RU2069386C1 - Method of sensibilization of halogen-silver photographic emulsion at spectrum range 400-520 nm - Google Patents

Abstract

FIELD: chemical-photographic industry. SUBSTANCE: method involves the addition of sensibilizing agent - monomethinecyanine of the formula (I) $$$ where Y,$$$ - S, Se, O; B,$$$ - H, alkyl, alkoxyl, halogen, benzo- or thieno-group; $$$ - ions of alkaline metals, n = 2-4, and supersensibilizing agent of the formula (II) $$$ where Z - residue of benzothiazole, benzoxazole, thiazoline, benzimidazole, pyridine and formula (III) $$$ where Z - residues of substituted or unsubstituted benzimidazole, pyridine, pyrazole or imidazole; n = 1-3; A - $$$; m = 0-3; X - $$$, Cl, Br, J taken at amount 0.3-2 mole per 1 mole sensibilizing agent (I). Proposed method ensures to enhance photolayer light-sensitivity. Use of supersensibilizing agents (II) + (III) increases sensitivity at much more degree than the separate use of (II) or (III) (by 40-60% as compared 10-30%). In the case of sensibilization of AgCl emulsion using supersensibilizing agent (II) + (III) photolayer sensibility is enhanced by 3-fold as compared 1.2- and 2.3-fold if (II) and (III) were used separately. EFFECT: improved method of sensibilization. 2 tbl

Description

 The invention relates to methods for spectral sensitization of silver halide photographic emulsions and can be used in the chemical-photographic industry.

(R этил, сульфопропил, R¹-этил при R-сульфопропил, Х=Н) (Патент США N 4250244, НКИ 430 217 (G03C 1/40, 1/16), опубл. 10.2.1981 г.).It is known that for the sensitization of silver halide emulsions to the spectral region of 400 520 nm, various thiamonomethincyanines are used, for example, 3,3'-disubstituted 4,5-benzothiocyanate betaines

(R ethyl, sulfopropyl, R ¹ -ethyl at R-sulfopropyl, X = H) (U.S. Patent No. 4,250,244, NKI 430,217 (G03C 1/40, 1/16), publ. 10.2.1981).

где Z' группа атомов для замыкания бензо- или нафтооксазольного, тиазольного, имидазольного ядра (возможно замещенного), R",R'" каждый (не)замещен. алкил, замещ. карбокси-, сульфогруппой, алкенил, арил, аралкил, алкоксиалкил, Z² группа атомов, замыкающая 2-тиогидантоиновое ядро, возможно замещенное в 1-м положении алкилом, гидроксилом, алкоксикарбонилом.A known application for sensitization of silver halide photographic emulsion, including for a blue-sensitive layer with a maximum of sensitization in the region of 445,490 nm of a spectral sensitizer of the formula

where Z 'is a group of atoms for the closure of a benzene or naphthoxazole, thiazole, imidazole nucleus (possibly substituted), R ", R""is each (un) substituted. alkyl, substituted. carboxy, sulfo group, alkenyl, aryl, aralkyl, alkoxyalkyl, Z ² group of atoms, which closes the 2-thiohydantoin core, possibly substituted in the 1st position by alkyl, hydroxyl, alkoxycarbonyl.

 It is also known the use of dyes f-crystals I for the sensitization of silver halide photographic emulsions with different sizes and habit microcrystals in the region of 400 520 nm.

где Z^'," группа атомов для замыкания бензотиазольного, нафтотиазольного, бензооксазольного, имидазольного, пиридинового или хинолинового ядра, возможно содержащих заместители галоген ОН, CN, арил, алкил, алкоксил, алкоксикарбонил, R², R³ каждый (не)замещ. алкил (заместители карбокси, сульфогруппа); R¹ H, CH₃, C₂H₅, X-анион, n 0 1, (Пат. США N 4469785, НКИ 430 572, МКИ G03C 1/02, опубл. 4.12.84 г.).

where Z ^{', "a} group of atoms for the closure of benzothiazole, naphthiazole, benzooxazole, imidazole, pyridine or quinoline nucleus, possibly containing halogen substituents OH, CN, aryl, alkyl, alkoxyl, alkoxycarbonyl, R ² , R ³ each (non) substituted. alkyl (carboxy substituents, sulfo group); R ¹ H, CH ₃ , C ₂ H ₅ , X-anion, n 0 1, (US Pat. No. 4,469,785, NKI 430 572, MKI G03C 1/02, publ. 4.12.84 g .).

 However, in many systems, the achieved level of photosensitivity of the photographic layers does not meet the requirements.

 To increase the photosensitivity of photo layers sensitized by various dyes, supersensitizers are used as one of the methods for increasing the photosensitivity of sensitized photographic materials.

 The use of styryl bases as a supersensitizer is known, for example, the combination of 1,1'-diethylquino-2-monomethine cyaninioide and 2-p-dimethylaminostyryl benzothiazole is widely known, in which case a ten-fold increase in the photosensitivity of the corresponding layers is achieved. (R.A. Gershtein, L.G. Kurkina et al. "On the supersensitizing effect of dimethylaminostyrene derivatives of heterocyclic bases", Collection of scientific works, Gosniikhimfotoproekt, issue 28, 1979, p. 144 153).

и суперсенсибилизаторов бисчетвертичной соли бензимидазолия формулы

где если Х-тозилат, то R-этил, В-СН₃, B¹-5-хлор, n 2 или 1; или если Х-перхлорат, то R-этил, В-Н,СН₃, B¹=H, n 2, или если Х=перхлорат, то R=C₂H₅, B=CH₃, B¹=5-трифторметилсульфонил или 5-карбэтокси; или если Х=1, то R=C₂H₅, B= CH₃, B¹=5,6-дихлор. (Патент РФ N 1790175 от 21.11.80 г, МКИ C07Д 235/04, опубл. Бюл. N 45-46, 1993 г).It is also known to use various polymethine dyes, for example, the pyridinium salt of 3,3'-di-γ-sulfopropyl-4,5,4 ', 5'-dibenzo - in the process of spectral sensitization of silver-silver emulsion (d 0.17 1.1 nm) 9-ethylthiacarbocyanin betaine

and supersensitizers of the bis-quaternary benzimidazolium salt of the formula

where if X-tosylate, then R-ethyl, B-CH ₃ , B ¹ -5-chloro, n 2 or 1; or if X is perchlorate, then R-ethyl, BH, CH ₃ , B ¹ = H, n 2, or if X = perchlorate, then R = C ₂ H ₅ , B = CH ₃ , B ¹ = 5- trifluoromethylsulfonyl or 5-carbethoxy; or if X = 1, then R = C ₂ H ₅ , B = CH ₃ , B ¹ = 5,6-dichloro. (RF patent N 1790175 from 11.21.80 g, MKI C07D 235/04, publ. Bull. N 45-46, 1993).

 However, the effect of supersensitization is very specific and depends both on the conditions of application of the dye (Cr) + supersensitizer system and on the structure of these components.

 The purpose of the invention is to increase the photosensitivity of silver halide emulsions to the spectral region 400 520 nm.

где Y, Y¹ S, Se, O; B, B¹=H, алкил, алкоксил, галоген, бензо- или тиеногруппа,
/K⁺/ ионы щелочных металлов, HN(Alк)₃, C₅H₅NH, п 2 4, в эмульсию дополнительно вводят суперсенсибилизатор строения

где Z остаток бензтиазола, бензоксазола, тиазолина, бензимидазола, пиридина и строения

где Z остатки замещенного или незамещенного бензимидазола, пиридина, пиразола или имидазола, n 1 3, A (CH₂OCH₂)_m, m 0 3, X=ClO₄, CH₃C₆H₄SO₃, Cl, Br, I, в количестве 0,3 2 моль на 1 моль сенсибилизатора 1.The specified technical effect is achieved by the fact that in the method of sensitization of silver halide photographic emulsions with different sizes and habit of microcrystals to the spectral region 400 520 nm by the introduction of a sensitizer monomethincyanine, structure

where Y, Y ¹ S, Se, O; B, B ¹ = H, alkyl, alkoxyl, halogen, benzo or thieno group,
(K ⁺ ) ions of alkali metals, HN (Alк) ₃ , C ₅ H ₅ NH, n 2 4, the structure is additionally introduced into the emulsion with a supersensitizer

where Z is the residue of benzthiazole, benzoxazole, thiazoline, benzimidazole, pyridine and structure

where Z is the residue of substituted or unsubstituted benzimidazole, pyridine, pyrazole or imidazole, n 1 3, A (CH ₂ OCH ₂ ) _m , m 0 3, X = ClO ₄ , CH ₃ C ₆ H ₄ SO ₃ , Cl, Br, I , in an amount of 0.3 to 2 mol per 1 mol of sensitizer 1.

 The styryl bases of structure II are obtained by the known method of heating heterocyclic bases with p-dimethylaminobenzaldehyde in the presence of anhydrous zinc chloride, followed by distillation of the excess starting materials with steam. The residue is dissolved in dilute (1: 1) hydrochloric acid and alkalinization with ammonia gives the free base (R. A. Gershtein et al. "On the Supersensitizing Effect of Dimethylaminostyrene Derivatives of Heterocyclic Bases", Proceedings, Gosniikhimfotoproekt, issue 28, 1979, p. 145,146).

Bis-quaternary salts of benzimidazolium III are prepared by reacting 1-alkylbenzimidazole with bis-methane, p-toluene or benzenesulfonic esters of di- or triethylene glycol f-ly
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 R
R = H, methyl, n 1,2, m 0,1.

 The reaction is carried out without solvent or in a polar organic solvent (dioxane, nitrobenzene) (E.B. Lifshits et al. "On the effect of bis-quaternary salts of benzimidazoles on the photographic properties of carbocyanines of various structures", Collection of scientific papers Gosniikhimfotoproekta, 1984, p. 167).

 The use of a new composition of sensitizers of formula I and supersensitizers II and III for sensitization of silver halide photographic emulsions can significantly increase the photosensitivity of photolayers, while the use of supersensitizers II + III increases the sensitivity to a greater extent than the use of II or III (by 40 60% versus 10 30%) .

 In the case of sensitization of AgCl emulsion with the use of supersensitizers II + III, the photosensitivity of the photo layers increases 3 times against (1.2 and 2.3) when using II or III individually.

 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 table 1.

и затем делят на 4 порции (1₁-1₄).Example 1. In 1 liter of molten emulsion N1 containing stabilizers 5-methyl-7-hydroxy-1,3,4-triazaindolycin (N1) and 1-phenyl-5-mercaptotetrazole (N2) at a temperature of 38-40 ^o C with stirring 225 ml of 0.075% aqueous sensitizer I ₁ (I, Y = Y '= S, n 3, B = 5-OCH ₃ , B' 4,5-benzogroup,

and then divided into 4 servings (1 ₁ -1 ₄ ).

Example 1 ₁ . After 15 minutes of aging at 38 ^° C, the first portion of the emulsion is poured onto the film and, after drying, exposed to a FSR-41 sensor at a color temperature of the light source of 5000 K and developed in an X-ray developer at 20 ^° C for 8 minutes.

The composition of the developer X-ray-2: metol 2.2 g; Na ₂ SO ₃ 72.0 g; hydroquinone 8.8 g; Na ₂ CO ₃ b / w 48.0 g; KBr 4.0 g; water - up to 1 liter.

The densitogram field densities are measured on a densitometer and according to GOST 10691.1-73, the values of the veil density and the photosensitivity value of the photo layers are determined according to the criteria D _o +0.85 and D _o +0.2, as well as the contrast coefficient.

 Sensitometric parameters of the photo layers are shown in table 2.

Example 1 ₂ . Into the second portion of the emulsion, 30 ml of a 0.028% alcohol solution of the supersensitizer II ₁ (II, Z-benzthiazole) (0.5 mol / mol I) is introduced with stirring and, after 15 minutes of standing, it is poured onto the film. Further, as in example 1 ₁ .

Example 1 ₃ . In a third portion of the emulsion, 20 ml (1 mol / mol I ₁ ) of 0.18% aqueous solution of the supersensitizer III ₁ , (III, Z 1-ethylbenzimidazole, n 1, m 2, X = ClO ₄ ) is introduced with stirring and after 15- minute standing watered according to example 1 ₁ .

Example 1 ₄ . Into the fourth portion of the emulsion, 30 ml (0.5 mol / mol I ₁ ) of the supersensitizer II ₁ are introduced and after 15 minutes of standing, 20 ml (1 mol / mol I ₁ ) of a 0.18% solution of the supersensitizer III _{1 are} introduced. After 15 minutes of standing, it is poured onto a film. Further, as in example 1 ₁ .

и делят на 4 порции.Example 2. Analogously to example 1 in 1 l of the emulsion is injected 225 ml of 0.075% aqueous solution of the sensitizer I ₂ (I, Y = Y ¹ S, B = Cl, B ¹ = 5-CH ₃ , 6 OCH ₃ , n 3,

and divided into 4 servings.

Example 2 ₁ . Analogously to example 1 _{1 the} first portion of the emulsion is poured onto glass and then according to example 1 ₁ .

Example 2 ₂ .

Into the second portion of the emulsion, 28 ml (0.5 mol / mol I ₂ ) of 0.023% alcohol solution of the supersensitizer II ₂ (II, Z-thiazoline) are added and then in accordance with Example 1 ₁ .

Example 2 ₃ . In a third portion of the emulsion, 20 ml (1 mol / mol I ₂ ) of 0.2% aqueous solution of the supersensitizer III ₂ (III, Z 1-ethylbenzimidazole, n 2, m 0, X = CH ₃ C ₆ H ₄ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ and further according to example 1 ₁ .

Example 2 ₄ . In the fourth portion of the emulsion, analogously to example 1 to ₄ , 28 ml (0.5 mol / mol I ₂ ) of a 0.023% alcohol solution of supersensitizer II ₂ and 20 ml (1 mol / mol I ₂ ) of a 0.2% aqueous solution of supersensitizer III _{2 are} successively added and further according to example 1 ₁ .

и делят на 4 порции.Example 3. Analogously to example 1, in 1 l of a molten emulsion N2 containing a stabilizer of 5-methyl-7-hydroxy-1,3,4-triazaindolycin, 90 ml of a 0.075% aqueous solution of sensitizer I ₃ (Y = Y ¹ = Se, B = OCH ₃ , B ¹ = CH ₃ , n 4,

and divided into 4 servings.

Example 3 ₁ . Analogously to example 1 _{1, the} first portion of the emulsion N2 is poured onto glass and then according to example 1 ₁ , but using developer N1. The composition of the developer: methanol 1 g, Na ₂ SO ₃ (b / c) 26 g, hydroquinone 5 g, Na ₂ CO ₃ (b / c) 20 g, KBr 4 g, water up to 1 l.

Example 3 ₂ . Into the second portion of emulsion N2, 6 ml (0.3 mol / mol I ₃ ) of 0.023% alcohol solution of the supersensitizer II ₃ (II, Z-benzenelenazole) are introduced and further according to examples 1 ₁ and 3 ₁ .

Example 3 ₃ .

In a third portion of emulsion N2, 8 ml (1 mol / mol I ₃ ) of 0.25% aqueous solution of supersensitizer III ₃ (III, Z = 1-ethyl-2-methyl-5-chlorobenzimidazole, n 2, m 0, X = CH ₃ C ₆ H ₄ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ and further on examples 1 ₁ and 3 ₁ .

Example 3 ₄ .

In a fourth portion of emulsion N2, 6 ml (0.3 mol / mol I ₃ ) of a 0.023% solution of II ₃ and 8 ml of a 0.25% solution of the supersensitizer III ₃ are successively introduced. Further, according to examples 1 ₁ and 3 ₁ .

 Example 4. 1.5 L of molten N2 emulsion is divided into 6 parts of 250 ml.

. Далее по примерам 1₁ и 3₁.Example 4 ₁ . In the first portion of the emulsion is injected 24 ml of a 0.07% alcohol solution of the sensitizer I ₄ (I, Y = Y '= O, B ₁ = Cl, B ₂ = 5,6 -CH ₃ , n 3,

. Further, according to examples 1 ₁ and 3 ₁ .

Example 4 ₂ . 24 ml of a 0.07% alcohol solution of sensitizer I ₄ and 6 ml (0.3 mol / mol of I ₄ ) 0.023% alcohol solution of supersensitizer II ₄ (II, Z-pyridine-2) are introduced into the second portion of the emulsion from one container. Further, according to examples 1 ₁ and 3 ₁ .

Example 4 ₃ . In the third portion of the emulsion, 24 ml of a 0.07% alcohol solution of the sensitizer I ₄ are added and then, analogously to example 1 _2, 8 ml (1 mol / mol I ₄ ) of 0.20% alcohol solution of the supersensitizer III ₄ (III, Z = 2.3) is introduced , 5-trimethylpyrazolium, m 0, n 1, X = CH ₃ C ₆ H ₄ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ) .. Further on examples 1 ₁ and 2 ₁ .

Example _4-4 . The fourth batch emulsion similar to Example _{2 was} given 4 from one tank 24 ml 0.07% solution of sensitizer I ₄ and 6 mL (0.3 mol / mol I ₄₎ 0.023% solution supersensibilizatora II ₄ and then 8 ml (1 mol / mol I ₄ ) 0.20% alcohol solution of the supersensitizer III ₄ . Further, according to examples 1 ₁ and 3 ₁ .

Example _4-5 . The fifth portion emulsion similar to Example 4 ₄ injected solutions from one tank ₄ sensitizer I and II supersensibilizatora ₄ and then 16 ml (1 mol / mol I ₄₎ 0.20% aqueous solution of ₄ supersensibilizatora III. Further, according to examples 1 ₁ and 3 ₁ .

Example _4-6 . In a sixth portion of the emulsion according to Example 2 ₄ III supersensibilizatora introduced and then a solution of ₄ from one container ₄ sensitizer solution I and II supersensibilizatora _4. Further, according to examples 1 ₁ and 2 ₁ .

и делят на 4 порции.Example 5. Analogously to example 1 in 1 l of molten emulsion N3 containing a stabilizer of 5-methyl-7-hydroxy-1,3,4-triazindolycin, 400 ml of a 0.035% aqueous solution of sensitizer I ₅ (I, Y = Y ¹ = S , n 3, B = B ¹ = 5-OCH ₃ ,

and divided into 4 servings.

Example 5 ₁ . The first portion of the emulsion is poured onto the film and then analogously to example 1 ₁ , but using the developer (UP-2).

The composition of the developer UP-2: methanol 5 g, Na ₂ SO ₃ (b / c) 40 g, hydroquinone 6 g, Na ₂ CO ₃ (b / c) 31 g, KBr 4.0, water up to 1 l.

Example 5 ₂ . Into the 2nd portion of the emulsion, 12 ml (0.3 mol / mol I ₅ ) of a 0.035% alcohol solution of the supersensitizer II ₅ (Z-benzoxazole) are added and further according to examples 1 ₁ and 5 ₁ .

Example 5 ₃ . In a third portion of the emulsion, 12 ml (1 mol / mol of I ₅ ) of 0.13% alcohol solution of the supersensitizer III ₅ (III, Z = 1-methylimidazole, m 0, n 2, X = Br ^- ) are introduced and further according to Examples 1 ₁ and 5 ₁ .

Example 5 ₄ . 12 ml (0.3 mol / mol I ₅ ) of a 0.035% alcohol solution of supersensitizer II ₅ and 12 ml (1 mol / mol of I ₅ ) 0.13% alcohol solution of supersensitizer III ₅ and are introduced into the fourth portion of the emulsion, similarly to 1 ₄ and further on examples 1 ₁ and 5 ₁ .

и делят на 4 порции.Example 6. Analogously to example 1 in 1 l of molten emulsion N5 injected 200 ml of 0.070% aqueous solution of the sensitizer I ₆ (I, Y = Y ¹ = S, B = 5-OCH ₃ , B ₁ = 5-Cl, n 3,

and divided into 4 servings.

Example 6 ₁ . The first portion of the emulsion is poured onto the wafers and then according to example 1 ₁ , using the developer D-76/2.

Composition of the developer: Na ₂ SO ₃ 100 g, hydroquinone 5 g, Na ₂ B ₄ O ₇ • 10H ₂ O 2 g, benztriazole 0.2 g, phenidone 0.2 g, water up to 1 liter.

Example 6 ₂ . Into the second portion of the emulsion, 75 ml (0.5 mol / mol I ₆ ) of a 0.023% alcohol solution of the supersensitizer II ₂ (II, Z-thiazoline) are added and further according to examples 1 ₁ and 5 ₁ .

Example 6 ₃ . In the third portion of the emulsion, 50 ml (1 mol / mol I ₆ ) of 0.2% solution of supersensitizer III ₂ (III, Z = 1-ethylbenzimidazole, m 0, n 2, X = CH ₃ C ₆ H ₄ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ) and further on examples 1 ₁ and 5 ₁ .

Example 6 ₄ . 75 ml (0.5 mol / mol I ₆ ) of 0.023% alcohol solution of the supersensitizer II ₂ and 50 ml (1 mol / mol of I ₆ ) 0.20% aqueous solution of the supersensitizer III ₂ and are introduced into the _fourth portion of the emulsion similarly to 1 ₄ and further on examples 1 ₁ and 5 ₁ .

 From table 2 it follows that the photosensitivity of the photolayers sensitized by the dyes of structure I when using the composition of supersensitizers II + III increases to a greater extent than when applying II or III individually (by 40–60% versus 10–30%). In the case of an AgCl emulsion (N5), composition II + III also leads to a greater increase in photosensitivity (3 times) than II and III individually (1.2 and 2.3 times).

Claims (1)

The method of sensitization of silver halide photographic emulsions with different size and habit of microcrystals to the spectral region 400-520 nm by the introduction of a monomethincyanine sensitizer structure

where Y, Y ¹ S, Se, O;
B, B ¹ H, alkyl, alkoxyl, halogen, benzo or thieno;
/ K ⁺ / alkali metal ions;

(AI _k ) ₃ ,

n 2-4,
characterized in that the supersensitizer of the structure is additionally introduced into the emulsion

where Z is the residue of benzthiazole, benzoxazole, thiazoline, benzimidazole, pyridine
and buildings

where Z is the residue of substituted or unsubstituted benzimidazole, pyridine, pyrazole or imidazole, n 1 3, A = (CH ₂ OCH ₂ ) _m , m 0 3, X = ClO ₄ , CH ₃ C ₆ H ₄ SO ₃ , CI, Br, J
in the amount of 0.3 2 moles each per 1 mol of sensitizer.

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