RU2006053C1 - Antiseptic for gelatinous systems in the process of silver halide photographic material making - Google Patents

Abstract

FIELD: antiseptics. SUBSTANCE: polyhexamethylene guanidine hydrochloride of the general formula 1 is used as an antiseptic for gelatinous photographic systems. Formula 1 is given in description of invention. New antiseptic provides more effective antiseptic protection of gelatinous systems, improves retention of photographic materials and ecology of theirs production as compared with phenol. EFFECT: enhanced quality of new antiseptic. 3 tbl

Description

 The invention relates to new antiseptic agents and can be used in the manufacturing process of silver halide photographic materials.

 Silver halide photographic materials usually consist of a substrate, at least one silver halide emulsion layer and at least one hydrophilic colloidal layer, for example a protective, primer. Gelatin is usually used as a hydrophilic colloid.

 It is known that gelatin systems-solutions and suspensions, for example, silver halide emulsions, undergo bactericidal decomposition. This process is exacerbated if necessary, their storage before application to the substrate.

 During bactericidal decomposition of gelatin, a decrease in the viscosity of gelatin solutions and emulsions is observed, which does not allow uniform deposition of layers on the substrate and leads to a deterioration in the sensitometric properties of photographic materials.

 To prevent bactericidal decomposition of gelatins, antiseptic agents are used that are introduced into gelatin solutions and emulsions at one of the stages of their manufacture, for example, antiseptics are introduced into silver halide emulsions at the end of the dispersion of the emulsion or at the end of chemical sensitization.

Known antiseptic agents include the following classes of compounds:
compounds containing a carbonyl group, for example formaldehyde, paraformaldehyde, chloroacetaldehyde, chloroacetamide;
carboxylic acids or their esters, for example, benzoic acid, monobromoacetic acid esters, p-hydroxybenzoic acid esters;
amines, for example, hexamethylenetetraamine, nitromethylbenzylethylenediamine;
N-containing heterocyclic compounds - 2- (4-thiazolyl) benzimidazole, 2-methoxycarbonylaminobenzimidazole;
organic mercury compounds - mercury phenylacetate, mercury phenylpropionate;
antibiotics - neomycin, polymycin, streptomycin;
aromatic hydroxy compounds - phenol, thymol, p-chloro-m-cresol, trichlorophenol, tetrachlorophenol, 2,2'-dihydroxy-5,5'-dichlorophenyl monosulfide.

 Most of the antiseptic agents listed do not find application in photographic chemistry due to toxicity, low efficiency in photographic systems or chemical interaction with other photographic additives, which leads to a deterioration in the sensitometric properties of photographic materials, for example, aldehydes have an unpleasant odor, tanning properties and contribute to the growth of veil, compounds mercury is ineffective, unhealthy, known heterocyclic antiseptics and antibiotics cause vayut desensitization of the silver halide emulsion.

 The most effective and common known antiseptic in gelatin photographic systems is phenol.

 The use of phenol prevents the bactericidal decomposition of gelatin during storage of gelatin solutions and emulsions before application to the substrate for several weeks (3-4) without significant changes in photo properties. With longer storage of gelatin systems containing phenol as an antiseptic, a decrease in their viscosity, a noticeable decrease in the photosensitivity of emulsions and an increase in the density of the veil are observed.

In addition, the use of phenol leads to desensitization of photographic materials and an increase in the density of the veil during storage, especially when stored in adverse climatic conditions (elevated temperature and humidity). It should also be noted that phenol has a sharp unpleasant odor and is toxic (the maximum permissible concentration (MPC) of phenol in the air of the working area of industrial premises is 0.3 mg / m ³ ). Exceeding the maximum permissible concentration leads to phenol vapor poisoning, as well as skin irritation and burns. When phenol is introduced into gelatin systems, a toxic substance, methanol, is used as a solvent.

 The aim of the invention is to provide antiseptic protection of gelatin systems in the manufacture of photographic materials, as well as improving their preservation and environmental conditions of production.

The specified technical effect is achieved by the use of polyhexamethylene guanidine hydrochloride formula
NH˙ HCl
| |
[-NH-C-NH- (CH _{2) 6} -] _{10 000} as an antiseptic agent for gelatin systems in the manufacture of photographic materials.

 The polyhexamethylene guanidine hydrochloride (PHMHC) of the above formula is known, is produced according to TU 10-09-41-90, has complete solubility in water, in accordance with the classification of GOST 12.1-007-76 it belongs to class III of moderately hazardous compounds when introduced into the stomach and class II low hazard in case of contact with skin, inhalation of PHMHH is little dangerous due to low volatility.

 PHMHH is used for technical purposes in electroplating as a substitute for cyanide compounds in galvanizing and cadmium electrolytes, in drilling equipment as a stabilizer for clay drilling fluids in oil production, aqueous solutions of this compound are an effective cutting fluid in diamond-abrasive glass processing.

 In photographic chemistry, this compound has not previously been used.

 As an antiseptic, it is introduced into gelatin systems used for the manufacture of non-photosensitive hydrophilic colloidal layers of photographic materials, and into silver halide emulsions at one of the stages of their manufacture (at the end of dispersion of the emulsion, at the end of chemical sensitization).

Providing prevention of bactericidal decomposition of gelatin during storage of gelatin solutions and silver halide emulsions of various types before application to the substrate for two months versus 3-4 weeks for phenol, PHMHH satisfies the requirements for photographic additives, namely:
does not affect the sensitivity level of emulsions with different particle size characteristics and the composition of halides;
Do not lead to an increase in the density of the veil;
does not affect the contrast ratio.

 Moreover, in comparison with phenol, PHMHH reduces the decrease in photosensitivity and increase in the density of the veil during storage of photographic materials.

 Thus, in comparison with phenol, PHMHH is a more effective antiseptic for gelatinous photographic systems, contributes to the improvement of the retention of film and photo materials and the environmental cleanliness of the film production process.

 PRI me R 1 (prototype). The manufacturing technology of a gelatin suspension 1, intended for the manufacture of non-photosensitive hydrophilic colloidal layers of photographic materials, for example, protective or ground, is as follows.

Prepare solutions:
Inert Gelatin I solution 31.5 kg Desalted water 200 l
Temperature 35 ^о С
Solution 2
Antiseptic
the remedy is phenol,
50% aqueous methanol (1: 1) solution 2.0 L
Supplement I
Wetting agent - sodium salt of diethylhexyl ether sulfosuccinic acid (C-1)
(in terms of the main substance) 4.7 kg
Additive 2 Desalted water 235 l Temperature 70-80 ^о С
The temperature of the gelatin solution 1 N was adjusted to 40 ^{° C} for 30 min and injected into the additive has N 2, and then the solution temperature was adjusted to it in small portions N additive 1. The resulting solution was stirred for 60 min at ⁶⁰ ° C, then introduced into him a solution of N 2 and continue to mix for 10 minutes The concentration of antiseptic is 0.032 g / g gelatin.

From the resulting solution, a sample (10 ml) and the viscosity measured last by capillary pipette using a glass capillary with constant K = 0.338 at ⁴⁰ ° C in a solution of the expiration time.

The viscosity value (η) is calculated by the formula
η = K ˙ τ where η is the viscosity in cP; K is the capillary constant (0.338), τ is the time the solution flows through the capillary, sec.

 The arithmetic mean of three parallel viscosity measurements is taken as the final result.

A solution jelly and stored at a temperature not exceeding 12 ^C. After 15, 30 and 60 days of storage of the slurry was sampled and measured solution viscosity. The magnitude of the change in viscosity of the gelatin solution characterizes the measure of bactericidal decomposition of gelatin.

 The composition of the gelatin solution 1 and the values of its viscosity during storage for 0, 15, 30 and 60 days are given in table. 1.

 PRI me R 2. The gelatin suspension 1 for sample 2, intended for the manufacture of a hydrophilic colloidal layer of photographic materials is prepared according to example 1 using solution 2 of the following composition.

Solution 2
Antiseptic - PHMHH formulas
NH˙ HCl
| |
[-NH-C-NH- (CH _{2) 6} -] _{10 000} 5% aqueous solution.

 The concentration of PHMHC in the finished gelatin suspension I is 0.005 g / g gelatin.

 The tests are carried out as in example 1.

 The composition of the gelatin solution 1 and the values of its viscosity during storage for 0, 15, 30 and 60 days are given in table. 1.

 PRI me R s 3-4. A gelatin suspension for samples 3-4, intended for the manufacture of hydrophilic colloidal layers of photographic materials, for example protective or ground, is prepared according to example 2, varying in accordance with the data in table. 1. The amount of injected solution N 2 (the concentration of PHMHC for the sample according to example N 3 is 0.04 g / g gelatin, for the sample according to example 4 - 0.09 g / g gelatin).

 The tests are carried out as in example 1.

 The composition of the samples of gelatin solution 1 N 3-4 and the values of their viscosity during storage for 0, 15, 30 and 60 days are given in table. 1.

PRI me R 5 (prototype). Gelatin suspension II for sample 5, intended for the manufacture of non-photosensitive hydrophilic colloidal layers of photographic materials, for example protective or ground, is made as follows. Prepare solutions:
Solution N 1 Gelatin inert 33 l
Wetting agent - mixture
mono-sodium salts,
di- and tributylnaphthalene
1-sulfonic acid (C-2), 4% aqueous solution 1.65 L; Desalted water 148.5 L
Temperature 35 ^о С
Solution N 2
Ammonia, 25% aqueous solution of 3.1 l
Solution N 3
Bisubstituted phosphate
formic acid potassium, anhydrous 2.01 kg
Wetting agent С-2, 4% aqueous solution 1.65 L Desalted water Up to 30 L Temperature 35 ^о С
Additive 1 Ammonium chloride 4.65 kg
Additive 2 Zinc chloride 1.39 kg
Additive 3 Desalted water 80 l Temperature 35 ^о С
Additives N 1 and N 2 are added to solution N 1, mixed for 15 minutes, then solutions N 2 and N 3, additive N 3 are added sequentially and mixed for 20 minutes.

Next, the solution is gelled, crushed into worms and washed with demineralized water to an electrical conductivity of 2800 × 10 ^-6 Ohm ^-1 cm ^-1 .

The resulting suspension was introduced 1.3 liters of a 4% aqueous solution of wetting-2 and washed until its conductivity 1850˙10 ^-6 ohm ^-1 cm ^-1.

Further gelatin suspension was melted for 60 minutes at ⁴⁰ ° C for 10 minutes until the end of melting suspension it is introduced antiseptic - 50% aqueous methanol (1: 1) solution of phenol in an amount of 0.032 g / g of gelatin.

 At the end of the melting of the suspension, a sample is taken from it to measure the viscosity.

The emulsion is then jelly and stored at a temperature not higher than 12 ^{° C} for 15, 30 and 60 days.

 The determination of the viscosity of the suspension immediately after manufacture and after 15, 30 and 60 days of storage is carried out according to example 1.

 The composition of the gelatin solution II and the values of its viscosity during storage for 0.15, 30 and 60 days are given in table. 1.

PRI me R s 6-8. Gelatin suspension II for samples N 6-8, intended for the manufacture of non-photosensitive hydrophilic colloidal layers of photographic materials is prepared according to example 5, but in accordance with the data in table. 1 as an antiseptic, use PHMHH in the form of a 5% aqueous solution. At the same time, the concentration of PHMHC in gelatin suspension II samples is varied as follows:
Sample according to example 6 0.005 g / g gelatin
Sample according to example 7 0.04 g / g gelatin
Sample according to example 8 0.09 g / g gelatin
Testing of samples is carried out according to example 1.

 The composition of the samples of gelatin suspension II according to examples N 6-8 and the values of their viscosity during storage for 0, 15, 30 and 60 days are given in table. 1.

PRI me R 9 (prototype). A polydispersed negative bromio-silver (3.6 mol% AgI) emulsion 1 with isometric microcrystals with an average size d _cf = 1.1 μm (C _v = 35%) is prepared as follows. In a single-jet emulsification installation in 50 l of a 10% aqueous solution of inert gelatin containing 10.26 kg of ammonium bromide and 0.42 kg of potassium iodide (temperature 46 ± 1 ^о С), 1000 rpm are sequentially immediately injected with stirring 1, 45 l of 16.5% aqueous solution of completely ammirovannogo silver nitrate (temperature 25 ° ^C), followed by incubation for 3 min - 30 l of 16.5% aqueous solution of completely ammirovannogo silver nitrate (temperature 25 ° ^C). The resulting emulsion was introduced 8.4 kg of gelatine added to obtain <N> rho <N> = 1,3 ± 0,1 and the emulsion was allowed to stand for 20 minutes at a temperature (46 ± 1) ^° C (stirring speed 600 rev / min).

Further jelly emulsion at a temperature of 6-10 ^{° C,} milled, washed, and adjusted to a pBr and pH values of 2.8 ± 0.2 and 7.0 ± 0.5 with 1M aqueous solution of potassium bromide and a 10% aqueous sodium carbonate solution respectively. From the resulting mass take 10 g and subjected to an emulsion of chemical sensitization as follows.

At a temperature of (58 ± 1) ^о , 1.0 ml of a 20% aqueous solution of sodium benzenesulfinic acid, 1.4 ml of a 0.01% aqueous solution of sodium thiosulfate and 0.6 ml of a 0.004% aqueous solution are successively introduced into the emulsion potassium chloraurate, which is respectively 2.5˙10 ^-2 , 1.36˙10 ^-5 and 1.44˙10 ^-7 mol / mol AgHal. The duration of maturation is 3.5 hours, ten minutes before the end of ripening, an antiseptic is introduced into the emulsion - phenol in the form of a 50% aqueous methanol (1: 1) solution in the amount of 0.04 g / g of gelatin, five minutes before the end maturing - stabilizer - 5-methyl-7-hydroxy-1,3,4-triazaindolycin (sta-salt) in an amount of 1.4˙10 ^-2 mol / mol AgHal.

The resulting emulsion jelly and stored until application to the substrate at a temperature not higher than 12 ° ^C. Immediately after the production of the emulsion, 15, 30 and 60 days of storage the samples sampled and measured their viscosity according to Example 1.

 The particle size characteristics of the emulsion are determined by electron microscopy using an EMV-100 AK microscope.

 Granulometric, physico-chemical characteristics of emulsions and their viscosity values during storage of 0, 15, 30 and 60 days are given in table. 2.

 PRI me R s 10-12. Silver bromide photographic emulsion 1 for samples N 10-12 is made according to example 9, but in accordance with the data in table. 2 as an antiseptic, use PHMHH (administered as a 5% aqueous solution in an amount of 0.005, 0.04 and 0.09 g / g gelatin for samples 10, 11 and 12, respectively).

 Tests of emulsions are carried out according to example 9.

 Granulometric, physico-chemical characteristics of emulsion samples and their viscosity values during storage of 0, 15, 30 and 60 days are given in table. 2.

PRI me R 13 (prototype). Monodispersed silver bromide photographic emulsion (3 mol% AgI) P with cubic microcrystals with an average size d _cf = 0.4 μm and a coefficient of variation C _v = 20 ± 2%, is made according to the following technology: solutions are prepared:
Solution 1 Silver nitric acid, g 119 Water, l Up to 0.250
solution 2 Potassium bromide, g 83 Potassium iodide, g 12.45 Water, l Up to 0.250
Inert gelatin solution 3, g 25
Ammonia, 25% aqueous solution, 4.8 ml. Water, l Up to 0.5 l
Bring the pBr of solution N 3 to a value of 3.4 ± 0.2 1 N. a solution of potassium bromide, then at the installation of controlled two-jet emulsification in a solution of N 3 at a temperature of 40 ± 1 ^about With simultaneously with a constant speed for 40 min serves solutions N 1 and N 2, while maintaining a constant value of pBr = 3.4 ± 0, 2 by subtitling the reaction medium with a 1N potassium bromide solution (stirring speed 600 rpm).

 At the end of physical maturation, the pH of the emulsion is adjusted to a value of 5.4 ± 0.3 with a 10% solution of acetic acid and the solid phase is precipitated by adding 40.0 ml of a 10% solution of the polysulfonic acid sodium salt with 600 rpm stirring. Then, after 2-3 minutes, the stirrer is stopped and the emulsion is held for 30-40 minutes, the liquid phase is decanted. The resulting precipitate was washed with demineralized water and dispersed for 20 minutes in 1.0 l of a 7% aqueous gelatin solution to obtain <N> rho <N> = 1.0 ± 0.1 (Mixing speed 600 rpm) and then the pH and pBr of the resulting emulsion is adjusted with a 10% aqueous solution of sodium carbonate and 1 N. potassium bromide solution to values of 6.6 ± 0.5 and 3.2 ± 0.2, respectively.

 From the emulsion obtained, 100 g are taken and subjected to its chemical sensitization as follows.

At a temperature of 50 ± 1 ^{° C} are introduced successively 3.8 ml of 0.01% aqueous sodium thiosulfate solution, 3.5 ml of 10% aqueous sodium benzolsulfinovokislogo that suitably 3,75˙10 ^-5 and 8, 2-10 ^-2 mol / mol AgHal. After 120 minutes from the start of chemical sensitization, 5 ml of a 0.008% aqueous solution of hydrochloric acid (2.0 × 10 ^-5 ) mol / mol AgHal) is introduced into the emulsion and incubated for 20 minutes. Then, an antiseptic agent, phenol, is introduced into it in the form of a 50% aqueous methanol (1: 1) solution in an amount of 0.04 g / g gelatin. After lowering the temperature of the emulsion ^to 40 ° C is introduced into it hundred salt in an amount 3,2˙10 ^-3 mol / mol AgHal.

 Testing the resulting emulsion is carried out according to example 9.

 Granulometric and physico-chemical characteristics of the emulsion and the values of its viscosity during storage of 0, 15, 30 and 60 days are given in table. 1.

 PRI me R s 14-16. Silver bromide photographic emulsion P for samples N 14-16 is made according to example 13, but in accordance with the data in table. 2. PHMHH is used as an antiseptic (injected at the end of the chemical sensitization of the emulsion in the form of a 5% aqueous solution in the amount of 0.005, 0.04 and 0.09 g / g gelatin for samples 14, 15 and 16, respectively.

 Testing of samples of gelatinous emulsions is carried out according to example 9.

 Granulometric and physico-chemical characteristics of the emulsion samples and their viscosity values during storage for 0, 15, 30 and 16 days are given in table. 2.

PRI me R 17 (prototype). Monodispersed bromochlorosilveric emulsion (3 mol% AgCl) III with cubic microcrystals with an average size d _cf = 0.2 μm and a coefficient of variation C _v = 16 ± 2% is made according to Example 13, but the solutions N 2 and N 3 of the following are used for emulsification composition:
Solution 2 Potassium bromide, g 83 Potassium chloride, g 5.6 Water, l Up to 0.25
Inert gelatin solution 3, g 25
Ammonia, 25% aqueous solution 1.8 Water, l 0.5
The precipitate is dispersed in a 7% aqueous gelatin solution to obtain <N> rho <N> = 2.0, the pH and pBr of the resulting emulsion are adjusted to 6.0 ± 0.5 and 3.5 ± 0.2, and then antiseptic agents, phenol, are introduced in the form of a 50% aqueous methanol solution in an amount of 0.06 g / g gelatin.

The chemical sensitization of the emulsion is carried out according to example 13, but sodium thiosulfate and hydrochloric acid are used in an amount of 1.2 × 10 ⁻⁴ , 5.8 × 10 ⁻⁵ xx mol / mol AgHal, respectively.

 Tests of the obtained gelatin silver-bromine-silver emulsion III are carried out according to example 9.

 Granulometric, physico-chemical characteristics of the emulsion and the values of its viscosity during storage of 0, 15, 30 and 60 days are given in table. 2.

 PRI me R s 18-20. Silver bromochlorine photographic emulsion III for samples 18-20 is made according to example 17, but in accordance with the data in table. 2, as an antiseptic agent, PHMHC is used (administered at the end of the dispersion in the form of a 5% aqueous solution in an amount of 0.005, 0.04 and 0.09 g / g gelatin for samples 18, 20 and 21, respectively.

 Testing of samples of gelatinous emulsions is carried out according to example 9.

 Granulometric, physico-chemical characteristics of emulsions and their viscosity values during storage of 0, 15, 30 and 60 days are given in table. 2.

 PRI me R 21 (prototype). The production of samples of silver bromide photographic material using emulsion 1 made in accordance with Example 9 and a gelatin suspension 1 made in accordance with Example 1 is carried out as follows.

Preparations for watering silver bromide-iodide photographic emulsion 1 was taken immediately after production - the sample material 21 and after 15 days of storage at a temperature of - not more than 12 ^C - specimen material 21 b, after 30 days of storage at a temperature not exceeding 12 ^{° C.} - the sample material 21 into and through the 60 days of storage at a temperature not exceeding 12 ^{° C} - sample 21 g of material, which in the emulsion samples at ⁴⁰ ° C sequentially administered following additives (per 100 g of the emulsion): 2.0 ml 1% alcohol solution of α-naphthol, 0.5 ml of 10% aqueous solution pyracatechin thief, spectral sensitizers: 35 ml of a 0.1% alcohol solution of 3,3'-di- (β-hydroxyethyl) -5,5 '-dimethoxy-9-ethylthiacarbocyanine-p-toluene sulfonate (dye 1), 2 , 0 ml of a 0.1% alcohol solution of 3,3'-di- (β-hydroxyethyl) -9-methylthiacarbocyanine chloride (dye 2) and 10 ml of a 0.1% alcohol solution of 3,2-diethyl-5- hydroxy-6-methylthia-2-quinocyanine-p-toluenesulfonate (dye 3). The interval between the introduction of dyes 5 minutes Then, 4.0 ml of a 1% aqueous solution of sta salt, 15 ml of a 5% aqueous solution of wetting agent C-1 are introduced into the emulsion, tanning agents - 0.5 ml of a 5% alcohol solution of chromium acetate and 0.6 ml 10% alcohol solution of phloroglucin. Before applying to the substrate, the emulsion is incubated for two hours.

Prepare for watering the gelatin protective layer. The gelatinous suspension of 1 (made according to Example 1 using as an antiseptic phenol means taken directly after its production - the sample material 21 and after 15 days of storage at a temperature not above 12 ^{° C} - sample 21-b, after 30 days storage at a temperature not above 12 ^{° C} - sample 21 into and through the 60 days of storage at a temperature not above 12 ^{° C} - sample 21-g, is poured demineralized water in an amount of 2.3 l per 1 kg of the suspension is melted to a temperature of ^about 40 C for 90 minutes and the following additives are administered:
3.0 ml of a 10% aqueous solution of a mixture of sodium carbonate and bicarbonate (1: 1);
4.5 ml of a 4% aqueous solution of tanning agent - formalin;
10 ml of a 25% aqueous solution of potassium nitrate.

Prepare for watering a solution of a gelatinous soil layer. The gelatinous suspension of 1 (made according to Example 1) taken immediately after its manufacture - pattern material N 21-a through 15 days of storage at a temperature not above 12 ^{° C} - sample 21-b of the material after 30 days of storage at a temperature not higher than 12 ^о С - sample of material 21-c and after 60 days of storage at a temperature not higher than 12 ^о С - sample 21-g, add desalted water in the amount of 1.3 L per 1 kg of suspension and melt for 80 minutes.

On reaching temperature a solution of 40 ^C. The following additives are added to it:
55 ml of a 5% aqueous solution of chromium acetate;
15 ml of a 10% aqueous solution of sodium carbonate.

 Carry out the production of samples of material 21-a-21-g.

The corresponding solution of the soil layer by extrusion is applied to the OTP-14 brand triacetate base (flow rate 90 ml / m ² , then an appropriate sample of the emulsion is applied to the dry soil layer simultaneously with the application of the corresponding sample of the protective layer (flow rate of the protective layer solution 100 ml / m ² , silver 4.3 g / m ² ).

Sensitometric tests of the obtained samples 21-a-21-g are carried out according to GOST 10691-84. Exposure is carried out on an FSR-41 sensor at TTsV 5000K with a shutter speed of 1/20 s. The manifestation is carried out in the developer UP-2 at 20 ^about C for 8 minutes

 Resolvometric tests are carried out according to GOST 2819-84 on a resolvometer RP-2M as absolute contrast.

 The photosensitivity of sample 21-a by the criterion of 0.85 over the density of the veil is taken as 100 relative units.

To determine the persistence material samples 21 and 21-g are subjected to accelerated aging by standing still in a thermostat at ⁵⁰ ° C and relative humidity φ = 50% for 30, 60, 90 and 120 hours, which corresponds to the natural storage for 3, 6 , 9 and 12 months, and conduct sensitometric tests in the above conditions.

 The composition of the layers of samples of photographic material and the test results are given in table. 3.

PRI me R s 22-25. The images of silver bromide silver photographic materials (22-a-22-g) - (25-a-25-g) are made according to example 21, but in accordance with the data in table. 3 for manufacturing the light-sensitive emulsion layer is applied samples 1 (Made in Examples 10-12 using as an antiseptic PGMGH) taken immediately after production and after 15, 30 or 60 days of storage at a temperature not higher than 12 ^{° C,} and for producing a security and precoat layers are used gelatin suspension of 1 (made according to examples 2-4) taken immediately after production, after 15, 30 or 60 days of storage at a temperature not higher than 12 ° ^C.

 Testing the obtained samples of materials is carried out according to example 21.

 The composition of the layers of material samples and the test results are given in table. 3.

PRI me R 26 (prototype). Specimen silver bromide-iodide photographic material is carried out according to Example 21, but for making the photosensitive emulsion layer used P obtained according to Example 13 and taken directly after its manufacture, after 15, 30 and 60 days of storage at a temperature not higher than 12 ° ^C.

Preparation of emulsion samples for sequential administration watering is carried on 100 g of the emulsion at 36 ^C. 1.0 ml of an aqueous solution of pyrocatechol 6.5 ml of a 0.1% alcoholic solution a spectral sensitizer - 3.3 -dietiltiazolinokarbotsianina salt and 3,3 '- di-γ-sulfopropyl-3-ethyl-4,5,4 ', 5-dibenzothiakarbocyanin betaine (dye 4), 2.6 ml of a 0.1% alcohol solution of a spectral sensitizer - 1,1'-diethyl-2 salt, 2-quinocyanine and 3,3'-di-γ-sulfopropyl-9-ethyl-5,5-dimethoxythiocarbocyanine betaine (dye 5) and 10 ml of a 0.1% alcohol solution of spectral sensitizer - salts of 3.3 ', 9-triethyl-5,5'-diphenyloxacarbocyanil and 3,3'-di-γ-sulfopropyl-5-phenyl-5, 9-dimethyloxythiocarbocyanine betaine (dye 6), 10 ml 0.20% of a water-alcohol solution of an activator of spectral sensitization - ditosylate 3.3 - [I``, 2 '' bis- (ethoxy) ethyl] bis- [1-ethyl-2-methyl-5-chlorobenzimidazolium] (activator 1), 10 ml of a 4% aqueous solution of C-2 wetting agent and 3.0 ml of a 5% aqueous solution of tanning agent - N, N, N ', N' -tetraisopropoxymethyldiamide malonic acid. Before applying to the substrate, the emulsion samples (26-a-26-g) can withstand 2 hours

In preparation for a protective glaze gelatin and gelatin precoat layers are used gelatin slurry P (manufactured according to Example 5) taken immediately after production, after 15, 30 and 60 days of storage at a temperature not higher than 12 ° ^C.

Preparation for watering the protective layer is performed by introducing 1 kg of slurry poise at 40 ^C. 2.3 l of demineralized water, 3.0 ml of a 10% aqueous solution of a mixture of carbon dioxide and sodium bicarbonate (1: 1) 4.5 ml of 4% - aqueous solution of formalin and 10 ml of a 25% aqueous solution of potassium nitrate.

Preparation for watering the precoat layer is performed by introducing 1 kg of slurry II at 40 ^C. 4.3 l of demineralized water, 55 ml of 5% aqueous solution of chromium acetate, 13 ml of a 10% aqueous solution of sodium carbonate.

Samples of the solution of the soil layer are applied by extrusion to the adhesive sublayer of the PETF-38 polyethylene terephthalate base with a serial blue-green anti-rheumatic counter layer (OST 6-17-507-82) with a flow rate of 100 ml / m ² , then the corresponding extrusion method is applied to the dry soil layer by the extrusion method emulsion samples simultaneously with the application of the corresponding samples of the solution of the protective layer. The flow rate of the solutions of the protective layer is 100 ml / m ² . Deposition of metallic silver 2.0 g / m ² .

 Tests of the obtained samples of material 26-a-26-g are carried out according to example 21.

 The composition of the layers of material samples and the test results are given in table. 3.

PRI me R s 27-29. Samples of silver bromide photographic materials (27a-27g) - (29a-29g) are made according to example 26, but in accordance with the data in table. 3 for manufacturing the light-sensitive layer applied samples emulsion II (manufactured according to Examples 14-15 using as an antiseptic PGMGH) taken immediately after production at 15, 30 and 60 days of storage at a temperature not higher than 12 ^{° C,} and for the production of solutions precoat and protective gelatin layers - gelatin suspension P (made according to examples 6-8 using PGMHH as an antiseptic), taken immediately after manufacture after 15, 30 or 60 days of storage at a temperature not exceeding 12 ^about S.

 Testing of material samples is carried out according to example 21.

 The composition of the layers of material samples and the test results are given in table. 3.

PRI me R 30 (prototype). Samples of silver bromochlorine photographic material are prepared according to Example 21, but emulsion III samples obtained according to Example 17 (made using phenol as an antiseptic) are used to produce the photosensitive layer, taken immediately after production after 15, 30, and 60 days of storage at a temperature not above 12 ^° C, and for the manufacture of a solution of soil and protective layers - gelatin suspension P (made according to example 5), taken immediately after manufacture, after 15, 30 and 60 to storage at a temperature not higher than 12 ^about C.

When preparing the emulsion samples for irrigation, the same irrigation additives and spectral sensitizers are introduced into them as in Example 26, and the yellow color-forming component of Zh-8 (2-methyl-octadecylamino-5-sulfo-aniline benzoic acid) in the amount of 2.6˙10 ^-3 mol / mol AgHal.

 A solution of gelatin protective and soil layers is prepared according to example 26.

 The application of layers on a cellulose triacetate base grade OTP-14 is carried out according to example 21.

 Sensitometric tests of samples of material 30a-30g are carried out on a color sensor TsS-2M at Tsv 3200 K with a shutter speed of 0.05 s behind the mask (5 M + HSC).

The manifestation of material samples is carried out in the developer of the composition, g / l: hydroxylamine sulfate 2; ethyleneoxyethylparaphenylenediamine sulfate 4,5; potassium carbonate 75; sodium sulfate anhydrous 0.5; potassium bromide 0.5; water to 1 liter, for 6 min at 18 ^{° C,} the samples were rinsed in water, fixed in the fixer composition, g / l: sodium hyposulfite 165; ammonium chloride 50; sodium metabisulfite 17; water to 1 liter for 11 minutes, and then bleached in a 3% aqueous solution of potassium ferric sulphide and washed in running water for 15-20 minutes.

 Optical densities are measured on a Macbeth densitometer DD-504 with the status "A".

 Resolvometric tests are carried out as in example 21.

 The application of layers on a substrate is carried out according to example 21.

 The composition of the layers of material samples and the test results are given in table. 3.

PRI me R s 31-32. Samples of silver bromochloride materials (31a-31g) - (32a-32g) are made according to example 30, but in accordance with the data in table. 3 for manufacturing the light-sensitive layer applied samples emulsion III (prepared according to Examples 18, 20 using, as an antiseptic PGMGH) taken immediately after production, after 15, 30 and 60 days of storage at a temperature not higher than 12 ^{° C,} and for the production of solutions soil and protective gelatin layers - samples of gelatin suspension P (made according to examples 6, 7 using PGMHH as an antiseptic), taken immediately after production after 15, 30 and 60 days of storage at a temperature not above 12 ^about C.

 Testing of material samples is carried out according to example 30.

 The composition of the layers of material samples and the test results are given in table. 3.

From the data table. 1, 2 and 3 that the use PGMGH provides a more effective antiseptic protection of various gelatin systems (viscosity reduction gelatin systems containing PGMGH when stored for 60 days at a temperature of 12 ^{° C} does not exceed 8% in the fall photosensitive silver halide emulsions to 3 % and maintaining the density of the veil against 17% when the photosensitivity drops to 8% and the density of the veil increases by 1.4 times, observed with phenol); improving retentivity different types of photographic materials (samples fall photosensitivity containing PGMGH under accelerated aging for 120 hours at ⁵⁰ ° C and 50% relative humidity is not more than 8%, while the fog density by 1.4 times against sensitivity drop to 20% with a 2-fold increase in veil density observed with phenol;
improvement of environmental conditions for the production of film and photo materials. (56) Fundamentals of photosensitive photo material technology. / Ed. Sheberetova V.I.M.: Chemistry, 1977, p. 64.

Claims (1)

The use of polyhexamethylene guanidine hydrochloride formula

NH-

NH __ (CH ₂ )

as an antiseptic for gelatin systems in the manufacture of silver halide photographic materials.

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