JPH0359552A - Photographic material and manufacturing method of the same - Google Patents

Abstract

PURPOSE: To obtain a silver halide photographic material excellent in photosensitive characteristics by incorporating a sterilizing agent by <=5mg/m<2> in an unprocessed state. CONSTITUTION: The amt. of a detectable sterilizing agent in an unprocessed material consisting of a substrate and a silver halide emulsion layer formed on the substrate by coating is regulated to <=5mg/m<2> . The silver halide emulsion layer is formed after starting material liable to fouling with microorganisms is treated with gaseous CO2 under at least 2 bar pressure. Fouling with microorganisms can be prevented and the objective photographic material excellent in photosensitive characteristics is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a support and one or more light-sensitive silver halide emulsion layers coated thereon, and if necessary other non-light-sensitive layers such as subbing layers, interlayers and protective layers. A typical silver halide photographic material consisting of:

To summarize the invention, in the untreated state 5mg/m2
Silver halide photographic materials containing the following fungicides have excellent ecological and photosensitive properties and can be obtained by treating the starting material with CO□ gas at a pressure of more than 5 bar or in the presence of water using the following formula: It is prepared by treating the starting material with a compound of the formula % where R and R' represent lower alkyl residues.

The binder used in these layers is exclusively or primarily gelatin, which, being a natural product, is highly susceptible to contamination by microorganisms. As a result, undesirable phenomena such as the generation of mold and odor, photographic defects, and decomposition of gelatin resulting in a decrease in the viscosity of its aqueous solution occur. However, other organic components, such as polymers used in photographic materials, are also susceptible to microbial contamination [F, L. Stickley, J. Photo, J.
Sci, 34, l1l-112 (1986)].

For efficient production of photographic materials, the necessary additives may be stored in the form of aqueous solutions or dispersions for 1 to 6 months before use.

Due to ecological and strict safety standards, these solutions and dispersions must not contain low boiling point solvents such as ethanol, metal or ethyl acetate. These additives have traditionally been safely stored as storage solutions free of microorganisms.

In order to prevent these disadvantages, it has been necessary to add considerable amounts of bactericides to the photographic materials or rather to the photographic additives used in their production, in particular to gelatin or aqueous gelatin solutions.

These disinfectants largely remain in the photographic material after processing or are washed out during processing and contaminate the waste fluids.

It is known that fungicides are only active at certain concentrations. The amount is always determined based on the total volume of the aqueous solution. The lower the concentration of active substances, eg thickeners, in the solution, the greater the amount of disinfectant solution used when applying the photographic material.

For example, solutions of thickeners have a concentration of 0.3% due to their high viscosity. When using phenol as a fungicide, 2 to 2
．． It must be added in a ratio of 52/Q (minimum limit of activity). Therefore, 2 to 2.5 for 31 thickeners
2 phenols are present and this phenol is transferred into the photographic material.

Very ancient photographic materials, especially those used before the advent of color photography, were manufactured by conventional methods and sold commercially without the use of fungicides.

These materials were difficult to contaminate with microorganisms for a variety of reasons: First, gelatin-containing emulsions and other easily contaminated solutions did not need to be stored for very long periods of time because the manufacturing process was relatively simple at the time. Therefore, it did not cause much difficulty during the manufacturing process. Second, the perfect photographic material did not have very high sensitivity in terms of sensitivity characteristics, so the possibility of deterioration was small. The requirements for stability under abnormal weather conditions (in the tropics) are not as strict as the conditions that current amateur color photographic materials must satisfy.

Finally, black and white photographic materials after processing contain metallic silver, and because this silver has some bactericidal properties, color photographic films and contact photographic materials from which silver is extracted during processing are susceptible to bacteria. not easily contaminated by

Due to differences in manufacturing conditions and requirements for stability before and after processing, color photographic materials are currently available in quantities ranging from 10 to several hundred mg/
m'' of disinfectant per unit area.

It has now been found that large quantities of disinfectants, such as those commonly used in photographic materials, are only necessary when the starting materials and the conditions of manufacture of the photographic material result in photographic materials containing large amounts of microorganisms. .

If the initial microbial content is reduced during production by using suitable measuring methods or by using microbial-free starting materials, precautionary measures known to the expert during packaging and storage of the product, e.g. methods such as keeping the temperature and moisture content low, suppressing the activity of water in photographic materials, or filling the inside of the package with inert gas.
The sufficient long-term stability of the photographic material is demonstrated by the use of no or very small amounts of fungicides [Ullmann's Encyclopedia of Industrial Chemistry].
a ofr industrial chemistry)
, 5th edition, 1988, Vol. 7, p. 523-618 1° Eliminate the need to add fungicides, or at least significantly reduce the amount added, from the point of view of ecological and photosensitivity properties. is highly desirable.

The purpose of the present invention is to obtain (in concentration per unit area) 5mg/
The object of the present invention is to provide a photographic material which contains less than m2 of detectable bactericide, but which is nevertheless uncontaminated by microorganisms.

Therefore, the present invention provides that the content of detectable fungicide in the untreated material is below 5 mg/m2, preferably 0.5 mg/m2.
The present invention relates to a photographic material comprising a support and at least one silver emulsion layer coated thereon, characterized in that the material has an average molecular weight of 2 or less.

Such photographic materials with sufficient stability are produced by sterilizing the starting material, for example using a sterilization process with carbon dioxide, or with a sterilizing agent I which self-decomposes at a sufficiently rapid rate.

The photographic material according to the invention is produced by treating a starting material (which is susceptible to contamination by carbon dioxide gas at a pressure of, for example, 2/<-) or more. There is no upper limit to the pressure, but from a technical point of view it is desirable to limit the treatment to a pressure of 40/(-/) or less. Therefore, the pressure treatment is preferably carried out under a pressure of 4 to 40 bar. The pressure treatment is carried out by initially filling a container at normal pressure containing the solution or dispersion to be sterilized, such as an aqueous solution of gelatin, with CO2 at the desired pressure. The container is mainly used for removing air that is filled with C.
In some cases, it may be exhausted before being filled with O2.

Since the product is damaged at high temperatures, especially
Pressure treatment is carried out at a temperature of 90°C.

The time of the pressure treatment is not very critical and can be varied within a wide range. Generally, a treatment time of 5 minutes to 3 hours is sufficient, but a treatment time of 5 minutes to 1 hour is desirable.

Substances susceptible to contamination may be treated in dry powder form or in wet form, such as an aqueous suspension, emulsion or solution. It is entirely possible and effective to inject CO2 into the coating solution or aqueous starting material solution or to pressure-treat the coated photographic material with carbon dioxide, but for technical reasons (when removing the gas from the solution For reasons of cost and risk of foaming, it has been found appropriate to sterilize the starting material before entering the manufacturing process.

It is clear that sterilizing the starting material in this way and carrying out its production in a strictly controlled atmosphere makes it possible to effectively reduce the bacterial content in the photographic material produced therefrom.

It is now possible to use clean air technology, which is being developed in the electronics industry and the confectionery industry, among others, for this purpose (see, for example, H. H. Schicht, W. W.
iss Parma 4 (12), 23-25 (
1982)].

In particular, gelatin can be pressure treated with carbon dioxide. The gelatin (dry or wet) is preferably processed in an aqueous solution.

In the production of silver halide photographic materials, it is desirable to process all types of gelatin used in this process. Any special treatment (after gelatin production and before photosensitive solution application) can be carried out.

The treatment with CO□ is preferably carried out immediately before using the gelatin to avoid recontamination due to microbial counts.

Another sterilization method is to prepare an aqueous suspension, emulsion or solution of a photographic additive with the following formula (1) (pyrocarboxylic acid ester) R○-CO-0-CO-RO' (1) where: R and R
' is carried out by so-called pasteurization, by treatment with appropriate amounts of compounds represented by alkyl, aralkyl or aryl, preferably lower alkyl residues, particularly preferably ethyl and methyl.

The invention therefore also relates to the use of pyrocarboxylic esters of the general formula (I), preferably their lower alkyl esters, particularly preferably methyl or methyl esters, as fungicides during the production of photographic materials.

For pasteurization at room temperature, gelatin-free stock aqueous solutions are sterilized by continuously pumping pasteurizer into a relatively large storage liquid container through an automatic metering device.

However, the pasteurizer can also be homogenized by simply stirring after addition.

The advantage of (I) over known disinfectants is that it completely converts photographically and ecologically safe products (COt and lower alcohols) in the presence of water in a short period of time (several minutes). This means that it is hydrolyzed.

After only 7 hours, no product could be detected in the solution.

The pasteurizer is used in a concentration of 4 to 1 OOrrtl/100a, depending on the degree of bacterial contamination and the pH value. Thus, the amount of pasteurizer can be reduced at low pH values and high CO2 pressures (synergistic disinfection effect). It is also possible to heat briefly before adding the fungicide.

After only 5 hours at pH 2.8, depending on the temperature, no pasteurizer was present in the aqueous solution, as can be seen from the following table: Table 1 Residual percentage of disinfectant at each temperature ( %) Time after addition lOoC20℃
30℃ 15 minutes 78% 50% 30% 30 minutes 60% 25% 7% 1 hour 3
6% 5% 0%2 hours 13% 0%
0%5 hours 0% 0% 0%Herbert Ott GmbH
) [7250 Leonberg (suburbs of Stadtgart)]
An automatic weighing device of the DAQ LEWA type manufactured by the company can also be used for weighing.

The aqueous solution after treatment was free of bacteria and remained free of bacteria even after several months. The solution is tested by any of the conventional methods, such as the Koch bacterial enumeration method.

The bacterial counts are determined for the stock solution and the 10-'' and 10-'' dilutions immediately after sampling and after 1, 2, and 6 months.

At the same time, the solution is also tested for mold.

The number of bacteria should not exceed 100 cells/cc.

This pasteurization can be done, for example, by short-term heating, ultraviolet irradiation, or
It can also be used in conjunction with a variety of other ecologically safe methods, such as 1 treatment.

If all aqueous preservation solutions or aqueous dispersions are sterilized in this way before their use as coating solutions, they will be able to maintain normal ecological conditions without causing the deterioration caused by bacterial and fungal growth that occurs during storage of photographic materials. The amount of biocide that is safe for use can be significantly reduced.

Pasteurization can even be applied to gelatin-free aqueous solutions and water. However, it is especially suitable for the following solutions and dispersions:

l) Sodium polystyrene sulfonate 1.1 Solution for antistatic layer 1.2 Solution for coagulation of photographic emulsion 2) Dispersion of matting agent 2.1 Methyl methacrylate copolymer, particle size: IO
, 5-1 μm 2.2 Methyl methacrylate copolymer, particle size 2-2
3 μm 2-3 S i Ox dispersion 〆20-4 (ln, 1
゜2.4 5i02 dispersion 〆1-2 p m3) Plasticizer dispersion 3.1 Polyethyl acrylate dispersion 40-00n
m-Eyue polybutyl acrylate dispersion liquid 40~00n
m 4) Additives that increase the covering power of silver 1 Polydextran and polydextran derivatives 4.2 Polyvinylpyrrolidone 5) Aqueous solutions of polyvinyl alcohol and its derivatives 6) Solutions of thickeners L Cellulose sulfate barrels Polyacrylamide / Polyacrylamide in butylene sulfonic acid copolymer 7) Dispersion of curing agent Polymethyl methacrylate and its copolymer, particle size:
20-80 nm 8) Wetting agent solution Salt in lauryl sulfate Salt in dodecyl sulfonate 9) Color coupler latex (water-insoluble polymer coupler) 10) Water-insoluble, low molecular weight color coupler adsorbed on a polymer latex support Latex (charged latex) 11) Latex with photographically active additives such as ultraviolet absorbers.

Water, which on the one hand is a very important starting material and on the other hand is also a cleaning and rinsing agent widely used in manufacturing processes, can also be sterilized with the compounds according to the invention. In this case, however, in order to save costs, sterilization, for example by ultrafiltration or microfiltration (see, for example, DE 37 26 865), ultraviolet irradiation, or as described by C. Nebel and W.
Nezg.

d),Solid State Technol
It is also possible and preferred to use sterilization methods known to the expert, such as ozone oxidation as described in J. Ogy 1984, (10), 185-198.

It could not have been expected that pasteurization could keep the aforementioned preservation solutions sterile for several months.

The method therefore not only removes the bacteria themselves, but also microspores, which are extremely difficult to remove and cause recontamination of the solution during storage. This effect on microspores has not been developed from phenolic derivatives that kill bacteria, as evidenced, for example, by the fact that they always had to be added in fairly large quantities. Therefore, when diluting the solution with water, the amount of this phenol derivative had to be correspondingly increased in order to keep the solution sterile (kinetic equilibrium). It was also unexpected that pasteurization methods would yield photographically inert solutions or dispersions.

The pyrocarboxylic acid esters (low-temperature seedlings) used in the present invention are applied to the finished photographic material by sprinkling or dipping the photographic material in a dilute aqueous solution or water-alcohol mixture. You can also do that. Pyrocarboxylic acid esters can also be used in gaseous form.

The halogen silver photographic material may be, for example, a black and white photographic material such as a black and white film or a black and white photographic paper, an X-ray photographic material, a color photographic material or any other halogen silver photographic material, particularly preferably substantially A material used in the production of silver-free photographic materials (color images).

Examples of color photographic materials are, for example, high- and ultra-high-sensitivity color negative films of DIN 20 or higher, color reversal films, color positive films, color photographic papers: color reversal photographic papers, light-sensitive materials for dye diffusion transfer methods and silver dye bleaching methods. These include pigment materials.

Supports compatible with the manufacturing method of color photographic materials include, for example:
Films of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyralate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate, and laminated with baryta layers or σ-polyolefins (such as polyethylene) It's paper. These supports can also be dyed with dyes and pigments, such as titanium dioxide. They can also be dyed black to block light. The surface of these supports is generally treated to improve the adhesion of the photographic emulsion layers, such as by exposure to a corona discharge as a pretreatment of the support.

Color photographic materials usually include at least one red-sensitive layer, at least one green-sensitive layer and at least one blue-sensitive silver halide emulsion layer, and, in some cases, intermediate layers and protective layers. Contains layers.

Gelatin is preferred for use as a binder in these layers.

The gelatin used in each layer of silver halide photographic materials is
All or part of the polymer may be replaced by other synthetic, semi-synthetic or natural polymers.

Synthetic materials replacing gelatin are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide, polyacrylic acid and derivatives thereof, especially copolymers. Natural substances that can replace gelatin are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.

Semi-synthetic substitutes for gelatin are generally modified natural products.

Cellulose derivatives such as hydroxyalkylcellulose, carboxymethylcellulose, and phthalylcellulose, as well as gelatin derivatives obtained by reaction with alkylating agents or acylating agents, or gelatin derivatives grafted with polymerizable heptamers, etc., have been modified. This is an example of a natural product.

Gelatins suitable for use are obtained by ripening in acidic or alkaline conditions. Oxidized gelatin can also be used. The production of such gelatin is described, for example, by A.G. Ward and A.C.O.
urts) co-edited “Science and Technology of Gelatin (The 5
Science and Technology of
Gelatine)” (Academic Pr
ess, 1977), p. 295 et seq. Particularly preferred gelatins to be used are those with as low a content of photographically active impurities as possible (inert gelatins). Particularly advantageous are gelatins with high viscosity and low swelling.

Silver halogen, which is present as a photosensitive component in photographic materials, is
Halides include chloride, bromide, iodide or mixtures thereof. For example, in at least one layer of halide, 0 to 40 mol% is iodide, 0 to 100 mol% is chloride, and 0 to 100 mol% is bromide. The halogen silver is mainly in the form of dense crystals, such as cubes, octahedrons, and intermediate shapes. However, the silver halide is a disc-shaped crystal with an average diameter-to-thickness ratio of preferably 5:1 or more, where the diameter of the crystal is defined as the diameter of a circle having the same area as the projected area of the crystal. It is also preferable that the term also includes . However, the layer may also contain tabular silver halide crystals with a diameter to thickness ratio much greater than 5=1, for example from 12:1 to 30:l.

The halogen silver grain has a multilayer grain structure, the simplest of which is the structure of an inner and outer shell region (core/shell);
The halide composition and/or other additives, such as implants in each region, may be different.

The average grain size of the emulsion is preferably 0.2-2. ON+11, and the particle size distribution may be monodisperse or polydisperse.

A monodisperse particle size distribution means that 95% of the particles are within ±3 of the average particle size.
This means that it is within 0%. In addition to silver halides, the emulsions may also contain organic acid silvers, such as silver penztriazoleate or silver behenate.

It is also possible to use a mixture of two or more types of silver halide emulsions prepared separately.

In the specification of the present invention, bactericidal agents refer to bacteria,
This refers to compounds that kill mold, algae, etc., and most of which remain in photographic materials. Depending on its effectiveness, it can also be called a bacterial sterilizer, mold sterilizer, etc.

Fungicides whose required amounts are greatly reduced or even eliminated by the method of the present invention include, for example, phenol, 2-propenylphenol, 2-isopropyl-5
-Methylphenol, 2-itubrovir-4-chloro-
5-methyl-7enol, 3-methyl-4-chlorophenol, 2゜5-dimethyl-4-chlorophenol,
2-benzyl-4-chlorophenol, benzoic acid, 5-
Promo 5-nitro 1,3-dioxane, 2-buta
% -2-nitro-1,3-7'robilene glycol,
Benzisothiazolone-3,5-chloro-2-methyl-
4-inthiazolin-3-one and the like.

In addition to the aforementioned ingredients, silver halide photographic materials also contain sensitizers, stabilizers, color couplers, UV absorbers, matting agents,
Contains known additives such as hardeners and correction dyes.

Example 1 This shows the importance of disinfectants or pasteurization methods to protect solutions containing gelatin during the manufacturing process: The following 10% gelatin solutions A-F are shown in Table 2. of phenol was added and then left in a closed container at 37° C. for 14 days. The viscosity of the solution was initially 30 mPa,s. Changes in viscosity were measured over the entire period.

Table 2 A, 2 None <10%B
,02 None 20%C,00
2 None 50% Do None 80%E,
002 5 bar/30 minutes/20℃〈lO%F
0 30 bar/60 min/20℃<10% solution 1
Only solution A, which added 21 7-enols per kt,
The stability was comparable to that of solutions E and F, which were sterilized by pressure treatment with carbon dioxide and contained either a small amount of phenol or no phenol.

Example 2 This demonstrates the importance of disinfectants or pasteurization to the stability of photographic materials.

For this purpose, the resistance to mold growth was determined as follows: The photographic material was applied to a paper support and dried. Then, a circular specimen with a diameter of 30 mm was cut out, and a sterilized nutrient (bacterial culture medium containing malt extract, Merck No. 5
No. 398) and cultured at room temperature for 2 weeks.

The next emulsion layer G-M was produced by adding phenol at the concentration shown in Table 3 to the coating solution.

Emulsion layer G- was produced by a known method without any special antibacterial treatment, but the emulsion layer and Ml were heated at 40°C before coating.
treated with carbon dioxide at a pressure of 30 bar for 30 minutes and then applied under aseptic conditions.

After culturing for 2 weeks, the following results were obtained (see Table 3): G 2 800 of emulsion layer after coating (comparative example) 3H,2
200 (comparative example) 3 1. 02 30 (comparative example) 2K
, 002 3 (comparative example) 1L
,002 3
3M 0 0
3 evaluation value: 113+1. Mold-free specimen, 112+1. Mold grew on 30-50% of the test pieces.

“l#; Mold grew on more than 50% of the test piece.

Example 3 Sterilization of Photographic Material Solutions During Storage All solutions and dispersions were prepared in ion-exchanged industrial water.

In a container 5a equipped with an effective stirrer, pyrocarboxylic acid dimethyl ester was added in a ratio of 22 parts to 9 parts to 1 part of the solution being stored to be sterilized. After stirring for 5 minutes, the solution was allowed to stand for 12 hours before being tested for microbial contamination. In each case untreated solutions were also used for comparison.

The measurements were carried out by Koch's bacterial counting method using meat broth or glucose solutions of three different dilutions after storage at room temperature for 1 to 3 months.

Solution 1 Viscosity increaser (thickener) Sodium salt of a copolymer of acrylamide and acrylamide isobutylene sulfonic acid (weight ratio 1:4).

A 0.5% solution was prepared in ion-exchanged industrial water.

Solution 2 Emulsion flocculant solution 3 Viscosity enhancer (thickener) Sodium polystyrene sulfonate (M=40.00
0) 10% aqueous solution 4 Matting agent 20 of polymethyl methacrylate particles with a particle size of 2 to 3 μm
% dispersion Dispersion liquid 5 Matting agent of silicon dioxide 30% aqueous dispersion of particles with a particle size of 1 to 2 μm Partitioning liquid 6 Matting agent particle size of polymethyl methacrylate dispersion liquid
= 30% water latex dispersion of particles of lOOnm 7 Dispersion of plasticizer 30% water latex solution of polyethyl acrylate with particle size 1100 nm 8 Additives to increase the covering power of silver M-100,000 poly 10% aqueous solution of dextran As is clear from Table 4, the aqueous solution of the additive can be prevented from being contaminated for more than 3 months by the addition of the pyrocarboxylic acid ester according to the present invention.

Example 4 The following test was conducted to demonstrate that pasteurization is photographically harmless.

Solutions 1.3.4 and 8 of Example 3 were added to a red-sensitive silver halide emulsion consisting of the following ingredients: gelatin
17.667 Cyan Cut Blur 〇-14,5
5,? Dibutyl 7 tallate 4.551AgN0.2
A containing 2 mol% iodide prepared from 0.41
gBr/I halogen silver water
The ratio was such that 3 to 6 parts of active substance were added to 100 parts of 4002 gelatin.

The above mixture was applied so that the individual layers had a thickness of 6 μm.

Measurement of photographic characteristic data after development of negative processing type.

Before processing the photographic material was heated to 7°C at 60°C/34% relative humidity.
or 7 days at 35° C./90% relative humidity.

As is clear from the data in Table 5, the sensitivity characteristics of the moderately sensitive emulsions varied only within experimental error. Solutions sterilized by treatment with pyrocarboxylic acid esters are thus photographically harmless.

Processing color development 38℃ 195 seconds bleaching
38℃ 30 seconds bleaching constant 3
8°0 90 seconds rinse 38°C100
Second stabilization 38°0 40 seconds dry developer diethylenetriaminetetraacetic acid 1.02 Hydroxyethane-1,1- diphosphonate Sodium sulfite Potassium carbonate Potassium bromide Hydroxylamine sulfate 4-(N-ethyl-N-β-) 1 2.0 ton 4.02 30.0j1 1.41 2.42 Droxyethylamino)-2-methylaniline sulfonate Add water l OOOmQ pH 10.0 Bleach solution Ammonium Bromide Ethylenediamine Tetraacetate Iron (III) Ammonium Disodium ethylenediaminetetraacetate Ammonium nitrate Bleach accelerator Add aqueous ammonia i o o QmQ pH 6,5 Constant bleaching solution Ammonium bromide Iron (III) ethylenediaminetetraacetate Ammonium Disodium ethylenediaminetetraacetate 4.52 1 002 202 10, Oj? 10, oI 2.01 17, M 50.01 50.07 5, O2 Ammonium nitrate 5.02 Sodium sulfite 2.02 Ammonium thiosulfate (70% by weight aqueous solution) Add aqueous ammonia l pH 7.3 Stabilizing solution 00 〇 - Formaldehyde (40% by weight aqueous solution) 2.0 - Polyoxyethylene-(p-monononylphenyl)-ether 0.39 Add water was manufactured by applying the following layers in the following order to a paper support laminated with polyethylene: The amounts are in each case per l m 2 .

The amount of silver halide applied was determined by the corresponding AgN0. It is shown in the amount of

Five samples were prepared by varying the method of sterilization of the starting solution and the amount of disinfectant.

Sample 1 A) Use ion-exchanged industrial water after all applications.

B) Add 21/(l of phenol) after every application.

Sample 2 A) Use on-exchanged industrial water pasteurized with pyrocarboxylic acid dimethyl ester 0.21/Q after all applications.

Sample 3 A) Use on-exchanged industrial water sterilized with pyrocarboxylic acid dimethyl ester 0.52/Q after all applications except gelatin-containing solutions.

B) Gelatin-containing solutions were pressurized with CO2.

Sample 4 A) Using ion-exchanged industrial water for all coating solutions,
Sterilization with (0,5,?/12) 4-chloro-3-methylphenol L f:.

Sample 5 A) Ion-exchanged industrial water to which no bactericide was added was used in all coating solutions.

Layer arrangement 1st layer (subbing layer) Gelatin 0.2.9 2nd layer (blue-sensitive layer) Gelatin 1.38. ? Yellow Kaglar 0.95. ? Contains tricresyl phosphate (TCP) 0.299, AgNo1
Blue-sensitive silver halide emulsion prepared from O-63j+ (99.5 mol% chloride, 0.5 mol% bromide, average grain size 0.8 μm) Third layer (intermediate layer) Gelatin 1.1. ? 2.5-dioctylhydroquinone 0.06. ? Dibutyl phthalate (DBP) 0.06# 4th layer (bad color light layer) Gelatin 1.081 Magenta coupler 0.4112.5-Dioctylhydroquinone 0.08#DBP
'0.31/TCP
O,041 and AgN Os 0.45. ?
A silver halide emulsion of ill-fringed color (99% chloride) prepared from
．． 5 mol%, bromide 0.5 mol%, average particle size 0.6 μm
) 5th layer (UV filter layer) Gelatin 1.1! M UV absorber 0.612.5-dioctylhydroquinone 0.045. ? TCP
O,04 6th layer (red sensitive light layer) Gelatin 0.757 Cyan coupler 0,362TCP
O,36I, AgNOs 0-
A far red silver halide emulsion prepared from No. 39 (99.5 mol% chloride, 0.5 mol% bromide, average grain size 0.5
μm) 7th NI (ultraviolet filter layer) Gelatin 0.352 Ultraviolet absorber 0.15.9 TCP
'0.22 8th layer (protective layer) Thickener V O,3,? hardening agent
HI O,:1 wetting agent NMI
10 ■V: Copolymer (-CH2-CH-)! 6(-CJ-CH)y+CON
H2G.

NH-C(CH,) 3 CH2-3o, ○NaΦ These layers were applied using a curtain-type applicator according to German Patent Publication No. 3238905, but only the coating liquid for the 8th layer was applied using the terminal end of the above-mentioned applicator. It was then coated together with the coating solution for other layers.

This superimposed layer was exposed through the gray scale and rapidly processed by the RA-4 method known in the literature. Compounds used in Example 5: Yellow coupler: Q Magenta coupler: Q: Cyan: UV absorber: Curing agent: Hl: Wetting agent: NMl: 5o3e-CH-COo-i-OctylNaΦ-CI
-COo-i-Octyl The photographic material was evaluated according to the following criteria.

l) Coatability evaluation Even in the case of long-term coating over several days at a coating speed of 150 to 250 m/min, the quality of the coated layer, 2) Surface evaluation of color photographic paper after processing 2.1 Ease of staining 2.2 Surface irregularities 3) Condition of photographic material after storage for 7 days under tropical conditions (35°C/90% relative humidity) Evaluation of contamination by bacteria and mold 4) Contamination of developer by discharged disinfectant , grams per unit area of photographic paper.The main features and aspects of the present invention are as follows.

1. Consisting of a support and at least one silver halide emulsion layer applied thereto, characterized in that the content of detectable fungicides in the untreated material is less than 5 mg/m2; Halogen silver photographic material.

2. The photographic material as described in 1 above, wherein the content of a detectable bactericide is 5 mg/mg or less.

3. The photographic material according to item 1 or 2 above, which is a photographic material capable of forming a photographic image substantially free of silver.

4. Contain at least 2 starting materials susceptible to contamination by microorganisms.
4. A method for producing a silver halide photographic material according to any of the above items 1 to 3, characterized in that the material is treated with carbon dioxide gas at a pressure of bar.

5. Process according to item 4, characterized in that the pressure is between 4 and 40 bar.

6. The method described in items 4 to 5 above, characterized in that all the coating liquids used for producing the silver halide photographic material containing gelatin are pressure-treated with carbon dioxide.

7. 6. The method according to items 4 to 5 above, characterized in that the pressure treatment is carried out at a temperature of 10 to 90°C.

8. The method described in 4 to 5 above, wherein the treatment time is 5 minutes to 3 hours.

9. Starting materials susceptible to microbial contamination in the form of aqueous suspensions, emulsions or solutions of photographic additives are prepared by formula (I) RO-CO-0-CO-OR' (I) where: , R and R
The method for producing a silver halide photographic material as described in item 1 above, characterized in that the material is treated with an appropriate amount of a compound formed by , where ' represents a lower alkyl residue.

10. Use a pyrocarboxylic acid ester having the following formula () % formula % () where R and R' represent lower alkyl residues as a bactericide during the production of photographic materials.

Claims (1)

[Scope of Claims] 1. A support and at least one layer coated thereon, characterized in that the content of detectable fungicides in the untreated material is less than or equal to 5 mg/m^2 A silver halide photographic material consisting of a silver halide emulsion layer. 2. At least 2 starting materials susceptible to contamination by microorganisms
A method for producing a silver halide photographic material according to claim 1, characterized in that it is treated with carbon dioxide gas at a pressure of bar. 3. Starting materials susceptible to microbial contamination in the form of aqueous suspensions, emulsions, or solutions of photographic additives are expressed as follows: RO-CO-O-CO-OR' (I) where: , R and R' represent lower alkyl residues, and the method for producing a silver halide photographic material according to claim 1, characterized in that the material is treated with an appropriate amount of a compound formed by: , R and R' represent lower alkyl residues. 4. The following formula (I) RO is used as a fungicide during the production of photographic materials.
Use a pyrocarboxylic acid ester represented by -CO-O-CO-OR' (I) where R and R' represent lower alkyl residues.