RU2045767C1 - Process of manufacture of ammonia bromine-iodine-silver photographic emulsion - Google Patents

Abstract

FIELD: manufacture of photographic materials. SUBSTANCE: process of manufacture of ammonia bromine-iodine-silver photographic emulsion with size of microcrystals of 1.0 ± 0.1 μm and content of silver iodide 4-0.1 mole per cent involves fractional emulsification, physical maturing, separation of solid phase with sulfopolysterene, washing of deposit, its dispersion in distilled water, adjustment of pBr up to 2,8± 0,1 and of pH up to 6,7± 0,1, chemical maturing with the use of stage of repeat dispersion of latex based on copolymer of butylacrylate and styrene in proportion 7:1 or copolymer of butylacrylate, styrene and metacrylic acid in proportions 7.0:0.5:0.5; 6.0: 1.5: 0.5; 5.0:2.5:1.5; 1.9:0.5:0.5 in the amount of 5.6-18.9 g/kg of emulsion. EFFECT: improved quality of photographic emulsion. 1 tbl

Description

 The invention relates to methods for the manufacture of silver halide photographic emulsions, and in particular to methods for the manufacture of ammonium bromide silver photographic emulsions for registration in the visible spectrum, and can be used in the production of photographic materials for various purposes.

A known method of manufacturing ammonia bromide-silver photographic emulsions, which consists in sequentially carrying out the following stages:
obtaining in a colloidal protective medium microcrystals of silver halide (emulsification and physical maturation);
removal of water-soluble salts by chemical precipitation of a solid phase, by introducing a coagulant into a photographic emulsion;
siphoning or decanting the supernatant;
washing the precipitate;
dispersing the washed precipitate in distilled water and a gelatin solution;
chemical maturation;
applying the finished emulsion to the substrate.

 (Sheberstov V.I. "Fundamentals of the technology of photosensitive photo materials", M. Chemistry, 1977, p.106).

 The disadvantage of this method is that it does not provide the necessary level of sensitivity to the visible region of the spectrum.

1,0 ± 0,1 мкм, содержащий AgI 4,0 ± 0,1 мол. путем проведения дробной эмульсификации, физического созревания, выделения твердой фазы сульфополистиролом, промывки осадка, диспергирования осадка дистиллированной водой и повторного диспергирования в водно-желатиновом растворе, доведения эмульсии до pВr 2,8 ± 0,1 и рН 6,7 ± 0,1, химического созревания в присутствии тиосульфата натрия и роданистого золота, введения поливных добавок: стабилизатора (5-метил-7-окси-1,3,4-триазаиндолицина), дубителя (нейтрализованного раствора ацетата хрома и флороглюцина, спектральных сенсибилизаторов: 1) соль 1,1'-диэтил-2,2'-хиноцианина и 3,3'-ди-(γ-сульфопропил)-3-этил-4,5-бензо-4',5'. 4'', 5''-диметилтиено- (2'',3''-тиатиозолокарбоцианинбетаина, 2) 1,1'-диэтил-2,2'-хиноцианина и 3,3'-ди-γ-сульфопропил-9-этил- 5,5'-диметокситиакарбоцианинбетаина; смачивателя (натриевой соли ди-2-этилгексилтетраэтиленгликолевого эфира сульфоянтарной кислоты) (технический регламент изготовления фотографической пленки тип 4 N 18119, Переславль-Залесский, ПОЗ Госниихимфотопроект"а, 1987, прототип).There is also known a method of manufacturing ammonia silver bromide photographic emulsions with the size of microcrystals of silver halide

1.0 ± 0.1 μm, containing AgI 4.0 ± 0.1 mol. by fractional emulsification, physical maturation, isolation of the solid phase by sulfonated polystyrene, washing the precipitate, dispersing the precipitate with distilled water and redispersing in an aqueous gelatin solution, adjusting the emulsion to pВr 2.8 ± 0.1 and pH 6.7 ± 0.1, chemical ripening in the presence of sodium thiosulfate and gold rhodanum, the introduction of irrigation additives: a stabilizer (5-methyl-7-hydroxy-1,3,4-triazaindolicin), tanning agent (neutralized solution of chromium acetate and phloroglucinol, spectral sensitizers: 1) salt 1, 1'- ietil hinotsianina-2,2'-and 3,3'-di- (γ-sulfopropyl) -3-ethyl-4,5-benzo-4 ', 5'. 4``, 5 '' - dimethylthieno- (2``, 3 '' - thiothiolocarbocyanine betaine, 2) 1,1'-diethyl-2,2'-chinocyanine and 3,3'-di-γ-sulfopropyl-9- ethyl 5,5'-dimethoxythiocarbocyanine betaine; wetting agent (sodium salt of di-2-ethylhexyltetraethylene glycol ether sulfosuccinic acid) (technical regulation for the manufacture of photographic film type 4 N 18119, Pereslavl-Zalessky, POZ Gosniikhimfotoproekt "a, 1987, prototype).

When using this method, a high level of photosensitivity is achieved, but the required deformation temperature (T _def ) and moisture capacity (W) of the emulsion layer of the photographic film are not provided.

 The purpose of the invention is to increase the temperature of deformation and reduce the moisture capacity of the emulsion layer of the photographic film while maintaining photographic properties and resolution.

1,0 ± 0,1 мкм, содержанием иодида серебра AgI 4,0 ± 0,1 мол. путем проведения дробной эмульсификации, физического созревания, выделения твердой фазы сульфополистиролом, промывки осадка, диспергирования осадка в дистиллированной воде, повторного диспергирования в водно-желатиновом растворе, доведения эмульсии до pBr 2,8 ± 0,1 и рН 6,7 ± 0,1 химического созревания в присутствии тиосульфата натрия и роданистого золота, введения спектральных сенсибилизаторов: соль 1,1'-диэтил-2,2'-хиноцианина и 3,3'-ди-(γ-сульфопропил-)-3-этил-4,5-бензо-4',5',4'', 5''- диметилтиено (2'',3''-тиатиозолокарбоцианинбетаина; 1,1'-ди-этил-2,2' -хиноцианина и 3,3'-ди-γ-сульфопропил-9-этил-5,5'- диметокситиакарбоцианинбетаина, в нее на стадии повторного диспергирования дополнительно вводят латексы на основе полимерных соединений: формул I или II, или III, или IV, или V. а) сополимера бутилакрилата со стиролом, формулы
[-CH₂-

[-CH₂-

(I) при соотношении мономеров m:n 7:1, мас.ч. б) сополимера бутилакрилата, стирола и метакриловой кислоты, формулы
[-CH₂-

[-CH₂-

[-CH₂-

(II) при соотношении мономеров m: n: q 7: 0,5:0,5 мас.ч. в) сополимера бутилакрилата, стирола и метакриловой кислоты, формулы
[-CH

[-CH

[-CH₂-

(III) при соотношении мономеров m:n:q 6: 1,5: 0,5 мас.ч. г) сополимера бутилакрилата, стирола и метакриловой кислоты, формулы
[-CH

[-CH

[-CH

(IV) при соотношении мономеров m:n:q 5: 2,5: 0,5 мас.ч. д) сополимера бутилакрилата, стирола и метакриловой кислоты, формулы
[-CH₂-

[-CH₂-

[-CH₂-

(V) при соотношении мономеров m:n:q 19: 0,5: 0,5 мас.ч. в количестве 5,6-18,9 г на 1 кг эмульсии, что соответствует 10, 20 и 30% замены желатины.This goal is achieved by the fact that in the method of manufacturing ammonium bromide silver photographic emulsion with the size of microcrystals

1.0 ± 0.1 μm, silver iodide content AgI 4.0 ± 0.1 mol. by fractional emulsification, physical maturation, isolation of the solid phase by sulfon polystyrene, washing the precipitate, dispersing the precipitate in distilled water, redispersing in an aqueous gelatin solution, adjusting the emulsion to pBr 2.8 ± 0.1 and pH 6.7 ± 0.1 chemical maturation in the presence of sodium thiosulfate and gold thiocyanate, the introduction of spectral sensitizers: the salt of 1,1'-diethyl-2,2'-chinocyanine and 3,3'-di- (γ-sulfopropyl -) - 3-ethyl-4,5 -benzo-4 ', 5', 4``, 5 '' - dimethylthieno (2``, 3 '' - thiothiolocarbocyanine betaine; 1,1'-di-ethyl-2,2 '-quinocia Nina and 3,3'-di-γ-sulfopropyl-9-ethyl-5,5'-dimethoxythiocarbocyanin betaine; latex based on polymer compounds: formulas I or II, or III, or IV, or V. a) a copolymer of butyl acrylate with styrene, of the formula
[-CH ₂ -

[-CH ₂ -

(I) when the ratio of monomers m: n 7: 1, parts by weight b) a copolymer of butyl acrylate, styrene and methacrylic acid, of the formula
[-CH ₂ -

[-CH ₂ -

[-CH ₂ -

(II) when the ratio of monomers m: n: q 7: 0.5: 0.5 parts by weight c) a copolymer of butyl acrylate, styrene and methacrylic acid, of the formula
[-CH

[-CH

[-CH ₂ -

(III) when the ratio of monomers m: n: q 6: 1.5: 0.5 parts by weight g) a copolymer of butyl acrylate, styrene and methacrylic acid, of the formula
[-CH

[-CH

[-CH

(IV) when the ratio of monomers m: n: q 5: 2.5: 0.5 parts by weight d) a copolymer of butyl acrylate, styrene and methacrylic acid, of the formula
[-CH ₂ -

[-CH ₂ -

[-CH ₂ -

(V) when the ratio of monomers m: n: q 19: 0.5: 0.5 parts by weight in the amount of 5.6-18.9 g per 1 kg of emulsion, which corresponds to 10, 20 and 30% gelatin replacement.

 These latexes are produced by the Tasma pilot plant in accordance with TU 6-17-872-P-87 and technological regulations N 03-389-88 and N 03-392-88. Previously, the latexes of formulas II, III, IV and V were used as substances that increase photosensitivity and improve retention. In this case, they were introduced into the emulsion at the stage of preparing it for application to the substrate (ed. Application No. 4509236/04 of 02.16.89).

 The claimed combination of distinctive features is unknown in other technical solutions, therefore, the technical solution meets the criterion of "Significant differences".

PRI me R 1 (prototype). Silver bromide-ammonia (AgI iodide content 4.0 mol%) photographic emulsion with an average AgHal microcrystal size of 1.0 μm is obtained using the method of fractional single-jet emulsification: in the first solution containing gelatin in an amount of 17 g / l of solution and alkali metal halides (KBr and KI), aminated silver nitrate solutions are introduced in three portions. The silver metal content in the reaction medium is 190 g / l. The total duration of the physical ripening for 24 minutes at 40 ^C. Stirring speed 1000 rev / min.

After physical maturation, the emulsion is acidified with acetic acid (225 ml of a solution with a mass fraction of 50%) to a pH of 6.4 and the solid phase is isolated by introducing sulfon polystyrene in an amount of 0.25 ± 0.05 g / g of gelatin. The precipitate is washed with distilled water in two doses of 15 minutes each. The temperature of the wash water 10 ± 1 ^about C.

The washed precipitate was dispersed for 30 minutes in distilled water at 43 ± 1 ° ^C. If redispersion additional gelatin is administered in an amount of 63 g per 1 kg of emulsion. The duration of the re-dispersion of 30 minutes at 43 ± 1 ^about C.

Then the emulsion is adjusted to pBr 2.8 ± 0.1 and pH 6.7 ± 0.1 by introducing a KBr solution (1 ml of a solution with a mass fraction of 10%) and sodium carbonate solution (3.5 ml of a solution with a mass fraction of 11 %) per 1 kg of emulsion. Chemical ripening was carried out for 3 hours at 46 ± 0,5 ^{° C} in the presence of sodium thiosulfate (6 ml of a solution with a mass fraction of 0.1%) and gold thiocyanate (1 ml of a solution with a mass fraction of 0.04% for gold) 1 kg of emulsion.

Before applying to the substrate, the usual irrigation additives (per 1 kg of emulsion) are introduced into the emulsion:
stabilizer (5-methyl-7-hydroxy-1,3,4-triazindolycin) 30 ml of solution with a mass fraction of 1%
spectral sensitizers: salt of 1,1'-di-ethyl-2,2'-chinocyanine and 3,3'-di- (γ-sulfopropyl) -3-ethyl-4,5-benzo-4 ', 5', 4 '', 5 '' - dimethylthieno (2``, 3 '') - thiothiozolocarbocyanin betaine (70 ml of solution with a mass fraction of 0.1%). b) 1,1'-di-ethyl-2,2'-chinocyanine and 3,3'-di-γ-sulfopropyl-9-ethyl-5,5'-dimethoxyxythiocarbocyanine betaine (35 ml of a solution with a mass fraction of 0, 1%);
wetting agent sodium salt of di-2-ethylhexylethylene ether sulfosuccinic acid (10 ml of a solution with a mass fraction of 8%);
tanning agent neutralized solution of chromium acetate (10 ml of a solution with a mass fraction of 5%) and phloroglucinol (6 ml of a solution with a mass fraction of 10%).

 The emulsion is applied to a cellulose triacetate or polyethylene terephthalate substrate.

The resulting sample of photographic material is exposed in the FSR-4 sensitometer at a color temperature of 5500 and developed in the developer N-3M of the following composition, g / l: metol 1.0; hydroquinone 2.0; methylphenidone 0.7; sodium sulfite, b / w 100.0; sodium carbonate 16.0; potassium bromide 2.5; polyox-100 1.0; benzotriazole 0.1. The development time is 8 minutes at a temperature of 19 ± 1 ^about C.

Photosensitivity (according to the criterion S0,2 + Д _о ) and contrast ratio (γ) are determined according to GOST 2817-50. In addition, determine the density of the veil (D _about ) and resolution according to GOST 2819-68.

 The characteristics of physical and mechanical properties (deformation temperature and moisture capacity) are determined in accordance with OST V-6-17-427-76.

 Characteristics of the photographic and physico-mechanical properties of silver halide photosensitive material made from the resulting emulsion are given in the table.

 PRI me R 2. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula I, in the amount of 5.6 g per 1 kg of emulsion.

 PRI me R 3. The manufacture of the emulsion is carried out analogously to example 1, but in the stage the size of the microcrystals of AgHal is 1.1 μm, and in the stage of re-dispersion additionally enter the compound of formula I in the amount of 12.6 g per 1 kg of emulsion.

 PRI me R 4. The manufacture of the emulsion is carried out analogously to example 1, but the size of the AgHal single crystals is 0.9 μm, and in the stage of re-dispersion additionally enter the compound of formula I in the amount of 18.9 g per 1 kg of emulsion.

 PRI me R 5. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula II in the amount of 5.6 g per 1 kg of emulsion.

 PRI me R 6. The manufacture of the emulsion is carried out analogously to example 1, but the AgI content is 4.1 mol. and in the re-dispersion step, a compound of formula II is further added in an amount of 12.6 g per 1 kg of emulsion.

 PRI me R 7. The manufacture of the emulsion is carried out analogously to example 1, but the AgI content is 3.9 mol. and in the re-dispersion step, a compound of formula II is further added in an amount of 18.9 g per 1 kg of emulsion.

 PRI me R 8. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula III in the amount of 5.6 g per 1 kg of emulsion.

 PRI me R 9. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula III in the amount of 12.6 g per 1 kg of emulsion.

 PRI me R 10. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula III in the amount of 18.9 g per 1 kg of emulsion.

 PRI me R 11. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula IV in the amount of 5.6 g per 1 kg of emulsion.

 PRI me R 12. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula IV in the amount of 12.6 g per 1 kg of emulsion.

 PRI me R 13. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula IV in the amount of 18.9 g per 1 kg of emulsion.

 PRI me R 14. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula V in the amount of 5.6 g per 1 kg of emulsion.

 PRI me R 15. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula V in the amount of 12.6 g per 1 kg of emulsion.

 PRI me R 16. The manufacture of the emulsion is carried out analogously to example 1, but in the stage of re-dispersion additionally enter the compound of formula V in the amount of 18.9 g per 1 kg of emulsion.

 Characteristics of the photographic and physico-mechanical properties of silver halide photosensitive materials obtained using the claimed compounds are shown in the table.

 The data in the table indicate that the introduction of the inventive polymer latexes into the emulsion can increase the deformation temperature by 25-60% and reduce the moisture capacity of the emulsion layer by 20-40%

Claims (1)

METHOD FOR PRODUCING AMMONIA BROWN-SILVER PHOTOGRAPHIC EMULSION with microcrystal size d _{with p} (1.0 ± 0.1) μm, AgJ content (4 ± 0.1) mol. by fractional emulsification, physical maturation, isolation of the solid phase by sulfonated polystyrene, washing the precipitate, dispersion in distilled water, re-dispersion in distilled water, re-dispersion in an aqueous gelatin solution, adjusting pBr 2.8 ± 0.1 and pH 6.7 ± 0.1, chemical maturation in the presence of sodium thiosulfate and gold rhodanide, the introduction of spectral sensitizers of 1,1 ′ diethyl 2,2′-quinocyanine salt and 3,3 ′ di (γ sulfopropyl) -3-ethyl-4,5-benzo 4 ′, 5 ′, 4 ″, 5 ″ dimethylthieno- (2 ″, 3 ″) - thiazolok bopicyanin and salts of 1,1′-diethyl-2,2 ′ quinocyanine and 3,3′-di (γ-sulfopropyl) -9-ethyl-5,5 ′ dimethoxythiocarbocyanine betaine, characterized in that, in order to increase the deformation temperature and reduce the moisture capacity of the emulsion layer, latex based on a copolymer of butyl acrylate and styrene of the formula I is additionally introduced into the emulsion at the stage of re-dispersion

where mn 7 1 (parts by weight),
or a copolymer of butyl acrylate, styrene and methacrylic acid of the formula II

where mnq 7 0.5 0.5 (wt.h),
or a copolymer of butyl acrylate, styrene and methacrylic acid of the formula III

where mnq 6 1.5 0.5 (wt.h),
or a copolymer of butyl acrylate, styrene and methacrylic acid of the formula IV

where mnq 5 2.5 1.5 (wt.h),
or a copolymer of butyl acrylate, styrene or methacrylic acid of the formula V

where mnq 19 0.5 to 0.5 (parts by weight),
in the amount of 5.6 to 18.9 g / kg of emulsion.

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