RU2177487C1 - 3,3'-DI-γ-SULFOALKYLTHIACARBOCYANIMINE BETAINE SALTS AS SPECTRAL SENSITIZERS AND METHOD OF SPECTRAL SENSITIZATION OF HALOGEN-SILVER PHOTOGRAPHIC EMULSIONS AND USE THEREOF - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: described are new 3,3'-di-γ-sulfoalkylthiacarbocyanine betaine salts (I) wherein A is lower alkyl, R is 0-AIK -γ- is halogen, R¹ is 3.3'-diethylthiazoline carbocyanine, 3.3'- diethyloxacarbocyanine, or 1.1'-diethyl-quino-2,2-monomethinecyanine as spectral sensitizer of halogen-silver photographic emulsions, and method of spectral sensitization of halogen-silver emulsions and use thereof. Compounds (I) make it possible to attain higher level of light sensitivity of photolayers especially behind filter OC-H after chemical photographic treatment. EFFECT: improved properties of the salts. 3 cl, 27 ex, 3 tbl

Description

 The invention relates to photographic chemistry, namely to new salts of 3,3'-di-γ-sulfoalkylthiacarbocyanin betaines and their use for sensitizing silver halide photographic emulsions, and can be used in the chemical photographic industry for the manufacture of photographic materials sensitive to the visible spectrum.

где B - алкил, алкоксил, арил, галоген, R = (CH₂)₃SO₃ ^-, C₂H₅, X= N⁺H(C₂H₅)₃ N⁺HC₅H₅, галоген. [Э.Б.Лифшиц, Е.В.Родовицкая и др. О фотографических свойствах и компонентоустойчивости в различных фотоэмульсиях некоторых тиакарбоцианинов с сульфоалкильными группами при атомах азота. Журнал научной и прикладной фотографии и кинематографии, N 6, 1975 г., с. 400-404].Known application for sensitization of silver halide photographic emulsions to the visible spectrum of sensitizing dyes of the formula

where B is alkyl, alkoxyl, aryl, halogen, R = (CH ₂ ) ₃ SO ₃ ^- , C ₂ H ₅ , X = N ⁺ H (C ₂ H ₅ ) ₃ N ⁺ HC ₅ H ₅ , halogen. [E.B. Lifshits, E.V. Rodovitskaya et al. On the photographic properties and component stability in various photoemulsions of certain thiacarbocyanines with sulfoalkyl groups at nitrogen atoms. Journal of Scientific and Applied Photography and Cinematography, N 6, 1975, p. 400-404].

However, these dyes do not provide the necessary level of photosensitivity in the spectral region of 620 - 635 nm, and dyes with B = C ₆ H ₅ give a color to the photo layers after chemical photographic processing.

где Z - остатки гетероциклических оснований, n = 0-3, m = 0- 5, А,В,В' = H, различные заместители, А¹ = H, CH₂C(CH₃)₂CH₂, R = алкил, (CH₂)₃SO₃ ^-, [К]⁺ = ион щелочного металла, C₅H₅ NH, (Alk)₃ NH. [Тезисы докладов VI симпозиума "Физика и химия полиметиновых красителей", Москва, 26-28 ноября 1996 г., с. 124-130].It is also known to use for sensitization of silver halide emulsions of cyanines of anionic structure - N, N ¹ -disulfopropylcyanines of the formula

where Z are residues of heterocyclic bases, n = 0-3, m = 0-5, A, B, B '= H, various substituents, A ¹ = H, CH ₂ C (CH ₃ ) ₂ CH ₂ , R = alkyl , (CH ₂ ) ₃ SO ₃ ^- , [K] ⁺ = alkali metal ion, C ₅ H ₅ NH, (Alk) ₃ NH. [Abstracts of the VI Symposium "Physics and Chemistry of Polymethine Dyes", Moscow, November 26-28, 1996, p. 124-130].

 These dyes are not effective enough in the orange part of the spectrum and, in addition, if higher alkyl or benzogroups are present as a substituent, they also give coloring to the photo layers after chemical photographic processing.

 The aim of this invention is to expand the range of sensitizing dyes, providing a high level of overall photosensitivity of photographic materials and additional photosensitivity in the range of 620-635 nm, i.e. behind the OS-14 light filter, as well as the elimination of the coloring of photo layers after chemical-photographic processing.

где А = низший алкил, R = 0-Alk, R¹ = галоген, [К]⁺ = 1,1'-диэтил-хино-2,2'-монометинцианин, 3,3'- диэтилтиазолинокарбоцианин или 3,3'-диэтилоксакарбоцианин, в качестве спектральных сенсибилизаторов галогенсеребряных фотографических эмульсий, а также способом спектральной сенсибилизации галогенсеребряных фотографических эмульсий к видимой зоне спектра введением в эмульсию суперсенсибилизатора, сенсибилизирующего красителя или смеси их, при этом в качестве сенсибилизирующего красителя вводят соединение формулы

где А = низший алкил, R = 0-Alk, R¹ = галоген, [К]⁺ = 3,3'- диэтилтиазолинокарбоцианин, 3,3'-диэтилоксакарбоцианин или 1,1'-диэтил-хино-2,2'-монометинцианин, или вводят соединения формулы I и соединение формулы

где

A' = низший алкил, [K]⁺ = C₅H₅NH (Alk)₃ NH, 3,3'-γ-диэтилтиазолинокарбоцианин, 3,3'-диэтилоксакарбоцианин или 1,1'-диэтил-хино-2,2'-монометинцианин, Y= O, S, B,B¹=H, CH₃, OCH₃, Cl, C₆H₅, 4,5-бензо,
и суперсенсибилизатор формулы

где B= H, низший алкил, B¹=H, алкил, галоген, m = 1-2, n = 0,2, X^- = ClO₄ ^-, пара-CH₃C₆H₄SO₃ ^-, галоген, R²=C₂H₅, C₈H₁₇ или формулы

где: X^- = галоген, алкилсульфат, тозилат, R = низший алкил, n=2-5.The specified technical result is achieved by new salts of 3,3'-di-γ-sulfoalkylthiocarbocyanin betaine of the formula

where A = lower alkyl, R = 0-Alk, R ¹ = halogen, [K] ⁺ = 1,1'-diethyl-quino-2,2'-monomethinocyanine, 3,3'-diethylthiazolinocarbocyanine or 3,3'- diethyl oxacarbocyanin, as spectral sensitizers of silver halide photographic emulsions, as well as a method of spectral sensitization of silver halide photographic emulsions to the visible spectral region by introducing a supersensitizer, a sensitizing dye or a mixture of them into the emulsion, and introducing the compound as a sensitizing dye

where A = lower alkyl, R = 0-Alk, R ¹ = halogen, [K] ⁺ = 3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine or 1,1'-diethyl-quino-2,2'- monomethine cyanine, or the compounds of formula I and the compound of the formula are administered

Where

A '= lower alkyl, [K] ⁺ = C ₅ H ₅ NH (Alk) ₃ NH, 3,3'-γ-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine or 1,1'-diethyl-quino-2,2 '-monomethine cyanine, Y = O, S, B, B ¹ = H, CH ₃ , OCH ₃ , Cl, C ₆ H ₅ , 4,5-benzo,
and supersensitizer of the formula

where B = H, lower alkyl, B ¹ = H, alkyl, halogen, m = 1-2, n = 0.2, X ^- = ClO ₄ ^- , para-CH ₃ C ₆ H ₄ SO ₃ ^- , halogen, R ² = C ₂ H ₅ , C ₈ H ₁₇ or the formula

where: X ^- = halogen, alkyl sulfate, tosylate, R = lower alkyl, n = 2-5.

 Compounds of formula I are prepared by a known method for the synthesis of cation anionic dyes, namely, the interaction of the salt of 3,3'-di-γ-sulfopropyl-9-methyl-5-chloro-5'-methoxythiocarbocyanine betaine with N, N "- dialkylcyanines [Lifshitz E. B ., Levkoev I.I. Collection of scientific works of GNIIHFP, 1986 p. 67]. Compounds of formula II can be prepared by one of the known methods for the synthesis of N, N'-di-γ-sulfopropylcyanine betaines by the reaction of γ-sulfopropyl betaine 2-β-methylmercaptopropenyl-5-methoxybenzothiazole with γ-sulfo-propyl betaine 2-methyl-5-chlorobenzothiazole in absolute ethyl alcohol in the presence of triethylamine while boiling. [Lifshits E.B., Raikhina R.D., Formina L.I. Abstracts of the VII Symposium "Physics and Chemistry of Polymethine Dyes", M., 1999, p.23].

Bis-quaternary salts of formula III are obtained by the analogous method by reacting 1-alkylbenzimidazole with bis-methane, n-toluene or benzosulfine esters of di- or triethylene glycol of the formula R (C ₆ H ₄ ) m - SO ₃ CH ₂ (CH ₂ OCH ₂ ) n CH ₂ O ₃ S (H ₄ C ₆ ) _m , where R = H, methyl, n = 1,2, m = 0, 1. [RF Patent N 1790175 from 11.21.80, IPC ⁵ C 07 D 235/04, publ. BI N 13, 1995].

Bis-quaternary pyridine salts of formula IV are obtained by the analogous method by reacting 1-alkyl-1,2-dihydrothiopyridine-2 with dibromoalkanes or bis-methane- or n-toluenesulfonic glycol ethers. [RF patent N 1790172 of 05.17.84, IPC ⁵ C 07 D 213/18, G 03 C 1/08].

В качестве соединений формулы II наиболее эффективными являются:
II₁(A¹=C₂H₅,

B=B¹=4,5-бензо, Y=S, [K]⁺=C₅H₅NH),
II₂(А¹= C₂H₅,

B=B¹=4,5-бензо, Y=S, [K]⁺=3,3'-диэтилтиазолинокарбоцианин),
II₃(A¹= C₂H₅

B=В¹=4,5-бензо, Y=S, [К]⁺,1,1'-диэтил-хино-2,2'-монометинцианин),
II₄ (A¹= C₂H₅,

B=4,5-бензо, B¹=5-OCH₃, Y=S, [K]⁺=(C₄H₉)₃ NH),
II₅(A¹= C₂H₅

B=4,5-бензо, Y=S, [К]⁺ = 3,3'-диэтилтиазолинокарбоцианин),
II₆ (A¹= C₂H₅,

B=4,5-бензо, Y=S, [K]⁺=1,1'-диэтил-хино 2,2'-монометинцианин),
II₇7 (A¹=С₂Н₅

B=5-Cl, B¹=5-OCH₃ Y=S, [K]⁺=N⁺H(C₂H₅)₃,
II₈ (A¹=C₂H₅,

B=B¹= 5,5'-C₆H₅, Y=0 [K]⁺=C₅H₅N⁺H),
II₉(A¹=CH₃,

B=5-Cl, B¹=5'-OCH₃, Y=S, [К]⁺=N⁺H(C₂H₅)₃,
II₁₀(A¹=C₂H₅

B=5-CH₃ В¹=5,5'-C₆H₅, Y=S, [K]⁺= (C₄H₉)₃N⁺H),
Из соединений формулы III интерес представляют следующие:

Из соединений формулы IV наиболее эффективным является соединение формулы:

Предлагаемые соединения I и указанный способ сенсибилизации галогенсеребряных эмульсий обеспечивают более высокий уровень светочувствительности фотослоев, особенно за фильтром ОС-14 при отсутствии прокраса слоев после химико-фотографической обработки.As compounds of formula I, the following are of interest:

As compounds of formula II, the most effective are:
II ₁ (A ¹ = C ₂ H ₅ ,

B = B ¹ = 4,5-benzo, Y = S, [K] ⁺ = C ₅ H ₅ NH),
II ₂ (A ¹ = C ₂ H ₅ ,

B = B ¹ = 4,5-benzo, Y = S, [K] ⁺ = 3,3'-diethylthiazolinocarbocyanine),
II ₃ (A ¹ = C ₂ H ₅

B = B ¹ = 4,5-benzo, Y = S, [K] ⁺ , 1,1'-diethyl-quino-2,2'-monomethincyanine),
II ₄ (A ¹ = C ₂ H ₅ ,

B = 4,5-benzo, B ¹ = 5-OCH ₃ , Y = S, [K] ⁺ = (C ₄ H ₉ ) ₃ NH),
II ₅ (A ¹ = C ₂ H ₅

B = 4,5-benzo, Y = S, [K] ⁺ = 3,3'-diethylthiazolinocarbocyanine),
II ₆ (A ¹ = C ₂ H ₅ ,

B = 4,5-benzo, Y = S, [K] ⁺ = 1,1'-diethyl-quino 2,2'-monomethine cyanine),
II ₇ 7 (A ¹ = C ₂ H ₅

B = 5-Cl, B ¹ = 5-OCH ₃ Y = S, [K] ⁺ = N ⁺ H (C ₂ H ₅ ) ₃ ,
II ₈ (A ¹ = C ₂ H ₅ ,

B = B ¹ = 5.5'-C ₆ H ₅ , Y = 0 [K] ⁺ = C ₅ H ₅ N ⁺ H),
II ₉ (A ¹ = CH ₃ ,

B = 5-Cl, B ¹ = 5'-OCH ₃ , Y = S, [K] ⁺ = N ⁺ H (C ₂ H ₅ ) ₃ ,
II ₁₀ (A ¹ = C ₂ H ₅

B = 5-CH ₃ B ¹ = 5.5'-C ₆ H ₅ , Y = S, [K] ⁺ = (C ₄ H ₉ ) ₃ N ⁺ H),
Of the compounds of formula III, the following are of interest:

Of the compounds of formula IV, the most effective is the compound of the formula:

The proposed compounds I and the specified method of sensitization of silver halide emulsions provide a higher level of photosensitivity of the photo layers, especially behind the OS-14 filter in the absence of layer coloring after chemical-photographic processing.

 In addition, the use of a compound of formula I in a sensitization method in combination with a compound of formula II and a supersensitizer III or IV ensures uniform photosensitivity in the visible spectrum.

 The following examples illustrate the invention but do not limit it.

 For sensitization, various silver halide photographic emulsions are used, the parameters of which are shown in the following table 1.

Example 1. Obtaining compounds I ₁
Dye I _{1 is} obtained by mixing hot methanol solutions of the starting compounds, namely: 0.39 g of the triethylammonium salt of 3,3'-di-γ-sulfopropyl-9-methyl-5-chloro-5-methoxythiocarbocyanine betaine in 2.5 ml of methanol and 0, 18 g of 1,1'-diethyl-quino-2,2'-monomethine cyanine chloride in 2 ml of methanol are drained and boiled for 15 minutes.

Yield 0.45 g (94%). Mp 227-228 ^° C. After crystallization from ethanol, 0.35 g (73%) of dark cherry crystals are obtained with a melting point of 229-230 ^o C.

λ $\genfrac{}{}{0ex}{}{\text{εton}}{\text{Max}}$ 492, 526, 554 nm ε ₅₅₄ / ε ₅₂₆ = 0.98.
Found,%: C 59.97, 60.10; H 5.20; N, 5.75; 5.65; S, 13.63; 13.28.

 Calculated,%: C 60.20; H 5.16; N, 5.85; S 13.40.

C ₄₈ H ₄₉ ClN ₄ O ₇ S ₄ .

 Example 2

The dye 12 is obtained analogously to example 1 by mixing hot methanol solutions:
0.39 g of triethylammonium salt of 3,3'-di-γ-sulfopropyl-9-methyl-5-chloro-5'-methoxythiacarbocyanine betaine in 2.5 ml of methanol and 0.18 g of 3,3'-diethylthiazolinocarbocyanine iodide in 2 ml of methanol drained and boiled for 20 minutes.

The yield of 0.25 g (55.6%) of dark cherry crystals after crystallization from ethanol with so pl. 220-221 ^o C. λ $\genfrac{}{}{0ex}{}{\text{εton}}{\text{Max}}$ 442, 554 nm, ε ₅₅₄ / ε ₄₄₂ = 0.76.
Found,%: C 50.69, 50.83; H 5.30, 5.00; N, 6.00, 5.97; S 21.68, 21.95.

Calculated,%: C 50.73; H 5.27; N, 6.23; S 21.83. C ₃₈ H ₄₇ ClN ₄ O ₇ S ₆ .

 Example 3

The dye I _{3 was} obtained analogously to example 1 by mixing a methanol solution of 0.19 g of triethylammonium salt of 3,3'-di-γ-sulfopropyl-9-methyl-5-chloro-5'-methoxythiocarbocyanine betaine with 0.12 g of 3,3'-diethylthiazolinocarbocyanine iodide in 2 ml of methanol by boiling for 10 minutes.

Yield 0.2 g (82%). After crystallization from ethanol, dark violet crystals with t pl. 229-230 ^o C. Yield (62%).

λ $\genfrac{}{}{0ex}{}{\text{εton}}{\text{Max}}$ 482, 552 nm, ε ₅₅₂ / ε ₄₈₂ = 0.80.
Found,%: C 57.85, 57.92; H 5.00, 4.90; N, 5.85, 6.00; S 13.35, 13.30.

 Calculated,%: C 57.76; H 5.05; N, 5.72; S 13.12.

Sensitizing dyes are introduced into the emulsion in the form of alcohol solutions with a concentration of 5 • 10 ^-4 - 1 • 10 ^-3 M / L.

Supersensitizers in the form of aqueous or alcoholic solutions with a concentration of 5 • 10 ^-4 - 1 • 10 ^-3 M / L.

 Example 4 (prototype).

In 200 ml of molten emulsion N 1, 800 ml of a 6% gelatin solution are added, then 90 ml of a 1% aqueous solution of a stabilizer: 5-methyl-7-hydroxy-1,3,4-triazoindomecin (F-1) and after stirring an alcohol solution of a sensitizer formula (I) in an amount of 26 • 10 ^-5 M / M Ag.

After 20-30 minutes of standing at 38-40 ^o C, the emulsion is poured onto a substrate (glass or film), exposed in an FSR-41 sensor at a color temperature of a light source of 5000 K without a filter and behind filters: ZhS-18, OS-14 and KS -14 and show 8 minutes in the developer N 1 of the following composition, g / l:
Hydroquinone - 6
Metol - 5
Na ₂ SO ₃ b / w - 40
Used Na ₂ CO ₃ - 31
KBr - 4
Water up to 1 liter.

The densitogram field densities are measured on a densitometer and according to GOST 10691-73, the values of the veil density and the photosensitivity value of the photo layers are determined by the criterion D ₀ +0.85, as well as the contrast coefficient.

 The sensitometric parameters of the photolayers of this example and the following are given in table 2.

 Example 5 (comparative).

Analogously to example 4, but 2-3 minutes after the introduction of the sensitizer with stirring, an aqueous solution of supersensitizer III ₁ in the amount of 26 • 10 ^-5 M / M Ag is introduced, then proceed as in example 1.

 Examples 5-8.

 Analogously to example 4, but the number of injected compounds and properties of the photolayers are shown in table 2.

 Example 9

Analogously to example 4, but alcohol emulsion of sensitizer II ₃ in the amount of 26 • 10 ^-5 M / M Ag is introduced into the emulsion N 1 and after 20-70 minutes of aging, the supersensitizer IV ₁ in the amount of 26 • 10 ^-5 M / M Ag is introduced, then the sensitizer 1 is introduced in an amount of 13 • 10 ^-5 M / M Ag, and after 20-30 minutes of standing, the supersensitizer IV is introduced in an amount of 13 • 10 ^-5 M / M Ag. Then proceed as in example 4, the sensitometric characteristics are shown in table 3.

 Examples 10-12.

 Analogously to example 4, but the number entered in the emulsion N 1 compounds, their quantities and properties of the obtained photolayers are presented in table 3.

 Example 13

1 liter of molten emulsion N 1 is divided into 2 portions of 500 ml. In the first portion, a sensitizer II ₁ is introduced in an amount of 26 • 10 ^-5 M / M Ag and a supersensitizer III ₃ in an amount of 26 • 10 ^-5 M / M Ag.

In the 2nd portion, the sensitizer II ₁ is introduced in an amount of 26 • 10 ^-5 M / M Ag, after 20-30 minutes of standing, the supersensitizer III ₃ in an amount of 26 • 10 ^-5 M / M Ag is introduced.

Then the sensitizer I ₃ in the amount of 20 • 10 ^-5 M / M Ag is introduced, and after 20-30 minutes of standing, the supersensitizer II ₃ in the amount of 20 • 10 ^-5 M / M Ag is introduced.

 Then proceed as in example 1, the properties are presented in table 3.

 Example 14

1 liter of molten emulsion N 2 is divided into 2 equal portions. In the 2nd portion, the sensitizer II ₃ is introduced in an amount of 26 • 10 ^-5 M / M Ag.

After 30 minutes of standing, the supersensitizer III ₁ in an amount of 26 • 10 ^-5 M / M Ag is introduced into the emulsion. Then enter the sensitizer 2 in an amount of 20 • 10 ^-5 M / M Ag. Then, after 20-30 minutes of aging, the supersensitizer III ₂ is introduced in an amount of 20 • 10 ^-5 M / M Ag. Then proceed according to example 4.

 Examples 15-21.

 The sensitization of emulsion N 2 is carried out analogously to example 14, the introduced compounds, their quantities and properties of the obtained photolayers are presented in table 3.

 Example 22

In 1 l of molten emulsion N 4 add 250 ml of distilled water, then 45 ml of a 1% solution of stabilizer F-1. The emulsion is divided into 3 equal portions, a sensitizer II ₅ in an amount of 20 • 10 ^-5 M / M Ag and a supersensitizer III ₂ in an amount of 20 • 10 ^-5 M / M Ag are introduced into a first portion, a sensitizer is introduced into a second portion II ₅ in an amount of 20 • 10 ^-5 M / M Ag, a sensitizer (1) in an amount of 13 • 10 ^-5 M / M Ag and a supersensitizer III ₂ in an amount of 20 • 10 ^-5 and 13 • 10 ^-5 M / M Ag . A sensitizer II ₅ in an amount of 20 • 10 ^-5 M / M Ag, a sensitizer 1 in an amount of 16 • 10 ^-5 M / M Ag and a supersensitizer III ₂ in an amount of 20 • 10 ^-5 and 16 • 10 ^- are introduced into the third portion ⁵ M / M Ag, respectively.

 Then proceed as in example 4. The properties of the obtained photo layers are presented in table 3.

 Example 23-24

 The sensitization of emulsion N 4 is carried out analogously to example 22, the introduced compounds, their quantities and properties of the obtained photolayers are presented in table 3.

 Example 25

In 180 ml of molten emulsion N 3, 820 ml of a 6% gelatin solution and 90 ml of the stabilizer F-1 are introduced. Into the emulsion are introduced 26 • 10 ^-5 M / M Ag sensitizer II ₃ and 20 • 10 ^-5 M / M Ag sensitizer 2, then after each sensitizer, the supersensitizer III ₂ is added in an amount of 26 • 10 ^-5 and 20 • 10 ^-5 M / M Ag, respectively. Further, as in example 4.

 Examples 26-27.

 The sensitization of emulsion N 3 is carried out analogously to example 25, the introduced compounds, their quantities and properties of the obtained photolayers are presented in table 3.

As follows from tables 2 and 3, the claimed compounds and the proposed method of sensitization provide a higher level of photosensitivity of the photo layers, especially behind the OS-14 filter (cf. example N 14 and 15 -% S _0.85 ^OS-14 33 and 41%, examples 16 and 17-27 and 33%) in the absence of layer coloring after chemical-photographic processing.

The use in the sensitization method of a sensitizer of formula I ₁ in combination with a sensitizer of formula II and a supersensitizer III or IV ensures uniform photosensitivity in the wavelength range of 530-680 nm, usually Δl _g ≤ 0.1 l

Claims (2)

1. Salts of 3,3'-di-γ-sulfoalkylthiacarbocyanin betaine of the formula:

where A = lower alkyl;
R = O-Alk;
R ¹ = halogen;
[K] ⁺ = 3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine, or 1,1'-diethyl-quino-2,2'-monomethinocyanine,
as spectral sensitizers of silver halide photographic emulsions. 2. The method of spectral sensitization of silver halide photographic emulsions to the visible spectrum by introducing into the emulsion a supersensitizer, a sensitizing dye or a mixture thereof, characterized in that a compound of the formula is introduced as a sensitizing dye

where A = lower alkyl;
R = O-Alk;
R ¹ = halogen;
[K] ⁺ = 3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine, or 1,1'-diethyl-quino-2,2'-monomethinocyanine,
or administering a compound of formula I and a compound of formula

Where

A ¹ = lower alkyl;
[K] ⁺ =

3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine or 1,1'-diethyl-quino-2,2'-monomethine cyanine;
Y = O, S, B, B ¹ = H, CH ₃ , OCH ₃ , Cl, C ₆ H ₅ , 4,5-benzo,
and supersensitizer of the formula:

where B = H, lower alkyl;
B ¹ = H, alkyl, halogen;
m = 1, 2, n = 0, 2;
X ^- = ClO ₄ ^- para-CH ₃ C ₆ H ₄ SO ₃ ^- , halogen, R ² = C ₂ H ₅ , C ₈ H ₁₇ ,
or supersensitizer of the formula

where X ^- = halogen, alkyl sulfate, tosylate, R ³ = lower alkyl, n = 2 - 5.3

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