05 to 12 moles, particularly about 0.1 to 1.2 moles, per mole of the dye in the color chart resin component.

In addition, it is preferable that the maximum absorption wavelength of the que 7 char is equal to or longer than the maximum absorption wavelength of the dye used.

As a result, reproduction deterioration becomes extremely small.

In this case, the difference between the two is preferably 0 or 35 Q nm or less.

In order to form such a recording layer, coating may be performed in accordance with a conventional method using - as the role.

The thickness of the recording layer is usually 0.03 to 10 μm8.
It is considered a degree.

In addition, such a recording layer may contain other ingredients such as this song, other dyes, other polymers or oligomers, various plasticizers, surfactants, antistatic agents, lubricants, flame retardants, stabilizers, dispersants, and crosslinking agents. etc. may be contained.

K for forming such a recording layer may be coated on the substrate using a prescribed heating medium and dried.

The heating medium used for coating includes, for example, ketone systems such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester systems such as butyl acetate, ethyl acetate, carpitol acetate, and butyl carpitol acetate, methyl cellosolve, ethyl cellosolve, etc. ):r
-- Chill type or aromatic type such as toluene or xylene,
If you use dichloroethane or other alkylated alkyl or alcohol thread, there are no particular restrictions on the purchase of the substrate on which such a recording layer is to be formed. It may be.

In addition, the shape varies depending on the purpose of use, such as tape, disk,
It may be any one such as Drano\, belt, etc.

Note that the base body usually has a groove for shifting. 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, resin materials for the base include polymethyl methacrylate, acrylic resin, epoxy resin, polycarboy,
-1.) Stain-free substrates such as sulfur oil, polysulfone resin, polyethersulfone, methylpente/polymer, etc. are suitable.

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

As the primer, for example, titanium-based, cyano-based, or aluminum-based coupling agents or various photosensitive materials (61 resin, 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 layers,
It is also possible to provide a single layer of half-mirror.

The medium of the present invention may have the above-mentioned recording layer on one side of such a substrate, or may have recording layers on both sides thereof. In addition, two recording layers are coated on one track of the substrate, and the recording layers are placed facing each other with a predetermined gap between them, and they are sealed to prevent dust and scratches. You can also choose not to have one.

(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-resin component melts due to the heat generated by the dye in the color-resin component in the recording layer.
A pit is formed.

The human body formed in this way is also caused by the movement of the medium 7'.
Reading is performed by detecting the reflected light or transmitted light of the readout light, especially the reflected light, as the wheel rotates.

In this case, it is preferable that the recording layer d and W' be extruded from the substrate side, but may be performed from the recording layer side.

It is also possible to erase the hits once formed on the recording layer using light or heat to perform 4j4: merging.

In addition, as a recording or reading source, a semicircular body laser, l-1e-Nc L/- laser, Ar laser, 1-
1e -Cd laser etc. can be used.

(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/IN ratio. especially,
After recording and storing at a high temperature, the deterioration of the read S/N ratio becomes extremely small.

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

According to the second invention, in addition to these, the light resistance against playback deterioration and the like is significantly improved.

■Specific embodiments of the invention Specific examples of the present invention are shown below.

Example 1゜As shown in Table 1 below, the above dye and the following resin were used in the molar ratio and weight ratio shown in Table 10, and this was transesterified with the following catalyst to obtain a dye-resin component. Ta.

In this case, the catalyst amount was 1 wt%, dichloroethane was used as the solvent, and the reaction was carried out at a reaction temperature of 50° C. for 2 hours.

Then, the solvent was distilled off to separate the dye-resin component.

As a result of thin layer chromatography and liquid chromatography measurements, it was confirmed that the dye was linked to the tree.

Next, these dye-dendritic components or dyes were dissolved in dichloroethane, and 0.07μ
It was applied to a thickness of m.

The resins and catalysts used are as follows.

Resin ILL Polyvinyl butyral (number average molecular weight 100,000, 0H25%) R2 cellulose acetate (number average molecular weight 100,000, esterification rate 39.4%) R3 polymethyl methacrylate (number average molecular weight 100,000) Catalyst CITB'f: C2 G i- Globoxybis (acetylate) Each sample thus prepared was heated to ts
A semiconductor laser (830
nm) to 1μ and φ, the power of the condensing part iomW),
Writing was performed with a pulse width of IQQnSec.

After this, 1mW semiconductor laser readout light was applied to 1μ5e.
cri], 3 KHz pulse, and the reflected light was detected to measure the C/N ratio.

Each sandal was then heated at 50°C and 90% relative humidity.
After storage for 000 hours, 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 effectiveness of the present invention is clear.

Example 2 In Example 1 Su/Pull/162, quencher Q14 was added at a heavy liquid ratio of 40% to the pigment in the pigment-resin component.
I obtained S/Pu/f624 with the addition of

Table 2 shows the deterioration rate (%) of reflectance when sample rot 1 was irradiated with readout light of 1 mW, 1 μS', 3 KHz for 4 minutes.

2 Sample A 2 24 Quencher-Q14 C/N ratio deterioration rate High temperature storage deterioration (%) 32 Reflectance deterioration rate Reproduction deterioration (%) 35 2 From the results shown in Table 2, the effect of the second invention is clear. be.

Applicant TDC Co., Ltd. agent Patent attorney Yo Ishii - Kanne Teito Ichimasa (Voluntary) Commissioner of the Japan Patent Office Kazuo Wakasugi Patent application filed on June 16, 1981 (2)\2 , Name of the invention Optical recording medium 3, Relationship with the case of the person making the amendment Patent applicant's office
Nihonbashi-chome 13-1, Chuo-ku, Tokyo Name
(306) Representative of TDC Co., Ltd.
Kan Okura 4, Agent 171 Address 5-17-11 Nishiikebukuro, Toshima-ku, Tokyo
Goyabe Building 1st floor Phone 988-16806 Sode j1
Contents of M11. -: j'39 Invention, the description in the column ``■-Detailed explanation'' is amended as follows.

Mn, i means rNi, Co, Cu, Mn.

Correct as P-d, PI;, :.

J゛1) Acetylacetonate chelate QI
N1(II) Acetylacetonate Q2 Cu(II
) Acetylacetonate Q3 Mn(III) acetylacetonate)・Q4Co(II) acetylacetonate 2) Hisdithio-α-diketone system Here, R, (1), and R(4) are substituted or unsubstituted represents an alkyl group or an aryl group, M is Ni,
Contains transition metal atoms such as Co, Cu, Pd, and 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) cythiobiacetyl Q7 N”(C4H9)4 3) Hisphenyldithiol system (5) (8) Here, R and R are an alkyl group such as a methyl group, or CJlj M represents a halogen atom such as Ni or Co.

Represents a transition metal atom such as Cu, Pd, PL, etc. Furthermore, a and b are each 0 or an integer of 4 or less.

Furthermore, M in the above structure has a single charge and may form a salt with a cation, and furthermore, another ligand may be bonded to the north side of M.

Examples of this include the following:

QIOPA-1ool (manufactured by Mitsui Toatsu Fine Co., Ltd.) Qll PA-1002 (same) Ni-bis(toluenethiol)tetho(7-butyl) ammonia 1,] Q12 PA-1003 (same) Q13
FA-1005 (JINi-his(dichlorobenzene)tetra(7-butyl)ammonium) Q14 FA-1006[: Ni-bis(trichlorobenzenedithiol) tetra(butyl)ammonium] Q15 Co-bis(benzene) -1,2-dithiol)tetrabutylammonium Q16Co-bis(0-xylene-4,5-dithiol)tetra(L-butyl)ammonium Q17Ni-his(benzene-1,2-dithiol)tetrabutylammonium Q18Ni-bis( 0-xyL/7-4,5-dithiol)tetrabutylammonium Q19 Ni-bis(5-chlorohensen-1,2-
dithiol) tetrabutylammonium Q20 Ni-bis(3,4,5,6-tetramethylbenzene-1,2dithiol)tetrabutylammonium Q21 Ni-bis(3,4,5,6-tetrachlorobenzene-1,2dithiol) ) Tetrabutylammonium 4) Dithiocarbamine chelate system (7) (8) Here, R and R represent an alkyl group. Moreover, M is Ni, Co, or Cu.

Represents a transition metal atom such as Pd or Pt.

Q22Ni-His (dibutyl dithiocarbamine) [
Anchiken NBC (manufactured by Sumitomo Chemical Co., Ltd.) 5) Hisphenylthiol Q23 Ni-bis(octylphenyl) sulfide 6) Thiocatechol chelate 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)tetrabutylammonilla J, 11A 7) Salicylaldehyde oxime system (9) (10) Here, R and R represent an alkyl group, and M is Ni, Co, Cu.

Represents a transition metal atom such as Pd or Pt.

Q25 Ni (II) o -(N-isopropylformimidoyl) phenol Q26 Ni (II) o - (N-dodecylformimidoyl) phenol Q27 Co (H) o - (N-dodecylformimidoyl) phenol Q28 Cu(II)o -(N-dodecylformimidoyl)phenol Q29 Ni(II)2.2'-(trilomethylidine on ethylene bis)] -diphenol Q30 Co(II)2.2'-(trilomethylidine on ethylene bis) ] -Diphenol Q31 N1 (II) 2.2 '-(1,8-naphthylene bis trilomethylidine)] - Diphenol Q32 Ni (II) = (N-phenylformimidoyl) Phenol Q33 Co (II) (N 7x Nylformimidoyl) Phenol Q34 Cu (II) -(N-7,=Lformimidoyl) Phenol Q35 N1(II) Salicylaldehyde Phenylhydrazone Q36 N1(II) Salicylaldehyde oxime 8) Thiobisferrate chelate system R (ll)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 Ni (II) n-butylamino [2゜2
'-Thiobis(4-tert-octyl)-ferulate) CCyasorb-UV-1084 (American Cyanamid Co., Ltd.) Q3
8 Co(II) n-butylamino[2゜2″-thiohis(4Lert-octyl)-ferulate] Q39 N i (II)-2,2′-thiohis(
4-tert-octyl)-ferulate 9) I Phosphonous chelate system Here, M is the same as above, and R(+3), (14) and R represent a substituent such as an alkyl group or a hydroxyl group. .

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

10) Benzate Q41 Existing chemical substance 3-3040 (tinuvin-1
20 (manufactured by Ciba Geigy)] 11) Hindered amine Q42 Existing chemical substance 5-3732 (5ANOI.

LS-770 (manufactured by Sankyo Pharmaceutical Co., Ltd.)]

Claims (1)

[Scope of Claims] 1. At least one cyanine dye having an indole ring at both ends to which an aromatic ring may be fused and the tree J]1 are composed of a -COO- group or -COO- base 2
1. An optical recording medium comprising, on a substrate, a recording layer consisting of a dye-resin component connected by two or more divalent or higher-valent linking groups. 2. The optical recording medium according to claim 1, wherein the atom or atomic group on the bond side of the linking group is 0 and/or CO. 3. The connecting group is -COO- group, RCOO- group, ■
CE0CO- group (herein, ■ (and l ('respectively represent an alkyl group or an aryl group) and HO
1 or 2 or more cyanine dyes having at least one of the - group, at least one of the following: RCOO- group, R' OCO- group, and 1''- group. between the RCOO- group and the resin
The light according to claim 1 or 2, wherein the cyanine dye and the resin are linked by transesterifying an O- group and/or an OC〇- group with a HO- group. recoding media. 4. As a linking group, it has a divalent or higher group containing two or more -COO- groups, RCOO- group, (l OCO- group (herein, 1 (and R' are each an alkyl group or an aryl group) One or more types of cyanine dyes having one or more of at least one type of HO- group and HO- group representing a group, RCOO- group, It OCO-4 OYOHI IO- group. ηIJ] “
)tcOo -M,R? OC'0- Group Oyohi H
RC ( '
0CO-,! I! The optical recording medium according to claim 1 or 2, wherein the cyanine dye and the resin are linked by transesterification with HO- and 1. 5. Transesterification of titanium and zirconium
The optical recording medium according to any one of claims 1 to 4, which is produced using an alkoxide of L aluminum as a catalyst. 6. At least one cyanine dye having an indole ring to which an aromatic ring may be fused and a resin are combined into -CO〇-
2 consisting of a group or containing two or more -Coo- groups
1. An optical recording medium comprising, on a substrate, a recording layer consisting of a dye-resin component and a phenochar connected by a linking group having a valence or higher. 7. The optical recording medium according to claim 6, wherein the atom or atomic group on the bond side of the linking group is O and/or CO. 8. The linking group is -COO- group, acoo group, lce(
JCO- group (where 1 (and H4 represents an alkyl group or an aryl group, respectively) and l-10-
One type of cyanine dye having at least one or two or more of the groups, Tah 28f or more,! :,,1(Co
o-group, R'0CO-4': k, i. and a resin having at least one of the HO- groups, transesterify the RCOO- group with the ['Y0CO- group, and/or the R'OC〇- group with the 1-10- group. The optical recording medium according to claim 6 or 7, wherein the cyanine dye and the resin are linked. 9. As a linking group, it has a divalent or higher group containing two or more -COO- groups, such as I'tCOO- group, I7oco- group (
Here, R and R' each represent an alkyl group or an aryl group) and a cyanine dye having at least one or more of l-10- groups.
Species or 2 ; E1m or more, ItCOO- group, (l
A resin having at least one of 0CO- group and IIo- group, RCOO- group, i(0CO- group and l
l(,C0U-
Claim 6 or 7, wherein the cyanine dye and the resin are linked by transesterification between the group and the 1(40CO- group and/or the 1(40CO- group and the 10-group). 10. The optical recording medium according to any one of claims 6 to 9, which is carried out using an alkoxide of titanium, zirconium, or luminium as a catalyst. Medium. 11. The optical recording medium according to any one of claims 6 to 10, wherein the phenochar is a transition metal chelate compound.