JPH04149433A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To prevent contamination of processing solution by incorporating a specified cyclic phosphazene compound to at least one layer of the constituting layers. CONSTITUTION:On the supporting body, the photosensitive material having silver halide emulsion layer and to at least one layer of the constituting layer of sensitive material, cyclic phosphazene compound expressed as in formula I are incorporated. In the formula (I), R<1> and R<4> is the same or may be differed from each other and represent carbon number 2-20 substituted or unsubstituted alkyl, alkenyl or alkynyl radical respectively. Also, R<2> and R<3> is the same or may be differed from each other and represent alkyl radical consist of 1-4 carbon number and q and r is not allowed to became zero simultaneously and represent integers of 0-5 and X is 3 or 4. By this means, contamination of the processing solution is prevented and image blur is not generated at the time of processing treatment.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, and particularly to a silver halide photographic material having good antistatic properties.
Moreover, the present invention relates to a silver halide photographic material (hereinafter referred to as photographic material) which does not contaminate a developing solution and does not cause image unevenness when processed in an automatic processor.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling between surfaces of the same or different materials is avoided during the manufacturing process and during use of the photographic materials. Electrostatic charges often accumulate due to exposure to This accumulated electrostatic charge causes many problems, but the most serious one is that the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated electrostatic charge before processing, and when the photographic film is processed. This is to produce point-like spots or dendritic feather-like line speeds. This is what is called a static mark, and it significantly reduces the commercial value of photographic film, and in some cases causes the film to lose its commercial value altogether. This reduction becomes apparent only after development, and is one of the most troublesome problems. Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the surface of the film before or after processing or the inability to apply uniformly.

Static marks on photographic materials induced by such accumulation of electrostatic charges become more serious as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, the occurrence of stack marks has become even more likely due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. . Furthermore, opportunities to handle processed photographic materials have increased in recent years, and dust has become a serious problem.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials must not have any adverse effect on the photographic properties of the photographic light-sensitive materials, such as sensitivity, capri, graininess, sharpness, etc. Does not adversely affect the film strength of the photosensitive material, does not adversely affect the adhesion resistance, does not accelerate the fatigue of the processing solution for the photographic material, does not contaminate the conveyance roller, and does not cause any damage between the constituent layers of the photographic material. Application of antistatic agents to photographic materials is subject to numerous restrictions, as performance such as not reducing adhesive strength is required.

One way to eliminate these problems caused by static electricity is to increase the electrical conductivity of the surface of the photographic material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. It's here.

Among these, surfactants are important in terms of antistatic ability.
, No. 251, No. 3,519,561, No. 3,625,
No. 895, Rooster German Patent No. 1゜552.408, No. 1
, No. 597,472, JP-A-49-85826, No. 5
No. 3-129823, No. 54-1592234, No. 4B
-19213, Special Publication No. 46-39312, 49-
No. 11567, No. 51-46755, No. 55-144
Anionic, betaine and cationic surfactants described in No. 17, etc., or Japanese Patent Publication No. 4817882,
JP-A-52-80023-1+, West German Patent No. 1.4
Nonionic surfactants are known, such as those described in Australian Patent No. 22.809, Australian Patent No. 1,422.818, and Australian Patent No. 54.44/1959.

However, these substances exhibit specificity depending on the type of film support and the photographic composition, and do not fully satisfy the above-mentioned performance, making it extremely difficult to apply them to photographic light-sensitive materials.

Further, it is described in Japanese Patent Publication No. 51-96104 that the ethylene oxide addition polymer of phenol-formalin condensate has excellent antistatic properties even when used in combination with various coating agents. However, this method did not solve problems caused by contamination during the development process.

Furthermore, JP-A No. 5:3-29715 describes a photographic material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant, but it does not cause contamination of the developing processing solution or contamination of the transport roller. Film failures may occur due to this.

Furthermore, W090108978 proposes a method of using a cyclic phosphazene compound as an antistatic composition. Although this technology has excellent antistatic properties, it also causes significant staining and unevenness of images during the development process, making it unsatisfactory as a photographic light-sensitive material.

Methods for reducing the amount of washing water during processing from the viewpoint of environmental conservation, water resources, cost, and simplifying and compacting the processing equipment; methods for reducing the amount of replenishing processing liquid from the viewpoint of cost; and furthermore, processing time. Attempts have been made to thicken the processing solution in order to shorten the processing time, but with the development of such processing methods, the above-mentioned processing solution contamination and adhesion of water-insoluble matter to the conveyor rollers are becoming more common. This is becoming a serious problem.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a photographic material which is prevented from being charged and which does not cause contamination of a processing solution.

The second object is to provide a photosensitive material which is prevented from being charged and which does not cause image unevenness during development processing.

The third object is to provide a photographic material that is antistatic without adversely affecting coating properties.

(Means for Solving the Problems) These objects of the present invention are to provide a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. This is achieved by containing a cyclic phosphazene compound represented by the above general formula (1).

The compound of the present invention is a cyclic phosphazene compound having a repeating unit consisting of a branched alkylene oxide and a repeating unit consisting of ethylene oxide in at least one side chain. It has been found that prevention of liquid contamination, prevention of image unevenness, and excellent coating properties are all satisfied at the same time.

The cyclic phosphazene compound represented by the general formula CI) of the present invention will be explained in detail.

General formula CI) ゝ---------' In the formula, R1 and R4 may be the same or different and are substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms,
Represents an alkenyl group, an alkynyl group, or an aryl group. Examples of substituents include halogen atoms, cyano groups, sulfo groups,
Hydroxy group, carboxyl group, alkyl group, aryl group, aralkyl group, acyloxy group, acylamino group,
Amino group, sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxy Examples include a sulfonyl group, a carbamoylamino group, a sulfamoylamino group, a carbamoyloxy group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group.

R and R4 are preferably an alkyl group having 1 to 14 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a fluorine atom, or a substituted or unsubstituted oryl group having 6 to 14 carbon atoms. .

R2 and R3 represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and are preferably a methyl group or an ethyl group, with a methyl group being particularly preferred; p and S are 0 to 50; Represents an integer and may be the same or different. However, p and S do not become 0 at the same time. The values of p and S are preferably from 1 to 25, particularly preferably from 1 to 15.

q and r never become 0 at the same time. represents an integer of 0 to 5, preferably 1 to 3, particularly preferably 2
to 3. X is 3 or 4.

Preferred specific compounds of the present invention are illustrated below,
The present invention is not limited to these compound examples.

Compound Examples (General Formula Ex-1) (General Formula Ex-2) Above General 2 Ex
In -1, R2 to R16 In the above general formula Ex-1, R,, -R□CH.

=0-(-CHCH, OhiCH, CH, 0hCH.

In the above general formula Ex 1, R21 to R7° In the above general formula Ex-1, R21 to Ros In the above general formula Ex 1, Rx + to R51 CH.

Tsu0i CHCHsOMCHaC1 (*0hCHsR2g
”CH.

0(C)IC) [Rs+-Ri+CI( in the above general formula Ex-2).

= O(CHCHhOhKCHaCHzO)rCHs Compound in the above general formula Ex-2, R's l-Rs t In the above general formula Ex-2, Rx+-RssCH.

The compound of the present invention can be easily synthesized by the reaction of a cyclic phosphazene halide with an alkali metal alcoholade.This nucleophilic substitution reaction This is a well-known general synthesis method for cyclic phosphazenes, for example, as described by Schreiber et al. in Journal of the American Chemical Society, Vol. 106, p. 6854 (1984) (D, F
,5hriveret al., J.Am.,Chem.
Soc, supra. 08.8854 (1984)).

Synthesis Example 1 Synthesis of Exemplified Compound P-1 18.1 g (0.7 mol) of metallic sodium and 350 g of tetrahydrofuran were placed in a dry 1000-3-meter flask equipped with a reflux tube, and diethylene glycol 1. 79.3g (0
, 66 mol) was slowly added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 30 minutes to confirm that a completely homogeneous solution had been obtained.

Cool again on ice and add 78.4 g (1,
32 mol) was added dropwise over 30 minutes, the mixture was returned to room temperature, and reacted for 5 hours while remaining at 85° C. to obtain a transparent, homogeneous solution. A solution of 34.8 g (0.1 mol) of hexachlorocyclotriphosphazene dissolved in 350 g of tetrahydrofuran was added dropwise to the solution over a period of 1 hour at room temperature. After confirming that a white precipitate had formed, the reaction solution was heated under reflux for 4 hours, then returned to room temperature, and stirring was continued for 10 hours to complete the reaction. The reaction solution was filtered to remove the white precipitate (salt), and the filtrate was reduced to 0. After neutralizing with 1 mol/i hydrochloric acid to adjust the pH to 8.8, the solvent was distilled off under reduced pressure and further dried under high vacuum at 40°C to obtain an oily compound. Ethyl acetate 5001s1, which had been previously dried with a molecular sieve, was added to this, stirred thoroughly, and some residual salt was filtered off.The solvent was distilled off under reduced pressure, and a reddish-brown color was obtained. 6 g of the target compound P-1142 was obtained as an oily compound. Yield 92
゜2% The structure of the obtained compound was confirmed by elemental analysis, 'H-NMR, and IR.

Synthesis Example 2 Synthesis of Exemplified Compound P-7 Octylphenoxytriethoxyethanol (TORI
168.3 g (0.44 mol) of TON , filter,
Calcium hydride was removed to obtain a dry octylphenoxytriethoxyethanol solution. On the other hand, add 1 part of metallic sodium to a 11-three-meter flask that has been dried and equipped with a reflux tube.
1.5g (0.5 mol), 150y of tetrahydrofuran
d, and while stirring on water cooling, 30% of the dried octylphenoxytriethoxyethanol solution obtained above was added.
It was added dropwise slowly over several minutes and stirred at room temperature for 1 hour, and it was confirmed that the solution was completely transparent. This flask was cooled on ice again, and 51.2 g of propylene oxide (
0.88 mol) was added dropwise over 30 minutes, the mixture was returned to room temperature for 1 hour, and then refluxed at 80° C. for 8 hours to obtain a clear, homogeneous solution. A solution of 17.4 g (0.05 mol) of octachlorotetraphosphazene dissolved in 100 Id of tetrahydrofuran was added dropwise to this solution over 1 hour at room temperature. Confirm the formation of white fine precipitate, heat for 3 hours,
After refluxing, the temperature was returned to room temperature and stirring was continued for 20 hours to complete the reaction. The reaction solution was filtered to remove the generated white precipitate, and the filtrate was neutralized with 1% hydrochloric acid to give p)(=Ei,
5, add 2°Og of activated carbon and heat at 40° for 15 minutes.
The mixture was stirred at C, cooled to room temperature, and the activated carbon was removed by filtration to obtain a transparent solution. After distilling off the solvent from this solution under reduced pressure, fresh tetrahydrofuran 50III!
Add and dissolve again, add 100% of tetrahydrofuran to this
A mixture of af and hexane 900111 was added and washed in a separatory funnel. The lower layer was taken out, the solvent was removed under reduced pressure, 600 ml of ethyl acetate was added to the resulting viscous liquid, it was melted again, 20 g of anhydrous sodium sulfate was added and dried, this was filtered off, and the solution was removed under reduced pressure. The solvent was removed to obtain the desired compound P-7 as a yellowish-brown compound at
．． I got 5g. Yield 82.9%.

Other preferred compounds of the present invention can also be synthesized by the above synthesis method or a method equivalent to the above synthesis method.

The cyclic phosphazene compound represented by the general formula CI) or the general formula CI[ ] is preferably used in combination with a salt of a metal ion belonging to group Ia or IIa of the periodic table in order to improve antistatic performance. Preferred examples of metal ion salts are listed below, but of course the salts are not limited to these.

KCFaSOs, NaCF*SO*, LiCF
sSOs, Ca(CFtSOs)aMg(CFIS
OI)! , KBF4, NaBF4, LiB
F4, KCPICOINaCPsCO*, Lt
CPsCO*, KC*F7CO*, NaC*P
tC0zLjC*F7COi, KC*P7SOs
, NaC5FtSOs, KC4FsSOsKPF
, . Furthermore, two or more of these salts may be used in combination.

The cyclic phosphazene compound of the present invention can also be used as an antistatic agent by adding it to a hydrophilic organic colloid or an organic solvent-based coating solution for a support back layer.

The compound of the present invention is added to at least one of the silver halide emulsion layers or other constituent layers of the photographic light-sensitive material,
It may also be an undercoat layer. Other constituent layers are preferably hydrophilic colloid layers, such as a surface protective layer, a back layer, an intermediate layer, and an undercoat layer. Particularly preferred locations for addition are the surface protective layer, back layer or undercoat layer.

When the surface protective layer, back layer or undercoat layer consists of two layers, any of these layers may be used, and on top of the surface protective layer,
Furthermore, it can also be used as an overcoat.

When applying the compound of the present invention to photographic materials, water, methanol, ethanol, isopropanol,
After dissolving in an organic solvent such as methyl ethyl ketone or acetone, or a mixed solution thereof, it is added to a coating solution for a surface protective layer or back layer, and coated by dip coating, air knife coating, spraying, or using a hopper as described in U.S. Pat. No. 2,681.294. It is coated by an extrusion coating method using U.S. Pat.
．． Two or more layers may be applied simultaneously by methods such as those described in U.S. Pat. No. 898 and U.S. Pat. Further, if necessary, an antistatic liquid (solution alone or containing a binder) containing the compound of the present invention may be further coated on the protective layer.

The amount of each of the compounds of the present invention to be used is preferably 0.0001 to 2.0 g (particularly preferably 0.0005 to 0.3 g) per square meter of the photographic light-sensitive material.

Two or more types of each of the compounds of the present invention may be mixed.

The photographic material according to the present invention may be a conventional black-and-white silver halide photographic material (for example, black-and-white photographic material, X-r
black-and-white photosensitive materials for AY, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color negative films, color reversal films, color positive films,
(color negative films for movies, etc.), infrared light sensitive materials for laser scanners, etc.

Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention, manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, antistatic agents, couplers, There are no particular restrictions on plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc.
ductLicensing) Volume 92] 07-110
Page C December 1971) and Research Disclosure magazine.
Volume 176, pages 22-31 (December 1978), 238
The description in Vol. 44-46 (1984) can be referred to.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, hardening, etc.). Various surfactants may be included for various purposes such as sensitization, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactant diamino acids containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups,
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; heterocycles such as alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, and imidabrilam. Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These include Ryohei Oda et al.'s ``Surfactants and Their Applications'' (Yokoshoten, 1964), Hiroshi Horiguchi's ``New Surfactants'' (Sankyo Publishing ■, 1975), and ``Matsuku Cations Detergent and Emulsifier.''' (
Matsuf Cation Divisions, MC Publishing Company 1985) (rMc Cutc
heon's Detergents & Emulsi
fiers J (Me Cutcheon Div.
jsions, MCPubljshing Co,
1985) ), JP-A No. 60-76741, 6
No. 2-172343, No. 62173459, No. 62-
No. 215272, etc.

Although the compound of the present invention has an effect as an antistatic agent,
It may be used in combination with other antistatic agents to the extent that the effects of the present invention are achieved. Examples of antistatic agents that may be used in combination include fluorine-containing surfactants or polymers described in JP-A-61-109044 and JP-A-62-215272;
No. 76742, No. 60-80846, No. 60-808
No. 48, No. 60-80839, No. 80-78741, No. 58-208743, No. 62-172343,
Nonionic surfactants described in No. 62-173459, No. 62-215272, etc., JP-A-84
Polyphosphazene described in -68751, or JP-A-57-204540, JP-A-62-2152
Examples include conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 72.

Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, thiocyanates, and JP-A-Sho. Conductive tin oxide, zinc oxide, or a composite oxide obtained by doping antimony or the like with these metal oxides described in No. 57-118242 can be used.

Furthermore, various charge transfer complexes, π-conjugated polymers, and their dopings can also be used as antistatic agents, such as TCNQ.
, /TTF, polyacetylene, polypyrrole, etc. These are Morita et al., Science and Industry 59(3), 103-[
1 (1985), ¥L (4), ]48-152 (19
85).

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives: Various synthetic hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric substances can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, glycerin, and sorbitol can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention are regular (regular) grains such as cubes and octahedrons.
It may have a spherical, spherical,
It may have a crystal shape such as a plate shape, or a composite shape of these crystal shapes. Further beam search・
Disclosure Volume 225 & 22534.20-58
Page (198341) JP-A No. 58-127921, No. 5
The tabular grains described in No. B-111926 may also be used. It may also consist of a mixture of particles of various crystalline forms.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including H salts), rhodium salts (including complex salts), and iron salts. (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure & 1764a II Cl97.
It can be carried out based on the method described in [February 2008].

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. It shows the diameter when the image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

Further, the emulsion used in the present invention is disclosed in U.S. Patent No. 2゜996
．． 382, 3,397,987, 3°705.85
As described in Section 8, a mixed emulsion of a photosensitive silver halide emulsion and an internally fogged silver halide emulsion or an emulsion used in combination in a separate layer may be used.

Here, it is preferable to further use the mercapto compound described in JP-A-81-48862 in combination to suppress fogging and improve storage stability over time.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. benzotriazoles, nitrobenzotriazoles, mercaptotetrazole m (1-phenyl-5-mercaptotetrazole in #), etc.: mercaptopyrimidines; mercaptotriazines, such as thioketo compounds such as oxadorinthion; niazaindenes, such as triazine; Zainden, tetraazaindene (especially 4-hydroxy substituted (1,3,3a,7) tetraazaindene), pentaazaindene, etc.: benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. A number of compounds known as antifoggants or stabilizers can be added, such as.

The hydrophilic colloid layer of the photographic material of the present invention may contain polymer latexes well known in the art, such as homopolymers or copolymers of narkylacrylate and copolymers of vinylidene chloride. The polymer latex may be pre-stabilized with a nonionic surfactant as described in JP-A No. 6-230136.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-virapritones, and the like.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The support used in the present invention can also be provided with an antihalation layer. For this purpose, carbon black or various dyes such as oxonol dyes, azo dyes, allylmethane dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antihalation layer.

These are Research Disclosure Volume 176 N (L
] Section 7643.1 C197B December). In addition, in order to improve the color of developed silver,
Magenta dyes such as those described in No. 285,445 may also be used.

The hydrophilic colloid layer used in the present invention includes colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, and methyl methacrylate-styrene sulfonic acid described in JP-A-63-216046. Copolymer, JP-A-61-2301
A so-called matting agent made of particles containing fluorine groups as described in No. 36 can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), active vinyl compounds (1,3,5
-) lyacryloylhexahydro-8-triazine, 1
．． 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone. Or they can be used in combination.

The hardening agent preferably used is a vinyl sulfone compound represented by the following general formula.

(CH,=CH-3○,-CH,→goA In the formula, A is 2f
Although it represents an S group, it is not necessary.

The photographic material of the present invention contains a developing agent.

As a developing agent, Research Disclosure No. 17
rDeveloping agent in volume 6, page 29
Those described in the section sJ can be used.

In particular, hydroquinone and birapritones are preferably used.

In the present invention, a coupler that develops yellow, cyan, or magenta may be used, for example, in JP-A No. 62-21
It is described in detail in No. 5272.

In the present invention, the coating method for applying the layers constituting the photographic material is not particularly limited, and examples include bar coating, roll tube coating, knife coating, and flow coating (curtain coating). Conventional techniques such as gravure coating method, spray coating method, dip coating method and extrusion coating method can be mentioned.

The developing process for the photographic light-sensitive material of the present invention may be either a process for forming a silver image (black and white development process) or a process for forming a color image. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent. (Silver dye bleaching may also be used, in which a dye is contained in a photosensitive material, a black and white development process is performed after exposure to create a silver image, and this is used as a bleaching catalyst to bleach the dye.) As a black and white development process, , development process, fixing process,
A water washing process is performed. In the case where a stop treatment step is performed after the development treatment step or a stable residence treatment step is performed after the fixation treatment step, the water washing treatment step may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the photosensitive material, and the developing process may be performed using only an alkaline solution. A development process using a lithium developer as a developer may also be performed.

Color development processing includes a color development processing process, a bleaching processing process,
A fixing process, a water washing process, and a stabilizing process are performed as necessary, but instead of a process using a bleach solution and a process using a fixer, a one-bath bleach-fix solution is used for bleach-fixing. It is also possible to perform a monobath treatment process using a one-bath development, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed with an activator solution, or an activator solution may be used in the monobath process. Processing can be applied.

The processing temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

The black-and-white developer used in the black-and-white development process is commonly used in processing known black-and-white photographic materials, and can contain various additives that are generally added to black-and-white developers.

Typical additives include developing agents such as 1-phenyl-3-virapritone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds. can be mentioned.

Furthermore, in the case of X-ray sensitive materials, efforts have been made to shorten the development processing time. Furthermore, means to simplify processing have also been developed, and the compounds of the present invention can provide photographic materials that are extremely superior to these recent processing techniques.

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) After putting an appropriate amount of ammonia into a container heated to 55°C containing a monodisperse silver halide emulsion of gelatin, potassium bromide, and water, the pAg value in the reaction container was reduced to 7.
．． The average particle size was determined by adding a silver nitrate aqueous solution and a potassium bromide aqueous solution to which hexachloroiridate (I[) salt was added so that the molar ratio of iridium to silver was 0 to 7 mol while maintaining the average particle size at 60% by double jet method. is 0.
Monodisperse silver bromide emulsion grains of 55μ were prepared vI. 98% of the total number of milk sub-particles existed within 40% of the average particle size. After desalting this emulsion, the pH was adjusted to 6.2 and the pAg to 8.6, and then gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain desired photographic properties.

The (100) plane/(111) plane ratio of the second emulsion was measured by the Kubelkamunk method and was found to be 98/2. This emulsion was named A.

Next, monodisperse emulsions B and C having average grain sizes of 0.35μ and 0.25μ were prepared by changing A only by reducing the amount of ammonia added before grain formation.

(2) Preparation of emulsion coating solution After heating 0.333 kg each of emulsions A, B, and C to 40°C to dissolve the emulsions, add a methanol solution (9 x 10'') of an infrared sensitizing dye (structural formula A below) 4mol/f) to 70c
c, supersensitizer 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (4,4X
] 0” mol/1) Aqueous solution (4,4×10-f
[lol, #') 90cc, methanol solution of the following structural formula B (2,8X] O"n+ol#) 35cc
, 4-hydroxymethyl-6-methyl-1°3.3a,
7-chitrazaindene aqueous solution, coating aid dodecylbenzenesulfonate aqueous solution, thickener Bolibotacium P
- An aqueous solution of a styrene sulfonate compound was added to prepare an emulsion coating solution.

Structural formula A Structural formula B (3) Preparation of coating solution for surface protective layer of sensitive material layer 10 wt% aqueous gelatin solution (0.9 g/n (0.9 g/n) heated to 40°C
), polyacrylamide aqueous solution (molecular weight 40,000) (0,
1g/po), thickener polystyrene sulfonate sodium aqueous solution, capping agent polymethyl methacrylate (average particle size 2
．． A coating liquid was prepared by adding a hardening agent N, N'-ethylenebis-(vinylsulfonylacetamide), and a coating aid CCHtCOO-CHzCH-C4)1*(n).

(4) Preparation of back coating solution 1k of 10wt% gelatin aqueous solution heated to 40℃
g, thickener polystyrene sulfonate sodium aqueous solution, dye aqueous solution of structural formula C (5 x 10-z mol/j2) 50 c
c, hardener N, N'-ethylene bis-(vinylsulfonylacetamide) aqueous solution, coating aid CaHe CHzCOOCLCH-C-L(n) C) IcOOcLcI(-C,H,(n)50, Na
C2H4 was added to prepare a coating liquid.

Structural formula C (5) Preparation of coating solution for surface protective layer of back layer 10 wt% aqueous gelatin solution (Ig/rrf) heated to 40°C.
), an aqueous solution of sodium polystyrene sulfonate (20 μ/rrr) as a thickener, and methyl methacrylate-sodium styrene sulfonate (40 μ/rrr) as a matte.
(molar ratio 97:3), C as a coating aid,)Is CHzCOOCHzCH-CaI2(n)CHCOOC
HzCH-CaHe (b)SO, Na CJ.

(20 μ/f) and p-nonylphenoxybutylsulfonic acid sodium salt aqueous solution (2 μ/nf) were added.

Add and dissolve a predetermined amount of the compounds of Tables 11-2 to 1-5 as the compounds of the present invention to the solution of No. 2, add salts of metal ions shown in Tables 1-3 and 1-5, Dissolve,
Water was added to this to prepare a coating solution so that the gelatin content was 5 wt 96.

In addition, predetermined amounts of the compounds in Tables 11-6 to 1-10 were added and dissolved as comparative compounds, and in Table 1110, salts of metal ions shown in Table 1 were further added and dissolved, and water was added to make gelatin. A coating liquid was prepared so that the amount of 5 wt% was 5 wt%.

Table 11-1 is a control experiment without addition.

(6) Preparation of coating sample The above-mentioned back coating solution was coated on one side of a polyethylene terephthalate support together with the surface protective layer coating solution for the back layer so that the gelatin coating amount was 4 g/m. Subsequently, on the opposite side of the support, coat the emulsion coating solution containing the infrared sensitizing dye described in (2) and the surface protective layer coating solution so that the coated silver amount is 3.5 gyd. did. In addition, the amount of other additives added is as described above (g/m) or (■7
/rI ri. The obtained sample films were tested for static marks, image unevenness, fixer staining, and staining of the urethane lawn and nylon using the methods described below.
The number of spots on the coated sample was examined.

(7) The compositions of the developer and fixer are as follows.

<Developer> Potassium hydroxide 17g Sodium sulfite 60g Diethylenetriaminepentaacetic acid 2g Potassium carbonate
5g boric acid
3g hydroquinone
35g diethylene glycol 12g
4-hydroxymethyl-4-methylniphenyl-3-pyrazolidone
1. 65g5-methylbenzotriazole 0
．． 6g acetic acid 1.8g potassium bromide 2g Make II with water (adjust to pH 10.50) <Fixer> Ammonium thiosulfate 140g Sodium sulfite 15g Ethylenediaminetetraacetic acid disodium dihydrate 25■ Sodium hydroxide 6g Water to 11 (adjust to pH 4.95 with acetic acid).

The development process is as follows.

Processing temperature Time Development image 35℃ 11.5 seconds fixation
35℃ 12.5 seconds water washing 20℃
7.5 seconds drying 60℃ Dry to Dry processing time 60 seconds (8
) Static mark evaluation After conditioning an unexposed sample at 25°C, 110% RH for 2 hours, in a dark room under the same air conditioning conditions, evaluate the static mark on the sample against the material. In order to investigate this, the film was rubbed with a urethane rubber roller and a nylon rubber roller, and then developed using the method described above.

The degree of occurrence of static marks was evaluated in the following four stages.

A: No static marks were observed at all B:
＃ Slightly recognized C,
# # Considerably recognized D= # 〃 Observed almost on the entire surface (9) Image unevenness evaluation A sample film of 25 x 30 cm was irradiated with infrared light so that the image temperature after development became 1.5 using a Macbeth densitometer. The image was developed, fixed, washed, and dried as described above, and the unevenness on the image was evaluated on the following four scales.

8: No image unevenness observed at all.

B: # Slightly recognized.

C:　　　#　　Quite acceptable.

D=Image unevenness is observed over the entire surface.

0@ Fixer Contamination Evaluation 500 sheets of samples 25an x 30an, which had been exposed to infrared light to give a density of 1.5 using a Macbeth densitometer, were developed using newly prepared developer and fixer. The undissolved matter floating in the fixer was evaluated on the following four scales.

The replenishment amounts of the developer and fixer were 50 cc/sheet and 60 cc/sheet, respectively.

A: No floating matter observed B: 〃 Slightly observed C: 〃 Quite 〃 D: 〃 Severe 〃 Atsu Coating property evaluation Coating property evaluation is based on the number of particles on the emulsion layer side per square meter of film. Indicated. The larger the value, the worse the coating properties.

Comparison compound person C+ a H* *○+CH! CH,C)+rr-H
Comparative compound B (Mw = 2500) R, r 0 (CHaCHzO) *-CH- R, / 0 (C) 1 * CHtO) i (CdL) (C-] (,7
) Samples 2-I- using the compounds of the present invention as shown in Table 1
No. 5 had no static marks, no image unevenness, no fixer contamination, and had good coating properties.

On the other hand, sample knee 1 (control) did not contain the compound of the present invention, and therefore had poor static marks and image unevenness. Comparative samples I-6 and I-7 are samples containing a nonionic surfactant having a polyoxyethylene group, but are significantly inferior to the present invention in terms of image unevenness and fixer staining properties. Comparative samples I-8 to Nee-10 have similar structures to the compounds of the present invention, but are not as good as the present invention in terms of image unevenness and fixer staining properties.

As described above, the sample film prepared using the compound of the present invention satisfies all of the static marks, image unevenness, fixer staining property, and coatability, and it is clear that the present invention is superior. It is.

Example 2 (1) Preparation of tabular silver halide grains Potassium bromide, thioether 0to(CH,), 5(CH2), 5(CH,)
, OH) and gelatin were added and dissolved, and into the aqueous solution maintained at 70°C, a mixed solution of silver nitrate solution, potassium iodide, and potassium bromide was added by a double jet method while stirring.

After the addition was completed, the temperature was lowered to 35°C and soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C again and gelatin 60%
g was added and dissolved, and the pH was adjusted to 6.8. The obtained tabular silver halide grains had an average diameter of 1.24 μm, a thickness of 0.17 μm, an average diameter/thickness ratio of 7.3, and a silver iodide content of 3 mol %. Also, pAg at 40℃ is 8.9
It was 5.

This emulsion was chemically sensitized using gold and sulfur sensitization. The sensitizing dye anhydro-5,5'- is added to the solution after chemical sensitization.
Green sensitization was carried out by adding 500 µm of dichloro-9-ethyl-3,3' di(3-sulfoprobyl)oxacarbocyanine hydroxide sodium salt and 200 µm of potassium iodide per mole of silver. Additionally, 4-hydroxy-6-methyl-1+ as a stabilizer 3. 3a, ? -Tetrazaindene and 2,6-bis(hydroxyamino)-
4-diethylamino-1,3,5-)riazine, dextran with a weight average molecular weight (MW) of 40,000, and a latex solution of ethyl acrylate/acrylic acid (molar ratio 95:5) were added to form a coating solution for tabular emulsions. And so. The specific gravity of the coating solution is ]9]75, and the weight ratio of silver/gelatin is 1.
．． 30, and the dextran/gelatin weight ratio was 0.30.

(2) Preparation of coating solution for surface protective layer Gelatin, coating agent J- CH*C00CH-CH-C4H-(n)C)ICOO
CH* CH-CtL (n) JO, Na set hardener N, N'-ethylene bis-(vinylsulfonylacetamide), polyacrylamide with a weight average molecular weight (MW) of 8000, polymethyl methacrylate particles (average particle size 3. 5 μm) and adding a predetermined amount of Tables 22-2 to 2-5 as the compounds of the present invention shown in Table 2 to this solution,
Dissolve, further add and dissolve a prescribed amount of metal ion salts shown in Table 22-3.2-5, and add water to this to prepare a coating solution so that the gelatin content is 5 wt%. Buko.

In addition, as comparative compounds, prescribed amounts of compounds shown in Tables 22-6 to 2-10 are added and dissolved, and in Table 22-10, salts of metal ions shown in Table 2 are further added and dissolved, and water is added to this. A coating solution was prepared so that the gelatin content was 5 wt%.

Table 22-1 is a control experiment without addition.

(3) Method for producing photographic materials An emulsion layer and a surface protective layer are coated and dried in this order on an undercoated polyethylene terephthalate film support having a thickness of 180 μm by a simultaneous extrusion coating method, at which time the amount of coated silver is 2 0g/d, and the materials in the surface protective layer were O for gelatin and Bog/r for gelatin, respectively.
T! , coating agent C2H & CH2C00CH2C1 (-C,)1. (n)CHC
OOCH,CH-C,)Is(n)SOsNa
C2H& is 20■/r! ! , hardener is 40 x 7', polyacrylamide is 0.80 g/X1! The polymethyl methacrylate particles were coated at a ratio of 50 x 7/self.

The same layer structure was applied to the opposite side of the support.

The coating was done by extrusion and acid coating.

The obtained sample was tested in the same manner as in Example 1 for static marks, image unevenness, fixer staining, and coating spots. Development, fixing and washing were carried out in the same manner as in Example 1, except that 5 g of glutaraldehyde was added to the developer and 10 g of aluminum potassium sulfate was added to the fixer.

The results are shown in Table 2.

As is clear from the results in Table 2 above, only the compounds of the present invention satisfied all of the requirements for static marks, image unevenness, fixer staining, and coating properties.

(Effects of the Invention) As described above, according to the present invention, by adding the cyclic phosphazene compound represented by the general formula CI) as an antistatic agent to a photographic light-sensitive material, contamination of the developing processing solution does not occur. Furthermore, it is possible to provide an antistatic silver halide photographic material that does not cause image unevenness during development processing and has good coating performance.

Claims (2)

[Claims] (1) In a photographic material having at least one photosensitive silver halide emulsion layer on a support, a cyclic phosphazene compound represented by the following general formula [I] is added to at least one of the constituent layers of the photographic material. A silver halide photographic material comprising: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^4 may be the same or different and are an alkyl group, alkenyl group, alkynyl group, having 2 to 20 carbon atoms, Represents an aryl group. These substituents may be substituted with another substituent. R^2 and R^3 represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different. p and s represent integers from 0 to 50, and may be the same or different. However, p and s do not become 0 at the same time. q and r represent integers from 0 to 5, and may be the same or different. However, q and r do not become 0 at the same time. x represents 3 or 4. (2) In one layer of the constituent layers of the photosensitive material, the general formula [I
] and the periodic table of cyclic phosphazene compounds represented by
2. The silver halide photographic material according to claim 1, which contains a salt of a metal ion belonging to Group Ia or Group IIa.