JPS6111294A - Optical recording medium - Google Patents

Abstract

PURPOSE:To lower the refractive index of the titled recording medium while enhancing a S/N ratio, in the optical recording medium having a recording layer containing a dye and a conjugate of a color cation and a quencher anion so that one of them comprises two or more of the dyes or conjugates, by improving the primer layer interposed between asubstrate and the recording layer. CONSTITUTION:A recording layer contains a dye and an ion conjugate of a color cation and a quencher anion and at least one of the dye or color cation is an indolenin type cyanine dye or a cation thereof. At least one of the dye or the conjugate contains two or more of the dyes or conjugates. In the dye and/or the conjugate used in a combination of two or more of the dyes or conjugates, the absorption max. wavelength of at least one of the dye or the conjugate has a formula represented by lambdaW-40-lambdaW+70nm to the wavelength lambdaW of writing light while the reflective max. wavelength of at least one of the other dye or conjugate has a formula represented by lambdaR-40-lambdaR+70nm to the wavelength lambdaR of reading light (usually same to writing light). Further, a primer layer comprises a film formed of a colloid particle dispersion of a siliceous condensate.

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 the characteristic that the recording medium does not deteriorate due to wear and tear because the medium and the writing or reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical i-recording media are being actively developed because they do not require development in a dark room.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. For example, a part of the medium is melted or removed using recording light such as a laser, and a part of the medium is melted or removed to form a pit. There is a pit-forming type in which writing is performed by forming small holes, recording information using the pits, and reading by detecting the pits with a readout light.

In such bit-forming type media, especially those that use a semiconductor laser as a light source, which allows for miniaturization of devices, up until now, Te-based materials have been used as the recording layer.
Most of the things that I do.

However, in recent years, because Te-based materials are harmful, and there is a need to increase sensitivity and reduce manufacturing costs, organic materials, mainly dyes, are being used instead of Te-based materials. There are an increasing number of proposals and reports on media using recording layers.

For example, for He-'Ne laser, squarylium dye [JP-A-58-48221%V.

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

Technol,, 18' (1) 105 (IH
I)) and metal di-thalocyanine dyes (Japanese Patent Application Laid-Open No. 57-8
No. 2094, No. 57-82095), etc.

There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-Open No. 88795/1983).

All of these have a recording layer formed into a thin film by vapor deposition of a dye, and there is no major difference from the Te type in terms of medium production.

However, the reflectance of a dye-deposited film to a laser is generally small, and the current conventional method of obtaining a readout signal by changing (reducing) the amount of reflected light due to pits cannot achieve a large S/N ratio.

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

This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate).
In addition, the surface reflectance is relatively high (4%), and the reflectance through the substrate of the recording layer is about 601% or less for polymethyl methacrylate, for example, so it is difficult to detect a recording layer that exhibits only a low reflectance. Because you can't.

In order to improve the readout S/N ratio of a recording layer made of a dye-deposited film, Af is usually added between the substrate and the recording layer.
A vapor-deposited reflective film such as L is interposed.

In this case, the vapor-deposited reflective film is intended to increase the reflectance and improve the S/N ratio, and the reflective film may be exposed due to pit formation and the reflectance may increase, or in some cases, the reflective film may be removed. It removes the reflectance and reduces the reflectance.
Naturally, recording and reproduction cannot be performed through the substrate.

Similarly, in JP-A-55-181890, IR-13
A recording layer consisting of two dyes (manufactured by Kodak) and polyvinyl acetate;
'-diethyl-2,2''-) lycarpocyanine iodide and nitrocellulose;
s.

Lett, 311 (9) 71B (1981) describes a recording layer comprising 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate, etc.
A medium is disclosed in which a recording layer made of a dye and a resin is provided by a coating method.

However, these cases also have the same drawback as the dye-deposited film in that a reflective film is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the back side of the substrate.

In this way, recording and reproduction through the substrate is possible,
In order to realize a medium having a recording layer made of an organic material that is compatible with a medium having a recording layer made of a Te-based material, the organic material itself needs to exhibit a high reflectance.

However, conventionally, there are very few examples of a single layer of organic material exhibiting high reflectance without laminating a reflective layer.

It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance (P, Kivits et al.
Appl, Phys, Part A 28 (2)
101 (IHI), JP-A-55-137033], but the writing sensitivity is low, probably due to the high sublimation temperature.

In addition, cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes have been reported [Yamamoto et al., Proceedings of the 27th Japan Society of Applied Physics, 1p-P-9 (1980)].
A proposal based on this was made in JP-A-58-1127110, but these dyes have low solubility in solvents, are easily crystallized, and are more sensitive to readout light, especially when applied as a coating film. It is extremely unstable and immediately discolors, making it unsuitable for practical use.

In view of these circumstances, the present inventors first developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It is proposed to be used as a single layer film (patent application filed in 1973).
No. 7-134387, No. 577134170).

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. 57-182588, Patent Application No. 57-177778, etc.)
.

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a transition metal compound quencher to cyanine dyes to prevent regeneration and deterioration.
Patent Application No. 57-188832, No. 57-1111H4B
No. etc.).

Furthermore, we have proposed forming an ionic bond between a dye anion and a quencher, thereby further reducing regeneration deterioration and increasing stability (Patent Application No. 59-14).
No. 848, No. 511-18878, No. 59-1971
No. 5).

He also proposed a recording layer containing a mixture of an indolenine cyanine dye and a conjugate, and showed that the sensitivity and S/N ratio were further improved (Japanese Patent Application No. 59-915 Ei
No. 7).

Furthermore, we proposed a recording layer containing two or more types of at least one of an indolenine cyanine dye and an ionic conjugate, and proposed an optical recording medium that has optimal conditions corresponding to the maximum reflection wavelength and maximum absorption wavelength of lasers, etc. are doing.

Incidentally, such a dye or dye composition is applied as a coating film as a recording layer on a resin substrate that is transparent to writing light and reading light, and writing and reading are performed particularly from the back side of the substrate. In such cases, the surface of the resin substrate may be damaged by the coating solvent during coating.
This has the disadvantage that the reflectance of the recording layer decreases and the S/N ratio for reading cannot be sufficiently high.

Furthermore, during long-term storage, there is a risk that dyes and other additives may dissolve and diffuse into the substrate resin, resulting in a decrease in reflectance.

Furthermore, writing causes damage to the substrate such as dents and stripes due to heat, which also lowers the S/N ratio. Moreover, the noise after erasing increases.

On the other hand, the present inventors used Ti, Zn as the base layer.
, proposed the use of a hydrolyzed coating film of a chelate compound such as AM (Patent Application No. 57-2321H, No. 57-2).
32199 etc.).

Thereby, the above-mentioned disadvantages are improved.

However, the preparation conditions and coating conditions for the base layer coating solution are strict,
Furthermore, the coating solution lacks storage stability, and it is not easy to obtain a constant base layer. Furthermore, since it has a higher refractive index than the substrate, it has drawbacks such as a decrease in reflectance.

Furthermore, although silane solution hydrolyzate coatings and silicon oxide vapor deposited coatings are known, these are insufficient in terms of imparting solvent resistance and heat resistance to the substrate.

Further, examples in which an inorganic compound is provided as a protective layer on the surface are known, but in all cases, the film thickness is required to be 0.2 gm or more. In this case, it is known that sensitivity generally decreases.

In an optical recording medium made of a dye composition, pits are formed simultaneously with light irradiation, and subsequent irradiation light is no longer absorbed in the center where the energy is most concentrated. Therefore, the energy utilization efficiency is low, which is the reason why the sensitivity cannot be improved beyond a certain value.

The object of the present invention is to provide an optical recording medium having a recording layer containing a dye, a combination of a dye cation and a quencher anion, and two or more types of at least one of them, on a resin substrate. In this method, the underlayer interposed between the substrate and the recording layer is improved to lower its own refractive index and improve the S/N ratio.

Furthermore, a surface layer is provided on this recording layer, and the surface layer is improved to improve the writing sensitivity of the optical recording medium.

These objects are achieved by the invention described below.

That is, the first invention provides an optical recording medium having an underlayer on a resin substrate, and a recording layer on the underlayer containing a dye and an ionic combination of a dye cation and a quencher anion. , at least one of the dye and the dye cation is an indolenine cyanine dye or a cation thereof, and at least one of the dye and the ionic conjugate is contained, and at least one The maximum absorption wavelength of the dye or ionic conjugate is one wavelength of the writing light, On+w to +70n+w, and the maximum reflection wavelength of at least one dye or ionic conjugate is one 40 nm to +70 nm of the wavelength of the reading light, The optical recording medium is characterized in that the underlayer is made of a coating film of a colloidal particle dispersion of a silicon-based condensate.

Further, the second invention has a base layer on a resin substrate, a recording layer containing a dye and an ionic combination of a dye cation and a quencher anion on the base layer, and a recording layer containing a dye and an ionic combination of a dye cation and a quencher anion. In an optical recording medium having a recording layer and a surface layer thereon, at least one of the dye and the dye cation is an indolenine cyanine dye or a cation thereof, and at least one of the dye and the ionic conjugate is an indolenine cyanine dye or a cation thereof. and the maximum absorption wavelength of at least one dye or ionic bond is between 40 ns and +70 B■, the wavelength of the writing light, and the maximum reflection wavelength of at least one dye or ionic bond is 40 ns to +70 B■. is a wavelength of readout light of −40 nm to +70 nm, and the underlayer and surface layer are formed of a coating film of a colloidal particle dispersion of a silicon-based condensate.

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

The recording layer of the optical recording medium of the present invention contains a dye and an ionic combination of a dye cation and a quencher anion.

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

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

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

There are no particular restrictions on the indolenine cyanine dye, and various types can be used.

However, when incorporated into the recording layer as various indolenine cyanine dyes, the writing sensitivity is high;
A cyanine dye having a high readout S/N ratio is represented by the following general formula CI).

General formula CI) (In the above general formula (1), Z and 2' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R1 and R1' are , each represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, X- represents an acid anion, m is O or l, ) In the above general formula (I), Z and Z' are 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 Represents the atomic group necessary to complete the dibenzoindolecon ring.

The ring completed by Z (hereinafter referred to as Φ÷) and the ring completed by 2' (hereinafter, the following may be the same or different, but
They are usually the same, and various substituents may be bonded to these rings.

These i+ and! As the skeletal ring, the following formulas [Φwork] ~ [Φ■] and [! I]～[! (2) It is preferable to use the one shown in [2].

[Φm) (Ra)q (Ralq ('PIII) (R4') q') In various eggs such as These are an alkyl group, an aryl group, and an alkenyl group.

Groups R1 and R'1 bonded to the nitrogen atom in such a ring
There is no particular restriction on the number of carbon atoms in .

In addition, if this group further has a substituent,
Examples of substituents include sulfonic acid groups, alkylcarbonyloxy groups, alkylamido groups, alkylsulfonamide groups, alkoxycarbonyl groups, alkylamino groups, alkylcarbamoyl groups, alkylsulfamoyl groups, hydroxyl groups, carboxy groups, halogen atoms, etc. It may be.

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

Furthermore, at the 3-position of the indolenine ring, two substituents R2
, R3, R2'', and R3' are preferably bonded.

In this case, the two substituents R2, R3, R
2' and R3' are preferably an alkyl group or an aryl group.

Among these, unsubstituted alkyl groups having 1 or 2 carbon atoms, particularly 1, are preferred.

On the other hand, Φ+ and ! Further, other substituents R4 and R4' may be bonded to a predetermined position in the ring represented by. Such substituents include alkyl groups, aryl groups, heterocyclic residues, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, arylcarbonyl groups, alkyloxycarbonyl groups, aryloxy carbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamido group, arylamido group, alkylcarbamoyl group, arylcarbamoyl group, alkylamino group,
Various substitutions such as arylamide 7 group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfa, moyl group, cyano group, cotro group, etc. It may be a base.

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

s, t) are usually 0 or about 1 to 4. In addition, when p+q+r, s, and t are 2 or more, multiple R
4, 1 (4' may be different from each other.

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

On the other hand, L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, tri- or tetracarbocyanine dye, and is particularly preferably one of formulas (LI) to (LX[). .

Formula (LI) Formula [L■) CH=C)i-C=CH-CH formula [
L ■) CM-C=CH-CI (↓ Formula (LIX) C ↓ Here, Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group is a lower alkyl group such as a methyl group. group, a lower alkoxy group such as a methoxy group, a di-substituted amino group such as a dimethylamino group, a diphenylamino group, a methylphenylamino group, a morpholino group, an imidazolidine group, an ethoxycarbonylpiperazine group, and 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 or C1.

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

And the sentence is 0 or 1.

Furthermore, X- is an anion, and as a preferable example thereof,
For example, I, Br, C sentence 04, BF4.

CR3<>S 03- , C father 05O3-, etc. can be mentioned.

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

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

Color'shiyin sitting, -! K1-JLL
-WLDi (ΦI)
C) (3CH3D2 (ΦT)
CH3CH3D3 (ΦI)
C2H40HCH3D4 (Ol)
((,-glat (a 'gF two,
. CH3D5 [ΦH] CH3
CH3D 6 [9m) ((CI(2
) 3 303 2 CH3(CH
2) 3 303 Na” D7 (9m) CH2CH20H
CH3D8 (cam) (CH2)
2 0COCH3CH3D9 (ΦIII)
(CH2)2 0COCH3CH3D10
[9m) CH3CH3D11 (9
m) CH3CH3D12 [Φwork]
Cl8H37CH3D13 [ΦI]
C4) (9CH3D14 [Φ■] C3H1
80COCH5CH3D15 [ΦI]
CHC1(ORCI(3LL ↓-?
-X--(Llj) HI-(LII:) HCmata104-
(Lm) HBr-(LII:]
H- - [LII) H0 sentence 04- (L
IE: ] H' --
(LIT) H0 Sentence 04- (L
H) HBr(Lm) -N(C8
H5) 200 sentence 04- (Lll)
H0 sentence 04 (Lm) -N (
C8H5) 2 0 0 sentence 04-(I, II)
H'I-(Lll) H
ClO4(Lm)-N(CsHs)2
0 ClO4-(LTI) H
1 Renren Tsuta Men-Pun LL work 1 top and work 1 yu” D18 (Φn) C8H, 7CH
3-D17 [9m] C8H17CH3-Dl
B (Om) C7H14COO-CH3-
'C7H14C0OH DlB [Φ■] C7H14COOC2H5CH3
-D20 [9m] C4H8CH3-D21
[9m) c18H3□ CH
3-D22 [9m) C, H8CH3, -D23
[ΦI) CHCOOCH3CH3-D24 [
ΦI) C3H160COCH3CH3-D25
[Φr] C8H17C2H5-D26 [ΦI
) c, -t H15C2H5-D27 [Φn
) CHC00CI(3CH3-D28 [ΦI
I) Ca H16CH2'OCOCH3CH
3-D28 [ΦIl] C17H3S
CH3-LLL
”-Mataru-X--(Lll)
HC Mata 04- (LII)
H--(Lm) /-\
--N N-QID! )1
5 0-(Ll'l)
HBFa-(Lm)-N(C6H5)2
0 CfLO4-(Lll)
H0 sentence 04- (Lrl)
HC Mata 04- (LII)
HI-(Lm)-N(C8H5)2
0 I-(LII) 1(
I-(LH) l(I-(LII)
HC look 04ha. 1 - (Lm) -＼-2-雫"5 = (LIV) -N N-Momme85
0 C or 04 Mu imperial treatment beg v lL-shi-shi” YuD30 (OII) CHC00CH
C2H5031(Om) C7H1,CH20HC
H3D32 [Φ■] c7H14cH2ococ2H5c
H3D33 (OII[) C,7H34COO
C2H5CH3D34 (Om) C17H35
CH3D3a (Om) C7H15C2H3D
3El (OIV) CH3C) (3D37
(Off) (, H3CH3D38 (OI
V) C4H9CH3D39 (4+IV)
(CH2)20COCH3CH3D40 (OI)
CHCH0COCH3CH3D41 (OI)
CH2CH201 (CH3D 42 (OII
I) CH3CH3D43 (OI)
C2Hs CH35-C6D44
(()I) C2H5CH3,5-C6D45
(OI) C2H6CH35-CajLt
L--E-1 -X--(L■)
Hcio4-(LII) HClO4-(L
II) HI (L■) -N(C6H5)2 0 I
(III) HOI - (LII) HI - (Lll) HI - (LII) HCn0a - (LII)
H0 sentence 04- (LII)
HI-(LIT) HClO4-
(LII) HBr (L■) Br Cl0a
H5502 (LVI) B r
1 1Hs 50.2 (Lm)
C1I Cl0aH6SO2 (Lm)
CJL OI person anti-men-j
K1-JLL' k-work 1 46 [Φ
I) C2H6C)13D47 [ΦI)
C2H5CH3D48 [ΦI]
'C2H5CH3D49 [ΦI) C
2) (5CH3D50 [ΦI) C2H
5CH3D51 [ΦI] CH3CH3
D52 [ΦI] CH3CH3D53
[ΦI) n-C4Hg
CH3D54 [ΦI] n-C6H13C
H3D56 [ΦI] C2Hs
CH3D57 [ΦI]
CH3CH3D58 [ΦI) C2H
5CH3D53 [ΦI) C2H5CH
3D80 (ΦI) C2H5H3-andi L--E also-
X-5-Co H5302 (Lm) 0 sentences
0' CH3fl, 8)! 4SO35-C61 (53
02 (LVI) 0 sentences I
BF45-Ca Hs 302 (L■)
0 sentences I Cl045-Co
H5302 (LVI) Cl Ol5
-C8H5SO2(LVI) CI O0
H3C6)! , 5o35-C6Hs 502 (
LVI) 0 sentences OCCl045C6
H5SO2(LVI) CfL O
l5-Ca H5502 (LVI) 0 sentences
I CfLOa5-C8H5SO2(
LVI) C1l 0 sentence 04::a)I
sSO2(LVI) C11-5'-C6H53
02' (LVI) N-=C=C-CM
1-5-Ca H5302 (LVI)
N-=C-C-0Nl-5-Cs
H5Co (Lm) C view
I l5-Co H5CO (Lm)
B r I l5-C
6H5Co (Lm) ' 0 sentences
IC Mi O4 Jinjin Selection Mini J LL Engineering 1
Top 'C' D81 (ΦI)
C2H5CH3'D62 [ΦI) C2
H5C3 (3D63 [ΦI) C2H5C
H3D64 [ΦI] C2H5CH3D6
5 [ΦI] CH3CH3D6B [
ΦI) CH, 3CH3D67 [ΦI)
C2H40COCH3CH3D68 [ΦI
) CH3C) (3D68 [ΦI)
CH3CH3D70 [ΦI] CH2C
6Hs CH3D71 (Φm)
CH3CH3D72 [ΦI) C
H3CH3D73 [Φm) -CH3CH3-
1I L Y Cross -X-
5-C,a Ht, Co (Lm) Cl
l (:H3C6H,5O35-C6Hs
Co (LVI) C look I C intersection 045-C61 (,, co (I, Vl)
C-cross I I5-C8H5CO (LVI
) 0 sentences 0CH3C6H4S035-CH3C
o (Lll) HC9,0a5-CH3C
o (Lll) HI5-CH3Co
(LII) HI5-0 sentence
(LX) −=
(LX)
-5-0 sentences (LX)
--(LX)
--(LX[)
-1(LX[)
-Also, these cyanine dyes are nitrogen-containing heterocyclic compounds I
It can be easily synthesized according to the method described in the apparatus on page 432, etc.

That is, first, the corresponding Φ--CH3 (Φ" represents the ring corresponding to the above Φ) is heated with excess RI I (R1 is an alkyl group or an aryl group), and R1 is converted into nitrogen in Φ". into the atom to obtain ΦmCH5I-.
Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst.

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

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

For example, single or co-condensates of the above dyes having one or more functional groups such as -01(, -COOH, -3O3H, etc.), or combinations thereof with dialcohols, dicarboxylic acids, or their chlorides. , diamine, di- or triisocyanate,
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, aminoalcohols, enols) those with active hydrogen compounds, etc. as ligands)
, shearates of titanium, zircon, aluminum, etc.

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

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

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

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

In addition to the above, the recording layer of the optical recording medium of the present invention contains a combination of a dye cation and a quencher anion.

The conjugate is particularly preferably a combination of an indolenine cyanine dye cation and a quencher anion represented by the following general formula (n).

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

Z, Z', R, and R1' are the same as in the general formula [E] above.

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

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

Small-LL 1L-11uf 'FD”
l ΦlCH3CH3-? ID÷ 2ΦI
C2Hs CHs5-CH3SO2ψI
D+ 3 Om CH3CH3−'PmD”4
Φmc8H17CH3-! mD”5 0mcH
CH3-'I'mD”6 ΦmcH3CH3-9
■D”7 Φm CH20H20COCH3CH
3-'f IIIG 18 Φm 0820H,
,0COCH3CH3-'l'mD"9 Φm
cCH3CH3−%PI[[D”lO0mCH3CH3−
'l'ID+ 11 ΦITCH3CH3-'l'lID+
12 Φm C4H9CH3−ψ■D+13
+14 from ΦI 0H2CH20HCH3-ψ
Φm CH2C)120)1. CH3-
'I'm on top'Hibini'Yu'LL' L
Y-Also CH3CH3-L II H- C2Hs CH35-CH3SO2Lm N
(C6)15) 21CH3CH3-L II
H- C8H17CH3-LHH- C18H37CH3-LHH- CH3CH3-Lm N(C8)15)21CH2
CM20COC)13CH3-LHH-CH2CH20
COCH3CH3-LIIIN(C6H5)21CH3
CH3-LVI Br lCH3CH3,
LII H- CH3CH3-LrI H- C4H9CH3L II H- CHC) IOHCH3-Lrl H-CH2CH
20HCH3-LHH- Small RL LLLfii ui'
FD” +5 Om C4Hg
CH3-'I'mD+18 Φ Engineering CH2CH20C
+ 17 Φ work CH3 from OCH3CH3-ψ
+18 0mCH3CH3-'P from CH3-ψ
mD”19 ΦI CH3CH3−ψ +
20 ΦlCH3CH3-'PID+ 21
Φwork CH3CH3-! ID+22, Om
CH3, CH3-'I'mD+23 ΦT
CH3CH3-heavy D+ 24 ΦI CH
3CH3−ψ■−l上′Andneell′! L
L' ↓−η− Sentence Ca H9CH3L m N(
Ce)+5) 210H2CH20COCH3CH3-
LIT H-CH3CH3-L VI [H- CH3CH3L vII H- CH3CH3L m N(C8H5) 21CHa
CH3LVI Br I
CH3CH3-L II C5L-CH3CH3
-L II 0 sentences -CH3CH3-LI
I H- CH3CH3-Lm N(CH) 1 These indolenine cyanine dye cations usually take the form of a monomer, as already mentioned for the indolenine cyanine dye, but if necessary, they can be added to a polymer. It may be a shape.

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

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

On the other hand, Q- represents a quencher, -7ion. In this case, as the quencher anion Q- constituting the conjugate, various 7-ion forms of quenchers can be used, but in particular, regeneration deterioration is reduced and compatibility with the dye-binding resin is good. It is preferable that it is the 7-ion of the transition metal chelate compound because of the fact that it is 2.

In this case, the central metal is Ni or Co.

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

l) A bisphenyldithiol system represented by the following formula, where R1 to R4 represent hydrogen or an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C1, or an amino group such as a dimethylamino group or a diethylamino group. , M represent a transition metal atom such as Ni, Co, Cu, Pd, or Pt.

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

Examples of this include the following:

RRR34 12RM Q-1-I HHHHN1 Q-1-2H, CH3HHNi Q”'l-3H0 sentence C view HN1Q-1-4
CH3HHC[3Ni Q-1-5CH3G)13 CH3CH3N1Q
-1111H0 sentence HHNi Qml-70 sentence C view 0 sentence C again N1
Q-1-8HC10 sentence C again N1Q-18HH
HHC.

Q-1-10HCH3CH3HC.

Q-1-11HCH3C)+3HNt Q -1-12HN(CH3)2 HHN IQ-1-
+3 HN(CH) N(CH3)2HN iQ
”'1-14 HN(CH)()+3HNLQ-
1-+5 , )(N(CH) C HN
iQ-1-18HN(CH)2HHNi 2) Bisdithio-α-dike represented by the following formula,
R5 to R8 represent a substituted or unsubstituted alkyl group or aryl group, and M is Ni, Co, Cu, Pd.
, represents a transition metal atom such as Pt.

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

R5R11i R7R8M Q”'2-1φN(CH3)2pb Small N(C)+3
)2 Pb N 1Q-2-2'ph p
h ph ph N1Q-2-3(
N(OH3)2ph φN(Ci(3)2ph N
i3) Those represented by the following formula, where M represents a transition metal atom, and Ql represents the following.

M ship- Q-3-I Ni Q12Q
-3-2Ni Q"Q-3-3Co Q]2 Q-3-4Cu Q12 Q-3-5Pd Q12 4) Something represented by the following formula, where M represents a transition gold atom, all and R12 are CN, C0R1?14 respectively
15 1BCOOR,
C0NR, R or 5O2R17; H to R17 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group; Q2 represents an atomic group necessary to form a 5- or 6-membered ring; .

M A Q-4-I Ni 5Q-4-2
NiSQ-4-4NiC(CN)2Q”
'4-5 N i C (CN)
25) Those represented by the following formula Q-5-I N + In addition, those described in Japanese Patent Application No. 127075/1982.

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

Further, the benzene ring may have a substituent.

7) Those represented by the following formula, where R18 represents a monovalent group, the number is 0 to 6, and M represents a transition metal atom.

Mouse-R1- Q-7-I N i H0 Q-7-2Ni CH31 8) Thiobisferrate chelate system represented by the following formula, where M is the same as above, R85 and R6[1
represents an alkyl group.

RRM Q-5-1t-cs H17N IQ-8-2t-
C3H17CO Note that among the above quencher anions, the above 1)
Most preferred are those based on phenylbisdithiol.
This is because reproduction deterioration due to read light is further reduced and light resistance is extremely high.

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

D+ R Knee-5I
D”l Q-1-832
0”l Q-1-12S3
D" 2 Q-
1-12S4 D”l
Q-1-3S5 D”3
Q-1-8S6
D” 3 Q-1-1237D
-4' Q-1-838D”5
Q-1-8390”6
Q-1-8310D”7
Q-1-8Sll D” 7
Q-1-2S12
D” 8 Q-1-12
313D” 9 Q-1-12
314D" 10 Q-1-12
315D” 11 Q-1-12
S18 D” 3
Q"' L-73I7
D"+2 Q"' 1-12
S18 D” 13
Q-1-133191)” 14
Q-1-14S20D
” +5 Q-1-15S21
D+ 16
Q-1-1BS22 D+l?
Q"' l-1?S23 D
+ 17 Q-1-17S24
D+ 18 Q-
1-18325I)” 18 Q
-1-18826D+l Q-1-IS
27 D,” I
Q-1-2328D"l
Q~ 1-13329 I)+
t Q-t-+a330
D+19 Q-1-8331D+
20 Q-1-8332D+20
Q-1-12333D+ 21
Q-t-gS34 D”
21 Q-1-12335D+
21 Q-1-7S38
D+19 Q-1-12337D”
3 Q-1-7338D+9
Q-1-8339D” 9
Q-1-7340D+9 Q-1
-2S41 D+ 9
9-1-13342 D+
22 Q-1, 8S43
D+ 22 Q-1-12S4
4 D" 11
Q-1-8345D" 11 Q-
1-23480" 11 Q-1-
7347D" 11 Q'-1-1
33480+23 Q-1-8349
D+ 24 Q-1-2S50
D" I Q-1-
3351D+ 3 Q-3-IS
52 D+2 Q-2-I
S53 D+4
Q-8-IS54 D+6,
Q-7-IS55 D” 5
Q-5-2358D+7
Q-6-IS57 D+8
9-7-1358
D+9 Q-4-IS59
D” 11 Q”
-1-3S80 D+ 40
Q-1-83810" 41
Q-1-8382D÷ 42 Q-1-
12 Such a photostabilized cyanine dye, which is a conjugate of the present invention, is produced, for example, as follows.

First, a cationic indolenine cyanine dye bonded to an anion is prepared.

In this case, the 7-ions (An-) are I"', B
r-, ClO4-, BF4-.

CH3<> 303.0 sentence 03O3- etc. is sufficient,
It is synthesized as described above.

On the other hand, an anionic quencher bonded to a cation is prepared.

In this case, the cation (Cat'') is particularly N1.
Tetraalkylammoniums such as CH3)4, N''(C4N9)4 and the like are preferred.

In addition, these quenchers are
No. 2, Japanese Patent Application No. 58-183080, etc.

Next, equimolar amounts of the cyanine dye and quencher are dissolved in a polar organic solvent.

As the polar organic solvent used, N,N-dimethylformamide and the like are suitable.

Further, its concentration may be approximately 0.01 mol/cross.

Thereafter, an aqueous solvent, particularly water, is added to this to cause double decomposition and to obtain a precipitate. The amount of water added may be in excess of 10 times or more.

Incidentally, the reaction temperature is preferably room temperature to 90°C.

This operation is then repeated as necessary.

Next, the two liquid phases are separated, filtered and dried, and recrystallized with DMF-ethanol or the like, thereby converting the light-stabilized cyanine dye into a light-stabilized cyanine dye.

In addition to the above method, a neutral quencher cation intermediate may be dissolved in methylene chloride or the like, and an equimolar amount of cyanine dye may be added thereto, concentrated, and recrystallized.

Alternatively, nickel may be oxidized to form an anionic salt while blowing air according to Japanese Patent Application No. 57-188832.

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

These preferably indolenine cyanine dyes and the preferably indolenine cyanine dye cations forming the conjugate may be the same dye or different.

The amount ratio of the ionic binder to the dye is 1 by weight of the dye.
It is 0 to 80 wt%, preferably 20 to 60 wt%.

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

The dyes and/or binders used in combination of two or more of these are such that at least one of the dyes or binders has a maximum absorption wavelength with respect to the wavelength input W of the writing light.
-40～, +7on Otori.

Further, the maximum reflection wavelength of at least one of the other dyes or conjugates is in the range of input R-40 to input B+70 nm with respect to the wavelength input R of the reading light (usually the same as the writing light).

The input R and input W are usually 830n or 78
A 0 nm, 750 nm semiconductor laser light is used.

Therefore, for example, when input R = input ν = 830 nm, the reflection maximum wavelength is input R-40 to input R + 7 On fat indolenine-based cyanine dye or conjugate is group A, and the absorption maximum wavelength is input, -40 nm. If the indolenine-based cyanine dyes or 2-conjugates containing .

Group A I) 1, D, D3. D4. D9. Dll.

D12. D13. DI4. D15. D18゜1vzo,
n2s, n2s, n2e, nas.

D49,050. D51. n5e, n5e.

060, D64. D65,066.067 etc. 31, S
2, 33, 34, 35, 56°S7, 313, 515,
317,318°S19,520,324. S25,3
26゜327, S28, 329, 331.332゜52
7, S38, 339, 340, 341° 344.345
．． 346.347.348.

350, S51, 352. S53. S58゜S59 etc. Group B D5. D6. D7. D8. D9. Dlo.

Dll, 014,016,017,018°019.
020. D21. D2.2. D24°D27. D28.
D29,030. D31°D32. I)33. D34.
D35. n3e.

D37, D38, D39, D43, D
44.

D47. n4e, D53. D54. D55゜n5e, D
57. D61, D62. D63 etc. 3B, 39. SIO
, Sll, S12°313, S14. S15,321.
S22°323.324. S25, 330, 331
.

S32. S33. S34, 335, 336°S38. S
39. S40. S41,342°343. 344
, S45 , S46 , S47 .

348. 349. 354, S55. 356
.

S57. S58, 359, etc. On the other hand, as an indolenine cyanine dye whose maximum reflection wavelength when input = input w = 780 nm is input R-40 to input + 70n, the above group B is preferable, and the maximum absorption wavelength is As the indolenine cyanine dye having a wavelength of -40 to +70ne, the following group C is preferable.

Group 0 D40. D41. D42 etc.S60,361. Regarding the dyes or conjugates used in combination, such as S62, one may meet the above conditions only at the maximum reflection wavelength, and the other may meet the above conditions only at the maximum absorption wavelength.

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

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

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

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

Moreover, the ratio is absorption maximum wavelength λv 40~λ, +
and a total of 70 n■ dyes or conjugates.

The total molar ratio of dyes or conjugates having maximum reflection wavelengths λR-4 to 11+70 ns may be about 8:2 to 228.

Two or more types of such dyes or combinations 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 a resin if necessary.

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

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

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

ii) Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, engineered ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-maleic anhydride copolymer,
such as ethylene propylene terpolymer (EPT).

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

ii) Vinyl chloride copolymer, for example, vinyl acetate-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-maleic anhydride copolymer, acrylic ester or methacrylic ester and vinyl chloride copolymers, acrylonitrile-vinyl chloride copolymers, vinyl chloride ether copolymers,
Ethylene or propylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer with vinyl chloride graft polymerized, etc.

In this case, the copolymerization ratio can be arbitrary.

Vinylizone chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-7crylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

m) Polystyrene m) Styrene copolymer such as styrene-acrylonitrile copolymer (As resin), styrene-7crylonitrile monobutadiene copolymer (ABS resin), styrene-maleic anhydride copolymer (SMA resin) ), styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer (SBR), styrene-vinyritine chloride copolymer, styrene-methyl methacrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

ii) Styrenic polymers such as α-methylstyrene, p-methylstyrene, 2
, 5-dichlorostyrene, α.

β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinylanthracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic acid ester.

m1ii) Coumarone-indene resin Coumarone-indene-styrene copolymer.

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

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

In the above formula, R10 represents a hydrogen atom or an alkyl group, and R2O represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R10 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. A group, especially a hydrogen atom or a methyl group, is preferred.

Further, R2O may be a substituted or unsubstituted alkyl group, but the number of carbon atoms in the alkyl group is preferably 1 to 8, and when R2O is a substituted alkyl group, the alkyl group is The substituent to be substituted is preferably a hydroxyl group, a halogen atom, or an amine group (particularly a dialkylamino group).

The atomic group represented by the above formula may form a copolymer with other repeating atomic groups to constitute various acrylic resins, but usually one of the atomic groups represented by the above formula An acrylic resin is formed by forming a homopolymer or copolymer in which the species or two or more species are repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer, for example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer , acrylonitrile-methyl methacrylate copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile niacrylmibutyl copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

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

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

The copolymerization ratio may be arbitrary.

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

xiii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-1o, nylon 6-12. In addition to regular homonylons such as nylon 9, nylon 11, nylon 12, and nylon 13, nylon 6/6-676-1
0, nylon 6/6-6/12, nylon 6/6-6/
Polymers such as No. 11 or modified nylon may be used as the case may be.

xv i i i) Polyesters with various dibasic acids such as aliphatic dibasic acids such as oxalic acid, succinic acid, maleic acid, adipic acid, sebastenic acid, or aromatic dibasic acids such as isophthalic acid and terephthalic acid. , condensates and cocondensates with glycols such as ethylene glycol, tetramethylene glycol, and hexamethylene glycol are suitable.

Among these, condensates of aliphatic dibasic acids and glycols and cocondensates of glycols and aliphatic dibasic acids are particularly suitable.

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

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

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

xx) Polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

In particular, polyurethane resins obtained by the condensation of glycols and diisocyanates - 1 and polyurethane resins obtained by the condensation of alkylene glycols and alkylene diisocyanates are particularly suitable.

xi) Polyether styrene formalin resin, ring-opening polymer of cyclic acetal, polyethylene oxide and glycol, polypropylene oxide and glycol, propylene oxide-ethylene oxide copolymer, polyphenylene oxide, etc.

xxii) Cellulose derivatives such as nitrocellulose, acetylcellulose, ethylcellulose, acetylbutylcellulose, hydroxyedylcellulose, hydroxypropylcellulose,
Various esters and ethers of cellulose, such as methylcellulose and ethylhydroxyethylcellulose, or mixtures thereof.

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

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

Li, Zn, Mg salts, etc.

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

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

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

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

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

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

In order to form such a recording layer, the underlayer of the present invention may be formed on the substrate, and then the recording layer may be coated on the underlayer.

The thickness of the recording layer is usually about 0.03 to 2 pLm.

The thickness of the recording layer is 0.04 to 0.12 m, especially 0.0 m.
It is preferable that it is 5-0.08 gm.

Below 0.04 pLm, particularly 0.05 pLm, both the absorption and reflection amounts are small, and neither the writing sensitivity nor the reproduction sensitivity can be made large.

If it is 0.12 gm 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 crosslinking agent and a crosslinking agent may also be included.

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 substantially transparent to writing light and reading light.

The base body is made of resin.

Various materials are possible for the resin.

However, among such resins, acrylic resins are particularly susceptible to the various coating solvents mentioned above, especially ketones, esters, halocare alkyls, etc., and the effect of the base layer of the present invention is particularly large. Or polycarbonate resin.

Since these are substantially transparent to writing and reading light, writing and reading can be performed from the back side of the substrate, which is advantageous in terms of sensitivity, S/N, ratio, etc., and is also dust free. This is also advantageous in terms of implementation, such as countermeasures.

Furthermore, since the moldability is good, it is easy to form tracking grooves.

Acrylic resins include polymethyl methacrylate, etc.
chain or cyclic Arno v+-t having 1 to 8 carbon atoms;
A copolymer or homopolymer mainly composed of methacrylic acid ester having b'Lt-2 is preferred.

Furthermore, as the polycarbonate resin, bisphenol A type is preferred.

When these acrylic resins or polycarbonate resins are formed by injection molding, the effect of the base layer of the present invention becomes even greater.

In addition, it is preferable that the number average degree of polymerization of these acrylic resins or polycarbonate resins is about 800 to 6,000.

Further, it is preferable to form tracking grooves on the recording layer side surface of the substrate.

The base layer consists of a coating film of a colloidal particle dispersion of a silicon-based condensate.

The colloidal particles of the silicon-based condensate are preferably hydrolyzed condensates of halogenated silicon, especially silicon tetrachloride, or realkyl silicic acid, especially tetra-lower alkyl (methyl, ethyl) silicic acid.

And the colloid particle size is 30 to 100, especially 50
~80 people.

Further, as the fractional medium, an alcohol, particularly one aliphatic alcohol, an alkyl acetate, or a mixed solvent of these and an aromatic hydrocarbon is used.

Moreover, for hydrolysis, a mineral acid is added as necessary.

Then, a stabilizer such as ethylene glycol, a surfactant, etc. are added as necessary.

An example of such a colloidal particle dispersion is silicon tetrachloride (S i
CJla) and a monohydric aliphatic alcohol are dissolved in acetic acid alkyl ester. Then, a base layer made of this coating film is formed, and a recording layer is coated on this base layer.

Alternatively, 1 to 20 wt % of ethylene glycol may be added to a solution of tetraalkyl silicic acid, monovalent aliphatic alcohol, alkyl acetate, and mineral acid described in Japanese Patent Publication No. 36-4740.

Furthermore, an alcohol solution of tetra-lower alkyl silicic acid described in Japanese Patent Publication No. 45-35435 may also be used.

In such cases, monohydric aliphatic alcohols to be used include methyl alcohol, ethyl alcohol, denatured alcohol, isopropyl alcohol, butyl alcohol, or mixtures thereof, and alkyl acetates include methyl acetate, ethyl acetate, amyl acetate, and acetic acid. Butyl or a mixture thereof may be used, and as the mineral acid, hydrochloric acid, sulfuric acid, etc., which are commonly used in industry, may be used.

Incidentally, these dispersions may be applied by spinner coating or the like according to a conventional method.

Then, drying may be performed at 40 to 80°C for about 20 minutes to 2 hours.

The coating film thus formed is a silicon oxide coating film containing hydroxyl groups.

The thickness of the base layer is approximately 0.005 to 0.05 gm. Particularly preferably, the thickness is about 0.08 to 0.012 m.

If the base layer exceeds 0.05 lm, the pre-group will be buried, making it impossible to obtain a tracking signal.

Normally, a recording layer is directly provided on such an underlayer, but if necessary, another intermediate layer may be provided between the underlayer and the recording layer. You can also do it.

Further, in the recording layer having an underlayer of the present invention, it is preferable that a surface layer is provided on the side opposite to the underlayer.

However, it is preferable that the reflective layer is not laminated.

The surface layer may be of various known types, but
It is preferable that the base layer be produced in exactly the same manner as the base layer already described.

The thickness of the surface layer is 0.005-0.03 pm.
Particularly preferably, it is 0.08 to 0.012 gm.

If the surface layer is less than .0.O05#L'm, the effect of improving the writing and reading sensitivity as an optical recording medium cannot be obtained.

If the surface layer exceeds 0.03 gm, the writing/reading sensitivity of the optical recording medium will actually decrease.

Pits are formed in the recording layer at the same time as the light is irradiated, and the subsequent irradiated light is no longer absorbed in the center where the energy is most concentrated. Therefore, the energy utilization efficiency is low, which is the reason why the sensitivity cannot be improved beyond a certain value.

In the present invention, by providing a hard film with a high melting point on the surface and the substrate, especially on the surface, it is possible to prevent the formation of pits when exposed to light for a certain period of time, wait for the temperature to rise to a sufficient level, and then - This allows pit formation to occur.

The medium of the present invention may have the above-mentioned recording layer on one side of such a substrate with an underlayer interposed therebetween, or may have two recording layers coated on both sides thereof with an underlayer interposed therebetween. It is also possible to use two discs, place them so that the recording layers face each other with a predetermined gap between them, and seal it tightly to prevent dust and scratches from forming.

(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 pits formed in this manner are read out by detecting the reflected or transmitted light of the readout light, especially the reflected light, while the medium is running or rotating.

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

■Specific Effects of the Invention The optical recording medium of the present invention has a recording layer containing an indolenine cyanine dye, a combination of an indolenic cyanine dye cation, and a quencher anion, and in which two or more of them are contained. Therefore, it has the optimum maximum reflection wavelength and maximum absorption wavelength for writing light and reading light, and has excellent sensitivity and S/N.
ratio is improved.

If the underlayer of the present invention is formed between the substrate and the recording layer, the deterioration of the resin substrate due to the coating solvent of the recording layer will be extremely small, so the decrease in the reflectance of the recording layer will be small, and the readout S/N ratio will be reduced. is significantly improved.

Furthermore, there is no deterioration in reflectance over time due to storage.

In this case, such effects are extremely high compared to the case where another base layer or a silicon oxide base layer made of a solution coating film or a vapor deposited film is provided.

Furthermore, when the recording layer has a surface layer made of a coating film of a colloidal particle dispersion of a silicon-based condensate, the writing sensitivity is improved.

Further, a threshold value appears in the sensitivity-light intensity characteristic curve, and the sensitivity is changed to a certain level at an intensity above the threshold value, resulting in the advantage that it is stable against fluctuations in the output of the light source.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

EXAMPLE Using the dyestuff shown in Table 1 below and the conjugate S of dyestuff cation and quencher anion in the amount ratio shown in Table 1, this was dissolved in a predetermined solvent, and the underlayer shown in Table 1 was provided. 0.06 on an acrylic disk substrate with a diameter of 30 cm.
7 was coated to a thickness of about 100 ml, and the surface layer shown in Table 1 was further formed to obtain various media.

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

Also, (input V=in*)-40=b (On, = OnR)+70=90On+*.

D 2 795 8
65D Io 835
905D 5 840
910D I3 790
860S 3
795 865 Underlayer and surface layer were prepared by mixing ethyl acetate and ethyl alcohol at a ratio of 10:11, and gradually adding 5t(OC2Hs)a at a ratio of 2/25 to ethyl acetate while stirring, and then adding The solution left for 4 days was further diluted 10 times with n-propertool, and then a coating layer was formed on the substrate by processing at 60° C. for 30 minutes.

In this case, the particle size of the silicon oxide colloid was between 50 and 80 particles.

Furthermore, for comparison, a sample was obtained in which a propatool solution of tetraethoxysilane was applied to form an underlayer of 0.01 pm.

In addition, in Table 1, NC is nitrogen content, 11.5 to 12
．． 2%, based on JIS K6703 (nitrocellulose with a viscosity of 20 seconds).

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

Sensitivity was measured at a light converging unit output of 10 μm.

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

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

Next, a semiconductor laser (830 m, condensing part output is 1
(--) was used as the readout light, the reflected light through the substrate was detected, and the C/N ratio was measured using a spectrum analyzer manufactured by Hewlett Paracard Co., Ltd. with a band width of 30 KHz.

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

These results are shown in Table 1.

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

Claims (2)

[Claims] (1) An optical recording medium having a base layer on a resin substrate, and a recording layer on the base layer containing a dye and an ionic combination of a dye cation and a quencher anion, the dye and At least one of the dye cations is an indolenine cyanine dye or a cation thereof, and contains two or more types of at least one of the dye and the ionic bond, and at least one dye or ion. The maximum absorption wavelength of the conjugate is −40 nm to +70 nm of the wavelength of the writing light, and the maximum reflection wavelength of the at least one dye or ionic conjugate is −40 nm to +70 nm of the wavelength of the read light, and the underlayer is made of silicon. An optical recording medium comprising a coating film of a colloidal particle dispersion of a system condensate. (2) A base layer is provided on a resin substrate, a recording layer containing a dye and an ionic combination of a dye cation and a quencher anion is provided on the base layer, and a surface layer is provided on the recording layer. In the optical recording medium having a layer, at least one of the dye and the dye cation is an indolenine cyanine dye or a cation thereof, and at least one of the dye and the ionic binder is included. and the maximum absorption wavelength of at least one dye or ionic conjugate is −40 nm to +70 nm of the wavelength of the writing light, and the maximum reflection wavelength of at least one dye or ionic conjugate is −40 nm to +70 nm of the wavelength of the reading light. 40 nm to +70 nm, and wherein the underlayer and surface layer are made of a coating film of a colloidal particle dispersion of a silicon-based condensate.