JPH02289652A - Light stabilization of cyanine dyestuff - Google Patents

Abstract

PURPOSE:To improve light resistance of cyanine dyestuff, to eliminate deterioration of characteristics caused by light rays during preservation in a dark chamber, further to increase water-vapor resistance and to improve storage stability by forming a bonded material of cyanine dyestuff cation and quencher anion. CONSTITUTION:In stabilizing a cyanine dyestuff containing a cyanine dyestuff cation shown by the formula [Z and Z' are atomic group required to complete indolenine ring, benzoindolenine ring or dibenzoindolenine ring; R1 and R1' are (substituted) alkyl, aryl or alkenyl; L is polymethylene bonded group to form cyanine dyestuff] as a dyestuff part, a bonded material of the cyanine dyestuff cation and a quencher anion is formed. The quencher anion is preferably an anion of chelated substance of transition metal.

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 laser electrophotographic photoreceptors, and optical recording media. Among cyanine dyes, the present inventors have previously developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. An optical recording medium that is used as a layered film has been proposed (Japanese Patent Application Laid-Open No. 59-24692, etc.). Furthermore, in indolenine-based cyanine dyes, it has been proposed that long-chain alkyl groups can be introduced into the molecule to improve solubility and prevent crystallization (Japanese Patent Laid-Open No. 59-7
No. 1895, etc.). Furthermore, it has improved photostability, especially decolorization by readout light (
In order to prevent this (regeneration deterioration), it has been proposed to add a quencher to indolenine-based cyanine dyes (Japanese Patent Laid-Open No. 59-55735, etc.). By the way, cyanine dyes are usually combined with an anion such as CI204. Further, a typical transition metal chelate compound quencher is bonded to a cation such as an ammonium ion. Therefore, these unnecessary counter-anions and counter-cations are present in the recording layer, and generate acids, alkalis, etc. through hydrolysis, causing problems 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. ■ Purpose of the Invention The main purpose of the present invention is to provide a method for photostabilizing indolenine-based cyanine dyes, which has improved storage stability and moisture resistance against light in the red to near-infrared region and extremely little photodeterioration. There is a particular thing. Such objects are achieved by the invention described below. That is, in the present invention, the dye moiety is represented by the following general formula [1
] 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 cyanine dye cation represented by the formula. General formula [I] {In the above general formula [I], Z and Z' each represent an atomic group necessary to complete the indolenine ring, penzoindolenine ring or dibenzoindolenine ring, and R1 and R1 represents a substituted or unsubstituted alkyl group, aryl group or alkenyl group, and L represents a polymethine linking group for forming a cyanine dye. } ■Specific structure of the invention The specific structure of the present invention will be explained in detail below. In the photostabilization method of the present invention, a conjugate of an indolenine cyanine dye cation and a quencher anion is formed. In this case, there is no restriction on the ionic valence of the indolenine cyanine dye cation and the quencher anion, and various combinations are possible, but usually both are monovalent. That is, the indolenine cyanine dye cation is D+
, the quencher anion is Q1, then the conjugate is usually D′″・Q−. There is no particular restriction on the cation of the indolenine cyanine dye that constitutes the ionic conjugate in the present invention, and various cations can be used. However, when incorporated into the recording layer as a cation of such various dyes, those with high writing sensitivity and high reading S/N ratio can be expressed by the following general formula [ It is a cyanine dye represented by I[]. General formula [I1] In the above general formula [II1, Z and Z' are respectively Represents a necessary atomic group, 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 X- is represents an acid anion, and m is 0 or 1. More specifically, Z and Z' represent an indolenine ring to which a benzene ring, a naphthalene ring, etc. may be fused as an aromatic ring, that is, an indolenine ring. , represents the atomic group necessary to complete the penzoindolenine ring or dibenzoindolenine ring. El completed with Z (hereinafter Φ゛) and the ring completed with Z′ (hereinafter A) are the same Although they may be different, they are usually the same, and various substituents may be bonded to these rings.The skeletal rings of Φ0 and A are represented by the following formula [Φ ■〕～[ΦIV] and [ψI]～[WIV]
It is preferable that it is shown in the following. [ΦI] p+ [ψI] [Φold ~ R, p+ [ψ■] ~ R, [ΦIII] [A■old■ R1' [ΦIVI [AIVI] In these various rings, the bond to the nitrogen atom in the ring The group R1 . Ri is a substituted or unsubstituted alkyl, aryl, or alkenyl group. Groups Rl, Rl' 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 group, alkylamino group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, carboxy group, halogen atom, etc. It may be either. Among these, unsubstituted alkyl groups or alkyl groups substituted with alkylcarbonyloxy groups, hydroxyl groups, etc. are particularly preferred. Furthermore, at the 3-position of the indolenine ring, two substituents R.
．． R. ,R! ' It is preferable that Rs be bonded. In this case, the two substituents Ra, R-
．． R-Rs 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, other substituents R4. R. may be combined. Such substituents include alkyl groups, aryl groups,
Heterocyclic residue, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkyloxy carbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, alkylamide group, arylamide basis,
Alkyl groups Rubamoyl group, arylcarbamoyl group, alkylamino group, arylamino group, carboxylic acid group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group , a cyano group, a nitro group, and the like. And the number of these substituents (p, q+ r, s, t
) is usually 0 or about 1 to 4. In addition, p
, q, r, s, t are 2 or more, multiple R. ,R
4 may be different from each other. The cyanine dye cation has a condensed or non-condensed indolenine ring, has excellent solubility, coating properties, and stability, and exhibits extremely high reflectance. On the other hand, L represents a polymethine linking group for forming a cyanine dye such as simple cyanine, carbocyanine, dicarbocyanine, trivalent lupocyanine or tetracarpocyanine dye, but especially any of the formulas [LI] to [LIX] Preferably. Formula [LI] CH=CH-CH=CH-C=CH-CHY CH-CH Formula [LII] CH=CH-CH=C-CH=CH-CHY Formula [LIII] Here, Y is a hydrogen atom or Represents a monovalent group. In this case, monovalent groups include lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups, imidazolidine groups, and ethoxyl groups. Preferable examples include a di-substituted amino group such as a biverazine group, an alkylcarbonyloxy group such as an acetoxy group, an alkylthio group such as a methylthio group, a cyano group, a nitro group, and a halogen atom such as Br and Cρ. Furthermore, Rδ and R9 each represent a hydrogen atom or a lower alkyl group such as a methyl group. And β is 0 or 1. D" I D"2 D"3 D"4 D"5 D"6 D'7 D"8 D'9 D010 D"ll D112 D" 13 D"l4 D"l5 D"l6 D'"l7 D' ″l8 D″″l9 D020 D” 21 D022 D023 D024 ?L CH. C＊H* CH. CsH+7 C+Jxt CH. .CH.CH.OH CH■CH20H C4Hs CH,CH.OCOC}l. CH. CH s CH. CH. CH s CH. CH. CHs CHs CH. CHs CH. CHs CH. CHm CH. CH. CHs CHs CHs CH. CHs CHs CHs CHs CHs R4 5-C}IISOt? H.CH. C.H ■ CHs C + a H s t C H sCH.
CH. Mouth I* CH-OCOCH- CH xCH. Mouth M {α1. CH. CHI CHs CH. CH. CHI CH. C. H. Cl{. C}+! 01! O}I CHsC8.01■O
}I CHs C4H@CH. CH. CH. OCOCHs CH. CH*
CHs CH. CH. CH. cH* CHs CHs CHm CHs CHm cHw CH. CH. CHI CH. and ζ 5-CH. som Yg. H N(C6}1s)t I H H H N(C.Hl). I H N (CaH@) x l Br I H H H H H N (CaHJ t l H H H N (CsHs)s' Br I CI2 C°C H N (CaHs) The target is a cationic dye having such a dye cation. Such an indolenine cyanine dye cation is
I-, Br-, CI204B F4-
CHa −0− SOm − , Cj2−Q− SO
．． It is known as a conjugate with a primary acid anion. Further, these combinations of indolenine cyanine dye cations and acid anions can be easily synthesized according to the method described in Dai Organic Kagaku (Asakura Shoten) Nitrogen-Containing Heterocyclic Compound Engineering, page 432. That is, first, the corresponding Φ'-CH. (Φ′ represents a ring corresponding to the above Φ), the excess R. By heating with I (R, is an alkyl group or an aryl group), R1 is introduced into the nitrogen atom in Φ' to obtain Φ1CHs I''.
The method of ld et al. (Synthesis, 958. 1
Indolenine derivatives are obtained from acetylene alcohol according to the method of 981). Next, this may be subjected to dehydration condensation with an unsaturated dialdehyde or an unsaturated hydroxyaldehyde using an alkali catalyst. Alternatively, viridine may be cleaved according to the ZINCκ reaction to obtain glutaconaldehyde, and this may be reacted with a quaternary salt of an indolenine derivative to obtain trivalent lupocyanin. These indolenine cyanine dye cations are usually
It takes the form of a monomer, but it may take the form of a polymer if necessary. In this case, the polymer has two or more molecules of indolenine cyanine dye cations, and may be a condensate of these indolenine cyanine dye cations. For example, single or co-condensates of the above indolenine cyanine dye cations having one or more functional groups such as -OH, -COOH, -SOs H, etc., or with these, dialcohols, Dicarboxylic acids or their chlorides, diamines, di- or triisocyanates,
There are cocondensation components such as dieboxy compounds, acid anhydrides, dihydrazides, diiminocarbonates, and cocondensation products with other dyes. Alternatively, the indolenine cyanine dye cation having the above functional group may be crosslinked with a metal crosslinking agent alone or together with a baser component or other dyes. In this case, metal crosslinking agents include alkoxides such as titanium, zircon, and aluminum; chelates such as titanium, zircon, and aluminum (e.g., β-diketones, ketoesters, hydroxycarboxylic acids and esters thereof, ketoalcohols, aminoalcohols, enolic Those with active hydrogen compounds, etc. as ligands)
, shearates of titanium, zircon, aluminum, etc. Furthermore, an indolenine cyanine dye cation having at least one of 10H group, -0COR group and -COOR group (wherein R is a substituted or unsubstituted alkyl group or aryl group) It is also possible to use one type or two or more types, or combinations of these and other spacer components or other dyes through a single COO group through 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 above-mentioned indolenine cyanine dye cation 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. If necessary, indolenine cyanine dye cations are linked via a substrate component or the like. On the other hand, various quencher anions can be used as the quencher anion constituting the conjugate, but in particular, quencher anions can be used to reduce regeneration deterioration in the medium and have good compatibility with the dye and the binding resin. Therefore, an anion of a transition metal chelate compound is preferable. In this case, the central metal is Ni, Co
, Cu, Mn, Pd, Pt, etc. are preferred, and the following compounds are particularly preferred. 1) Represents an amino group such as a bisphenyldithiol ethylamino group shown by the following formula, where M is Ni,
Co. Represents a transition metal atom such as Cu, Pd, or Pt. Furthermore, other ligands may be bonded above and below M. These include the following: Here, R1 to R4 are hydrogen, an alkyl group such as a methyl group or an ethyl group, a halogen atom such as Cρ, or a dimethylamino group, or a dimethylamino group, or a dimethylamino group. Q- Q- Q- Q1Q- Q- Q1Q- Q- H H H cos H C β C β H H CH. CH. C I2 H C I2 0 β C I2 H H H CH. CH. CH. CH. N(CHI),a H N(CHs)z N(CH*)i N(CHs)i CHs N(CHs)i C 12 N(C*Hs)iH Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Co C O Ni Ni Ni Ni Ni Ni Ni 2) Bisdithio-α-diketone system represented by the following formula, where R" to R" 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 addition, 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 benzene group in which adjacent groups on the ring are bonded to each other. This represents the formation of a ring. R'R'R'
R” MQ-2-1 φN(CHs)t
ph φN(CHs)* ph NiQ
-2-2 ph ph ph
ph NiQ-2-3 φN(C
*Hs)m ph φN(CJs)x. ph
Ni is represented by the following formula, where M represents a transition metal atom, and Q1 represents. M represents a transition metal atom;
GOOR” CONR”. R" or SO2R", R1 to Rl7 each represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, and Q8 represents an atomic group necessary to form a 5- or 6-membered ring. . MA CI4-I Ni SQ
-4-2 Ni S A compound represented by the following formula b CI4-4 Q-4-5 Ni Ni C (CN) . C (CN). N Represented by the following formula: Where M represents a transition metal atom. Q-5-1 M Ni In addition, those described in Japanese Patent Application No. 127075-1982. Thiocatechol chelate system represented by the following formula, where Hl'' represents a monovalent group, C is 0 to 6, and M represents a transition metal atom. Q- Q- ?-1 M Ni N l R 1g H C H s l Thiobisphenolate chelate system represented by the following formula, where M represents a transition metal atom such as Ni, Go, Cu, Pd, pt, etc. Also, the benzene ring is a substituent M where M is the same as above, and RIIS and R 8
6 represents an alkyl group. R"R" M Q- 8-1 t-Ca Hat
N iQ- 8-2 t
-Cm Hl? Among the above-mentioned quenchers, the phenylbisdithiol-based ones mentioned in 1) above are most preferred. 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. DI D2 D3 D 4 D 5 D 6 D 7 D 8 D 9 DIO Dll Dl2 D 13 D14 D15 D 16 D17 D 18 D19 D3 D” I D” I D”2 D” I D”3 D”3 D”4 D”5 D”6 D”7 D”7 D”8 D ”” 9 D”lO D”ll D”3 D”l2 D ゝ l3 D 0 14 D20 D21 D22 D23 D24 D25 D26 D27 D28 D29 D30 D31 D32 D33 D34 D35 D36 D37 D38 D39 D”l5 D”l6 D 1 17 D”l7 D 4 18 D ′″ 18 D ′″ I D” I D” I D ′″ I D ′″ 19 D + 20 D ′″ 20 D 0 21 D ′″ 2l D 0 21 D”l9 D”3 D'9 D”9 Q1Q1Q- Q- Q- Q- Q- Q1Q- Q- Q- Q- Q- Q 1Q- Q- Q1Q1Q- Q- D40 D41 D42 D43 D44 D45 D46 D47 D48 D49 D50 D51 D52 D53 D54 D55 D56 D57 D58 D59 D'9 D''' 9 D 9 22 D '''' 22 D”ll D"ll D"ll D"ll D 2 23 D "" 24 D" I D'" 3 D"" 2 D"4 D"6 D"5 D"7 D"" 8 D"9 D"ll Q - Q-1-8 Q-1-12 Q"1-12 Q61-3 Q61-8 Q-1-12 Q"1-8 Q-1-8 Q-1-8 Q-1-2 Q-1 -12 Q-1-12 Q-1-12 Q-1-12 Q-1-7 Q61-12 Q-1-13 Q-1-14 Q-1-2 Q-1-13 Q-1-8 Q-1-12 Q-1-8 Q"1-2 Q-1-7 Q-1-13 Q-1-8 Q-1-2 Q-1-3 Q-3-I Q-2-I Q-8-I Q-'7-1 GI5-2 Q-6-I Q-7-I Q-4-I Q61-3 Such a photostabilized cyanine dye of the present invention can be prepared, for example, as follows. First, a cationic cyanine dye bonded to an anion is prepared. In this case, the anion (An-) is I-Br.
- CAO4- , BF4cHs -0- sos-
．． cxOSow etc. is sufficient. Such cyanine dyes are known and synthesized according to conventional methods. That is, for example, the method described in Dai Organic Chemistry (Asakura Shoten) Nitrogen-Containing Heterocyclic Compounds I, page 432, or the method of Harald et al. and ZINCK may be followed. On the other hand, prepare an anionic quencher that combines with a cation. In this case, the cation (Cat") is particularly N
Tetraalkylammoniums such as "(CHs) 4,N" (C4He) are preferred. Furthermore, these quenchers are disclosed in Japanese Patent Application No. 57-16683
No. 2, Japanese Patent Application No. 163080/1983, etc. Next, equimolar amounts of these cyanine 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 712. Thereafter, an aqueous solvent, particularly water, is added to the mixture to cause double decomposition and to obtain a precipitate. The amount of water added may be in excess of 10 times or more. The reaction temperature is preferably room temperature to about 90°C. In addition, cyanine dyes such as p-toluenesulfonate and p-
If the dye is highly soluble, such as chlorobenzene sulfonate, if it is dissolved in methanol or the like and mixed, the desired stabilizing dye will precipitate. Next, the two liquid phases are separated, filtered and dried, and recrystallized with DMF-ethanol or the like, thereby converting the light-stabilized cyanine dye into a light-stabilized cyanine dye. In addition to the above method, a neutral quencher cation intermediate may be dissolved in methylene chloride or the like, an equimolar amount of cyanine dye 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, carbitol acetate, and butyl carbitol 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. It may also be used by molding it as it is or by coating it on various supports. These mixtures can be used as optical recording media in the visible to infrared range,
It is useful as various photoreceptors. IV. Specific Effects of the Invention According to the present invention, the light resistance of indolenine cyanine dyes is improved, and there is little deterioration of properties due to light when stored in a bright room. Furthermore, it has high moisture resistance and improved storage stability. In this case, in the present invention, since the dye cation and the quencher anion are ionicly bonded, the optical properties are high;
Because it has a high and distinct melting point, these effects are even greater than when a dye and quencher are used in combination. Furthermore, the conjugate 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 (Synthesis of Di) 1,3,3.1',3',3''-hexamethylindolinotricarbocyanine iodide [NK-125 D''l iodide manufactured by Japan Photosensitive Color Research Institute] ( 0.000
5 mol, o. 2sg) and bis(3,4.6-
}Rekuroro 1. 2-dithiophenolate) nickel (II) tetra-n-butylammonium [manufactured by Mitsui Toatsu Co., Ltd. PA''-1006Q-1-8 tetrabutylammonium salt J (0.0005 mol, 0.39 g) was added with N,
Dissolved in 20 ml of N' dimethylformamide, kept at 70°C for 3 hours, poured into cold water, filtered the precipitate, washed with water and dried under reduced pressure to obtain 1,3,3.1',3',3'- Hexamethylindolinolupocyanine bis(3.4.15- }
-lichloro1,2-dithiophenolate)nickel (
I got I[)[DI]. Yield: 0.40 g (Yield: 88%) This was dissolved again in 10 ml of DMF by heating, and 301 t of hot ethanol was added and allowed to stand for recrystallization. mp 181-182°C (reddish brown) The content of Ni was determined by atomic absorption spectrometry, and the following results were obtained. N! Content rate (%) Calculated value 6.15 Measured value 6.
07 Dye stabilizer l:1 Calculated value as mixture 4.43 Example 2 (D5
synthesis) 1,3,3.1',3",3'-hexamethyl-4
．． 5.4',5''-dibenzoindotripotocyanine bark sulfate (0.00025 mol, 0.15
3 g) (E.) [Odak HD I
TC-15073 D″″3 perchlorate J and PA-1006 (0.00025 mol, 0.197
g) [(Tetrabutylammonium salt of I 1-8] was metathesized in the same manner as in Example 1 to obtain photostabilized dye D5. Yield: 0.23 g (yield: 87%) Recrystallized from DMF-ethanol Let.mp177~1
79°C (gray green) Ni content (%) Calculated value 5.56 Measured value 6.
20 Calculated value as a mixture 4.2 Example 3 (Synthesis of D2) Iodide of D' 1

[NK-1 manufactured by Japan Photosensitive Color Research Institute
Example 1 Tetrabutylammonium salts of 2 53 and Q-1-12 [NIRC-2 manufactured by Teikoku Kagaku Sangyo Co., Ltd.]
Using the same method as above, photostabilized dye D2 was obtained. Yield 9l% mp Gradual decomposition (black) Ni content (%) Calculated value 7.04 Measured value 6.
93 Example 4 (Synthesis of D3) Perchlorate of D”2 [manufactured by Japan Photosensitive Color Research Institute NK
-2905] and the tetrabutylammonium salt of Q-1-12 [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% mp 240°C (decomposed) (black edge color) Ni content (%) Calculated value 4.85 Measured value 4.
77 Example 5 (Synthesis of D4) Iodide of D”l [NK-125 manufactured by Japan Photosensitive Color Research Institute
] and the tetrabutylammonium salt of Q-1-3 [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% mp 219-220°C (green) Ni content (%) Calculated value 6.63 Measured value 6.
51 Example 6 (Synthesis of D6) Park mouth rate of D”3 (E. Manufactured by Kodak 1
5073) and the tetrabutylammonium salt of Q-1-12 were used in the same manner as in Example 1 to obtain photostabilized dye D6. Yield 89% mp 210-212°C (dark green) Ni content (%) Calculated value 6.28 Measured value 6.
41 Example 7 (Synthesis of D7) Park mouth rate of D”4 [manufactured by Japan Photosensitive Color Research Institute NK
-28651 and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Example 1 to obtain photostabilized dye D7. Yield 75% mp 137-140°C (black edge color) Ni content (%) Calculated value 4.69 Measured value 4.
10 Example 8 (Synthesis of D8) Park mouth rate of D”5 [manufactured by Japan Photosensitive Color Research Institute NK
-2866] and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Example 1 to obtain photostabilized dye D8. Yield 88% mp 73-75°C (black edge color) Ni content (%) Calculated value 3.83 Measured value 4.
22 Example 9 (Synthesis of D9) Park mouth rate of D”6 [manufactured by Japan Photosensitive Color Research Institute NK
-2873] and the tetrabutylammonium salt of Q-1-8 were used in the same manner as in Example 1 to obtain photostabilized dye D9. Yield 100% mp 217-218°C (magenta) Ni content (%) Calculated value 4.70 Measured value 4.
55 Example 10 (Synthesis of DIO) Bromide of D”7 [NK-290 manufactured by Japan Photosensitive Color Research Institute
The photostabilized dye DIO was obtained using the tetrabutylammonium salts of 23 and Q-1-8 in the same manner as in Example 1. Yield 92% mp Gradual decomposition (dark green) Ni content (%) Calculated value 4.90 Measured value 4.
97 Example 11 (Synthesis of Dll) Bromide of D”7 (NK-290 manufactured by Japan Photosensitive Color Research Institute)
2) and tetrabutylammonium salt of Q-1-2 [
NIRC-1 manufactured by Teikoku Kagaku Sangyo Co., Ltd.] was used in the same manner as in Example 1 to obtain a photostabilized dye Dll. Yield 97% mp 183-184°C (black edge color) Ni content (%) Calculated value 5.75 Measured value 5.
88 Example 12 (Synthesis of D12) Park mouth rate of D”8 (manufactured by Japan Photosensitive Color Research Institute, NK
-2910) and the tetrabutylammonium salt of Q-1-i2 were used in the same manner as in Example 1 to obtain photostabilized dye Dl2. Yield 81% mp193-194℃ (dark green) Ni content (%) Calculated value 4,62 Measured value 4,
75 Example 13 (Synthesis of D13) Park mouth rate of D”9 (manufactured by Japan Photosensitive Color Research Institute, NK
-2921) and (II-12) in the same manner as in Example 1, the photostabilizing dye Dl
I got 3. Yield 88% mp 140°C (decomposition) (black border color) Ni content (%) Calculated value 5.57 Measured value 5.
48 Example 14 (Synthesis of D15) Park rate of D”ll [manufactured by Japan Photosensitive Color Research Institute N
Using the tetrabutylammonium salts of K-28803 and Q-1-12 in the same manner as in Example 1, photostabilized dye D
I got 15. Yield Yield 96% m p 2 0 9°C (bright yellow) Ni content (%) Calculated value 6.28 Measured value 6.
32 Example 15 (Synthesis of D1B) Park mouth rate of D”3 [E. Kodak HDI
TC-15073] and (II-7 tetrabutylammonium salt [PA-10033 manufactured by Mitsui Toatsu Co., Ltd.] were used in the same manner as in Example 1 to obtain photostabilized dye D16. Yield 7l% mp200-201°C (Green) Ni content (%) Calculated value 5.22 Measured value 5.
35 The absorption spectrum λIIIax of each photostabilized dye in dichloroethane was almost the same as that of the raw cyanine dye. Experimental Example Using dye D shown in Table 1 below, it was dissolved in cyclohexanone or dichloroethane, and coated with Svin.
A layer of 0.06p was coated on a glass plate. 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. In addition, the dye used was No. exemplified above. I used the one from The reflectance through the substrate was then measured using a semiconductor laser (830 nm), and then a 1.5 kW Xe
After irradiating the lamp at a distance of 20 cm for 20 hours and after storing it at 40° C. and 88% RH for 1500 hours, the change (%) in reflectance from the back side of the substrate was measured. These results are shown in Table 1. Sample No. Photodeterioration of pigment surface resin reflectance (%) Change in reflectance during storage (%) From the results in Table 1, the effects of the present invention are clear. l. 〇1 0.5 -1. 〇11.5 10.5 10.5 -1.0 10. 5 -1.0 10. 8 10. 8 10. 8-2.0 Applicant TDC Co., Ltd. Agent Patent attorney Yo Ishii

Claims (1)

[Scope of Claims] 1. When stabilizing a cyanine dye having a cyanine dye cation represented by the following general formula [I] as a dye moiety, forming a bond between the dye cation and a quencher anion. A method for photostabilizing cyanine dyes, characterized by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula [I], Z and Z' complete an indolenine ring, a penzoindolenine ring, or a dipenzoindolenine ring, respectively. R_1 and R_1' each represent a substituted or unsubstituted alkyl group, aryl group or alkenyl group, and L represents a polymethine linking group for forming a cyanine dye. } 2. The method for photostabilizing a cyanine dye according to claim 1, wherein the quencher anion is an anion of a transition metal chelate.