JPS60118749A - Photostabilized cyanine coloring matter and its manufacture - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [Z and Z' are each atomic group for completion of indolenine ring, benzoindolenine ring or dibenzoindolenine ring; R1 and R1' are each (substituted) alkyl, aryl, or alkenyl; L is polymethyne-connecting group for forming cyanine coloring matter; Q<-> is anion of formula II (M is transition metal; R<1>-R<4> are each H, halogen, alkyl, or dialkylamino)]. USE:For photo-recording medium with heat mode, coloring matter laser, sensitizing coloring matter for use in the photosensitive material in electrophotograph, etc. Excellent in light resistance with the thin-film reflective characteristics inherent in cyanine coloring matter retained. PREPARATION:A cyanine coloring matter of formula III (An<-> is anion) and quencher of formula IV (Cat<+> is alkali metal cation or onium cation) are dissolved in a polar organic solvent followed by, if necessary, heating. An aqueous solvent is then added to the resulting system to perform metathesis.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to a novel photostabilized cyanine dye and a method for producing the same.

Prior art and its problems Indolenine-based cyanine dyes are used in various fields. Examples include silver halide photography, dye lasers, and electrophotographic photoreceptors.

Indolenine-based cyanine dyes are particularly suitable for optical recording media because of their good solubility and low crystallinity (Japanese Patent Application No. 1343117/1983,
No. 7-134170, No. 57-1777f1, etc.).

However, indolenine-based cyanine dyes have a drawback that they have low light resistance and are easily decolored by light.

Therefore, while conducting research on improving the decolorization (reproduction deterioration) of cyanine dyes caused by repeated irradiation with readout light, especially when used in the recording layer of a heat mode optical recording medium, the present inventors first discovered the following: We have proposed that regeneration deterioration can be significantly improved by mixing and adding a bisphenyldithiol-based quencher (Japanese Patent Application No. 57-16804).
No. 8, No. 57-17778).

However, in this 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.

In addition, cyanine dyes such as indolenine dyes are usually of the cation type bonded to acid anions, while quenchers are usually of the anion type bonded to onium cations.
This may be hydrolyzed, resulting in adverse effects such as deterioration of moisture resistance.

Furthermore, as a result of being diluted by these acid anions and onium cations, the reflectance becomes lower than the original value of the cyanine dye, lowering the reproduction S/N.

II. OBJECTS OF THE INVENTION The present invention was made in view of the above-mentioned circumstances, and its purpose is to provide an indolenine-based cyanine dye with excellent light resistance without losing its thin film reflection properties, and to be compatible with other anions and other anions. The object of the present invention is to provide a novel photostabilized cyanine dye that does not contain cations and has a directly bonded quencher, and a method for producing the same.

Such objects are achieved by the following first and second inventions.

That is, the first invention is a photostabilized cyanine dye characterized by being represented by the following general formula (I).

General formula CI) (In the above general formula [E], Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R1 and R1' each represents a substituted or unsubstituted alkyl group, aryl group, or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and Q- represents an anion represented by the following general formula (II). represents.

General formula (II) R order RL (J-2 In general formula (II), M represents a transition metal atom, 1(+, l(2, R3 and R4 are hydrogen atom, halogen atom, alkyl atom, respectively) group or dialkylamino group)) In addition, the second invention provides a method for producing a photostabilized cyanine dye represented by the following general formula (CI), in which a cyanine represented by the following general formula (II) is used. A dye and a quencher represented by the following general formula (IV) are dissolved in a polar organic solvent, heated if necessary, and then an aqueous solvent is added to perform double decomposition to obtain a compound represented by the following general formula (1). This is a method for producing a photostabilized cyanine dye, which is characterized by isolating a photostabilized cyanine dye.

In the general formula CI) (bipedal general formula CI), Z and Z' each represent an atomic group necessary to complete the indolenine ring, benzindolenine ring or dibenzoindolenine ring, and R1 and R1 'represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, Q- is represented by the following general formula (II) Represents an anion.

General formula (II) (In the above general formula (II), M is transition gold 11
represents an atom, and RI, R2, R3 and R4 each represent a hydrogen atom, a halogen atom, an alkyl group or a dialkyl atom (1)) General formula [■] (In the above general formula [■], Z , Z' + RI, R,' and L are the same as above, and An- represents an anion.) General formula (IV) Q-e Cat 10 (In the above general formula [IV), Q- is the above-mentioned and Cat+ represents an alkali metal cation or an onium cation. ) ■Specific structure of the invention The specific structure of the present invention will be explained in detail below.

The novel photostabilized cyanine dye of the present invention is an ionic combination of a cation of a predetermined cyanine dye and an anion of a predetermined quencher, and has a chemical structure represented by the above general formula CI).

(ii) In the general formula (I), Z and Z' represent an indolenine ring to which a chiaroscuro ring, such as a benzene ring or a naphthalene ring, may be fused, particularly an indolenine ring, a benzindolenine ring, or Represents 8 different atomic groups to complete the cyhenzoindolenine ring.

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

These Φ+ and! As the skeletal ring, the following formula [Φ■
] to [ΦIV) and [ψwork] to [heavy IV) are preferable.

1.

1 R1' In these various eggs, the group R,, R', bonded to the nitrogen atom in the ring is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group.

In such a ring, the group R,,R', which is bonded to the nitrogen atom,
There is no particular restriction on the number of carbon atoms in .

In addition, if this group further has a substituent,
Examples of the j6 substituent include a sulfonic acid group, an alkylcarbonyloxy group, an alkylamide group, an alkylsulfonamide group, an alkoxycarbonyl group, an alkylamino group, an alkylcarbamoyl group, an alkylsulfamoyl group, a hydroxyl group, a carboxy group, and a halogen group. It may be an atom or the like.

Among these, unsubstituted alkyl groups or alkyl groups substituted with an alkylcarbonyloxy group, a hydroxyl group, an alkyloxycarbonyl group, a carboxy group, a sulfo group, 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' + R3' is preferably an alkyl group or an aryl group I/X.

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

On the other hand, other substituents R4 and R4' may be bonded to predetermined positions in the ring represented by Φ+ and ψ. 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, 71-nolcarbonyloxy group, alkylamide group, arylamide group, alkylcar/<
Moyl group, arylcaroctamoyl group, alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group , a cyano group, a di] and a tetragroup, and the like.

The number of these substituents (p, q, r+s, t) is usually about 0 or about 1 to 4. In addition, p, q
, r, s, and t are 2 or more, multiple R4, R4'
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 an extremely high reaction Q1 rate.

L represents a polymethine linking group for forming a cyanine dye such as a mono-, di-, 1-li or tetracarbocyanine dye, and in particular, it is any one of formulas (LI) to [L■] I like it.

Formula (LI) CH=CH-CH=CH-C=CH-CH=CH-CH
Implicit formula (L II) CH=CH-CH=C-CH=CH
-CH 彊謬Y Formula (L Vll] CH=CH-C=CH-CD Mitsu formula [Lm) CH-C=CH Formula (LIX) C MoHere, Y represents a hydrogen atom or a monovalent group . In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamine groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxycarbonylpiperazine groups. Preferred examples include a di-substituted amine group such as Nato, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a halogen atom such as 2I, Br, and CJI.

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 l.

In addition, among these formulas (LI) to [L■], tricarbocyanine linking groups, especially formulas [LII), (Lm), (
L IV ), [LV] is preferred.

stomach.

Small, LL Ruler 1 Lord l1! D" l ΦI CH3CH3-heavy I D"2 ΦI C2R5CR35-CH3SO2 "3 ΦmcH3CH3-'I'm D"4 Φ[IC8H17CH3-'PIIID"5
Φ■■ Cl8H37CH3-heavy■D"6 ΦmcH3
CH3-'PH D”7 ΦIII C) 0CH3CH3 to 12CH20
- Heavy D+8 ΦIII CD2G820GOC113
0H3-D+ 9 Φm CH3CH3-'I'm
D410 ΦIII CH3CH3-heavy ID+ 11
ΦII CH3CH3-heavy IID÷ 12 ΦIII
C4Hg CH3-! mD413 ΦI CHCHOH
CH3-Heavy industry 2 D+ 14 Φ[108G) 108 CH3-Heavy ■2 Once above'k-yu11'K1' ↓-X-Also CH3C
H3-Lll H- C2Hs CH35-CH3SO2LIII N(C6
H5) 21CH3CH3-LII H- C8H17CH3-LII H- C,8H37CH3-Lll H- CH3CH3L m N(CsR5) 21C) 1. ．．
0H20COC:)I3CH3-Lll H-CH2C
H20COCH3CH3LIIIN(C6H5)21C
H3CH3-LVT Br 1 (R8/ R' ”H) CH3CH3-LII H- CH3CH3-Lll H- C4R9CH3Lll H- CHCHO)l CH3-Lll H-2 CH2CH20HCH3-LII H-Low-LL un
Engineering 1 master h! D+ 15 Φmc4Hg CH3-'PIIID+1
6 ΦI OH,,C)120COC)13CH3-'
P ID"l? +18 from ΦI CH3CH3-ψ Φm CH3CH3-'!'mD+ 19
ΦlCH3CH3-'! 'ID+ 20 ΦI CH3
CH3-heavy■D"21 ΦI CH3CH3-'PID
"22 0111 CH3'CH3-'!'llID
"23 (I)I CH3CH3-'!'mD"24
OI CH3CH3-'Pm once up l;Llnuh'
And L' ↓-X-Also, C4H9CH3L m N(C6
H5) 2'Cl2CH2(IcOc)+3CH3,
LII H-CH3CH3-LVII H- CH3CH3-LVII H- CH3CH3Lm N(COH5) 21CH3CH3
LII 0 sentences - CH3CH3LII 0 sentences - CH3CH3LU H- CH3CH3L In N (C:OH5) 21 On the other hand,
Q- is a bisphenyldithiol-based quencher anion represented by the general formula (II). In the general formula (II), R1, R2, R3 and R4
may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group (particularly a carbon atom with 1
to about 4) or dialkylamino group (in particular, the number of carbon atoms in the two alkyl groups may be the same or different, but both are about 1 to 8).

Furthermore, in the general formula (II), M represents a transition metal atom, such as Ni, Co, Cu, Pd, Pt, etc., with Ni or Co being particularly preferred.

Next, examples of the quencher anion in the present invention will be given.

RI R2R3R4M Q”’IHHHHNi Q”’2HCH3I HN1 Q-3HC sentence 0 sentence HN i Q”’4 CH3HHCH3N1 Q-5CH3CH3CH3CH3N1 Q-6HC sentence HHN 1 Q-7C standing 0 sentences 0 sentences 0 sentences N1 Q-8HC cross CU C also N1 Q-9HHHHC.

Q""10 HCH3CH3HC0 Q-11HCH3CH3HN j Q'-12HN(CH3)2HHNi Q'-13HN(C)l ) N(C:R3)2 HN
i2 Q-14HN(083)2 CH3HN iQ'-+5
HN(C)+3)2C or HNi Next, specific examples of the photostabilized cyanine dye of the present invention will be given.

Ni Quantitative Analysis Ranney Niichi? LfLijLl-Star-DI D+
l Q-86,066,15D2 D+I Q-126
,937,04D3 D"2'Q'-124,77
4,8504D+ l Q-36,516,6305D
"3 Q-86,205,56 D6 D+ 3 Q-126,416,2807D"4
Q-84,104,69 D'8 D"5 Q-84,223,83D9 D"6
Q'-134,554,70D10 0"7 Q-8
4,974,90DIl D+ 7 Q-25,885
,75DI2 D"8 Q/"12 4.75 4.6
2DI3 0”9 Q”’! 2 5.48 5.57D
14 D”lOQ-126,516,64DI5 Do
lI Q-126,326,28DI6 0" 3 Q
-75,35+;, 24DI7 D"12 Q-25,
515,47D18 D”13 Q-146,456,
37D19 D"14 Q'-75,114,,96D
20 D+15 Q-34,894,65D2L D+
18 Q-135,615,52D22 D"17 to 18 6.44 6.32D23 D + 17 Q-
127,317,26D24 D+18 Q-85,6
65,70D25 D+18 Q”'12 6.55
6.46D2θ D”I Q-75,715,73D2
7 D+I Q-27,447,56028D+I
Q-136, 316, 38D29, D” I Q-
146,906,81D30 Dj19 Q-85,0
75,11D31 D + 20 Q-85,355,
47D32 D+20 Q-126,226,16D3
3 D+2I Q-85,815,93034D+2I
Q-126,826,'75D35 D"2I Q"
'7 5.49 5.54D38 D"18 Q"'
+2 5.75 5.72D37 D"3 Q-75,
115,22D38 D+9 Q-85,095,00
039D+ 9 Q-74,624,72D40 D”
9 Q-25,685,90D41 D+9 Q-1
35,015,15D42 D”22 Q-85,46
5,39D43 D+22 Q-126,186,06
D44 Doll Q”-85,515,56D45
D+ lI Q-26,486,70D4Ei D"l
l Q-75,095,22D47 D”lI Q-1
35,635,75D48 D”23 Q-85,78
The photostabilized cyanine dyes of the present invention, such as 5,84D49 D''24 Q-25,795,7, are prepared, for example, 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−, B F4−, C[3−C>S
O3-.

It suffices if it is 0 sentence 0803- etc.

Such cyanine dyes are known and synthesized according to conventional methods. That is, the method described, for example, in Nitrogen-Containing Heterocyclic Compound Engineering, Dai Organic Chemistry (Breakfast Shoten), page 432, etc. may be followed.

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

In this case, the cation (float+) is particularly N
” (CH3) 4,'N” (C1l H9) a
Tetraalkylammoniums such as are preferred.

Furthermore, these quenchers are disclosed in Japanese Patent Application No. 57-16683.
No. 2, Japanese Patent Application No. 58-163080, 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 degree of elasticity may be set to about 0.01 mol/liter.

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.

Note that the reaction temperature is preferably about room temperature to 90°C.

Next, the two liquid phases are separated, filtered and dried, and recrystallized from DMF-ethanol or the like to obtain a photostabilized cyanine dye.

In addition to the method described in -1- below, a neutral intermediate of the quencher cation is dissolved in methylene chloride, etc., an equimolar amount of cyanine dye is added thereto, the mixture is e-condensed, and recrystallization is performed. Good too.

Alternatively, nickel may be oxidized to form an anionic salt while blowing air according to Japanese Patent Application No. 57-Ifi8832.

■Specific embodiments of the invention Hereinafter, the present invention will be explained in more detail according to Examples.

Example 1 (Synthesis of Di) 1.3,3.1',3',3'-hexamethylindolino(-licarbocyanine iodide [Nippon Kanko Shiki Kenkyushin NK-125D" 1 iodide) (0,0
005 mol, 0.25 g) and bis(3,4,fl
-) Lichloro1,2-dithioferte) Nickel (
11) Tetra-n-butylammonium [tetrabutylammonium salt of P A -+006Q"-8 manufactured by Mitsui Toatsu Co., Ltd.] (0,0005 mol, 0.39 g) was mixed with N, N'
- dissolved in 20mM dimethylformamide.

After keeping it at 700C for 3 hours, pour it into cold water, filter the precipitate, wash it with water and dry it under reduced pressure.
, 3'-hexamethylindolinotricarbocyanine
Bis(3,4,fi-)lichloro=1,2-sithioferto)ningal(II) [D1] was obtained.

Yield: 0.40 g (yield: 88%) This was dissolved again in DMFlOmM by heating, and 30 ml of hot ethanol was added thereto and allowed to stand for recrystallization.

mp 181-182℃ (reddish brown) The Ni content was determined by atomic absorption spectrometry, and the following results were obtained.

Ni content (%) Calculated value 6.15 Measured value 6.07 Calculated value as a mixture of dye antioxidant 1:l 4.43 Example 2 (Synthesis of D5) 1.3, 3.1', 3',3'-hexamethyl-4,5°4',5'-dipenzointotripotocyanine perchlorate (0,00025 mol, 0,1
53 g) (E, Kodak HD ITC
-15073D"3 barchlorate] and FA
-1008 (0,00025moJL,,0.197g)
(Tetrabutyl 7 ammonium salt of Q-8) was metathesized in the same manner as in Example 1 to obtain photostabilized dye D5.

Yield: 0.23g (yield: 87%) Recrystallized from DMF-ethanol.

mp, 177-179°C (gray-green) Ni content (%) Calculated value 5.56 Measured value 6.20 Calculated value as mixture 4.2 Example 3 (Synthesis of D2) Iodide of D”l [Japan Photosensitive dye research new product NK-125
) and the tetrabutylammonium salt of Q-12 (NIRC-2 manufactured by Teikoku Kagaku Sangyo Co., Ltd.) were used in the same manner as in Example 1 to obtain photostabilized dye D2.

Yield 91% mp Gradual decomposition (black color) Ni content (%) Calculated value 7.04 Measured value 6.93 Example 4 (Synthesis of D3) D+2 (7) Berklore-1 [manufactured by Japan Photosensitive Color Research Institute] NK-2905) and the tetrabutylammonium salt of Q-12 (NIRC-2 manufactured by Teikoku Kagaku Sangyo Co., Ltd.) were used in the same manner as in Example 1 to obtain photostabilized dye D3.

Yield 80% mp240°C (decomposition) (black border color) Ni content (%) Calculated value 4.85 Measured value 4.77 Example 5 (Synthesis of D4) Iodide of D"l [■ Photosensitive dye research Manufactured by NK-+2
5) and the tetrabutylammonium salt of Q-3 (PA-1005, manufactured by Mitsui Toatsu Co., Ltd.) were used in the same manner as in Example 1 to obtain photostabilized dye D4.

Yield 95% rnp 219-220°C (green) Ni content (%) Calculated value 6.63 Measured value 6.51 Example 6 (Synthesis of D6) Barchlorate of D”3 (E, Kodak 1507
3) and the tetrabutylammonium salt of Q-12 were used in the same manner as in Example 1 to obtain photostabilized dye D6.

Yield 89% mp210-212°C (dark green) Ni content (%) Calculated value 6.28 M1 constant value 6.41 Example 7 (Synthesis of D7) Barchlorate of D”4 [Japan Photosensitive Color Research Institute Department N
Using the tetrabutylammonium salt of K-281(5) and Q-8 in the same manner as in Example 1, photostabilized dye D
I got a 7.

Yield 75% mp 137-140°C (black edge color) Ni content (%) Calculated value 4.69 Measured value 4.10 Example 8 (Synthesis of D8) D” 5(7) Barchlorate [Japan Photosensitive Dye Research Photostabilized dye D8 was obtained by using the newly manufactured NK-288f () and the tetrabutylammonium salt of Q-8 in the same manner as in Example 1.

Yield 88% mp73-75°C (black edge color) Ni content (%) Total 'n value 3.8311111 constant value 4.22 Example 9 (synthesis of D9) Barchlorate of D+6 Made in N
K-2873) 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 100% mp 217-218°C (reddish-purple) Ni content (%) Calculated value 4.70 Measured value 4.55 Example 10 (Synthesis of D 10) D+7 promide [Nippon Kanko Shiki Kenkyushin Co., Ltd. N K-2
902) and the tetrabutylammonium salt of Q-8 were used in the same manner as in Example 1. Photostabilized dye 010 was obtained using I7).

Yield 92% mp Gradual decomposition (dark green) Ni content (%) Calculated value 4.90 Measured value 4.97 Example 11 (Synthesis of Dll) Promide of D"7 NK-
2902) and the tetrabutylammonium salt of Q-2 (NIRC-1 manufactured by Teikoku Kagaku Sangyo Co., Ltd.) were used in the same manner as in Example 1 to obtain a photostable dye Dll.

Yield 97% mp 183-184°C (black edge color) Ni content (%) Calculated value 5.75 Measured value 5.88 Example 12 (DI2 combination 1&) D+8 barchlorate [Japan Photosensitive Pigment Research Institute type N
Using the tetrabutylammonium salt of K-2910) and Q"'+2 in the same manner as in Example 1,
I got 12.

Yield 81% mp 193-194°C (dark green) Ni content (%) Calculated value 4.62 Measured value 4.75 Example 13' (Synthesis of D13) Barchlorate of D''9 [Japan Photosensitive Dyes Research Co., Ltd. Place N
K-2921) and the tetrabutylammonium salt of Q-12 were used in the same manner as in Example 1 to produce photostabilized dye D1.
I got 3.

Yield 88% mp 140'O (decomposition) (black edge color) Ni content (%) Calculated value 5.57 Measured value 5.48 Example 14 (I) Synthesis of 15) Barchlorate of D+11 [Japan Photosensitive Dyes Research Place N
Photostabilized dye D
I got 15.

Yield Yield 96% mp, 209°C (llii orange) Ni content (%) Calculated value 6.28 Measured value 6.32 Example 15 (Synthesis of D IEI) Barchlorate of D”3 (E, Kodak) Manufactured HD I
TC-15073) and the tetrabutylammonium salt of Q-7 (PA-1003, manufactured by Mitsui Toatsu) in the same manner as in Example 1 to obtain a photostabilized dye DiB.

Yield 71% mp 200-201°C (green) Ni content (%) Calculated value 5.22 Measured value 5.35 In addition, WaX of the absorption spectrum of each photostabilized dye in dichloroethane is the raw material cyanine It was almost the same as that of the pigment.

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

The measured value of the Ni quantitative analysis of the valley compound is attached to the above compound example along with the calculated value.

■Specific effects of the invention The photostabilized cyanine dye of the invention
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 is no benevolent influence based on these.

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

The present inventors conducted various experiments to confirm the effects of the present invention. The following 4 is the 01 example.

Experimental example A light fastness test was conducted using the above dye.

Gee each dye? loethane-cyclohexanone (3:l)
A spin cord film with a thickness of 1.5 mm was formed on a boat board with a thickness of 1.5 mm.

A GaAsA laser beam was applied to this dye thin film from the substrate side using a lens with a diameter of approximately l.
It was irradiated by condensing the light into a beam.

Intra-membrane power (7) is 3 #Ls in imW, 3KHz
It was pulsed.

The reflected light at this time was detected by guiding it to a photodiode using an ITI beam splinter, and the change after 4 minutes was measured.

Further, the coating film was left in a constant temperature bath at 40° C. and 88% RH, and the permeation rate was measured after 1500 hours.

The results are shown in Table 1.

In addition, Table 1 shows D”3 barchlorate (HDITC
) and the tetrabutylammonium salt of Q-8 (PA −+
The results for a mixed film with 1:1 (molar ratio) with 1:1 (molar ratio) are also shown.

Table 1 Dl 36 0.6 2 D2 38 0.5 2 D5 30 1.0 'I D6 33 0.8 1 DIG 31 0.8 2 (1:1) 28 2.0 5 From the results shown in Table 1 , the effects of the present invention are obvious.

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

Claims (6)

[Claims] (1) A photostabilized cyanine dye characterized by having a structure represented by the following general formula (I). General formula CI) R1 and R1' each represent a substituted or unsubstituted alkyl group, aryl group or alkenyl group, L represents a polymethine linking group for forming a cyanine dye, and Q- is represented by the following general formula ( General formula (II) (In the above general formula (II), M represents a transition metal atom, R1, R2, R3 and R4 each represent a hydrogen atom,
Represents a halogen atom, an alkyl group or a dialkylamino group. )) (2) The light stabilizer according to claim 1, wherein two alkyl groups are bonded to the 3-position of the indolenine ring, benzindolenine ring or dibenzindolenin ring completed by Z and Z'. cyanine dye. (3) R+ and R1' are each substituted with a hydroxy group, sulfo group, carboxy group, alkyloxycarbonyl group, or alkylcarbonyloxy group, or are unsubstituted alkyl groups, Claim 1 Or the photostabilized cyanine dye according to No. 2 D1. (4) The photostabilized cyanine dye according to any one of claims 1 to 3, wherein the number of methine groups in L is 7 or 9. (5) The photostabilized cyanine dye according to any one of claims 1 to 4, wherein M is Ni. (6) In producing a photostabilized cyanine dye represented by the following general formula CI). A cyanine dye represented by the following general formula (III) and a quencher represented by the following general formula (IV) are dissolved in a polar organic solvent, heated if necessary, and then an aqueous solvent is added. A method for producing a photostabilized cyanine dye, which comprises performing metathesis at 91 and isolating a photostabilized cyanine dye represented by the following general formula (I). General formula CI) (In the above general formula CI), Z and Z' 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, and Q- represents an anion represented by the following general formula (II). In the general formula [II] (General formula C11), M represents a τ transition metal atom, and R1, R2, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, or a dialkylamino )) General formula (III) (In the above general formula (III), Z, Z' + R1, R1' and L are the same as above, and A and n- represent an anion.) General formula (IV) Q-Cat÷ (In the above general formula (IV), Q- is the same as above, and Cat+ represents an alkali metal cation or an onium cation.)