RU2065461C1 - BIS-(3,3'-DI-γ-SULFOPROPYL-9-ALKYLTHIOCARBOCYANINE-BETAINE AND 3,3'-[1'',2''-DI-(ETHOXY)-ETHYLENE]-BIS-(1-ETHYLBENZIMIDAZOLIUM) SALTS AS SPECTRAL SENSITIZING AGENTS OF BROMINE-IODINE-SILVER PHOTOGRAPHIC EMULSIONS - Google Patents

Abstract

FIELD: chemical-photography industry. SUBSTANCE: product: new sensitizing agents - bis-(3,3'-di-g-sulfopropyl-9-alkylthiocarbocyanine-betaine) and 3,3'-[1'', 2''-di-(ethoxy)-ethylene] -bis-(1-ethylbenzimidazolium) salts exhibiting sensitization maximum at 580-650 nm. These substances were used for synthesis of spectral sensitizing agents of bromine-iodine-silver photographic emulsions. EFFECT: improved method of synthesis. 2 tbl

Description

The invention relates to polymethine dyes, specifically to bis salts
(3,3'-di-γ-sulfopropyl-9-alkylthiacarbocyanin betaines) and 3,3- [1 ", 2" bis- (ethoxy) ethylene] bis- (1-ethylbenzimidazolium, which are more effective panchromatic sensitizers, than known with a maximum sensitization in the range of 580-650 nm, and can be used in the chemical-photographic industry.

где А метильная или этильная группа;
В водород или метокси группа;
R (CH₂)₂OH, X^⊖-I, Cl, R(CH₂)₃SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , K^⊕-C₅H $\genfrac{}{}{0ex}{}{\text{+}}{\text{5}}$ NH.The use of panchromatic sensitizers of the structure is known:

where A is a methyl or ethyl group;
A hydrogen or methoxy group;
R (CH ₂ ) ₂ OH, X ^⊖ -I, Cl, R (CH ₂ ) ₃ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , K ^⊕ -C ₅ H $\genfrac{}{}{0ex}{}{\text{+}}{\text{5}}$ NH.

 These sensitizers have a maximum sensitization of 600 and 650 nm.

 However, for the developed technical films, especially designed for photographing under adverse conditions, a significant increase in photosensitivity is necessary.

 The purpose of the invention is to increase the photosensitivity of panchromatic photographic materials with a maximum of sensitization in the range of 580-650 nm.

где А метил или этил, В атом водорода, метильная или метоксигруппа.This goal is achieved by a new structure of dyes of salts of bis (3,3'-di) - γ-sulfopropyl-9-alkylthiacarbocyanine betaine) and 3,3 '- [1 ", 2" -bis- (ethoxy) ethylene] -bis (1- ethylbenzimidazolium) structures

where A is methyl or ethyl, B is a hydrogen atom, methyl or methoxy.

 Dyes of structure I are obtained by the known method of heating two moles of the pyridinium salt of 3,3'-di-γ-sulfopropyl-9-alkylthiacarbocyanin betaine with a mole of ditosylate 3,3- [1 ", 2" -bis- (ethoxy) ethylene] bis ( 1-ethylbenzimidazolium).

 Dyes I can be used in silver bromide (mono and polydispersed emulsions with different sizes of microcrystals), the main parameters of which are shown in table 1.

Dyes I are introduced into the emulsion in the form of solutions in ethyl alcohol or dimethyl sulfoxide (DMSO) at a concentration of 5.10 ^-4 1.10 ^-3 mol / L (0.08-0.2%) in an amount of 100.10 ^-6 200.10 ^-6 mol / mol AgHal into coarse-grained emulsion N1 and 320-10 ^-6 440.10 ^-6 mol / mol AgHal in a fine-grained emulsion N2.

 The invention is illustrated by the following examples 1-17 and table 1.2.

 Table 2 shows the data characterizing the photographic parameters of the photolayers obtained using the sensitizers of structure I and analogues of structure II.

PRI me R 1. Obtaining a salt of bis (3,3'-di-g-sulfopropyl-5,5-dimethoxy-9-ethylthiacarbocyanine betaine) and 3.3 '- [1 ", 2" -bis- (ethoxy ) ethylene] bis (1-ethylbenzimidazolium) (I ₁ ).

 To a hot solution of 0.18 g of the pyridinium salt of 3,3'-di-g-sulfopropyl-5,5-dimethoxy-9-ethylcarbocyanin betaine (0,00025 gm) in 5 ml of ethyl alcohol is added a hot solution of 0.09 g of ditosylate 3, 3'-bis- [1 ", 2" -bis (ethoxy) ethylene] -bis (1-ethylbenzimidazolium) (0.000125 gm) in 1.5 ml of ethyl alcohol.

The mixture is boiled for 15 minutes and kept at 10-12 ^o C for 1 day. The precipitate formed is filtered off, washed with 5 ml of a mixture of alcohol with acetone (1: 1), 2 ml of alcohol.

Yield 0.17 g (73.9%), small green crystals with mp. 219-220 ^o C / smok. 190 ^o C.

After crystallization from ethyl alcohol, 0.15 g (65.2%) of small green crystals with a metallic luster are obtained with a melting point of 219-220 ^o C.

 Found, C 51.36; H 6.28; N, 5.88.

C ₇₈ H ₉₄ N ₈ O ₁₈ S ₈ • 8H ₂ O.

 Calculated, C 51.13; H 6.05; N, 6.11.

 The amount of water in preparations I was determined using gas-liquid chromatography.

 The absorption maximum is 563 nm.

PRI me R 2. Obtaining salts of bis- (3,3'-di-g-sulfopropyl-6,6'-dimethyl-9-ethylthiacarbocyanin betaine) and 3.3 '- [1 ", 2" -bis- (ethoxy) ethylene] bis (1-ethylbenzimidazolium) (I ₂ ).

 To a hot solution of 0.18 g of the pyridinium salt of 3,3'-di-g-sulfopropyl-6,6-dimethyl-9-ethylthiacarbocyanin betaine (0,00025 gm) in 3 ml of ethyl alcohol, a hot solution of 0.09 g of ditosylate 3 is added. 3 '- [1 ", 2" bis (ethoxy) ethylene] bis (1-ethylbenzimidazolium) (0.000125 gm) in 1.5 ml of ethyl alcohol.

The mixture is boiled for 10 minutes and kept at 10-12 ^o C for 1 day.

 The precipitate formed is filtered off, washed with 2 ml of a mixture of alcohol with acetone (1: 1) and 2 ml of alcohol.

Yield 0.19 g (82.6%), dark green small crystals with a melting point of 218-219 ^o .

After crystallization from ethyl alcohol, 0.15 g (65.2%) of small dark green crystals with a metallic luster of so pl. 218-219 ^o C.

 Found, C, 51.40; H 5.72; S 14.00.

C ₇₈ H ₉₄ N ₈ O ₁₄ S ₈ • 2H ₂ O.

 Calculated, C 51.47; H 5.42; S 14.09.

 The absorption maximum is 554 nm.

PRI me R 3. Obtaining a salt of bis- (3,3'-di-g-sulfopropyl-9-methylthiacarbocyanin betaine and 3,3 '- [1 ", 2" -bis (ethoxy) ethylene] -bis- ( 1-ethylbenzimidazolium) (I ₃ ).

To a hot solution of 0.17 g of the pyridinium salt of 3,3'-di-g-sulfopropyl-9-methylthiacarbocyanin betaine (0,00025 gm) in 3 ml of ethyl alcohol is added a hot solution of 0.09 g of 3.3 '- [1 "ditosylate , 2 "-bis- (ethoxy) ethylene] -bis- (1-ethylbenzimidazolium) (0.000125 gm) in 1.5 ml of ethyl alcohol. The mixture is boiled for 10 minutes and kept at 10-12 ^o C for 1 day. The precipitate formed is filtered off, washed with 2 ml of a mixture of alcohol with acetone (1: 1) and 2 ml of alcohol.

Yield 0.18 g (78.2%), dark cherry crystals with mp. 199-200 ^o C.

After crystallization from ethyl alcohol, small dark cherry crystals are obtained with a melting point of 199-200 ^o C.

 Found, C, 47.25; H 5.19; S 14.11.

C ₇₈ H ₈₂ N ₈ O ₁₄ S ₈ • 9H ₂ O.

 Calculated, C 47.35; H 5.50; S 14.04.

 The maximum absorption is 542 nm.

Example 4. In 1 liter of molten negative polydisperse emulsion N1, an alcohol solution of 3,3'-di-b-hydroxyethyl-5,5-dimethoxy-9-ethylthiacarbocyanine chloride (N1) is introduced in an amount of 160.10 ^-6 m / m AgHal (40 mg / L). The sensitized emulsion is kept in a thermostat at 39 ± 1 ^o C for 30 minutes and then watered on a plate or film. Get panchromatic photographic material with λ $\genfrac{}{}{0ex}{}{\text{sense}}{\text{Max}}$ 650 nm and a zone boundary of 680 nm, the parameters of which are given in Table 2.

 To determine the sensitometric parameters, the photo layers are exposed in an FSR-41 sensitometer with a color temperature of a light source of 5000 K without a filter and behind filters ZhS-18, OS-14 and KS-14. Chemical-photographic processing of photolayers and determination of sensitometric parameters are carried out in accordance with OST 6-17-450-78 using GOST 10.691.0-73, GOST 10.691.1-73.

650 нм, параметры которого приведены в табл. 2.Table 2 shows the photosensitivity of the photo layers, determined by the criterion DD _o + 0.85 (S 0.85), the values of the contrast coefficients j and the density of the veil D _o
PRI me R 5. In 1.5 l of the molten emulsion N1 injected with an alcohol solution of the pyridinium salt of 3,3-di-γ-sulfopropyl-9-ethyl-5,5-dimethoxythiocarbocyanine betaine (N2) in an amount of 160.10 ^-6 m / m AgHal (50 mg / l) and stand in a thermostat at 39 ± 1 ^o C for 20 minutes Then the emulsion is divided into three equal parts: 5 ₁ , 5 ₂ and 5 ₃
The first portion of 5 _{1 is} poured onto a plate or film. Then they proceed analogously to example 4 and receive photographic material with

650 nm, the parameters of which are given in table. 2.

In a second portion 5 _{2, a} 2.5% aqueous alkaline solution of N- (3'-sulfo-6-methyl-octadecylamino) 1-hydroxy-2-naphthoic acid anilide (blue component) is introduced in an amount of 10 g / l and stand at 39 ± 1 ^o C 20 min. Then proceed analogously to example 4. Get panchromatic photographic material, the parameters of which are given in table. 2. With the color manifestation of the photo layers, a blue image is obtained.

In a third portion _of 5–3, 300 ml of a 6% gelatin dispersion of S- (2,4-di-tert-amylphenoxy) butylamide 1,2-hydroxynaphthoic acid in a solution of dibutyl phthalate and triphenyl phosphate (10 g of the blue component per 1 liter of emulsion) are added. Then proceed analogously to examples 5 ₂ and 4. Get panchromatic material, the parameters of which are given in table.2. With the color manifestation of the photo layers, a blue image is obtained.

PRI me R 6. In 1.5 l of the molten emulsion N1 inject a solution in DMSO dye I ₁ (according to example 1) in an amount of 160.10 ^-6 m / m AgHal (150 mg / l) then proceed analogously to example 5 (5 ₁ , 5 ₂ and 5 ₃ ). The processing of photolayers is carried out according to example 4. Get panchromatic photographic materials 6 ₁ , 6 ₂ and 6 ₃ with λ $\genfrac{}{}{0ex}{}{\text{ctyc}}{\text{Max}}$$\genfrac{}{}{0ex}{}{}{}$ 650 nm, the parameters of which are given in table.2. When the color manifestation of the photo layers according to examples 6 ₂ and 6 ₃ receive a blue image.

Example 7. In 1 liter of molten emulsion N1, an alcoholic solution of 3,3'-di-β-hydroxyethyl-9-methylthiacarbocyanine chloride (N3) was added in an amount of 192.10 ^-6 m / m AgHal (40 mg / l). The sensitized emulsion is allowed to stand for 15 minutes at 39 ± 1 ^o C and then proceed analogously to example 4. Photographic material λ is obtained $\genfrac{}{}{0ex}{}{\text{sense}}{\text{Max}}$ 600 and 525 nm and a zone boundary of 640 nm, the parameters of which are given in Table 2.

PRI me R 8. In 1 liter of molten emulsion N1 enter the alcohol solution of the pyridine salt of 3,3'-di-γ-sulfopropyl-9-methyl-thiacarbocyanin betaine (N4) in the amount of 128.10 ^-6 mol / mol AgHal (48 mg / l).

The sensitized emulsion stand for 15 minutes at 39 ± 1 ^o C and then proceed analogously to example 4. Get photographic material with λ $\genfrac{}{}{0ex}{}{\text{sense}}{\text{Max}}$ 595 and 520 nm and the boundary of the zone of 640 nm, the parameters of which are given in Table 2.

PRI me R 9. In 1 l of the molten emulsion N1 injected a solution in DMSO sensitizer I ₃ (according to example 3) in an amount of 128.10 ^-6 m / m (122 mg / l), the sensitized emulsion stand for 15 minutes at 39 ± 1 ^o C and then proceed analogously to example 4. Get photographic material with λ $\genfrac{}{}{0ex}{}{\text{ctyc}}{\text{Max}}$ 595 and 520 nm and the boundary of the zone of 640 nm, the parameters of which are given in Table 2.

Example 10. A solution of 3,3'-di-γ-sulfopropyl-6,6'-dimethyl-9-ethylcarbocyanine betaine (N5) in an amount of 128.10 ^-6 mol is introduced into 1 liter of molten emulsion N1 / mol AgHal 140 mg / L. Sensitized emulsion stand for 60 minutes at 39 ± 1 ^o C and then proceed analogously to example 4.

Get photographic material with λ $\genfrac{}{}{0ex}{}{\text{sense}}{\text{Max}}$ 580-590 nm and a zone boundary of 640 nm, the parameters of which are given in Table 2.

PRI me R 11. In 1 l of the molten emulsion N1 injected a solution in DMSO sensitizer I ₂ (according to example 2) in an amount of 128.10 ^-6 mol / mol AgHal (120 mg / l).

The sensitized emulsion is allowed to stand for 60 minutes at 39 ± 1 ^° C and then proceed analogously to Example 4. Photographic material with λ is obtained. $\genfrac{}{}{0ex}{}{\text{ctyc}}{\text{Max}}$ 580-590 nm and 630 and the boundary of the zone 645-650 nm, the parameters of which are given in table.2.

Example 12. In 1 liter of molten negative monodispersed silver bromide-silver emulsion N2, an alcohol solution of dye N2 in the amount of 192.10 ^-6 mol / mol AgHal (60 mg / l) was introduced and allowed to stand in a thermostat at 30 ± 1 ^o C for 20 minutes. The sensitized emulsion is watered on wafers. Get photographic material with a maximum and the boundary of the sensitization zone at 650 and 680 nm, the parameters of which are given in table 2.

PRI me R 13. In 1 l of the molten emulsion N2 injected alcohol solution of the sensitizer I ₁ (according to example 1) in an amount of 192.10 ^-5 mol / mol AgHal (150 mg / l) and stand in a thermostat at 39 ± 1 ^o C 20 minutes. The sensitized emulsion is watered on wafers. Get photographic material with a maximum and the boundary of the sensitization zone at 650 and 680 nm, the parameters of which are given in table 2.

PRI me R 14. In 1 liter of molten emulsion N2, an alcohol solution of dye N4 in the amount of 192.10 ^-6 mol / mol AgHal (72 mg / l) is introduced and allowed to stand in a thermostat at 39 ± 1 ^o C for 20 minutes. The sensitized emulsion is poured onto the film. Get panchromatic photographic material with a maximum and the boundary of the sensitization zone at 595 and 640 nm, the parameters of which are given in table 2.

PRI me R 15. In 1 liter of molten emulsion N2, an alcohol solution of dye I ₃ in the amount of 192.10 ^-6 mol / mol AgHal (180 mg / l) is introduced and allowed to stand in a thermostat at 39 ± 1 ^o C for 20 minutes. The sensitized emulsion is poured onto the film. Get panchromatic material with a maximum and the boundary of the sensitization zone at 595 and 640 nm, the parameters of which are given in table.2.

PRI me R 16. In 1 liter of molten emulsion N2, an alcohol solution of dye N5 in the amount of 256.10 ^-6 mol / mol AgHal (90 mg / l) is introduced and allowed to stand in a thermostat at 39 ± 1 ^o C for 20 minutes. The sensitized emulsion is poured onto the film. Get panchromatic photographic material, with a maximum and the boundary of the sensitization zone at 590 and 620 nm, the parameters of which are given in table 2.

PRI me R 17. In 1 liter of molten emulsion N2, an alcohol solution of dye I ₂ is introduced in an amount of 256.10 ^-6 mol / mol AgHal (220 mg / l) and stand in an thermostat at 39 ± 1 ^o C for 20 minutes.

 The sensitized emulsion is poured onto the film. Get panchromatic photographic material with a maximum and the boundary of the sensitization zone at 580-590 and 650 nm, the parameters of which are given in table 2.

 From the analysis of examples and tables it follows that dyes I cause a higher level of total and additional photosensitivity of the photo layers than the dye analogs of structure II in emulsion N1 by 1.3-1.7 times, and by 1.5-1.8 times in the emulsion N2.

It is also advisable to use sensitizers I in the emulsion in the presence of colored hydrophilic and hydrophobic components to obtain color photographic materials. As can be seen from the comparison of examples N5 ₁ , 5 ₂ and 5 ₃ with N 6 ₁ , 6 ₂ and 6 ₃ , the photosensitivity of the layers behind the KS-14 filter when using 1 ₁ is 1.5 times higher than that achieved with the analogue dye N2. TTT1 TTT2

Claims (1)

Salts of bis (3,3 ^, -di-g-sulfopropyl-9-alkylthiacarbocyanine betaines) and 3.3 ^, [1 <M ^ <D>, 2 ^,, -di (ethoxy) ethylene] bis (1-ethylbenzimidazoline) general formula

where A is methyl or ethyl;
To hydrogen, methyl or methoxy,
as spectral sensitizers of silver bromide photographic emulsions.

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