RU2184387C1 - Silver halide photographic material - Google Patents

Abstract

FIELD: light-sensitive materials. SUBSTANCE: material consists of underlayered support with gelatin counterlayer and silver halide emulsion layer disposed on the both sides of support, the gelatin layer containing antihalation dyes and emulsion layer containing (i) spectral sensitizers of formula I:

(I) wherein A denotes hydrogen or lower alkyl; R and R' denote lower alkyl or group (CH₂)₃SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; Z denotes beta-naphtho-, 4,5- benzo- or B-phenyl (B = H, alkyl, halogen); Z' denotes beta-naphtho-, 4,5- benzo-, thieno[3",2"]benzo-, 2,3-dimethylthiophene, B'-phenyl (B' = H, alkyl, alkoxy, aryl); or Z and Z' are missing; X^_ is halogen or p-toluenesulfonyl anion; [K]⁺ denotes ammonium, trialkylammonium, or pyridinium cations, 1,1'- diethyl-2,2'-quinomonomethyncyanine, 3,3'-diethyl-oxacarbocyanine, or 3,3'- diethylthiazoline-carbocyanine; (ii) activator of formula II:

(II), wherein B and B' denote hydrogen, lower alkyl, or halogen; m = 1 or 2; n = 0-2; X^- denote perchlorate, halogen or p-toluenesulfonyl anion; (iii) antihalation and stabilizing agent of formula III:

(III), wherein R and R' denote lower alkyls; and, additionally, (iv) ground layer, light-sensitive counterlayer, and protective layer containing butyl acrylate/styrene/methacrylic acid copolymer depicted by formula IV:

Description

 The invention relates to the field of photographic chemistry, namely to isopanchromatic silver halide photographic materials that can be used for aerial photography and shooting from space.

 Typically, black and white silver halide photographic materials include a substrate, a photosensitive silver halide emulsion layer spectrally sensitized to a particular spectral region, and a protective hydrophilic colloidal layer.

 At the same time as the main layers, many black-and-white photographic materials also include such functional layers as a counter-layer counter layer, an anti-twisting layer, an adhesive, and a primer.

где D₀ - плотность вуали.One of the important characteristics of photographic materials is their information content (I), which is characterized by a combination of the achieved level of sensitivity according to the criterion of 0.85 or 0.2 over the density of the veil (S _0.2 + D ₀ ) and resolution (R) with the same contrast ratio (γ) and deposit of silver and can be expressed by the formula

where D ₀ is the density of the veil.

Known silver halide photographic material consisting of a substrate, on one side of which a photosensitive layer is sequentially applied, made of silver bromide-gelatin emulsion with a silver iodide content of 2.9-3.1 mol. % with an average size of emulsion microcrystals d / _cp = 0.20 ± 0.02 μm, including spectral sensitizers: triethylamine salt of 3,3'-di-γ-sulfopropyl-9-ethyl-4,5-benzo-4 ',
5 '(thieno-3``, 2'') thiacarbocyanine betaine and a salt of 1,1'-diethyl-2,2'-chinocyanine and 3,3'-di-γ-sulfopropyl-9-ethyl-5,5'- dimethoxythiocarbocyanin betaine, spectral sensitization activator - 3,3 '- [1'',2''dipechlorate - bis (ethoxy) ethyl] bis- (1-ethylbenzimidazolium), tanning agent N, N, N', N'-tetraisopropoxymethyldiamide malonic acids and aminoiminomethanesulfinic acid, and a protective gelatin layer, including the same tanning agent and aminoiminomethanesulfinic acid, and on the other, a gelatin anti-oreole counter layer, including a blue-green filter dye - triet pentamethyloxanine iso-1- (4'-sulfophenyl-3-carbethoxypyrad / ash-5) lamine salt, yellow protivoreol dye is the condensation product of 2,4-disulfonic acid and hydroxyethionic naphthenic acid, fuchsin acid is the potassium salt of the fuchsin sulfonation product, tanning agent of acetatechrome and formalin. [RF patent 2085987, IPC ⁶ G 03 C 1/005, dated 10.02.88, publ. July 27, 1997, BI 21].

The specified material has good resolution, but insufficient photosensitivity, especially behind the OS-14 filter (S _0.85 ^OS-14 = 15.5, S _0.2 ^OS-14 = 3.5, R _{ct = 0.2} = 260 mm ^-1 ).

 Also known is silver halide photographic material, consisting of a layered substrate, on one side of which a gelatin anti-rheole counter layer is applied, including anti-rheum dyes: blue-green dye, yellow F-1 and fuchsin acid F, on the other - a ground gelatin layer, a photosensitive layer made of silver bromide iodine emulsion with a microcrystal size of silver halide 0.33 μm, AgJ content 3 mol. %, with pH = 6.0 - 6.3 and pBr = 3.0 ± 0.2, including pyrocatechol, stabilizers 5-methyl-7-hydroxy-1,3,4-triazindolycin, 2-n-heptyl-5- methyl-6-bromo-7-hydroxy-1,3,4-triazindolycin, activator of spectral sensitization - N-phenyl-N- (1,3,5-triazolinadamantyl-J) thiourea (FTT), spectral sensitizers: triethylamine salt 3 , 3 '-di-γ-sulfopropyl-9-ethyl-4,5-benzo-4', 5 '(thieno-3``, 2' ') thiacarbocyanine betaine and 1,1'-diethyl-2,2' salt -quinocyanine and 3,3'-di-γ-sulfopropyl-9-ethyl-5,5'-dimethoxythiocarbocyanine betaine, as well as the usual watering additives: wetting agents - disodium salt of N-γ diethyl ether -dehyloxypropyl-N-β-carboxy-β-sulfopropyl) aspartic acid and the sodium salt of di-2-ethylhexyl ether sulfosuccinic acid, the tanning activator is triethanolamine, and the protective gelatin layer containing a suspension of HC-13, the wetting agent is the di-2 sodium salt -ethylhexyl ether sulfosuccinic acid, tanning agent - formalin (4% solution). [Technological regulation 6-17-546, GOSNIIHIMPHOTOPROEKT, M. 1983].

However, the resulting photographic material has a higher level of photosensitivity behind the OS-14 filter (30-35 units of GOST), but insufficient resolution (as the contrast ratio is low, CT _0.2 105 min / mm), and also not an optimal photosensitivity / resolution ratio ability that determines information content.

 The aim of this invention is to expand the range of highly sensitive photographic materials with a sufficient level of resolution and increase the information content of photographic materials.

где А= Н, низший алкил, NH₂, R, R¹ = низший алкил, (СН₂)₃SО₃ ^-, Z = β-нафто,

где В = алкил, H, галоген, Z¹ = β-нафто, 4,5 бензо

, тиено-[3'', 2''] бензо,

, где В¹ = Н, алкил, алкоксил, арил, или Z и Z¹ - отсутствуют, X^- - галоген, пара-CH₃C₆H₄SO₃ ^-, [К] ⁺ = НN(А1к)₃, NH₄NHC₅H₅, 1,1'-диэтил-2,2'-хиномонометинцианин, 3,3'-диэтилтиазолинокарбоцианин, 3,3'-диэтилоксакарбоцианин, а в качестве активатора спектральной сенсибилизации содержит соединение формулы

где B, B¹ = H, низший алкил, галоген, m = 1, 2, n = 0-2, X^- = ClO₄ ^-, галоген, пара-СН₃С₆Н₄SО₃ ^-, а также антивуалент-стабилизатор формулы

где R, R¹ = низший алкил,
и дополнительно грунтовый светочувствительный и защитный слои содержат сополимер бутилакрилата, стирола и метакриловой кислоты формулы

при соотношении мономеров m:n:p = (5-19):(0,5-2,5):0,5 масс. ч.The specified technical result is achieved in that in a photographic silver halide material, consisting of a layered base, on one side of which there is a gelatinous counter layer, including anti-rheumatic dyes, on the other is a gelatinized primer layer, an emulsion silver halide layer containing spectral sensitizers, spectral sensitization activators, stabilizers and watering additives, and a protective gelatin layer, an emulsion silver halide layer is made of a silver bromide emulsion with a mer microcrystals of silver halide content of 0.15-0.50 micron AgJ 2-5 mol. % and contains as a spectral sensitizer more than one compound selected from a number of formulas

where A = H, lower alkyl, NH ₂ , R, R ¹ = lower alkyl, (CH ₂ ) ₃ SO ₃ ^- , Z = β-naphtho,

where B = alkyl, H, halogen, Z ¹ = β-naphtho, 4,5 benzo

, thieno [3 '', 2 ''] benzo,

where B ¹ = H, alkyl, alkoxyl, aryl, or Z and Z ¹ are absent, X ^is halogen, para-CH ₃ C ₆ H ₄ SO ₃ ^- , [K] ⁺ = HN (A1k) ₃ , NH ₄ NHC ₅ H ₅ , 1,1'-diethyl-2,2'-quinomonomethinocyanine, 3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyloxacarbocyanine, and as an activator of spectral sensitization contains a compound of the formula

where B, B ¹ = H, lower alkyl, halogen, m = 1, 2, n = 0-2, X ^- = ClO ₄ ^- , halogen, para-CH ₃ C ₆ H ₄ SO ₃ ^- , as well as anti-valent formula stabilizer

where R, R ¹ = lower alkyl,
and additionally the soil photosensitive and protective layers contain a copolymer of butyl acrylate, styrene and methacrylic acid of the formula

when the ratio of monomers m: n: p = (5-19) :( 0.5-2.5): 0.5 mass. h

 As stabilizers, the photographic material may contain 5-methyl-7-hydroxy-1,3,4-triazindolycin, 2-n-goethyl-5-methyl-6-bromo-7-hydroxy-1,3,4-triazoindolecin or a mixture thereof .

 As anti-rheumatic dyes, the counter layer can contain various compounds selected from the series: dipotassium salt of 2-benzal-3-hydroxy-thionaphthen-2,4-disulfonic acid (yellow Ф-1) (V), the product of the condensation of dioxethylamine with n-chlorobenzaldehyde followed by oxidation of the leuko compound (VI), the potassium salt of the condensation product of the glutacone aldehyde dianyl hydrochloride with 1- (4-sulfophenyl) -3-carboxypyrazolone-5 (VII), the middle potassium salt of bis- (1-p-sulfophenyl-3-carboxypyrazolono-5) trimethinoxanine (VIII) tartrazine (IX), fuchsin acid F (X), blue-see eny dye - triethylamine salt pentametiloksanina iso-1- (4-sulfophenyl, 3-karbetoksipirazolona-5) (XI).

Anti-rheumatic dyes are administered in an amount of 20-40 g each per 1 kg of gelatin. The compound of formula I is preferably administered in an amount of (100-500) • 10 ^-6 mol / mol AgHal, the compound of formula II in an amount (0.2-1.0) mol / mol of spectral sensitizer. It is desirable to administer the antivalent stabilizer of formula III in an amount of (0.01-0.1) g per 1 mol of AgHal.

 A copolymer of butyl acrylate, styrene and methacrylic acid of the formula IV is introduced in an amount of (5-30)% by weight of gelatin contained in the layer.

 The proposed photographic silver halide material manufactured using silver halide photographic emulsions with a microcrystal size of silver halide 0.15-0.5 μm, various spectral sensitization variants using the indicated spectral sensitizers of formula I, sensitization activators of formula II, stabilizers, and also copolymers of formula IV in a photosensitive , primer, counter-layer and protective, has a high level of resolution and the optimal ratio lnnost / resolution, and therefore, high information content.

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

 Example 1 (prototype).

For the manufacture of photographic material, a photographic silver bromide-silver emulsion is synthesized as follows:
400 ml of a 1.3 N solution of AgNO ₃ and 400 ml of a 1.3 N solution of a mixture of potassium bromide and potassium iodide (with a potassium iodide content of 3 mol%) are poured simultaneously with two jets of two dispensers at a constant speed into a vessel containing 500 ml 3% gelatin solution and 7 ml of 24% ammonia solution.

Throughout the duration of the emulsification, a constant excess of bromine ions is maintained, equal to 1 • 10 ^-3 mol / L (pBr = 3.0). The average size of the crystals formed is 0.35 ± 0.05 μm. After the end of the emulsification, the emulsion is kept for 10 minutes, cooled to 30 ^{° C.} , the solid phase is precipitated with polystyrene foam and the silver halide precipitate is washed with water to remove excess soluble salts. After that, the precipitate is dispersed for 15 minutes in water, and then a solution of additional gelatin in the amount of 80 g in 400-500 ml of water is introduced, the emulsion volume is adjusted to 1350 ml and dispersed for another 10 minutes. The pH and pBr value of the finished emulsion are adjusted to 6.0-6.3 and 3.0, respectively.

After this, the chemical maturation of the emulsion is carried out, during which 50 ml of 1 • 10 ^-2 N sodium thiosulfite solution, 50 ml of a 20% solution of sodium benzenesulfinic acid (c-salt) and 10 ml of 0.004% (in in terms of metallic gold) of a solution of hydrochloric acid. Chemical maturation is carried out at a temperature of 45 ± 2 ^o C for 110-150 minutes to achieve maximum photosensitivity. After that, 90 ml of a 1% solution of 5-methyl-7-hydroxy-1,3,4-triazoindolecin is introduced into the emulsion. Using a 0.1 M solution of Na ₂ CO _{3, the} pH of the emulsion is adjusted to 8.0-8.5 and stabilizers are added 3 ml of a 0.01% solution of tri-para-tolylphosphine, 20 ml of a 0.25% solution of 2-n -heptyl-5-methyl-6-bromo-7-hydroxy-1,3,4-triazoindolecin and 5 • 10 ^-3 g / kg of N-phenyl-N 'emulsion - (1,3,5-triazadamantyl-7) -thiourea (FFT). Then, 150 ml of 0.1% sensitizing dye, the triethylamine salt of 3,3'-di-γ-sulfopropyl-9-ethyl-4,5-benzo-4 ', 5' (thieno-3 '', 2 ', is introduced ') thiacarbocyanin betaine and 60 ml of a 0.1% solution of a sensitizing dye - salts of 3,3'-di-γ-sulfopropyl-9-ethyl-5,5'-dimethoxythiocarbocyanine and 1,1'-diethyl-2,2' -quinocyanine, and watering additives - 20 ml of a 1% solution of pyrocatechol, 15 ml of a 4% aqueous solution of SV-1147 - disodium salt of diethyl ether [N-γ-decyloxypropyl-N-β-carboxysulfopropionyl] aspartic acid, 5 ml 4% aqueous solution of Na-salt of di-2-ethylhexyl ether and sulfosuccinic acid (SW-102) and 7 ml of 5% aqueous solution of triethanolamine. The resulting emulsion is applied to a PET base with an anti-areola counterblock made from the composition: 16.500 l of demineralized water, 1780 ml of a suspension of HC-13, 2700 ml of a 5% solution of a blue-green filter dye, 227 ml of 15% are added per 1 kg of gelatin aqueous solution of yellow anti-rheumatic dye, 335 ml of acid fuchsin, 757 ml of a 4% aqueous solution of the wetting agent SV-102, 120 ml of a 25% aqueous solution of KNO ₃ , 242 ml of a 5% aqueous solution of neutralized chromium acetate and 227 ml 4% aqueous formalin solution. A protective layer is applied along the emulsion layer: 40 g of gelatin per 1 liter of water, 1.5 ml of a 10% aqueous solution of Na ₂ CO ₃ , 30 ml of a 4% wetting agent of the Na-salt of di-2-ethylhexyl ether sulfosuccinic acid and 8 ml of a 4% aqueous formalin solution.

Sensitometric tests are carried out on an FSR-41 sensor at T _col. 5000K according to GOST 10691.5-88, resolvoletric tests are carried out on a RP-2M resolvometer according to GOST 2819-84.

 The test results are presented in table 2.

 Example 2

For the manufacture of photographic material, the emulsion according to Example 1 is used, but at the stage of chemical maturation, the anti-valent stabilizer III (R = CH ₃ , R ¹ = C ₂ H ₅ ) is introduced in an amount of 0.1 g per 1 mol of AgHa1, but three-n- are not introduced tolylphosphine, as well as N-phenyl-N '- (1,3,5 triazadamantyl-7) thiourea.

нафто,

, А = С₂Н₅, R, R' = (CH₂)₃SO₃ ^-, [К]⁺ = 1,1'-диэтил-2,2'-хиномонометинцианин), а также активатор спектральной сенсибилизации II (B, B¹ = H, m= 2, n=0, X = n-СН₃С₆Н₄SO₃ ^-) в количестве 160•10^-6 М/М I.At the stage of preparation for irrigation, a sensitizing dye I (Z, Z '= absent, A = H, R, R' = C ₂ H ₅ , X = J ^- ) is added to the emulsion in an amount of 100 • 10 ^-6 M / M Ag, 160 • 10 ^-6 I (Z =

nafto

, A = C ₂ H ₅ , R, R '= (CH ₂ ) ₃ SO ₃ ^- , [K] ⁺ = 1,1'-diethyl-2,2'-quinomonetincyanine), as well as an activator of spectral sensitization II (B , B ¹ = H, m = 2, n = 0, X = n-CH ₃ C ₆ H ₄ SO ₃ ^- ) in an amount of 160 • 10 ^-6 M / M I.

 Further, everything is as in example 1, but only copolymer IV (m: n: p = 7: 0.5: 0.5) in an amount of 5% by weight of gelatin is additionally introduced into the soil, photosensitive, counter layer and protective layer, t. e. respectively 70 ml of aqueous solution IV with a mass fraction of 10%, 35 ml, 20 ml and 60 ml.

 Example 3

 For the manufacture of photographic material, bromide-silver emulsion is synthesized by the method of two-jet emulsification. An aqueous solution of ammonia with a mass fraction of 25% (150 ml) is introduced into an aqueous gelatin solution 1 containing 2.4 kg of gelatin in 80 l of demineralized water, then an aqueous solution is fed continuously from the dosing units at the same speed for 55 ± 5 minutes 2 silver nitrate (17.7 kg in 80 liters of water) and an aqueous solution of potassium halides containing 13 kg KBr, 0.6 kg KJ in 85 liters of water. Emulsification is carried out at a constant value of pBr = 3.2 ± 0.1. At the end of the emulsification, 0.3 L of acetic acid is added with a mass fraction of 56% to pH = 5.0 ± 0.5.

, A = C₂H₅, R, R' = (CH₂)₃SO₃ ^- [К]⁺ = 1,1'-диэтил-2,2'-хиномонометинцианин) с массовой долей 0,1%, 20 мл активатора спектральной сенсибилизации II (В,В'= Н, m= 2, n=0, Х=n-СН₃С₆H₄SО₃ ^-) с массовой долей 0,2%, затем 90 мл спирто-водного раствора спектрального сенсибилизатора I (

A=CH₃,

, R, R¹ = (CH₂)₃SO₃ ^- [K]⁺ = HN(C₂H₅)₃) с массовой долей 0,1% и 15 мл соединения II (В,В¹ = Н, m=2, n=0, Х^- = n-СН₃С₆Н₄SO₃ ^-) с массовой долей 0,2%, а также 10 мл водного раствора смачивателя (СВ-1129) - натриевой соли ди-2-этилгексилтетраэтиленгликолевого эфира сульфоянтарной кислоты молярной концентрации 0,1 моль/л. Эмульсию фильтруют и подают на полив.An emulsion is obtained with an average microcrystal size of silver halide d _cp. = 0.24, the content of AgJ = 3.0 mol% and the finished emulsion is poured into a precipitation apparatus, where it is cooled to 38 ± 2 ^° С, foam is quenched by spraying a 1% alcohol solution of tributyl phosphate. Then, with continuous stirring, 3 L of an aqueous solution of sodium polystyrenesulfonic acid with a mass fraction of 10% and 0.5 L of an aqueous solution of acetic acid with a mass fraction of 56% are driven. After brief stirring, the mixer is stopped, the precipitate settles, the liquid phase is drained, the precipitate is washed with demineralized water, then with the addition of 120 ml of an aqueous solution of potassium bromide with a mass fraction of 10%. The precipitate is dispersed in a water-gelatin solution containing 2 kg of gelatin in 25 l of demineralized water, 0.6 l of an aqueous solution of sodium carbonate with a mass fraction of 10%, 100 ml of an aqueous solution of potassium bromide with a mass fraction of 10%, 0.2 is added thereto. l of an alcoholic solution of tributyl phosphate with a mass fraction of 1% and 13.0 l of an aqueous solution of sodium salt of benzenesulfinic acid with a mass fraction of 20%, the precipitate is dispersed for 30 minutes, the dispersed precipitate of silver halides is poured into a second maturing apparatus containing a solution of 10.3 kg of gelatin in 65 liters of water, while erature 42-43 ^o C. copolymer is administered IV (m: n: p = 7: 0.5: 0.5) with a mass fraction of 10% in an amount of 20 l. Then at a temperature of 45-46 ^o With enter 0.7 l of an aqueous solution of sodium thiosulfate with a mass fraction of 1%, 1 l of an aqueous solution of antivalent III (R = CH ₃ , R ¹ = CH ₃ ) with a mass fraction of 0.2%, water a solution of hydrochloric acid with a mass fraction of 0.08% (for metallic gold) in an amount of 450 ml; at the end of chemical maturation, an alcohol-water solution of phenol with a mass fraction of 50% (1 l) and an aqueous-alkaline solution of 5-methyl-7- stabilizer are introduced into the emulsion hydroxy-1,3,4-triazaindolycin 4.5 l with a mass fraction of 1%, then in the emulsion lead per 1 kg: 20 ml of alcohol solution of stabilization ora, 2-n-heptyl-5-methyl-6-bromo-7-hydroxy-1,3,4-triazoindolecin with a mass fraction of 0.25%, 20 ml of an aqueous solution of pyrocatechol with a mass fraction of 1%, 50 ml of spectral I (A = H, R, R ¹ = C ₂ H ₅ , X = J ^- , Z and Z '= not present) with a mass fraction of 0.1%, then 150 ml of sensitizer I (Z = β-naphtho,

, A = C ₂ H ₅ , R, R '= (CH ₂ ) ₃ SO ₃ ^- [K] ⁺ = 1,1'-diethyl-2,2'-quinomonomethinocyanine) with a mass fraction of 0.1%, 20 ml activator of spectral sensitization II (B, B '= H, m = 2, n = 0, X = n-CH ₃ C ₆ H ₄ SO ₃ ^- ) with a mass fraction of 0.2%, then 90 ml of an alcoholic solution of spectral sensitizer I (

A = CH ₃ ,

, R, R ¹ = (CH ₂ ) ₃ SO ₃ ^- [K] ⁺ = HN (C ₂ H ₅ ) ₃ ) with a mass fraction of 0.1% and 15 ml of compound II (B, B ¹ = H, m = 2, n = 0, X ^- = n-CH ₃ C ₆ H ₄ SO ₃ ^- ) with a mass fraction of 0.2%, as well as 10 ml of an aqueous solution of a wetting agent (CB-1129) - the sodium salt of di-2-ethylhexyltetraethylene glycol ether sulfosuccinic acid with a molar concentration of 0.1 mol / L. The emulsion is filtered and fed to the watering.

 The emulsion is poured onto a layered PET base with an anti-areole counter-layer, for the manufacture of which 60 g of gelatin, 580 ml of demineralized water, 70 ml of an aqueous solution of copolymer IV are taken per 1 liter of solution (m: n: p = 7: 0.5: 0.5 ) with a mass fraction of 10%, 10 ml of an aqueous solution of a yellow protivoreolny dye (V) with a mass fraction of 15%, 13 ml of an aqueous solution of a protivoreolny dye (X) with a mass fraction of 8%, 30 ml of an aqueous solution of the wetting agent SV-102 with a mass fraction of 4 %, 10 ml of an aqueous solution of potassium nitrate with a mass fraction of 20%, 75 ml of a dispersion of polymethylmethacrylate paste that with a mass fraction of 1%, dye (XI) with a mass fraction of 5%, 9.5 ml of an aqueous-soda solution of chromate acetate neutralized with a mass fraction of 5%, 20 ml of an aqueous solution of formalin with a mass fraction of 2%.

 To water the soil layer, the composition is prepared on the other side of the base: 33 g of gelatin, 900 ml of demineralized water, 45 ml of an aqueous solution of copolymer IV (m: n: p = 7: 0.5: 0.5) are added per 1 liter of the soil layer mass fraction of 10%, 6 ml of an aqueous solution of wetting agent SV-1129 in a molar concentration of 0.1 mol / l, 20 ml of an aqueous solution of wetting agent SV-102 with a mass fraction of 4%, 4.5 ml of an aqueous-soda solution of neutralized chromacetate with a mass fraction of 5 %, 2 ml of an aqueous solution of sodium carbonate with a mass fraction of 10%.

 To water the protective layer applied over the emulsion layer, a composition is prepared: 46 g of gelatin, 840 ml of demineralized water, 70 ml of an aqueous solution of copolymer IV (2.6 g) are taken per 1 liter of the protective layer (m: n: p = 7: 0.5: 0.5) with a mass fraction of 10%, 8 ml of an aqueous solution of wetting agent SV-1129 with a molar concentration of 0.1 mol / l, 8 ml of an aqueous solution of wetting agent SV-102 with a mass fraction of 4%, 11 ml of an aqueous solution of nitrate potassium with a mass fraction of 20%, 15 ml of an aqueous solution of formalin with a mass fraction of 2% and 2 ml of an aqueous solution of sodium carbonate with a mass fraction of 10%.

 Then proceed, as in example 1. The characteristics of the material are shown in table 2.

 Example 4

 For the manufacture of photographic material proceed analogously to example 3, but in the manufacture of the emulsion in a water-gelatin solution before the start of emulsification, 300 ml of an aqueous solution of ammonia with a mass fraction of 25% is introduced.

A silver bromide-emulsion is obtained with a microcrystal size of silver halide d _cp. = 0.5 μm.

 Example 5

For the manufacture of photographic material, a monodispersed silver bromide-emulsion (4 mol% AgJ) with an average emulsion microcrystal size d _cp. = 0.15 μm and a coefficient of variation C _v = (23 ± 2)% is prepared according to the following technology: in 200 liters of a 1.45% aqueous gelatin solution (using inert gelatin) containing 0.3 l of 25% an aqueous solution of ammonia, providing a pH = 8.5 ± 0.5, at a temperature of (40 ± 1) ^o C for 70 minutes at the same time as a constant speed using a controlled two-jet emulsion, 140 l of a 1.3 N aqueous solution of silver nitrate and 114 l of 1 are added 6N aqueous solution of potassium bromide and potassium iodide (4 mol% AgJ). During the emulsification process, a constant excess of bromine ions pBr = 3.3 ± 0.1 is maintained in the system by subtitling the reaction medium with a 0.1N potassium bromide solution. After crystallization is complete, the emulsion is cooled to 40 ^{° C.} and the solid phase is precipitated by introducing a precipitant — an NF product obtained by sulfonation of naphthalene with sulfuric acid (1: 1.1) and subsequent condensation with formaldehyde and neutralization with sodium hydroxide in an amount of 1 liter with a mass fraction of 10% , upon preliminary acidification of the emulsion with acetic acid to pH = 4.1 ± 0.3, the precipitate is washed with demineralized water to remove dissolved salts. Then the precipitate is dispersed in 82 l of a 3% aqueous solution of gelatin. The resulting emulsion is mixed in 220 l of an 8% aqueous solution of gelatin to obtain ρ = 1.5 ± 0.1 and the pH and pBr of the emulsion are adjusted to 6.5 ± 0.2 and 3.2 ± 0.1 0, respectively. 1N sodium carbonate solution and 0.1N potassium bromide solution for optimal chemical sensitization.

In 1 kg of the obtained emulsion at (46 ± 1) ^o C, 3.0 ml of a 1% aqueous solution of sodium thiosulfate, 40 ml of a 25% solution of sodium benzenesulfinic acid are sequentially introduced, incubated for 60 minutes, and then 5 ml of 0 , A 04% solution of rhodanized gold (in terms of metallic gold), after 70 min of aging, 20 ml of a 1% solution of 5-methyl-7-hydroxy-1,3,4-triazoindolecin (sta salt) and the compound III (R, R '= CH ₃ ) in an amount of 30 ml with a mass fraction of 0.2%.

In a chemically sensitized emulsion, 70 ml of a 1% solution of sta-salt and spectral sensitizers I (A = C ₂ H ₅ , R, R '= (CH ₂ ) ₃ SO ₃ , Z = β-naphtho, Z ¹ = thieno are introduced [3``, 2 ''] benzo, [K] ⁺ = 3,3'-diethylthiazolinocarbocyanine) in an amount of 200 • 10 ^-6 M / M Ag and I (A = H, R, R ¹ = C ₂ H ₅ , X = J ^- , Z, Z ¹ - absent) in an amount of 100 M / M Ag, compound II (B, B '= H, m = 1, n = 2, X = ClO ₄ ^- in an amount of 1 mol / 1 mol of each sensitizer.

 Then proceed according to example 3.

 Example 6

 The material is produced analogously to example 3, but in the synthesis of the emulsion at the stage of chemical ripening, 1.5 ml of a 0.08% (in terms of metallic gold) solution of hydrochloric acid and 2 ml of a 0.04% solution of rhodanide are introduced per 1 kg of emulsion gold.

[K]⁺ = 1,1'диэтил-2,2'-хиномонометинцианина, а также вводят активатор спектральной сенсибилизации II (В= СН₃, В¹=5^-Сl, m=1, n=2, Х^-=пара-СН₃С₆Н₄SO₃ ^-) в количестве моль/моль I.When preparing the emulsion for irrigation, I (A = C ₂ H ₅ , R, R '= (CH ₂ ) ₃ SO ₃ , Z = Z ^l = β-naphtho, [K] ⁺ = 1,1' is introduced as spectral sensitizers -diethyl-2,2'-quinomonomethincyanine) in an amount of 1.5 • 10 ^-4 mol / mol AgHal, 5 • 10 ^-4 mol / mol AgHal I (A = H ₂ C ₅ , R, R ¹ = (CH ₂ ) ₃ SO ₃ ^-

[K] ⁺ = 1,1'-diethyl-2,2'-quinomonomethincyanine, and the spectral sensitization activator II is also administered (B = CH ₃ , B ¹ = 5 ^- Cl, m = 1, n = 2, X ^- = pair -CH ₃ C ₆ H ₄ SO ₃ ^- ) in the amount of mol / mol I.

 Example 7

The photographic material is made analogously to example 3, but for the manufacture of photographic material synthesize bromode silver photographic emulsion with an average microcrystal size d _cp. = 0.30 μm (AgJ 3 mol%) according to the following technology: in 200 ml of a 1.45% aqueous gelatin solution containing 0.5 l of a 25% aqueous ammonia solution (solution 1) having pBr = 3.3 ± 0.1 at a temperature of (45 ± 1) ^o C for 60 minutes simultaneously with a constant speed of 2.3 l / min, 140 l of a 1.3 N aqueous solution of silver nitrate (solution 3) are introduced with two jets 140 l of a 1.3 N aqueous solution containing potassium bromide and potassium iodide (3 mol% of iodide of the total amount of halides) (solution 2). Throughout the entire process of emulsification, a constant excess of bromions is maintained in the system: pBr = 3.3 ± 0.1.

After physical maturation is complete, the emulsion is cooled to 40 ^{° C.} and the solid phase is precipitated by separation in a separator with a speed of 5000-6500 rpm.

The precipitate obtained is twice dispersed for 20 minutes, first in 80 l of a 3% aqueous gelatin solution, then in 200 l of a 12.5% aqueous gelatin solution and the pH and pBr are adjusted to 6.5 ± 0.5 and 3.2 ± 0.2, respectively, 0.1 N solutions of Na ₂ CO ₃ and KBr.

The resulting emulsion is subjected to chemical sensitization by the sequential introduction of 1 ml of the emulsion of 4.5 ml of a 1% aqueous solution of sodium thiosulfate, 50 ml of a 25% solution of sodium benzenesulfinic acid and 2.5 ml of 0.08% (in terms of metallic gold ) solution of hydrochloric acid and kept at a temperature of (47 ± 1) ^o C for 120 minutes, then 20 ml of a 1% solution of 5-methyl-7-hydroxy-1,3,4-triazoindolecin are introduced.

At the stage of preparation for irrigation, dye I is introduced as a spectral sensitizer (A = H, R = C ₂ H ₅ , X = J ^- , Z, Z ¹ - absent) in an amount of 100 • 10 ^-6 M / M Ag, and sensitizing dye of the formula I (A = CH ₃ , R, R ¹ = (CH ₂ ) ₃ SO ₃ , Z = Z ¹ = 4,5-benzo, [K] ⁺ = С ₅ H ₅ NH) in an amount of 100 • 10 ^{- 6} M / M Ag and activator of spectral sensitization II (B = CH ₃ , B ¹ = Cl, m = 2, n = 0, X ^- = para-CH ₃ C ₆ H ₄ SO ₃ ^- ) in an amount of 0.2 mol / mol AgHal.

 Then proceed analogously to example 3.

 Examples 8-15.

 Photographic material is produced analogously to example 3, but the compounds introduced into the composition of the emulsion, soil, counter layer and protective layer are shown in table 1.

 Examples 16-17.

 For the manufacture of photographic silver halide material use the emulsion according to example 4, but the input compounds, their quantities are shown in table 1. The properties of the photo layers are presented in table 2.

 Examples 18-19.

 A photographic silver halide material is prepared according to Example 3, but the compounds introduced, their amounts are shown in Table 1. The properties of the resulting photolayer are shown in Table 2.

 As follows from table 2, the proposed photographic material has a sufficiently high resolution, the optimal ratio of photosensitivity / resolution and high information content.

Claims (3)

1. Photographic silver halide material, consisting of a layered base, on one side of which there is a gelatinous counter layer, including anti-rheumatic dyes, on the other is a gelatinized primer layer, an emulsion silver halide layer containing spectral sensitizers, spectral sensitization activators, stabilizers and watering additives, and a protective gelatin layer, characterized in that the silver-silver emulsion layer is made of silver bromide-silver emulsion with a microcrystal size of the halide and silver 0.15-0.5 microns, the content of AgJ 2-5 mol. % and contains as a spectral sensitizer more than one compound selected from the series of formula (I)

where A = H, lower alkyl, NH ₂ ;
R, R ¹ = lower alkyl, (CH ₂ ) ₃ SO ₃ ^- ;
Z = β-naphtho, 4,5-benzo,

B = halogen, alkoxyl, alkyl, H;
Z ¹ = β-naphtho, 4,5-benzo

thieno [3``, 2 ''] benzo,

where B ¹ = alkyl, H, alkoxyl or Z and Z ¹ are absent;
X ^- = halogen, a pair of -CH ₃ C ₆ H ₄ SO ₃ ^- ;
[K] ⁺ = NH ₄ , HN (Alk) ₃ , C ₅ H ₅ NH, 1,1'-diethylquino-2,2'-monomethinocyanine, 3,3'-diethylthiazolinocarbocyanine, 3,3'-diethyl- oxacarbocyanine,
and as an activator of spectral sensitization contains a compound of formula (II)

where B, B ¹ = H, lower alkyl, halogen;
m is 1, 2;
n is 0-2;
X = ClO ₄ ^- , halogen, steam —CH ₃ C ₆ H ₄ SO ₃ ^- ,
as well as anti-valent stabilizer of the formula (III)

where R, R ¹ = lower alkyl,
and additionally a primer, photosensitive, counter layer and protective layer contain a copolymer of butyl acrylate, styrene and methacrylic acid of the formula (IV)

when the ratio of monomers m: n: p = (5-19): (0.5-2.5): 0.5 wt. h  2. The photographic silver halide material according to claim 1, characterized in that the silver emulsion halide layer contains 5-methyl-7-hydroxy-1,3,4-triazoindolecin, 2-n-heptyl-5-methyl-6-bromo as a stabilizer -7-hydroxy-1,3,4-triazoindolecin or a mixture thereof.  3. Photographic silver halide material according to paragraphs. 1 and 2, characterized in that the gelatinous counter layer as antireolen dyes contains various compounds selected from the series: dipotassium salt of 2-benzal-3-hydroxy-thionaphthene-2,4-disulfonic acid, the product of the condensation of dioxyethylamine with n - chlorobenzaldehyde followed by oxidation leukocompounds, potassium salt of the condensation product of glutaconic aldehyde dianyl hydrochloride with 1- (4-sulfophenyl) -3-carboxypyrazolone-5, middle potassium salt of bis (1-n-sulfophenyl-3-carboxypyrazolono-5) trimethinoxane, tartrazine, fuchsin acid syn e-green dye - triethylamine salt of pentamethyloxanine iso -1- (4'-sulfophenyl-3-carbethoxypyrazolone-5).

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