JPH0341165A - Light stabilization of cyanine dye - Google Patents

Abstract

PURPOSE:To impart an excellent light resistance to a cyanine dye having a specified color cation by combining the color cation with a quencher anion, thus stabilizing the cyanine dye. CONSTITUTION:A cyanine dye having a color cation of formula l or II (wherein phiand psi are each a heterocyclic residue for forming a cyanine dye, provided that the case where both phi and psi are residues of indolenine rings which may have fused aromatic rings is excluded; and L is a polymethine bonding group for forming a cyanine dye) as a color part is prepared. By combining the color cation with a quencher anion, the cyanine dye is stabilized against light. Particular examples of the quencher anion include a compound of formula III (wherein M is Ni, Cu or the like; and R<1>-R<4> are each H, an alkyl or the like), and a compound of formula IV (wherein R<5>-R<8> are each an alkyl or an aryl).

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention relates to a method for photostabilizing cyanine dyes.

Prior Art and its Problems Cyanine dyes are used in various fields. Examples include silver halide photography, dye lasers, electrophotographic photoreceptors, and optical recording media.

Cyanine dye shows good reflectance when made into a thin film,
Although it is effective for use in the recording layer of heat mode optical recording media, it has the drawback of low light resistance and easy decolorization by light.

Therefore, the present inventors conducted research on improving the decolorization (reproduction deterioration) of cyanine dyes due to repeated irradiation with readout light, especially when the film is made thin and used in the recording layer of a heat mode optical recording medium. Previously, we proposed that the addition of a quencher such as bisphenyldithiol would significantly improve regeneration deterioration (Japanese Patent Application Laid-Open No. 59-1992).
-55794 etc.).

However, in such a method of mixing a cyanine dye and a quencher, the dye molecules and the quencher may not necessarily exist adjacent to each other, and there is a limit to the effect of improving light resistance.

Furthermore, cyanine dyes are usually of the cation type bonded to acid anions, while quenchers are usually of the anion type bonded to onium cations, and they may be hydrolyzed by these acid anions or onium cations. This may cause adverse effects such as deterioration of moisture resistance.

Furthermore, the dye is diluted by these acid anions and onium cations, and the reflectance of the film becomes lower than the original value of the cyanine dye, resulting in a reduction in the reproduction S/N ratio.

(2) Purpose of the Invention The main object of the present invention is to provide a method for photostabilizing cyanine dyes, which has extremely low storage stability and photodeterioration against light in the red to near-infrared region, and has improved moisture resistance.

Such objects are achieved by the invention described below.

That is, in the present invention, as a dye moiety, the following general formula [I]
A method for photostabilizing a cyanine dye, which comprises forming a bond between the dye cation and a quencher anion when stabilizing a cyanine dye having a dye cation represented by [II].

General formula [I] Φ°-L=General formula A [nl Φ=L-A゛ (In the above general formulas [I] and [■], Φ and A each represent a heterocyclic ring for forming a cyanine dye. (Although both Φ and A do not represent residues of an indolenine ring to which an aromatic ring may be condensed, L represents a polymethine linking group for forming a cyanine dye.) be.

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

In the photostabilization method of the present invention, an ionic bond is formed between a cation of a cyanine dye and a quencher 〇 anion.

In this case, there is no restriction on the ionic valence of the cyanine dye cation and quencher anion, and various combinations are possible, but usually both are monovalent.

That is, assuming that the cyanine dye cation is D+ and the quencher anion is Q-, the conjugate is usually D + ·Q-.

The cation of the cyanine dye constituting the ionic bond in the present invention is not particularly limited and may be of various types.

However, when incorporated as a conjugate using cations of various dyes into the recording layer of an optical recording medium, for example,
Those with high writing sensitivity and high reading S/N ratio have a chemical structure represented by the following general formula [III] or its isomer, general formula [IV].

General formula [III] Φ1-L=A/Q General formula [IV
] Φ=L-K゛・Q- In the above general formulas [Irl] and [IV], Φ is one of a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, or a pyridine ring, each of which may be fused with an aromatic ring. worth 2
A represents a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, each of which may be fused with an aromatic ring;
It 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.

To explain in more detail, Φ is a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring to which one or more aromatic rings such as a benzene ring, a naphthalene ring, a phenanthrene ring, a quinoxaline ring, etc. may be fused; Represents a monovalent or divalent residue of a pyridine ring.

In addition, A is a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, a pyridine ring, an indolenine ring to which one or more aromatic rings such as a benzene ring, a naphthalene ring, a phenanthrene ring, and a quinoxaline ring may be fused. represents a divalent' to monovalent residue.

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

In addition, in Φ゛ and A°, the nitrogen atom in the ring has a positive charge, and in A and Φ, the nitrogen atom in the ring is neutral.

The skeletal rings of these Φ and instep are the following formula [Φ■]
- [ΦX[l] and [A ■] - [W XVI] are preferable.

In addition, in the following, the structure of Φ and A is represented by the general formula [I[1
] is shown in the form of Φ゛− and A=.

[Φ■] ~“ 1 [Φ■] [ΦIII] [ΦIV] [ΦV] (~1 Ku [ΦVl] [ΦVn] [Φ■] [ΦIX] Bar [ΦX] [ΦXI] [ΦX[l] N [A ■] [A II] (R4°) 9 [A III] N R1゛ [A IV] [A V] [A Vl] N 1 [A ■] N R1 [A ■] (R4) Q [ A IX ] (R, °) 9 [A X] [A XI] [tPXII] [tIJXI[[] [A XIV] R1゜R1゛ [A In various rings such as, groups R, R,'(
R,,,R,,') is a substituted or unsubstituted alkyl, aryl, alkenyl group, especially an alkyl group.

Groups R,,R,' 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 group, alkylcarbonyloxy group, alkylamide group, alkylsulfonamide group, alkoxycarbonyl, alkylamino group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group,
It may be a carboxy group, a halogen atom, or the like.

Furthermore, when the ring of A (A0) is a fused or non-fused indolenine ring (formulas [A ■] to [A IV]), two substituents R,,R, ' is preferably combined.

In this case, the two substituents R2 and R3' bonded to the 3-position 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, at a predetermined position in the ring represented by Φ and instep,
Furthermore, another substituent R4R,' may be bonded.
Such substituents include alkyl groups, aryl groups,
Heterocyclic residue, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamide group, arylamide group, alkylcarbamoyl group, arylcarbamoyl 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 cyan group, a nitro group, and the like.

Then, the number of these substituents (1' + Q + r
.

s, t) are usually O or about 1 to 4. Note: When p, q, r, s, and t are 2 or more, multiple R
4 and 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.

Formula [LI] CH=CH-CH=CH-C=CH-CH=CH-CH
Formula [LII] CH=CH-CH=C-CH=CH-CH formula [Lr11
1 Formula [LIV] Formula [LV] Formula [LVT] Formula (LVn[ CH=CH-C=CH-CH Formula [L■] CH-C=CH Rose formula [LrX] Here, Y is a hydrogen atom or Represents a monovalent group. In this case, the monovalent group includes a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group, a diphenylamino group, a methylphenylamino group, a morpholino group, and an imidazo group. Preferred are disubstituted amino groups such as lysine groups and ethoxycarbonylpiperazine groups, alkylcarbonyloxy groups such as acetoxy groups, alkylthio groups such as methylthio groups, cyano groups, nitro groups, and halogen atoms such as Br and Cβ. .

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

And C is 0 or 1.

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

D"　I D”2 D"3 D”4 D′″ 5 D”6 D′″7 D″″　8 D′″9 D410・ D'　11 Φ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ ΦX ΦX ΦX Φ■ 1 zHs C,H.

CeH+7 CaH3t CaHlt CaHly Ca Hlma zHs C,H.

C,H.

2H8 4 6-C flood -Cf1 6-Cβ Instep A VI A Vl A VI A■ A Vl A■ A■ A□ upper shoulder upper shoulder upper shoulder H1゛ C2H.

C2H,I C.H.

C.H.

C8Hl.

C.H.

C.H.

C,H.

C2H.

C,H.

C2H.

012 013 D”14 ΦIX　C2Hs Φ■　C2Hi ΦIX　CH2C00C,H.

Middle layer C, H5 Instep Xl[lC2H.

A→Rules CH, C00CJs H2゛ H3゛ R4゜ 6-Cβ 6-C flood 6-C flood H H LII H LII [ LII III L■ L■ L■ VT (R8゜ LII IX N　(Ca)Is)　2 N(C8H8)2 N (C-H8) 2 2 r R”=H) D′″　15 016 D′″　17 D”18 019 420 D′″　21 D+ 22 D′″　23 124 D′″　25 426 127 Φ Φ friend Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ ΦX Φ■ Φ■ Φ■ Φ■ R8 zHs tH1s CH.

C, Hi C,H.

C,, H, Ding C,H.

CH.

2H8 C3H7 C2H.

2H5 ΦVC2H5 4 6-C,H,0 6-N(CHs)g 6-C,)180 6-C,H,O 5-CH.

-CHa -CH50 5-(1:H,0 6-CH,0 Instep R1゜ 'PXVI C2Hs tIJ■　C,H,.

A X [ll CH.

A XI+I C2H8 A X [lIC2H.

A XOI C,,H,.

Ko XmC,H.

Ko XIV CH.

AVIC, H.

A'/IC, H.

AVIC, H.

A’/I Cz Hs AIXC, Hs D+ 28 ΦII C,, H3? A VT C+ e H3? R2' Ra.

4 6-C2H60 6-N (CH3) 2 6-C2Hs0 6-coi.

5-CH.

5-CH.

-CH50 5-CH,0 6-CH,0 III Ll'I L■ L■ III H H LII H VII L■ L■ N(C6H5)2 0℃ 0℃ N(C,H,).

Cβ H LII D029 D" 30 D’31 932 133 D"　34 935 sitting Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ R.

C+5Hst C,l(,.

C+5Hst CHICH20H C,H.

C,H.

ΦVC,H.

4 6-Cβ -CI2 6-(1 Instep A Vl A Vl A■ A■ A Vl A■ R1゛ C+s H3? 8 R17 IaH37 CH, CH, aOH aH- C2H.

AIX Ca Hs D”36 ΦlIC-H5 A rV C2H5 037 938 339 340 D”41 Φ■ Φ■ Φ■ Φ■ Φ■ CH.

C,H.

CH.

C4H.

CHa A■ A■ A1r [ A■ A■ CH.

C,H.

CHa C,H.

CH.

R2゛ R3' R4' 6-Cβ -CI2 6-Cβ II LI [I III II III III N(C6Hsh N(C6H5)2 N(C6H5)- Lllll! LII! N(CaI2)2 ／−＼ N NC00C2H.

\-/ ／−＼ N NC00CJs \-/ CHa CH.

CH.

H3 H3 H II III H LI [I N(CeHs)a N(CaHa)z D″″42 D′″ 43 D′″ 44 445 046 D″′47 D+ 48 349 D+ 50 051 952 Φ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ Φ■ R3 CH, CH, 0COCH.

CH.

H3 -HQ C.H.

C,H.

CH.

4 He C.H.

CH.

CaHa 4 Instep A■ A■ A I A I A■ A I A I A■ A I A I A I [Self-R2’ Rso R4゛ , CH, 0 COC) 13 CH.

[(, CH.

[(3CHs H, CH.

HI? CHs H, CH.

'(,CH.

H, CH.

H,,CH.

(, CH.

Hs CHa II ITI II II II III L■ II H ID IV The subject of the photostabilization method in the present invention is a cyanine dye having such a dye cation.

The cyanine dye used in the present invention is a combination of such a dye cation and a normal acid anion.

Each of these dye cations usually takes the form of a monomer, but
If necessary, it may be in the form of a polymer.

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

For example, one of the functional groups such as -0H1-COOHl-3o, H
Single or co-condensates of the above dye cations having one or more species, or together with these, dialcohols, dicarboxylic acids or their chlorides, diamines, di- or tonoisocyanates, jepoxy compounds, acid anhydrides, dihydrazides There are cocondensation components such as , diiminocarbonate, and cocondensation products with other dyes.

Alternatively, the 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) Examples include sialates of titanium, zircon, aluminum, etc.).

Furthermore, -OH group, -0COR group, and -COOR
One or more dye cations having at least one group (wherein R is a substituted or unsubstituted alkyl group or aryl group), or
It can be used after bonding with other spacer components or other dyes through a -COO- group by transesterification.

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

Additionally, the dye cations described above may be bound to a resin.

In such cases, a resin with a specific group is used,
Similar to the case of the above polymer, dye cations are linked to the side chains of the resin by condensation reaction, transesterification, or crosslinking, if necessary, via a spacer component or the like.

On the other hand, as the quencher anion constituting the conjugate, various anion forms of singlet oxygen quenchers can be used, but in particular, anion forms of singlet oxygen quenchers can be used. For some reason,
Preferably, it is an anion of a transition metal chelate compound. In this case, the central metal is Ni, Co, Cu
, Mn, Pd, Pt, etc. are preferred, and the following compounds are particularly preferred.

1) Bisphenyldithiol system represented by the following formula, where R1 to R4 represent hydrogen or a halogen atom such as an alkyl group Cβ such as a methyl group or an ethyl group, 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 M.

Examples of this include the following:

Q-1-1 Q″12 -13 -14 -15 -16 -1-7 -18 -19 -1-10 -1-11 -1-12 -1-13 -1-14 -1-15 -1-16 -1-17 2 CH3 j CH.

j C.I. j CH.

C.I.

C.I. N(CI(a)z N(CH,).

N(CHI)! N(CHa)i N(CJa)z 2) Bisdithio-α-diketone system represented by the following formula, where R8 to R8 represent a substituted or unsubstituted alkyl group or aryl group, and M is Ni, Co , C
Represents a transition metal atom such as u, Pd, or Pt.

In the following description, ph is a phenyl group, φ is a 1,4-phenylene group, φ° is a 1,2-phenylene group, and benz is a condensed group in which adjacent groups on the ring are bonded to each other. This represents the formation of a benzene ring.

Bibi [Bi M Q-2-1φN(CH,), ph φN(CHs
) i ph N1Q-2-2ph ph
ph ph N1Q-2-3φN(C2
H11)2 1)F' φN(C2HJ2 ph
Ni) Represented by the following formula, where M represents a transition metal atom, and represents.

-3-1 Ni I2 -3-2 1 Qll? -3-3 0 12 -3-4 Cu 1ffi -3-5 Pd 12 4) Those represented by the following formula, where M represents a transition metal atom, and R1 and R'' are CN and COR13COOR, respectively.
"C0NR' represents R16 or 5O2R1, R1 to R17 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and I2 represents an atomic group necessary to form a 5- or 6-membered ring. represent

M Sat Q-4-2Ni S Q“4-2 Ni 5Q-4-4Ni
C(CN)2Q-4-5Ni
C(CN) 25) Those represented by the following formula-5-1 i In addition, those described in Japanese Patent Application No. 1975.

6) Thiocatechol chelate system represented by the following formula Koni, M is 1 Represents a transition metal atom such as t.

Also, The benzene ring may have substituents. stomach.

-6-1 i 7) What is shown by the following formula Here, 8 is represents a monovalent group, β is in a the law of nature teeth, transition metal atoms vinegar.

I8 -7-1 i -2 i C.I.

8) Thiobisferrate chelate system represented by the following formula Here, M is the same as above, Raa and R111+ is Represents an alkyl group.

R68R118M (r8-1 t-Ca)ll?
NtQ-8-2t-CaHlt
C.

Furthermore, among the above quencher anions, the above 1)
Most preferred are those based on phenylbisdithiol.
This is because when used as a medium, reproduction deterioration due to read light is further reduced and light resistance is extremely high.

Next, specific examples of photostabilized cyanine dyes according to the present invention will be given.

D'" Q- D J Q -1-8 D "2 Q -1-8 D "3 Q -18 D""4 Q -18 D "5 Q -1-8 Dゝ3 Q -1-12 D "I Q -1-14 D'"2 Q -1-7 I 2 3 4 5 6 7 8 9 IO ll 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 D"6 D"? D ′″8 D ”10 D ′″11 D ′″12 D ″13 D ”14 414 D ”14 J5 116 D”17 D ”18 D ”19 D “20 D ′″21 D “22 123 D +24 − 1-8 Q -1-12 -1-8 -1-8 -1-8 Q -1-12 Q -1-12 -1-8 Q -1-12 -1-7 -1-8 -1- 2 Q -1-14 Q -1-13 -1-7 -13 -1-8 Q -1-12 Q "1-2 -1-14 29 D30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 425 D +26 D ゝ27 028 D "29 D"5 D "31 132 033 034 D ''35 D +36 037 038 339 140 D "41 342 443 D '44 Q -1-14 Q -1 -12 Q -1-12 -1-3 -1-7 -1-7 -1-7 -1-2 Q -1-14 -1-7 -1-8 -1-3 Q -1-13 Q -1-14 Q ``12 -1-7 Q ''1-2 -1-3 -1-8 61111 D49 D ''45 Q
-18D 50D ”46
Q-1-12D 51 D ”47
Q-1-8D 52 D ”48
Q -1-2D53 D"+
49 Q-1-14D54
D ″50 Q -1-7D 55
D”51 Q-1-3D 56
D ”52 Q -1-12D
57 D ”3 Q -2-
1D 58 D ”6 Q-1
3D 59 D "9 Q -
3-1D 60D J4 Q
-4-1D 61D J5
Q-5-2D 62 D ”17
Q-7-1D 63 D ”18
Q-6-1D 64 D”20
Q-8-1 Such a photostabilized cyanine color of the present invention is produced, for example, as follows.

First, a cation-type Shinine dye combined with an anion is prepared.

In this case, the anion (An-) is Br-,
CAO4-,BF,-,CH,OSowcI20so,
-, etc. are sufficient.

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 "(CH-)4N" (C4Hs)4 are preferred.

Note that these quenchers are known and synthesized according to conventional methods. In this case, the above 1) is particularly applicable to Japanese Patent Application No. 57-166832 and Japanese Patent Application No. 58-1630.
Synthesized according to No. 80 etc.

Next, equimolar amounts of these dyes and quenchers 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/°C.

Thereafter, an aqueous solvent, especially water, is added to this to cause double decomposition and to form 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, both phases are separated, filtered and dried, and this process is repeated 2 to 3 times if necessary, followed by recrystallization with DMF-ethanol or the like to obtain the conjugate of the present invention.

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 the dye may be added thereto, concentrated, and recrystallized.

Alternatively, according to Japanese Patent Application No. 57-166832, nickel may be oxidized while blowing air to form an anionic salt.

The conjugate thus photostabilized according to the present invention can be used for various purposes, and may be used after being dissolved in a solvent.

Examples of solvents used include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Ester systems such as butyl acetate, ethyl acetate, carpitol acetate, butyl carpitol acetate, ether systems such as methyl cellosolve and ethyl cellosolve, aromatic systems such as toluene and xylene, and halogenated alkyl systems such as dichloroethane are possible. be.

Furthermore, a thermoplastic resin and various additives may be added to the bonded body as necessary. Further, it may be used by being molded as it is or by being coated on various supports.

These mixtures can be used as optical recording media in the visible to infrared range,
It is useful as various photoreceptors.

rv Specific Effects of the Invention According to the present invention, the light resistance of the cyanine dye is improved, and there is little deterioration of characteristics due to light during storage in a bright room.

Furthermore, it has high moisture resistance and improves storage stability.

In this case, in the present invention, since the dye cation and quencher anion are ionicly bonded, these effects are even greater than when the dye and quencher are used as a mixture.

Furthermore, the conjugate has good solubility and less 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 (Synthesis of Dl) 1.1°-diethyldithiatricarbocyanine verchlorate (0,00025 mol, 0.135 g) [E,K
Barchlorate of DTTC-14306D”l manufactured by Odak Co., Ltd.] and bis(3,4,6-dolichloro-1,2-dithioferrate)nickel(II)tetra-n-butylammonium [PA-1006Q68 manufactured by Mikata Toatsu Chemical Co., Ltd. tetrabutylammonium salt] (0,00025 mol, 0.
197g) in 20m dimethylformamide (DMF)
1 and reacted at 70°C for 3 hours.

After the reaction, the solution was poured into cold water to cause precipitation.

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

Yield: 0.22g (yield 92%) Next, this was heated and dissolved in DMFloml, and after adding 30ml of hot ethanol, it was left to stand, recrystallized, and Dl
I got it.

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

Ni content 7wt% Calculated value 6. 1 Measured value 5.9 Calculated value as dye-stabilizer 1:l mixture 4゜5 Example 2 (Synthesis of Dl) Iodide of D"l and tetrabutylammonium salt of Q-8 were added in the same manner as in Example 1. The photostabilized dye Di
I got it.

Yield 90% mp 182°C (black edge color) Ni content 7wt% Calculated value 6.10 Measured value 5.90 Example 3 (Synthesis of Dl4) 1. lo-diethyltricarbocyanine iodide (0
,00025 mol, 0.130 g) [D”12 iodide Nippon Kanko Shiki Kenkyushin NK-123] and bis(4-dimethylamino-1,2-dithioferrate)nickel(rl)tetra-n-butylammonium (0,00025 mol, 0.167 g) [Tetrabutylammonium salt of Q-12 Teikoku Kagaku Sangyo N I
RC-2] was dissolved in 20 ml of DMF, Example 1
Double decomposition was performed in the same manner as above to obtain D14.

Yield 0.21 g (yield 100%) mp 175-176°C (reddish brown) Ni content 7 wt% Calculated value 7.1 Measured value 7.0 Dye-stabilizer l:1 Calculated value as mixture 5.0 Example 4 (Synthesis of D2) Barchlorate of D”2 [E, Kodak IR-
The tetrabutylammonium salts of 1401 and Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D2.

Yield 95% mp 183-184°C (dark green) Ni content 7wt% Calculated value 4.79 Measured value 4.83 Example 5 (Synthesis of D3) Barchlorate of D”3 [Nippon Kanko Shiki Kenkyushin Co., Ltd. N
K-2860] and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D3.

Yield 93% mp 134-135°C (dark green) Ni content 7wt% Calculated value 5.19 Measured value 4.78 Example 6 (Synthesis of D4) Barchlorate of D”4 [Nippon Kanko Shiki Kenkyushin NK
-28621 and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D4.

Yield 95% mp 124-127°C (reddish purple) Ni content 7wt% Calculated value 4.89 Measured value 4.61 Example 7 (Synthesis of D5) Barchlorate of D”5 [Nippon Kanko Shiki Kenkyushin NK
-28711 and the tetrabutylammonium salt of Q68 were used in the same manner as in Example 1 to obtain photostabilized dye D5.

Yield 94% mp167-168°C (reddish purple) Ni content 7wt% Calculated value 4.21 Measured value 4.16 Example 8 (Synthesis of D6) Barchlorate of D”3 [Nippon Kanko Shiki Kenkyushin NK
-28601 and Q-12 tetrabutyl ammonium salts [NIR-C-2 manufactured by Teikoku Kagaku Sangyo] were used in the same manner as in Example 1 to obtain photostabilized dye D6.

Yield 96% mp 109-111°C (deep reddish purple) Ni-containing fi/
wt% calculated value 5. '81 Measured value 5.66 Example 9 (Synthesis of D7) The iodide of D'1 and the tetrabutylammonium salt of Q-14 [N I R-C-3 manufactured by Teikoku Kagaku Sangyo] were
Using the same method as in Example 1, photostabilized dye D7 was obtained.

Yield 97% mp 173 (grayish black edge color) Ni content 7w
t% Calculated value 6.75 Measured value 6.47 Example 10 (Synthesis of D8) D+2 barchlorate [E, Kodak IR-
140] and the tetrabutylammonium salt of Q-7 [
PA1003 manufactured by Mikata Toatsu Kagaku Co., Ltd.] was used in the same manner as in Example 1 to obtain photostabilized dye D8.

Yield 68% mp 185°C (black edge color) Ni content 7wt% Calculated value 4.54 Measured value 4.59 Example 11 (Synthesis of D9) Toluene sulfonate of D+6 [Nippon Kanko Shiki Kenkyushin NK-2868 ] and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to produce photostabilized dye D9.
I got it.

Yield 76% mp 138-140°C (black edge color) Ni content 7wt% Calculated value 4.77 Measured value 4.56 Example 12 (Synthesis of DIO) Barchlorate of D”7 [Nippon Kanko Shiki Kenkyushin NK
-2870] and the tetrabutylammonium salt of Q-12 were used in the same manner as in Example 1 to obtain a photostabilized dye DIO.

Yield 95% mp 200-201°C (dark green) Ni content [i/wt% Calculated value 4.50 Measured value 4.31 Example 13 (Synthesis of Dll) Iodide of D”8 [cryptocyanin] and Q- The tetrabutylammonium salt of No. 8 was used in the same manner as in Example 1 to obtain the photostabilized dye Dll.

Yield 98% mp 114-115°C Ni content 7wt% Calculated value 6.53 Measured value 6.74 Example 14 (Synthesis of D12) Barchlorate of D”lO [Nippon Kanko Shiki Kenkyushin Co., Ltd. N
K-78] and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D12.

Yield 93% mp Gradual decomposition (gray-green color) Ni content 7wt% Calculated value 6.11 Measured value 6.07 Example 15 (Synthesis of D16) Barchlorate of D″14 [Nihon Kanko Shiki Kenkyushin Co., Ltd. N
K-2934] and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D16.

Yield 94% mp 171°C (reddish purple) Ni content 7wt% Calculated value 5.50 Measured value 5.51 Example 16 (Synthesis of D18) Barchlorate of D°14 [Nippon Kanko Shiki Kenkyushin Co., Ltd. N
K-2934] and the tetrabutylammonium salt of Q-7 were used in the same manner as in Example 1 to obtain photostabilized dye D18.

Yield 96% mp (dark reddish purple) Ni content 7wt% Calculated value 5.17 Measured value 5.21 Example 17 (Synthesis of D19) Barchlorate of D″15 [Nippon Kanko Shiki Kenkyushin Co., Ltd. N
K-2930] and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1 to obtain photostabilized dye D19.

Yield 100% mp 208-211°C (black edge color) Ni content 7wt% Calculated value 4.58 Measured value 4671 Note that the l wax of the absorption spectrum of each photostabilized dye in dichloroethane is the same as that of the raw cyanine dye. They were almost identical.

In this way, each of the above compounds was synthesized.

■Specific effects of the invention The photostabilized cyanine dye of the invention has a predetermined quencher.
Because it is bonded with anions, it has extremely high light resistance.

Furthermore, since the two are ionicly bonded, the light resistance is even higher than when they are used in combination.

And since there are no other anions or cations,
There are no adverse effects based on these.

For this reason, heat mode optical recording media, dye lasers,
It is extremely useful in applications such as sensitizing dyes for electrophotographic photoreceptors.

The inventors conducted various experiments to confirm the effects of the present invention. An example is shown below.

Experimental Example The pigments shown in Table 1 below were dissolved in cyclohexanone or dichloroethane in the proportions shown in Table 1, and coated onto a 5 cm square glass plate to a thickness of 0.06 m.

In this case, in Table 1, NC has a nitrogen content of 11.5 to
12.2%, viscosity 80 based on JIS K 6703
Second is nitrocellulose, its content is 10wt%
It is.

The dye used was No. exemplified above.

Next, semiconductor laser (830 nm) or He-
Reflectance through the substrate was measured using a Ne laser.

Next, a 1.5kW Xe lamp was placed at a distance of 20cm.
After irradiation for 20 hours and at 40°C and 88%RH
After storage for 500 hours, the change (%) in reflectance from the back side of the substrate was measured.

These results are shown in Table 1.

table (%) (%) 8 6 7 7 8 6 5 9 7 6 6 9 11 13 22 5 4 5 5 5 ≧5 4 6 5 5 5 6 10 9 15 From the results in Table 1, The effect of the present invention is clear. be.

Out wish Man TDC Co., Ltd. teenager Reason Man

Claims (1)

[Claims] 1. As the dye moiety, the following general formula [I] or [II]
A method for photostabilizing a cyanine dye, which comprises forming a bond between the dye cation and a quencher anion when stabilizing a cyanine dye having a dye cation represented by the formula. General formula [I] Φ^+-L=Ψ General formula [II] Φ=L-Ψ^+ {In the above general formulas [I] and [II], Φ and Ψ are respectively Although it represents a residue of a heterocycle, both Φ and Ψ do not represent a residue of an indolenine ring to which an aromatic ring may be fused, and L represents a polymethine linking group for forming a cyanine dye. . ) 2, Φ represents a monovalent or divalent residue of a thiazole ring, oxazole ring, selenazole, imidazole ring or pyridine ring to which an aromatic ring may be fused, and Ψ is a residue to which an aromatic ring may be fused. 2. The method for photostabilizing cyanine dyes according to claim 1, which represents a divalent to monovalent residue of a thiazole ring, an oxazole ring, a selenazole ring, an imidazole ring, a pyridine ring, or an indolenine ring. 3. The method for photostabilizing cyanine dyes according to claim 1 or 2, wherein the quencher anion is an anion of a transition metal chelate.