JPS5984237A - Photographic material - Google Patents

Abstract

PURPOSE:To improve the durability of a photographic image by incorporating a fluorodichloromethylthio-deriv. into a layer contg. a hydrophilic binder so as to prevent deterioration in the characteristics of the hydrophilic binder film. CONSTITUTION:A fluorodichloromethylthio-deriv. represented by formula I [where R1 is a group represented by formula II or III (where each of R3, R4 and R5 is alkyl or aryl), R2 is alkyl or aryl, and R1 and R2 may form a phthalimide ring together with N] is used. The deriv. includes a compound represented by formula IV. The deriv. is incorporated into a layer contg. a hydrophilic binder such as gelatin (deriv.) or a cellulose polymer, preferably a layer farthest from a support. The amount of the deriv. to be incorporated is >=about 0.1wt% basing on the amount of the hydrophilic binder.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material using a hydrophilic binder, and particularly to a photographic material with improved durability of photographic images.

Photographic materials generally have one or more light-sensitive layers;
If necessary, appropriate layers such as a subbing layer, an intermediate layer, a filter layer, an antihalation layer, an ultraviolet absorbing layer, a protective layer, etc. are coated on the support. This is generally subjected to photographic processing such as image exposure, revealing the image (development), and further stabilizing (fixing) the image to obtain a photographic image.

Gelatin is generally widely used as a hydrophilic binder used in photographic materials due to its ease of use, productivity, and usefulness in photographic emulsions. Furthermore, gelatin derivatives such as acylated gelatin, guanidylated gelatin, carbamylated gelatin, esterified gelatin, albumin, agar,
Water-soluble polymers such as cellulose polymers such as gum arabic and dextran, polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylpyridine may also be used.

It is known that these hydrophilic binders used in photographic materials are subject to decomposition and decay due to the action of bacteria, mold, yeast, and the like. For example, when manufacturing photographic materials, if a hydrophilic binder containing a photographic material is left in a gel or sol state for a long period of time, it will rot or decompose, resulting in a decrease in the viscosity of the coating solution and a decrease in the physical strength of the binder film after application. (e.g. scratch strength, melting temperature, etc.), and even worse, due to the proliferation of bacteria, mold, yeast, and their products, the photographic effects may deteriorate (e.g., capri outbreak, etc.).
This may lead to deterioration of product shelf life, etc.).

Bacteria, mold, and hydrophilic binders used in photographic materials
In order to prevent and control such spoilage and decomposition caused by yeast and the like, preservatives and anti-pecking agents have been added to hydrophilic binder liquids during the manufacturing process of photographic materials.

The above-mentioned preservatives and anti-piping agents include aromatic hydroxy compounds or salts thereof (for example, phenol, thymol, trichlorophenol, cresol, chlorophene,
2'-dihydroxy-5,5'-dichlorodiphenyl monosulfide, 3,4,5-trifluoromosalicylanilide, etc.), compounds having a carbonyl group (for example, formaldehyde, chloroacetaldehyde, geltaraldehyde, methylolchloroacetamide, etc.), Carboxylic acids or their esters (e.g. benzoic acid, sorbic acid,
monobromoacetate, etc.), amines, disulfides, nitrogen-containing heterocyclic compounds (e.g., 2-methoxycarbonylaminobenzimidazole, etc.), organic mercury compounds (e.g., mercuric phenylacetate, mercuric phenyloleate, etc.), or antibiotics (e.g., Neomycin, kanamycin, streptomycin, etc.) are known, and some are useful for photography.

However, hydrophilic binders require large doses to be administered, are harmful to living organisms and pose problems in terms of industrial hygiene or wastewater standards, and are biospecific so that their effectiveness is limited to specific bacteria. Alternatively, many exhibit unfavorable behavior such as interacting with photographic additives, impairing their effectiveness and damaging photographic reactions.

For example, phenols such as phenol and thymol used in photographic emulsions need to be added in an amount of 2% or more to the hydrophilic Binter K, and their effects are limited to bacteria and are not effective against molds and yeasts. It is also toxic to living organisms and poses a problem in terms of wastewater standards. Alternatively, aldehydes such as formalin are only effective against bacteria, are harmful to living organisms, and cause fog in photographic emulsions. Furthermore, many heterocyclic compounds such as benzthiazole have a photographic desensitizing effect.Furthermore, these compounds are often eluted during the development process, and remain in the hydrophilic binder film after processing. If a photographic print is stored for a long time because the remaining amount decreases and becomes below the effective concentration, the film of the photographic print may malfunction due to mold or the like. Bacteria, mold, yeast, etc. can attack the hydrophilic binder, resulting in changes in gloss, reduction in transparency, and even deterioration of the image. In the case of color photographic images, the pigments are often decomposed and the colors change. This failure often occurs when the book is placed in high temperature and high humidity conditions, or when it is stored between books or photo mounts made of paper containing a large amount of starch. This may damage long-term recordability.

On the other hand, in order to overcome this drawback, several methods have been devised in which the film is immersed in a bath containing a preservative or fungicide before drying in the development process. In addition to the above-mentioned compounds, the compounds used for this purpose are water-soluble zirconium and polycarboxylic acid (JP-A-49-83441), pyrogallol-1,3-dimethyl ether ('IJ No. 48-8241), surfactant ( JP-A-51-6-101529, JP-A-51-1 (US Pat. No. 13429 and USSR Patent No. 421,299), quaternary ammonium salts (US Pat. No. 3,506,433, US Pat. No. 3,816,129) ), and examples are also given in Photo Kogyo's June 1972 issue, pages 45-48.

By immersing it in a bath containing preservatives or fungicides in the final treatment bath,
The method of immersing in a stiff bath after drying is effective against deterioration of the binder film of photographic prints, but it is an additional process in addition to the general photographic process of development, (bleaching) fixing, and washing. The disadvantage is that the number of steps must be increased and existing processing cannot be used.

An object of the present invention is to solve the above-mentioned problems with photographic materials, and to prevent deterioration of the properties of the hydrophilic binder film of the photographic material, thereby improving the product shelf life of the photographic material over a long period of time as well as the visible effects of the photographic material. An object of the present invention is to provide a photographic material with good archival stability for photographic prints.

As a result of repeated research in line with this objective, the present inventors have found that in a photographic material comprising at least one layer containing a hydrophilic binder on a support, the layer contains a fluorodichloromethylthio derivative. The object of the invention has been achieved by a photographic material characterized in that it is advantageous for the hydrophilic binder layer containing the fluorodichloromethylthio derivative to be present on the outermost side with respect to the support.

Further, the fluorodichloromethylthio derivative used in the present invention is preferably one represented by the following general formula.

[General formula]

and R5 each represent an alkyl group or an aryl group), and R2 represents an alkyl group or an aryl group. Further, these alkyl groups and aryl groups may have a substituent. Further, R8 and R2 may form a phthalimide nucleus in cooperation with the nitrogen atom.

The phthalimide nucleus may have a substituent such as an alkyl group or a nitro group.

Next, the present invention will be explained in detail.

The fluorodichloromethylthio derivative used in the present invention (
Representative examples of the specific compounds represented by the general formula (I) of j), hereinafter referred to as the compounds of the present invention, include the following.

[Exemplary compounds]

9- -5 -6- 10- -9 C7 -10 I The method of adding the compound of the present invention to the hydrophilic binder liquid is preferably the same method as the method of dispersing the oil-soluble coupler 1 and introducing it into the hydrophilic binder. . Generally boiling point 18
After dissolving in a high boiling point organic solvent with a boiling point of 0°C or more or a low boiling point organic solvent with a boiling point of 30°C to 150°C, etc., it is added to a hydrophilic binder liquid containing a surfactant, such as a gelatin liquid, and protected and dispersed by pressure or ultrasonic waves. Ru. The high-boiling point organic solvent and the low-boiling point organic solvent are used by appropriately mixing them as required.

Examples of high-boiling organic solvents include phthalic acid esters such as dibsulfthalate and dioctyl phthalate, phosphoric acid esters such as diphenyl phosphate, dioctyl butyl phosphate, trioctyl phosphate, and trihexyl phosphate, octyl benzoate, and acetyl phosphate. Typical examples include tributyl citrate and dioctyl azelate.

Typical low-boiling organic solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl isobutyl ketone, methyl cellosolve acetate, and the like.

In addition to saponin, the surfactants used in the present invention include nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type, and acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfate ester group, and phosphate ester group. Anionic surfactants containing these are useful because they have little photographic color.

The compound of the present invention is 0.1% by weight based on the hydrophilic binder.
The above addition amount is appropriate. The optimum amount varies depending on the type of hydrophilic binder, pH, llAg, and other photographic material materials, but can be easily determined experimentally. The timing of addition is preferably at the time of preparation of the coating solution, and even if the coating solution is stored after addition, it can withstand storage sufficiently.

The compound of the present invention may be contained in at least one layer of the photographic material, but it is desirable that K, which is used effectively, be contained in the outermost hydrophilic layer. When the image is a layer formed of silver, the compound of the present invention may be used in a small amount, but when it is used in a color image layer or a non-photosensitive layer, it is preferably used in a larger amount.

The photographic materials of the present invention include halogenated materials such as color photographic paper, color negative film, color reversal photographic paper, color reversal film, black and white photographic paper, black and white film, X-ray film, and lithographic film that use gelatin as the main hydrophilic binder. Can be applied to silver photographic materials.

Known methods and processing solutions can be used for photographic processing of the various silver halide photographic materials to which the photographic material of the present invention is applied.

The method for measuring and evaluating the effect of preventing property deterioration of the hydrophilic binder 13 film of the photographic material of the present invention described above is as follows.

Evaluation method-1 A developed test piece is placed between shoji paper made of Japanese paper and left in an environment of 35° C. and 80% RH for a predetermined period of time, and then a change in the state of the surface of the test piece is observed.

Evaluation method-2 Cut the developed test piece into a size of 3 x 3 cTL,
Place Aapergillus niger Chast on the test piece and place it on the agar medium in a petri dish.
omium species, and cover with a lid and culture at 35° C. for varying incubation periods, and observe changes in the state of the surface of the test piece after culturing.

Evaluation criteria [Symbol]; [Situation] ◎: Bacteria are not growing ○: There are some traces of mycelium △; Traces of hyphae are located between ○ and × X: There are many traces of hyphae. ××; There are many traces of mycelium, and the gelatin is 114- Partly dissolved.

According to the results obtained by the above evaluation method, the photographic material of the present invention showed excellent resistance to deterioration of the hydrophilic binder film.

It is dispersed and suspended in one liquid and is made by a known method. For example, pH conditions include ammonia method, neutral method, and acidic method; liquid mixing conditions include single injection method, double injection method, and control injection method; and pAg conditions include forward mixing method, back mixing method, and conversion method. By appropriately combining several conditions, halogenated coins are generated. Furthermore, iridium salt, rhodium salt, palladium salt,
It is also possible to improve photographic properties by using iron salts and the like.

The silver halide emulsion used in the present invention may be sensitized by adding a small amount of silver chloride in addition to hypo, thiocyanate, gold salt, thioethers, and amines. Furthermore, the silver halide emulsion may be spectrally sensitized with a cyanine or merocyanine dye. The appropriate silver halide is selected depending on the intended use.

A hardening agent commonly used in photographic materials may be added to the photographic material of the present invention. Examples of the hardening agent include aldehydes, methylol, inoxazole, carbodiimides, active halogen-containing compounds, and active hinyl compounds.

The photographic material of the present invention may contain various dyes for the purpose of filtering, preventing irradiation, or preventing halation. For example, U.S. Patent No. 2゜274.782
No. 2,527,583, No. 2956.87
No. 9, No. 3,177.078, No. 3゜252
．． No. 921 and Japanese Patent Publication No. 39-22069.
The method described in No. 282,699 is used.

Further, the photographic material of the present invention may contain anticapri agents and stabilizers as disclosed in U.S. Pat. Nos. 2,131,038 and 2,694
, thiazolium salts as described in No. 2,886,437, azaindenes as described in No. 2.444.605, urazoles as described in No. 3.287.135, No. 3.287.135; Sulfocatecols described in No. 3,236,652, No. 2,403,927, No. 3,
266.897 and mercaptotetrazoles described in British Patent No. 3,397,987, British Patent No. 2°728.6
The nitrones and indoles described in No. 63 may be used alone or in combination.

The photographic materials of the invention may contain brightening agents such as stilbenes, triazines, oxazoles, coumarins.

Furthermore, when the photographic material of the present invention is applied as a color photographic material, various couplers known in the field of KFi photography can be used.

The couplers used in the present invention may react with any compound that reacts with an aromatic primary amino developing agent to form an image dye during photographic development as well as with an oxidized color developer, such as by a coupler release mechanism. Any compound that provides a useful image dye is included. These couplers can be included in photographic materials. Regarding this, see, for example, [Product Licensing Index], Volume 92, December 1971, Page 110, No.
X[The measures described in section can be applied.

When a coupler is included in a silver halide emulsion, Research Disclosure 148 Makiya 14850.19
The method described in 1976 and the conventionally known oil-in-water emulsion dispersion method are particularly effective.

Further, when the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic binder as an alkaline solution.

In the method of impregnating into anionic latex polymer particles and then adding into the emulsion, the amount of coupler to be impregnated is
It is preferably 0.02 to 2I, preferably 0.05 to 0.5 g per 1 g of polymer weight. The coupler used may be any arbitrary coupler, but typical examples include the couplers described below.

Examples include open-chain methylene yellow couplers, 5-pyrazolone magenta couplers, phenolic or naphthol cyan couplers, and these couplers may be of the 1i12-equivalent type, 18- or 4-equivalent type couplers. In addition, in combination with these couplers, it is also possible to use azo-type colored kabuwo, oxacin-type compounds, diffusible dye-releasing couplers, etc. for automasking. Furthermore, in order to improve the photographic properties, so-called combination cufflers and DIR colorants are used in combination with various couplers.
lopment I:nhibi-tor Rel'
easing coupler), BAR Kagler (
Bleach Accel-orator Recel
It can also include couplers called easin, g couplesr, and the like. As yellow couplers, conventionally used open-chain ketomethylene compounds, such as bivalylacetanilide type yellow couplers and benzoylacetanilide type yellow couplers, are effective, and active site -〇-aryl couplers, which are called 2-equivalent type couplers, are effective. Substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler,
Active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -
0-sulfonyl substituted couplers and the like can be used as effective yellow couplers.

Examples of the magenta coupler used in the present invention include pyrazolone threads, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indacylon-based compounds.

These magenta couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow cuff color.

Furthermore, useful cyan couplers used in the present invention include, for example, phenolic threads, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow couplers.

As the colored magenta coupler, a compound in which the active site of the colorless magenta coupler is substituted with arylazo or heteroarylazo is used.

As the colored cyan coupler, active site ri-luazo-substituted couplers and masking couplers of the type in which the dye flows out into the processing solution by reacting with the oxidized developer can also be used.

Also, U.S. Patent Nos. 2,646,421 and 2.82
Polymeric couplers such as those described in JP-A No. 8.289 and JP-A-55-85549 can be used.

In the present invention, a developing agent for developing silver halide in the light-sensitive material can be added to the light-sensitive material. Such developing agents are described in James [The Theory
Op the Photographic Process J (Th
e Theory of the Photography
phic Process) 1977, Macmillan Company, New Cork, pp. 291-334, U.S. Patent No. 3,813,244;
No. 791,827 can be referred to.

The photographic material of the invention may also contain UV absorbers, such as known compounds such as benzotriazoles, thiazolidines or thiazolidones.

Furthermore, as a color capri-preventing agent, U.S. Patent No. 2,735°76
Compounds such as conventionally known hydroquinone derivatives described in No. 5 and the like may be included.

Supports for photographic materials made using the hydrophilic binder liquid according to the present invention prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose night. Supports include polyurethane, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the intended use of each photographic material.

These supports are subjected to undercoat processing if necessary.

When the hydrophilic binder liquid according to the present invention is applied to the support to form a photographic material, dip coating method, air knife coating method, curtain coating method, or U.S. Pat. No. 2,681,2
It may be coated by a variety of coating methods including extrusion coating using a Hot 22-tube of the type described in No. 94. If desired, bilayers or multiple layers can be added in accordance with U.S. Pat.
, 761,791 and British Patent No. 837.095.

For the photographic processing of the photographic material of the present invention: - Known black and white photographic processing or color photographic processing is applied depending on the characteristics of the photographic material. The various known processing solutions, such as the developer, include preservatives,
Auxiliary agents such as antifoggants that are usually added to processing solutions may also be used.

Developing agents for producing black and white photographic images include hydroquinone, catechol, pyrogallol, l-7 minophenol, ascorbic acid, glycine, 1-phenyl-3-
Pyrazolidone, 4,4-dimethyl-1-phenyl-3-
Examples include pyrazolidone. As developing agents that produce color photographic images, there are aromatic primary amine color developing agents that form dyes through a coupling reaction between a coupler and an oxidized developing agent.A representative example of these is 4-amino-N. , N-diethylaniline hydrochloride, 4-amino-3-
Methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate hydrate, 4
-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-dimethylamine-N,N-diethylaniline sulfate hydrate, 4-amino-3-methoxy-N- Ethyl-N-β
-Hydroxyethylaniline salt [salt, 4-amino-
3-(β-methanesulfonamidoethyl)-N,N-diethylaniline dihydrochloride and 4-amino-N-methyl-NS(2temethoxyethyl)-m-)shiidine 2p-toluenesulfonate. .

Further, in the present invention, a precursor of a color developing agent can also be used. Its precursor is U.S. Pat.
No. 7,114, No. 2,695,234, No. 3, 3
42,599 and Research Disclosure Vol. 151 A 15159 Nov, 1979, the Schiff ring group type of color developer, Research Disclosure? -Volume 129 A I 29240at,
1976, Volume 121 A 12146 Jun, 19
1974, Volume 139 A13924 Nov, 1975
Those listed in the year etc. can be applied.

Next, the present invention will be specifically explained with reference to Examples.

The structures of the compounds indicated by symbols in the examples are as follows.

A 25- AF-14-human tetraxy-6-methyl-1,3゜3a-
7-Chitrazaindene AF-21-phenyl-5-mercaptotetrazole AF-3 Adenine AF-42-mercaptobenztriazole 26- S-I C2H51 Naps 5-CH-Coo-CH2CH-(CH2)
3CH3CH2-COO-CH2CH-fCl-12)
3CH32H5 -2 Shi! T(-3 Example-1 Silver chloroiodobromide (composition: silver chloride 5 mol%, odor fl[lx, s mol%, In iodide 3.5 mol%) emulsion with an average grain size of 0.55μ was made of gold. -After chemical ripening by hypo-sensitization method, add appropriate amounts of 2-mercaptobenzothiazole and hardener H-3 to undercoat to give a coated silver amount of 2-5 g/z and a coated gelatin amount of 3.0 g/7. Next, a gelatin solution consisting of a mixture of Solution A and Solution B listed in Table 1 was prepared, and the amount of gelatin coated was 1.5 E//m''. Samples 1 to 10 were prepared by coating on the coated emulsion and drying to form a protective film layer.

Stepwise exposure (△D=0
．． 2) was carried out, the film was developed, and the change in sensitivity and the degree of mold growth in the high concentration area were examined using the evaluation method described above.

Development processing conditions, 29- 30- Table 2 Specific sensitivity is expressed as relative sensitivity on the same day when sample 1 is used as a reference.
Samples 9 and 10 using . Similar results were obtained using evaluation method-2. It can be seen from Samples 1.7.8 that formalin, ethyl acetate, dibutyl phthalate, and sodium dodecylbenzenesulfonate used in Samples 9 and 10 had no particular effect. Samples 5 and 6
Although the anti-bacterial effect is touted, the sensitivity decreases, whereas the sensitivity of 9 and 10 does not change and there is no negative photographic effect, which is a feature of the present invention.

Example 2 Coating solutions for the first to sixth layers were prepared by the following method, and six layers were simultaneously coated on polyethylene laminate paper using an extrusion method, cooled, and then dried. The effects of the compound of the present invention were compared and contrasted by changing the composition of the sixth protective layer.

Coating liquid for the first layer 200g of yellow coupler (Y-1) was mixed with dioctyl phthalate, ethyl acetate, alkanol XC (
A blue-sensitive silver chloroiodobromide emulsion (grain size 0.7μ, silver bromide 85 mol%, silver iodide 0.5 mol%) was protected and dispersed using a surfactant manufactured by Schwon Co., Ltd. (USA), and 1 mol added to.

Furthermore, stabilizers AF-10,4,9, AF-20,02,9
Add 33- coating size silver amount 0.359/g, gelatin amount 2.0 g/
yrl yelled.

Second layer coating solution 2.5-Dioctylhydroquinone was protected and dispersed using dioctyl phthalate, ethyl acetate, and alkanol XC, and added to the gelatin solution. Apply 2,5-dioctylhydroquinone o, oos,! i+.

Gelatin 1. It was made to be OI.

Weigh and mix 50.9 g of each magenta coupler (M-1, M-2), protect and disperse in the same manner as the yellow coupler, and green-sensitive silver chlorobromide emulsion (grain size 0). .43μ, silver bromide 67 mol%) was added to 1 mol. More coating liquid 11! Hit stabilizer AP'-10,3,9, surfactant S-10,
15.9 was added, and immediately before coating, hardener H-1 was added at a concentration of 0.029 per gram of gelatin.
g, gelatin 1.8, and S'/m.

4th layer coating solution UV mi absorbent Tinuvin 328, Tinuvin PS (manufactured by Ti34-Ba Geigy) and a small amount of 2,5-dioctylhydroquinone are protected and dispersed using dioctyl phthalate, ethyl acetate, and alkanol xC, Added to gelatin solution. Furthermore, 0.00% surfactant S-1 was added per 11 parts of the coating liquid.
15.9 was added, and 0.02 g of hardener H-1 per gram of gelatin was added before the coater.

0.3g of UV absorber and 0.8g of gelatin in coating
/ze.

Fifth layer coating liquid cyan coupler C-1100,! It was protected and dispersed in the same manner as the 9Y yellow coupler, and added to 1 mol of red-sensitive silver chlorobromide emulsion (grain size 0.37 μm, silver bromide 70 mol %). More coating liquid 1! Per unit stabilizer AF-10.3g, AF
-30,05,9, add 5-20.2g of surfactant,
Furthermore, just before coating, apply hardening agent 'H-2 at 0.00% per gram of gelatin.
029 was added.

The coating was coated to give a silver content of 0.3 g and a gelatin content of 1.8 g/r7L'.

Coating solution for 6th layer A protectively dispersed ultraviolet absorber for the 4th layer was added to the gelatin solution. Next, 0.30.9% of surfactant S-2 was added per 11 coating liquid, and then hardener H-2'&- was added immediately before coating.
0.035.9 was added per gram of L-latin. Add various anti-piping compounds to the dough as shown in Table 3, and...
A test sample was prepared by 5 km of cloth with a gelatin content of 1.59/m.

Samples 11 to 26 prepared in this manner were subjected to stepwise exposure (ΔD=0.1) and then subjected to the following development process to obtain prints.

Furthermore, in order to examine the extent of mold growth, the sample was subjected to an evaluation method.
Table 3 shows the results of applying 1 and -2.

Development process Color development 33.0±0.5°C 3 minutes 30 seconds White fixing 33.0±1°C 1 minute 30 seconds Water washing 2
Dry at 5-30℃ for 3 minutes and 30 seconds at 70±5℃
1 minute 30 seconds Color developing solution composition Bleach-fixing solution composition 37- 38- From Table 3, sample 17 in which a large amount of 5-methylbenztriazole was added exhibits the "Yagobobai" effect, but has the disadvantage of reduced sensitivity. Samples 18 to 20 using TBZ also did not show much of an antifungal effect, and it is thought that a considerable amount of K was eluted during the development process. Compounds c-1, c-6 of the present invention
It is clear that the samples using this method have a high antifungal effect and little change in sensitivity. In addition, the color of the prints of the samples in which C-1 and C-5 were not used changed to a reddish color.

Example-3 Coating liquids for the first to seventh layers were prepared by the following method,
Layers 1 to 7 were coated and dried in the same manner as in Example 2 in order from the side closest to the support to prepare samples of a reversal color photographic material.

Red-sensitive silver chloroiodobromide emulsion (grain size 0.55μ, silver iodide 2 mol%, silver bromide 89 mol%) containing cyan coupler (C-2'), stabilizer AF -10,4,lit, AF-40
, 1 g was added, and the amount of silver was coated so that the amount of silver was o, (4 g/m <' the amount of gelatin 12.0 g/rrl).

Coating liquid for second layer A gelatin solution containing yellow colloidal silver A and 2,5-di(t)octylhydroquinone was mixed with silver ito, osH.
12,5-di(t-octylhydroquinone amount o, 05
g/rrl, gelatin amount 1. og/lrl was applied.

Coating liquid for third layer Magenta coupler (M-1) Green-sensitive silver chloroiodobromide emulsion containing Y (grain size 0.55μ, silver iodide 1.5 mol%, silver bromide 8
7 mol%) with stabilizers AF-10, 3fl, AF-4
0.1 g was added so that the amount of silver was 0.41/m'' and the amount of gelatin was 1.8, !i'/rd.

4th layer coating liquid UV 1s absorber (manufactured by Ciba Geigy; Tinuvin 320,
Tinuvin 326, Tinuvin P8 1:1:1 respectively),
A gelatin solution containing 2,5-di(1)octylhydroquinone and yellow colloidal silver has a silver content of 0.15 I/I and an ultraviolet absorber content of 0.5. i'/rrl, gelatin amount 1, 39/Tr? It was applied so that

Blue-sensitive salt 41-Silver bromide emulsion containing fifth layer coating solution Ye 4-Kadalar (Y-1) (grain size 0.75μ, silver iodide 2.2 mol%, silver bromide 94 mol%) K stabilizer AP'-10,4, lit
, AP'-40,15,! In addition to 9 pieces, the amount of silver is 0 after coating.
．． 55.9/75, gelatin amount 2.0 g/t
ri''.

6th layer coating solution UV absorber (manufactured by Ciba Geigy, Tinuvin 328, Tinuvin PS Sowa 2:1) & gelatin solution containing UV absorber 0.39/m, gelatin amount 0.8
It was made to be g/go.

Coating Solution for Seventh Layer As shown in Table 4, a gelatin solution containing a fungicide was prepared and coated to give a gelatin amount of 0.7 g/rFIg.

The coupler, the ultraviolet absorber, and the compound related to the present invention were dispersed in dibutyl phthalate, ethyl acetate, and alkanol XC in the same manner as in Example 2, and then
added to the liquid.

Each sample was left unexposed and processed using the following development process and processing solution to obtain a black peta print.

42- Development process first development 38.0±0.3℃ 75 seconds water
Washing 35 ±3℃ 135 seconds exposure
500-2000 CMS color development 38.
0±0,5°C Wash with water for 90 seconds 35 ±3°C
45 seconds bleach fixing 38±1°C 120 seconds water washing 135 seconds First developer composition Color developer composition I'Kodak CD-359 Bleach-fix composition From these results, C-1, C-6'aj was used. It is clear that the antifungal effect is high only in the sample.

Agent Yoshimi Kuwahara 45- Procedural amendment Written by Kazuo Wakasugi, Commissioner of the Japan Patent Office 1. Indication of the case Patent Application No. 195620 filed in 1982 2. Name of the invention Photographic material 3. Person making the amendment Relationship to the case Patent application Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127 + Konishiroku Photo Industry Co., Ltd.) Former residence: 6, 1-1 Sakuracho, Hino-shi, Tokyo; "Detailed Description" Column 7, Contents of Amendment +1) The detailed description of the invention is amended as follows.

Specification pages 9-11 “[Exemplary compounds] C-1 to C-10
" has been corrected to "[Exemplary Compounds] P-1 to P-10J.

2-

Claims (3)

[Claims] (1) A photographic material comprising at least one layer containing a hydrophilic binder provided on a support, wherein said layer contains a fluorodichloromethylthio derivative. (2) The photographic material according to claim (1), characterized in that one of the layers provided on the support is the support. Thio (3) The photographic material according to claim (1) or (2), wherein the fluorodichloromethi i-conductor is represented by the following general formula. represents a general formula group), and R2h represents an alkyl group or an aryl group. Further, R8 and R2 may form a phthalimide nucleus in cooperation with the nitrogen atom. ]