JPS60162691A - Optical recording medium - Google Patents

Abstract

PURPOSE:To reduce deterioration on reproduction and contrive to enhance moisture resistance, by a method wherein a recording layer comprising a photo- stabilized cyanine coloring matter consisting of a coupled body of a cyanine coloring matter cation and a quencher anion is provided on a base. CONSTITUTION:A cation-type cyanine coloring matter coupled with an anion is prepared. Separately, an anion-type quencher coupled with a cation is prepared. Equimolar amounts of the cyanine coloring matter and the quencher are dissolved in a polar organic solvent to obtain a solution. Thereafter, an aqueous solvent is added to the solution, thereby causing double decomposition and obtaining precipitates. Both liquid phases are separated from each other, followed by filtration, drying and recrystallization to obtain a photo-stabilized cyanine coloring matter. The coloring matter thus obtained is applied to the base by using a predetermined solvent, followed by drying to provide a recording layer.

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

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

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. There is a pit-forming type in which a small hole is formed and one depression is performed, information is recorded by the pit, and the pit is detected with a readout light and read out.

Until now, most of these pit-forming type media, especially those that use a semiconductor laser as a light source that allows for miniaturization of devices, have recording layers made of materials mainly composed of Te. In recent years, since Te-based materials are harmful and there is a need for higher sensitivity and lower manufacturing costs, organic materials based mainly on dyes have been used instead of Te-based materials. Proposals and reports on media using layers are increasing.

For example, for He-Ne lasers, squalillium dye [JP-A-51-48221-V.

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

Technol, 18 (1) 105 (198
1) ) and metal phthalocyanine dyes (JP-A-57-8
No. 2094, No. 57-82085), 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 obtain 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. However, such a recording/reproducing method is also not possible with a dye-deposited film.

This is because a normal transparent resin substrate has a certain degree of refractive index (1.5 for polymethyl methacrylate), and the higher the surface reflectance, the higher it is (4% for polymethyl methacrylate). This is because, for example, the reflectance of polymethyl methacrylate-1 is about 60% or less, and therefore it cannot be detected with a recording layer that exhibits only a low reflectance.

Readout S/N of recording layer consisting of dye vapor deposition 11!2
In order to improve the ratio, a vapor-deposited reflective film such as AfL is usually interposed between the substrate and the recording layer.

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, IR-1
32 dye (manufactured by Kodak) and polyvinyl acetate.
'-diethyl-2.2''-tripotocyanine iodide and nitrocellulose, and furthermore, Y, Law, et al., Appl, Phy.
s.

Lett, 39 (9)? +8 (1981) discloses a medium in which a recording layer made of a dye and a resin is formed by a coating method, such as a recording layer made of 3,3'-diethyl-12-acetylthiatetracarbocyanine and polyvinyl acetate. has been done.

However, these cases also have the same drawback as the dye-deposited film in that a reflection layer is required between the substrate and the recording layer, and recording and reproduction cannot be performed from all four sides 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 the vapor-deposited film of vanadyl phthalocyanine has a slightly high reflectance (P, Kivits, etal, Ap
pl, Phys, Part A 2B (2) 1
01 (!1181), JP-A-55-97033], but the writing sensitivity is low, probably due to the high sublimation temperature.

It has also been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes exhibit high reflectance [Yamaki et al., Proceedings of the 27th Japan Society of Applied Physics 1j-P-8 (
11180) ) "Re-C8" A proposal based on this was made in JP-A-58-1127110, but these pigments have low solubility in solvents and are prone to crystallization, especially when applied as a coating film. Furthermore, it is extremely unstable against readout light and immediately bleaches, making it unsuitable for practical use.

In view of these circumstances, the present inventors first developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It is proposed to be used as a single layer film (patent application filed in 1973).
No. 7-134397, same 5'? -134170).

Furthermore, in other cyanine dyes such as indolenine, thiazole, quinoline, and selenazole, long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization. (Japanese Patent Application No. 57-182588, Patent Application No. 57-177778, etc.)
.

Furthermore, it has improved photostability, especially decolorization by readout light (
In order to prevent cyanine dyes from quenching (1811-1832, 1880)
No. 48, etc.).

By the way, cyanine dyes are usually bonded to an anion such as CJLO4-. Further, a typical transition metal chelate compound quencher is bonded to a cation such as ammonium ion.

For this reason, these unnecessary counteranions and countercations are present in the recording layer, and acid, alkali, etc. are likely to be generated by hydrolysis, which poses a problem in terms of moisture resistance.

Furthermore, the molecular weight of unnecessary portions increases, and the absorbance and reflectance per unit weight decrease, which is disadvantageous in terms of increasing sensitivity.

II. OBJECTS OF THE INVENTION The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide an optical recording medium having a recording layer containing a cyanine dye that exhibits extremely little reproduction deterioration and good moisture resistance. It's about doing. Such objects are achieved by the invention described below.

That is, the present invention is an optical recording medium characterized in that a recording layer containing a photostabilized cyanine dye consisting of a combination of a cyanine dye cation and a quencher anion is formed on a substrate.

■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 includes a combination of a '=r=cation and a quencher anion.

In this case, there is no restriction on the ionic valence of the elementary cation and the quencher anion, and various combinations are possible, but usually both are l.If the quencher anion is Q-, the conjugate is usually l) +, Q-.

There is no particular restriction on the cation of the following general formula (I) or (I).
It is a cation of cyanine dye shown by I).

General formula (I) Φ+-L=!・Q- General formula (II) Φ=L-! +・Q-The above general formula (I
) and (II).

Φ represents a monovalent or divalent residue of a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, or a pyridine ring to which an aromatic ring may be fused, and ψ represents a monovalent or divalent residue to which an aromatic ring may be fused. Good thiazole ring, oxazole ring, selenazole ring, imidazole ring,
Represents a divalent or monovalent residue of a pyridine ring or an indolenine ring, L represents a polymethine linking group for forming a cyanine dye, and Q- represents a quencher anion.

The above general formula [! ] and (II), Φ is a thiazole ring, oxazole ring, selenazole ring, imida [ , 1] represents a monovalent or divalent residue of a sol ring or a pyridine ring.

Also,! is an aromatic ring, such as a benzene ring, a naphthalene ring,
Divalent or monovalent rings such as thiazole rings, oxazole rings, selenazole rings, imidazole rings, pyridine rings, and indolenine rings to which rings, Funa'trene rings, chi'xalin (ΦII) rings, etc. may be condensed, and! may be the same ring or different rings.

In addition, Φ÷ and ! 1, the nitrogen atom in the ring has ten charges, and! and Φ are those in which the nitrogen atom [Φ■] in the ring is neutral.

These Φ and! As the skeletal ring, the following formula [Φ]
~ [ΦX] and [! I]～[! It is preferable that the

In addition, in the following, the structure of Φ and ψ is represented by the general formula (I)
It is shown in the form of Φ0− and weight= in .

(R4')Q ('P■) (R4')Q I! 11. (R4') q In these various rings, i &RR' (R
, R') is a substituted or 1'l 11 11 is an unsubstituted alkyl group, aryl group, alda,
Especially an alkyl group.

Groups R, +RI 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.

moreover,'? When the ring (P+) is a fused or non-fused indolenine ring (formula ('PI) to [ψIV)], two substituents R2'lR3' are preferably bonded to the 3-position. .

In this case, the two substituents R2' and R3' bonded to the 3-position
It is 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! At a given position in the ring represented by
Furthermore, other substituents R4 and R4' may be bonded.

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, and aryloxycarbonyl groups. group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamido group, arylamido group, alkylcarbamoyl group, arylcaroctamoyl group, alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group,
Arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group,
Various substituents may be used, such as an arylsulfamoyl group, a cyano group, and a nitro group.

The number of these substituents (p, ζ1rls, t) is usually O or about 1 to 4. Note that p+q
, r, s, and t are 2 or more, multiple R4, R4'
may be different from each other.

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 [L].

Formula (LI) 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, or a lower alkoxy group such as a methoxy group. group, disubstituted amino groups such as dimethylamino group, diphenylamino group, methylphenylamino group, morpholino group, imidazolidine group, ethoxycarbonylpiperazine group, alkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylthio group, cyano A nitro group, a halogen atom such as Br, C11, etc. are preferable.

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

And the look is O or l.

In addition, among these formulas (LI) to [L■], tricarbocyanine linking groups, especially formulas [Lll), (Lm), (
LIV) and (LV) are preferred.

Next, specific examples of the cyanine dye cation in the present invention will be given.

O1■ -l1 ヱL -andL' D+ 1 ΦII C2H5-'! 'VI C2H3D
÷2 ΦII C2H56-0 sentence! VI C2H6D
”3 ΦII C8H17−ψ■ C3H17D+ 4
4111 C8H17B-C1! vI C8H17D
+5 ΦII C8H176-Cl ψVI Cs H
t7D+6 ΦIII C8H17-'l'■ C3H
17D"7 Φ■ C8H17-ψ■ C3H17D+
8 ΦX C2H5-'P''"IS C2H3D+9
ΦX C2H5-ψX1ll C2H3D+10 ΦX
C2H5' store Cl2 H5D÷11 Φ■ C2H
5-%P)l C2H3D+12 ΦIX C2H5-
ψXI C2H3D+13 ΦIX C2H6-ri If
C2HsD+14 ΦIX CM2C0OC2H5-
! XXlCH2C00C2H5L21'-l1'I
, Y 1 - Lll H- -6-CjL Lm N(C6H5)2 l--Lll
H- -6-Cl LII H- -6-CI Lm N(08H5)21- - LIE
H- m-Lm N(C6H5)21 - LVI H- -LVII H- - -LVII C1- - -LIT Br 1 (R8, R9=H) - -Lll H- -LIX H- - -LII H- - Sat--l1 -1 Sat-! --1 k'D+15 Φ cutting C2H6-'PX91 C2H3D◆16 Φ■ C
7H15-ψXI C7H15D÷17 ΦTX CH
3B-C2H50I C) 13D◆18 ΦIX C
2H5B-N(CH3)2I c2H5D+19 Φ
■C2H5B-C2)! 50'P)If C21(5
D+20 Φ■ Cl8H37−ψXI Cl8H3?
D◆21 Φ■C2H5B-02)150'P)QI
C2H5D+22 ΦX CH3-'PXIII C
) (3D◆23 ΦII C2H65-CH3'PVI
C2H3D÷24 ΦII C3)17 5-CH3
ψVl (3H7D”25 eII C2H55-08
30'PVI C2H3D+27 ov C2H5-ψ
IX C2H6D÷28 ΦII Cl8H37-'P
VI C, 8H37D+29 ΦII Cl8H376
-Cl '1"II Cle H37D 130 ΦII
C8H17B-Cl ψVI C8H, 7LL21'-l1'L Y--text-L m N (C6)15
)2 1 - - Lll H- -13-C2H3OLvIl[C1- -8-N(CI5)2L■ Cl - -13-C2H3OL m N(C,)H5)21--
Lll H- -8-C2H3OLll H- 1-LII H- 15-CH3Lll H- 5-CH3LVII H- -5-CH30LVI[H- -5-CH30L■ 0 sentences - G-CHs O - -Lll H- - -Lll H- -6-CI Lll H- -6-CI Lm N(C6H5)21□□□□1' D+44 ΦII CH3-ψI -CH5D+45
ΦIX C4H9-ψI C4H9D”48 Φ■ C
8H17-Heavy industry C3H17D+47 ΦIX C4H
9-ψI C4H9D+48 ΦIX CH3-'PI
CH3D+49 ΦIT C4H9-ψI C4H9
D+50 ΦII C8H17- Heavy I C3H17D+
51 ΦII CH3-heavy I CH3D◆52 ΦIX
C2H5-Heavy industry C2H51L25'-1 Sat'L
Y--↓-CH3-L II H- CH3-1, II H- CH3-L II H- cH3LI[IN(C6H5)21 CH3-LM H- CH3-L II H- CH3-Lll H- cH3LmN(C6H5 )21 CH3-L rV Br 1 Such cyanine dye cations are I"', Br-, CMO4-, BF4-.

It is known as a conjugate with acid anions such as CH30SO3- and 0503-.

In addition, these combinations of siacone dye-based cations and acid anions can be easily synthesized according to the method described in the book "Nitrogen-Containing Heterocyclic Compound Engineering", Dai Organic Chemistry (Asakai Shoten), p. 432. be able to.

That is, first, the corresponding Φ' −OH5 (Φ' is +ii
It represents the ring corresponding to Φ. ), the excess R,I (
(R1 is an alkyl group or an aryl group), R1 is introduced into the nitrogen atom in Φ' to obtain Φ-CH31-. Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst.

These cyanine dye cations are usually in the form of a monomer, but may be in the form of a polymer if necessary.

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

For example, single or co-condensates of the above cyanine dye cations having one or more functional groups such as -OH, -COOH, -3O3H, etc., or with these, dialcohols, dicarboxylic acids, or their salts. There are cocondensation components such as diamines, di- and triisocyanates, jepoxy compounds, acid anhydrides, dihydrazides, and diiminocarbonates, and cocondensation products with other pigments.

Alternatively, the cyanine dye cation 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 -COOH
One or more cyanine dye cations having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or this and other spacer components or others It is also possible to use a compound in which the dye is bonded with a -COO- group by a transesterification reaction.

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

In addition, the cyanine dye cation 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 dye cations are linked via a spacer component or the like as appropriate.

On the other hand, as the quencher anion constituting the conjugate, various quencher anion forms can be used, but in particular, the quencher anion has the advantage of reducing restar degradation and having good compatibility with the dye-binding resin. For this reason, an anion of a transition metal chelate compound is preferable. In this case, the center metal and the metal are Ni, Co, and Cu.

Preferably M n , P d , P etc., especially,
The following compounds are preferred.

l) Bisphenyldithiol system 1 represented by the following formula Coconi, H to R4 are hydrogen or an alkyl group such as a methyl group or an ethyl group, a halogen atom such as C1, or a 7-mino group such as a dimethylamino group or a diethylamino group. Here, M represents a transition metal atom such as Ni, Co, Cu, Pd, Pt, etc., with Ni being particularly preferred.

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

Examples of this include the following:

1 2 3 RRR-已 鼠- Q-j-I HHHHNf Q-1-2H (H3HHNi Q"l-3HCI C1'HNj Q-1-4CH3HHCH3N1 Q-1-5CB5CH3Cl3CH3N1Q-1-8H
CI HHN1 Q-1-7CI CI CfL CI N1Q-18H
CI CI ClN1 Q-1-8HHHHC.

Q-1-10HCH3CH3HC.

Q-1-11H083(H3HN1 Q-1-12HN(OH3)2HHN1Q-1-138
N(OH,), 2 N(OH3)2 HN iQ-1-
14HN(OH3)2C83HN iQ-1-15HN
(OH3) If-188N (C2
145) 2HHN12) Bisdithio-α-dike represented by the following formula, where H to R8 represent a substituted or unsubstituted alkyl group or aryl group, and M is Ni,
Represents a transition metal atom such as Co, Cu, Pd, Pt, etc.

In the following description, pb is a phenyl group, φ is a 1,4-phenylene group, φ' is a 1,2-phenylene group, and benz is a group adjacent to each other on the ring! This represents that f is bonded to form a condensed benzene ring.

R5R6R7R8M Q-2-1φN(CH3)2ph φN(CH3)2
ph NIQ-2-2ph ph ph ph N1Q
-2-3φN(OH)ph φN(C2H5)2ph
N (52 3) represented by the following formula, where M represents a transition metal atom, and Ql is.

represents.

M ship- Q-3-I Ni Q12 Q-3-2Ni Q12 Q-3-3Co Q” Q-3-4Cu Q12 Q-3-5Pd QI2 4) The following formula shows the following: M IJ) Door aΔL 1- R11 and R12 are CN and COR, respectively? c.
o OR'9c ON RIgRte or 5O2R1
7, R13 to R17 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q2 represents an atomic group necessary to form a 5- or 6-membered ring.

M A Q-4-I Ni 5 Q-4-2Ni S Q "' 4-4 N i C(CN)2Q"' 4-
5 Ni C(CN)25) Those represented by the following formula Q-5-I Ni 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.

Also, the benzene ring has a substituent and is fuzzy.

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

8) 1 1- q-7-t Ni H0 Q-7-2Ni CH31 8) Thiobisferrate represented by the following formula,
M is the same as above, and R65 and R2O represent an alkyl group.

65 66 RRM Q ”' a-t t-c s H1? NIQ-8
-2t-C3H17C.

Note that among the above-mentioned quencher anions, the above-mentioned phenylbisdithiol-based ones are most preferable. 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 of the present invention will be given.

p+ Q knee DI D"I Q-1-8 D2 D+2 Q-1-8 D3 D"3 Q-1-8 D4 D+4 Q-1-8 D5 D"5 Q-1-8 D6 D" 3 Q- 1-12 D7 D+ I Q-1-14 D8 D"2 Q-1-7 D9 D+6 Q-1-8 DIOD+ 7 Q-1-12 Dll D◆8 Q-1-8 D12 D+ 10 Q-1- 8 D13 D+ 11 Q-1-8 D14 D÷12 Q-1-12 D15 D÷13 Q-1-12 Die D+ 14 Q-1-8 017D+ 14 Q-1-12 D18 D+ 14 Q-1-7 Dllll D+ 15 Q' l-8D20 D”
16 Q-1-2 D21 D" 1? Q-1-14 022D" 18 Q-1-13 D23 D" 1111 Q-1-7 024D÷ 20 Q-1-3 D25 D◆ 2IQ-1-8 D2B D+ 22 Q-1-12 D27 D+23 Q61-2 D28 D+ 24 Q-1-14 D28 D+ 25 Q-1-14 D30 D+ 28 Q-1-+2 D31 D+ 27 Q-1-12 D32 D+28 Q-1- 3 D33 D+29 Q-1-7 D34 D◆ 5 Q-1-7 D35 D+3I Q-1-7 D38 D÷ 32 Q-1-2 D37 D◆33 Q-1-14 038D+34 Q-1-7 0390+35 Q "'1-8 D40 D"3111 Q-1-3 D41 D" 37 Q-1-13 D, 42 D" 38 Q-1-14 D43 D"39 Q-1-2 D44 D+40 Q"1-7 D45 D"4I Q-1-2 0480"42 Q-1-3 D47 D"43 Q-1-8 D48 D"44 Q-1-8 D49 D+, 45 Q-1-8 D50 D+ 48 Q-1 -12 D51 D+47 Q-1-8 D52 D+48 Q-1-2 D53 D" 49 Q-1-14 D54 D+50 Q-1-7 D55 D+51 Q-1-3 D58 D◆ 52 Q-1-12 057D+3 ClI2 -1 D58 D+ 6 Q-1-3 059D+9 Q-3-1 D86 D+ 14 Q-4-1 D81 0+ 15 Q-5-2 DB2 D" 1? Q-7-1 D83 D"18 Q'-6 -1 DB4 D"20 Q-8-1 Such a photostabilized cyanine dye of the present invention is, for example,
It is manufactured as follows.

First, a cationic cyanine dye combined with an anion is prepared.

In this case, the anions (An-) include I-, B
r-, Cl 04-, BI4-, CH30S03
−.

It suffices if it is 0 sentence 0803- etc.

Such cyanine dyes are known and synthesized according to conventional methods. That is, for example, the method described in Nitrogen-Containing Heterocyclic Compounds, page 1432 of Dai Organic Chemistry (Breakfast Shoten) may be followed.

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

In this case, the cation (Cat") is particularly N"
Tetraalkylammoniums such as (CH3)4, N''(C4H9)4 are preferred.

These quenchers are disclosed in Japanese Patent Application Laid-Open No. 57-18683.
It is synthesized according to Publication 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/l.

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.

In addition, the reaction temperature is preferably about room temperature to 90°C.

Next, the two liquid phases are separated, the cancer is overdried, and recrystallized with DMF-ethanol or the like, and the photostabilized cyanine dye is changed.

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, according to Japanese Patent Application No. 57-188832, nickel may be oxidized by blowing air to form a salt in the anionic form.

Next, an example of synthesis of a conjugate according to the present invention will be given.

Synthesis Example 1 (Synthesis of Di) I11'-diethyldithiatricarpocyanine perchloride) (0,00025 mol, 0.135 g) (
E, Kodak DTT C-14308D
÷1 barchlorate] and bis(3,4,1ll-tricera-f,2-dithioferto)nickel(II)tetra-n-butylammonium [Mikata Toatsu Kagaku FA-1008Q-1-
Tetrabutylammonium salt of 8] (0°00025
moles, 0.197 g) in dimethylformamide (DM
F) Dissolved in 20m solution and reacted at 70°C for 3 hours.

After the reaction, the solution was poured into cold water and allowed to sink.

This was filtered, washed with water, and then dried under reduced pressure.

Yield: 0.22 g (yield 92%) Next, this was heated and dissolved in DMFlomJl, and after adding 30 IIlfL of hot ethanol, it was left to stand to crystallize 11 crystals to obtain DI.

mp 182°C (black border color) The content of Nf was determined by atomic absorption spectrometry, and the following results were obtained.

Ni content 11t=/wt% Calculated value 6.1 Measured value 5.9 Dye-stabilizer Calculated value as 1:l l1 compound 4.5 Synthesis example 2 (Synthesis of DI) D÷1 iodide and Q ~1-8 tetrabutylammonium salt was used in the same manner as in Synthesis Example 1 to prepare photostabilized dye D.
I got an i.

Yield 90% mp 1B2℃ (black edge color) Ni content 7wt% Calculated value 6.10 Measured value 5.9
0 Synthesis Example 3 (Synthesis of DI4) l, beadiethyltricarbocyanine iodide (0,
00025 mol, O, 130 g) (D+12 iodide Nippon Kanko Shiki Kenkyushin NK-123) and bis(4-dimethylamino-1,2-dithioferrate) nickel (■) tetra-n-butylammonium (
0,00025 mol, 0.167 g> (Tetrabutylammonium salt of Q-1-12 Imperial Chemical Industry Department NIR
-C-2) was dissolved in 20 mJL of DMF and subjected to metathesis in the same manner as in Synthesis Example 1 to obtain D14.

Yield 0.21g (yield 100%) mp 175-176°C (reddish brown) Ni content 41/wt% Calculated value 7.1 Measured value
7.0 Dye-stabilizer 1:1 Calculated value as a mixture 5.0 Synthesis example 4 (synthesis of D2) D+2 perchloride) (E, Kodak IR
-140) and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D2.

Yield 95% mp 183-184°C (dark green) Ni content 7wt% Calculated value 4.79 Measured value 4.8
3 Synthesis Example 5 (Synthesis of D3 *) Barchlorate of D+3 [Japan Photosensitive Pigment Research Institute Department N
K-2880) and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Synthesis Example 1 to prepare photostabilized dye D.
I got 3.

Yield 93% mp 134-135°C (dark green) Ni content 7wt% Calculated value 5.19 Measured value 4.7
8 Synthesis Example 6 (Synthesis I & of D4) Barchlorate of D+4 [Japan Photosensitive Pigment Research Institute Department N
K-2862) and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Synthesis Example 1 to prepare photostabilized dye D.
I got 4.

Yield 95% mp 124-127°C (reddish purple) Ni content 7wt% Calculated value 4.89 Measured value 4.6
1 Synthesis Example 7 (Synthesis of D5) Barchlorate of D+5 [Japan Photosensitive Color Research Institute Department N
K-2871) and the tetrabutylammonium salt of Q'-1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D5.

Yield 94% mp 167-168°C (reddish purple) Ni content 7wt% Calculated value 4.21 Measured value 4.1
6 Synthesis Example 8 (D6 combination J&) Barchlorate of D+3 (Japan Photosensitive Color Research Institute Department N
K-2880) and the tetrabutylammonium salt of Q-12 (Teikoku Kagaku Sangyo Department NIRC-2) were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D6.

Yield: 96% mp: 109~11''C (dark reddish purple) Ni content: 7w
t% Calculated value 5.81 Measured value 5.66 Synthesis example 9 (combination of D7 1 &) Iodide of D"l and tetrabutylammonium salt of Q-1-14 (Teikoku Chemical Industry Department NIRC-3) were added to 1
Using the same method as in Synthesis Example 1, photostabilized dye D7 was obtained.

Yield 97% mP 173°C (grayish black edge color) Ni content/
wt% Calculated value 6.75 Measured value 6.47 Synthesis Example 10 (Synthesis of D8) Barchlorate of D”2 (E, Kodak 1R
-140) and the tetrabutylammonium salt of Q-1-7 (FA-1003, manufactured by Mikata Toatsu Kagaku) in the same manner as in Synthesis Example 1 to obtain photostabilized dye D8.

Yield 68% mplB5℃ (black edge color) Ni content/t% Calculated value 4.54 Measured value 4.5
9 Synthesis Example 11 (Synthesis of D9) Using the toluenesulfone molten salt of D+6 [Nippon Kanko Shokuryo Kenkyu Topu NK-2888] and the t;-butylammonium salt of Q-1-8 in the same manner as in Synthesis Example 1. A photostabilized dye D9 was obtained.

Yield 76% mp 138-140°C (black edge color) Ni content 7wt% Calculated value 4.77 Measured value 4.5
6 Synthesis Example 12 (Synthesis of D 10) Barchlorate of D+7 [Japan Photosensitive Dye Research Top N
Photostabilized dye 010 was obtained using the tetrabutylammonium salts of K-2870) and Q-1-12 in the same manner as in Synthesis Example 1.

Yield 95% mp 200-201°C (dark green) Ni content 7wt% Calculated value 4.50 Measured value 4.3
1 Synthesis Example 13 (Synthesis of Dll) D+8 iodide [cryptocyanin] and Q-1-
The tetrabutylammonium salt of No. 8 was used in the same manner as in Synthesis Example 1 to obtain photostabilized dye Dll.

Yield 98% mp 114-115°C Ni content 7wt% Calculated value 6.53 Measured value 6.7
4 Synthesis Example 14 (Synthesis of D 12) Perc Lolate of D+10 (Japan Photosensitive Pigment Research Top
NK-78) and the tetrabutylammonium salt of Q"'l-8 were used in the same manner as in Synthesis Example 1 to produce photostabilized dye 01.
I got 2.

Yield 93% mp Gradual decomposition (gray-green) Ni content 7wt% Calculated value 6.11 Measured value 6.0
7 Synthesis Example 15 (Synthesis of 01B) Barchlorate of D+14 [Japan Photosensitive Dye Research Top N
K-2934) and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D16.

Yield 94% mp 171”C (reddish purple) Ni containing jjlH/wt% Calculated value 5.50 Measured value
5.51 Synthesis Example 1B (Synthesis of D18) Barchlorate of D+14 [Japan Photosensitive Dye Research Top N
K-2934) and the tetrabutylammonium salt of Q-1-7 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D1B.

Yield 96% mp (dark reddish purple) Ni content 7wt% Calculated value 5.17 Measured value 5.2
1 Synthesis Example 17 (Synthesis of Dlθ) Barchlorate of D′″!5 [Japan Photosensitive Dye Research Top
NK-21130) and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Synthesis Example 1 to obtain photostabilized dye D19.

Yield 100% mp 208-211"O (black edge color) Ni content 7wt% Calculated value per workpiece 4.58 Measured value 4.
71 Note that the absorption spectrum of each photostabilized dye in dichloroethane was almost the same as that of the raw cyanine dye.

The photostabilized cyanine dye composed of such a conjugate may be combined with other dyes to form a recording layer within the 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, heat illumination that can be used particularly suitably
Plastic resins 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, 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.

1ii) 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 copolymers, ethylene-vinyl acetate copolymers grafted with vinyl chloride, etc.

In this case, the copolymerization ratio can be arbitrary.

1) IM vinylidene copolymer Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl chloride-acrylonitrile copolymer, vinylidene chloride-butadiene-vinyl halide copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

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

In this case, the copolymerization ratio can be arbitrary.

ii) Styrene copolymers such as α-methylstyrene, p-methylstyrene, 2
．． 5-dichlorostyrene, α.

β-vinylnaphthalene, α-vinylpyridine, acenaphthene, vinyl 7thracene, etc., or copolymers thereof, such as copolymers of α-methylstyrene and methacrylic ester.

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

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

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 R20 represents a substituted or unsubstituted alkyl group. In this case, in the above formula, R1G is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methyl group.

Further, R2O may be a substituted or unsubstituted alkyl group, but the alkyl group preferably has 1 to 8 carbon atoms, and when R20 is a substituted alkyl group, the alkyl group The substituent to be substituted is preferably a hydroxyl group, a halogen atom, or an amide group (# is 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 type of atomic group represented by the above formula is used. Alternatively, an acrylic resin is formed by forming a homopolymer or copolymer having two or more repeating units.

xi) Polyacrylonitrile xii) Acrylonitrile copolymer, for example, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinyl chloride copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylpyridine copolymer , acrylonitrile-methacrylbutymethyl copolymer,
Acrylonitrile-butadiene copolymer, acrylonitrile-butyl acrylate copolymer, etc.

In this case, the copolymerization ratio can be arbitrary.

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

xii) Polyvinyl acetate xv) '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.

xvii) Polyamide In this case, polyamides include nylon 6, nylon 6-6, nylon 6-1O, nylon 6-12. In addition to regular homonylons such as nylon 9, nylon 11, nylon 12, and nylon 13, nylon 67 low 676-1
0, nylon 67 low 6712, nylon 6/6-6/
It may also be a polymer such as 11 or modified nylon in some cases.

X-Ma1ii) Polyesters For example, 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 co-condensates with glycols such as ethylene glycol, tetramethylene glycol and hexamethylene glycol are suitable.

Among these, condensates of aliphatic dibasic acids and glycols and collinear six products of glycols and aliphatic dibasic acids are particularly suitable.

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

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

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

! Tom) Polyurethane resin Thermoplastic polyurethane resin with urethane bonds.

Particularly suitable are polyurethane resins obtained by condensation of glycols and diisocyanates, particularly polyurethane resins obtained by condensation of alkylene glycol and alkylene diisocyanate.

xxi) 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.

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

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

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

Li, Zn, Mg salts, etc.

xxi) Ketone resins, for example, condensates of cyclic ketones such as cyclohexanone and acetophenone and formaldehyde.

xxi1) Xylene resin, for example, a condensate of m-xylene or mesitylene with formalin, or a modified product thereof.

X Tomi ii) Petroleum resins C5 type, C9 type, C3-C9 copolymer type, dicyclopentadiene type, or copolymers or modified products thereof.

! Tomima 1ii) A blend of two or more of the above items i) to XX), or a blend with other thermoplastic resins.

Incidentally, the amount of particles generated by the resin may be varied.

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 addition, a separate quencher is included in such a recording layer.
1, for example, those described in Japanese Patent Application No. 58-181388 may be included.

In order to form such a recording layer, it is generally necessary to apply it by coating according to a conventional method.

The thickness of the recording layer is usually about 0.03 to 10 m.

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, etc. may be contained.

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

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

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

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

Note that the base body usually has a groove for tracking.

Further, as the resin material for the substrate, a substrate without grooves such as polymethyl methacrylate, acrylic resin, epoxy resin, polycarbonate resin, polysal 7one resin, polyether sulfone, methylpentene polymer, etc. is suitable.

In order to improve solvent resistance, wettability, surface tension, thermal conductivity, etc., it is preferable to form a base layer on these bases. The material of the base layer includes Si, T, etc.
It is preferable to use an oxide formed by applying an organic complex compound or an organic polyfunctional compound such as i, AIL, Zr, In, Ni, Ta, etc. and drying it by heating.

In addition, various photosensitive resins can also be used as the base layer.

In addition, on the recording layer, various uppermost protective layers,
It is also possible to provide a single layer of half-mirror. however,
It is preferable that the recording layer is a single layer film, and that a reflective layer is not laminated above or below the recording layer.

The medium of the present invention may have the recording layer described above on one side of such a substrate, or may have recording layers on both sides of the substrate.

In addition, two substrates with recording layers coated on one side are used, and the recording layers are placed facing each other with a predetermined gap between them, which is then sealed tightly to prevent dust and scratches. You can also do it like this.

(2) Specific Effects of the Invention The medium of the present invention 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 from the substrate side through the substrate.The pits once formed in the recording layer can also be erased with light or heat and rewritten.

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

(2) Specific Effects of the Invention According to the present invention, reproduction deterioration caused by read light is extremely reduced.

Furthermore, the light resistance is improved, and there is little deterioration of characteristics due to storage in a bright room.

Furthermore, the characteristics are less likely to deteriorate even when erasing and rewriting are performed, and the storage stability is also improved.

Ru.

In this case, in the present invention, the dye cation and quencher anion form an ionic bond, so these effects are even greater than when the dye and quencher are used as a mixture. It becomes ivy.

Further, even without laminating a reflective layer, writing and reading can be performed satisfactorily through the substrate.

It also has good solubility and little crystallization.

(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 1 Using the pigment shown in Table 1 below, it was dissolved in a predetermined solvent, and a titanium chelate compound (T-50 (manufactured by Bhonsoda Co., Ltd.)) was applied and hydrolyzed to form a base layer (0 ,01pL)
Various media were obtained by coating a layer of 0.06p thick on an arylic display substrate with a diameter of 30cm.

In this case, in Table 1, NC has a nitrogen content of 11.5 to
12.2%, viscosity 80 based on JIS K 8703
Second nitrocellulose, its content is 10wt%
It is.

Separately, for comparison, D+4 barchlor rate (D
' 4) and the tetrabutyl imonium salt of Q-1-8 (Q 1-8) and the barchlorate of D+12 (
A medium containing a mixture of D'12) and the tetrabutylammonium salt of Q-1-12 (Ql-12) was prepared.

The dye used was the positive one exemplified above.

While rotating each of the media thus produced at 900 rpm, writing was performed from the back side of the substrate using a semiconductor laser (830 nm). In this case, the condenser output is 10 mW and the frequency is 2 MHz.

Next, a semiconductor laser (830nj, condensing part output is l)
mW) as readout light, reflected light through the substrate was detected, and the C/N ratio was measured using a spectrum analyzer manufactured by Hewlett-Paracard with a band width of 30 KH2.

In addition, the 1mW laser readout light was 1BsecII,
The change in reflectance (%) from the back side of the substrate was measured after irradiation as a 3 KHz pulse for 5 minutes in a static state and after storage at 40° C. and 88% R) for 1500 hours.

These results are shown in Table 1.

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

Applicant TDC Co., Ltd. Agent Patent Attorney Yo Ishii -

Claims (1)

[Scope of Claims] (1) An optical recording medium characterized in that a recording layer containing a photostabilized cyanine dye consisting of a combination of a cyanine dye cation and a quencher anion is formed on a substrate. (2) Claim 1 in which the photostabilized cyanogen dye has a structure represented by the following general formula CI) or (11).
Optical recording media described in section. General formula (I) Φ◆-L=ψ・Q- General formula (II) Φ=L-%I"・Q- (In the above general formulas (I) and (II), Φ is an aromatic ring, respectively. A thiazole ring, an oxazole ring that may be fused,
1 of selenazole ring, imidazole ring or pyridine ring
Represents a valent or divalent residue. are a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, each of which may be fused with an aromatic ring;
Represents a divalent or monovalent residue of a pyridine ring or indolenine ring, L represents a polymethine linking group for forming a cyanine dye, and Q- represents a quencher anion.) (3) Quencher 3. The optical recording medium according to claim 1, wherein the anion is an anion of a transition metal chelate. (4) The optical recording medium according to any one of claims 1 to 3, wherein Q- is an anion represented by the following general formula (m). In the general formula (m) (''2 general formula (III), M represents a transition metal atom, 1('l, l(2, R3 and H4 are respectively,
Represents a hydrogen atom, a halogen atom, an alkyl group or a dialkylamino group. ) (5) The optical recording medium according to any one of claims 1 to 4, wherein the recording layer contains a resin. (6) The dye cation according to any one of claims 1 q+ to 5, wherein the dye cation is a monomer, a polymer, or bound to a resin. optical recording medium. (7) The optical recording medium according to any one of claims 1 to 6, wherein the substrate has an underlayer on the recording layer-bearing surface. (8) Special 111 containing a dye in addition to the conjugate
An optical recording medium according to any one of claims 1 to 7. (9) The optical recording medium according to any one of claims 1 to 8, in which writing and reading are performed from the base side. (10) The optical recording medium according to any one of claims 1 to 9, in which a reflective layer is not laminated on the recording layer.