JPH04349451A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the adhesiveness to a tacky adhesive tape and to lessen the generation of unequal drying in spite of rapid processing with an automatic developing machine by incorporating a fluorine-contained surfactant having a sulfonic acid group and a fluorine-contained surfactant having a carboxyl group into the uppermost layer. CONSTITUTION:This photosensitive material contains the compd. expressed by formula I and the compd. expressed by formula II in the uppermost layer on the side having silver halide emulsion layers. In the formula I, Rf denotes a partially fluorinated or completely fluorinated substd. or unsubstd. alkyl group, alkenyl group or aryl group contg. 3 pieces of fluorine atoms. A denotes a bivalent combination group or alkyl group, aryl group and akylaryl group, which may be a bivalent substd. or unsubstd. combination group interrupted by heteroatoms, such as oxygen, ester group, amide group, sulfonyl group, and sulfur. M denotes a hydrogen atom, inorg. or org. cation. In the, formula II, Rf, A, n, and M are similar to those of the formula I.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material (hereinafter referred to as "sensitized material") that has excellent adhesion to adhesive tapes.

0002

[Prior Art] When developing a black and white negative photosensitive material for photography using a roller conveyance type automatic processor (hereinafter referred to as an automatic processor), one end of a thin and strong plastic plate such as polyethylene, generally called a leader, is One tip of the photosensitive material is joined with adhesive tape, and the photosensitive material is passed through an automatic processing machine with the leader at the beginning. In this case, if the adhesiveness between the photosensitive material and the adhesive tape is weak, the photosensitive material and the adhesive tape will peel off during the development process, leading to serious failures such as the photosensitive material wrapping around the rollers of the automatic processing machine. In addition, developer solution soaks into the space between the photosensitive material and the adhesive tape, and the soaked developer solution is squeezed out by a so-called crossover roller between the developer tank and fixer tank in the automatic processing machine, and the crossover occurs. It adheres unevenly to the roller, causing malfunctions such as uneven development.

On the other hand, nonionic surfactants are used in black-and-white negative photosensitive materials in order to improve drying unevenness that occurs during development processing using an automatic processor. A problem has arisen in that the adhesion with the material further deteriorates.

0004

SUMMARY OF THE INVENTION A first object of the present invention is to provide a photosensitive material that has excellent bonding properties with adhesive tapes. A second object of the present invention is to provide a photosensitive material that exhibits less uneven drying due to automatic processing and has excellent bonding properties with adhesive tapes.

[0005]

[Means for Solving the Problems] These objects of the present invention are directed to a light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a support. contains a compound represented by the following general formula (I) and a compound represented by the general formula (II) in the uppermost layer of the photographic constituent layer on the side having the silver halide emulsion layer. ) This was achieved by incorporating a glycerol group. General formula (I)

[0006]

[Chemical formula 3]

General formula (II)

[0008]

[C4]

General formula (I) and general formula (II) of the present invention
Specific examples of the compound represented by are shown below, but the invention is not limited thereto.

0010

[C5]

[0011]

[C6]

The compounds represented by formulas (I) and (II) of the present invention are added to at least one of the silver halide emulsion layers or other constituent layers of the sensitive material. The other constituent layers are preferably hydrophilic colloid layers. A particularly preferable addition site is the surface protective layer. or,
It can also be used as an overcoat on the surface protective layer. The amounts of the compounds represented by the general formulas (I) and (II) of the present invention are as follows:
It is preferable that 0.0001 to 0.2g is present, especially 0.0001 to 0.2g.
．． 0005-0.05g is desirable. General formula of the present invention (
Two or more of each of the compounds represented by I) and (II) may be mixed. In the present invention, it is preferable to use a surfactant having a (poly)glycerol group together with the compounds represented by general formulas (I) and (II). The (poly)glycerol group-containing surfactant used in the present invention is represented by general formulas (III) and (IV).

[0013]

[C7]

[0014] In the formula, A represents a necessary hydrophobic group exhibiting surface-active ability, specifically an alkyl group, an alkenyl group (
preferably 6 to 12 carbon atoms) and an aralkyl group (preferably 9 to 24 carbon atoms). X represents a divalent or trivalent linking group, specifically

[0015]

[Chemical formula 8]

Alternatively, these linking groups further contain an alkylene oxide chain. n is 2-50, preferably 2-20. B represents hydrogen, an alkyl group (preferably having 1 to 8 carbon atoms), a phenyl group, or a monovalent group having an anionic group, and also represents these groups via an alkylene oxide chain. R1, R of general formula (IV)
2 represents an alkyl group, and R2 represents an alkyl group, preferably R1 has 6 to 18 carbon atoms, and R2 has 1 to 6 carbon atoms. m is 2-50. Also, the general formula (
III) n The alkyl group of nA, the aralkyl group, and the phenyl group of general formula (IV) may be further substituted. A
As a preferable specific example,

[0017]

[Chemical formula 9]

[0018] etc. As a preferable specific example of B,

[0019]

[Chemical formula 10]

[0020] etc. Next, specific examples of the surfactant having a (poly)glycerol group used in the present invention will be shown, but the invention is not limited thereto.

[0021]

[Chemical formula 11]

[0022]

[Chemical formula 12]

[0023]

[Chemical formula 13]

[0024]

[Chemical formula 14]

General formulas (III) and (IV) of the present invention
The compound represented by is added to at least one of the silver halide emulsion layers or other constituent layers of the photographic light-sensitive material. 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 and back layer. When the surface protective layer or back layer consists of two layers, either layer may be used, or it may be used by further overcoating the surface protective layer. General formula (II) used in the present invention
When applying the compounds represented by I) and (IV) to photographic materials, they are dissolved in water or an organic solvent such as methanol, isopropanol, acetone, or a mixed solvent thereof, and then a surface protective layer or back layer is applied. It is added to a liquid and applied by dip coating, air knife coating, spraying, or exclusion coating using a hopper as described in U.S. Pat. No. 2,681,294.
U.S. Patent Nos. 3,508,947 and 2,941,89
No. 8, No. 3,526,528, two or more layers may be applied simultaneously, or immersed in an antistatic liquid. Further, if necessary, an antistatic liquid (solution alone or containing a binder) containing the compound of the present invention is further coated on the protective layer. General formula (III) of the present invention
The amount of each of the compounds represented by (IV) and (IV) used is 0.0001 to 2.0% per square meter of the photographic material.
It is preferable that 0g is present, especially 0.0005 to 0.3g.
is desirable. General formulas (III) and (IV) of the present invention
Two or more types of each of the compounds represented by these may be mixed.

Silver halides in the photosensitive silver halide emulsion used in the present invention include silver chloride, silver chlorobromide, silver bromide,
Silver iodobromide and silver chloroiodobromide can be used, but silver iodobromide is preferably used. Here, the content of silver iodide is preferably 30 mol% or less, particularly preferably 15 mol% or less. The distribution of iodine in the silver iodobromide grains may be uniform or may be different between the inside and the surface. The average particle size is preferably 0.4 μm or more. In particular, it is preferably 0.5 to 2.0 μm. The particle size distribution may be narrow or wide.

The silver halide grains in the emulsion have regular shapes such as cubes, octahedrons, tetradecahedrons, and rhombic dodecahedrons.
ar) crystal shape, or may have an irregular crystal shape such as spherical, plate-like, potato-like, etc.
ar) It may consist of a mixture of particles of various crystalline forms, which may have a crystalline form or a composite form of these crystalline forms. Further, the particles may be tabular grains having a particle diameter of 5 times or more the particle thickness. Further, among tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The structure and manufacturing method of the monodispersed hexagonal tabular grains referred to in the present invention are as described in JP-A-63-151618, but briefly, the emulsion is composed of a dispersion medium and silver halide grains. A silver emulsion in which 70% or more of the total projected area of the silver halide grains has a ratio of the length of the side with the maximum length to the length of the side with the minimum length of 2 or less. It is occupied by tabular silver halide grains that are hexagonal and have two parallel surfaces as outer surfaces, and furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains is Variation in particle size expressed in circular diameter (standard deviation)
divided by the average particle size] has a monodispersity of 20% or less. Although the crystal structure may be uniform, it is preferable that the inside and outside have different halogen compositions, and may have a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

The silver halide grains can be produced by nucleation, Oswald ripening and grain growth, the details of which are described in Japanese Patent Application No. 61-299155. Furthermore, the silver halide grains used in the present invention are
A core/shell type shallow latent type emulsion may be formed using the hexagonal tabular grain as a core, and then used. In this case, regarding the chemical sensitization method of the core, the method of attaching the shell, and development with a developer containing a silver halide solvent, JP-A-59
-133542 and British Patent No. 145816. The thickness of the shell in this case is
1 to 100 lattices, preferably 5 to 50 lattices are preferred.

The hexagonal tabular grains used in the present invention may have internal dislocation lines. The presence or absence of dislocation lines and their number can be determined by observing with a low temperature (liquid He temperature) transmission electron microscope. Hexagonal tabular grains containing dislocation lines are formed by adding iodide salt during the crystal growth period of the hexagonal tabular grains or using the hexagonal tabular grains as seed crystals and adding iodide salt during a certain period of the crystal growth period when the crystals are further grown. can do. In this case, a certain period refers to the entire crystal growth period from an instant (approximately 1/2 second). The rate of addition of the iodide salt is such that the iodide salt is added when the difference between the iodine content of the silver iodobromide which is piled up by the addition and the iodine content of the silver iodobromide of the substrate is 5 mol % or more.

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsion. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. A light-sensitive emulsion may be mixed with a substantially non-light-sensitive emulsion (which may or may not be covered on the surface or inside), or may be separated into separate layers (see details for details). is U.S. Patent No. 2,996,382
No. 3,397,987, etc.). For example, a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more than the grain thickness may be placed in the same layer or
It may be used in different layers as described in Japanese Patent No. 21. When used in different layers, the photosensitive silver halide emulsion consisting of tabular grains may be located on the side closer to the support or, conversely, on the side farther away.

The photographic emulsion used in the present invention is P. Gl
Chemie et Physiqu by afkides
e Photographique (Paul Mon
Tel Publishing, 1967), G. F. Photographic Emulsion Ch by Dullin
emistry (published by the Focal Press,
(1966), V. L. Zelikman et a.
Written by Making and Coating Photo
graphic emulsion chemist
y (published by The Focal Press, 1964) JP-A-58-127921 and JP-A-58-1139
It can be prepared using the method described in Publication No. 26 and the like. That is, any of the acidic method, neutral method, ammonium method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. A method of forming silver halide grains under excess silver ions (
It is also possible to use the so-called back-mixing method. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, it is easy to obtain a silver halide emulsion consisting of silver halide grains with a regular crystal shape and a nearly uniform grain size.

Even if the crystal structure of silver halide grains is uniform to the inside, there are also grains with a layered structure with different interior and exterior structures, as well as those in British Patent No. 635,841 and US Patent No. 3.
, 622, 318, or may be of the so-called conversion type, or silver halides of different compositions may be bonded by epitaxial bonding. It may be bonded with a compound other than silver halide or a compound other than silver compound. Further, either a surface latent image type or an internal latent image type may be used. Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. coexist in the process of silver halide grain formation or physical ripening during silver halide production. You may let them. Further, during grain formation, grain growth may be controlled by adding a so-called silver halide solvent such as ammonia, thioether compound, thiazolidine-2-thione, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, or amine compound.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As a method for chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and noble metal sensitization may be used, and these may be used alone or in combination. Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiosoles, and rhodanines can be used. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention may 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 {e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.}; mercapto compounds {e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.; Compounds; azaindenes {e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.}; benzenethiosulfonic acid, benzenesulfine Many compounds known as antifoggants or stabilizers can be added, such as acids, benzenesulfonamides, etc.

Specifically, RESEARCH DISC
LOSURE Item 17643 VI Item (19
December 1978 issue p. 24-p. 25) is described in or cited in the literature. Especially in the 1980s
-76743, nitrone and its derivatives described in JP-A No. 60-87322, mercapto compounds described in JP-A-60-80839, JP-A-57-164735
The heterocyclic compound and the complex salt of a heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole silver) described in the above publication can be preferably used.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As a sensitizing dye,
Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholic cyanine dye, styryl dye, hemicyanine dye,
Oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Ite.
m 17643 Section VI-A (December 1978, p.
．． 23), Item 1831 Section X (1979
August, p. 437) or in the literature cited. The sensitizing dye can be used at any stage of the photographic emulsion manufacturing process, or at any stage after manufacturing until immediately before coating. Examples of the former include silver halide grain formation step;
These include physical ripening process, chemical ripening process, etc.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration). Various surfactants other than the compounds represented by formulas (I), (II) and (III) may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. 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 sorbidan esters, polyalkylene Nonionic interfaces such as glycolalkylamines 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. Activator; alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinate, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphate esters; Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betainates, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Cationic surfactants such as heterocyclic quaternary ammonium salts such as phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, persalt salts, sulfates, acetates, phosphates, and thiocyanates. Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 118242, etc., can be preferably used.

In the present invention, as matting agents, homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium,
Fine particles of an inorganic compound such as barium can be used. The particle size is 1.0 to 10 μm, especially 2 to 5 μm.
It is preferable that it is m.

The surface layer of the photographic light-sensitive material of the present invention contains as a slipping agent US Pat. Nos. 3,489,576 and 4,047.
, No. 958, etc.;
In addition to the colloidal silica described in JP 23139, paraffin wax, higher fatty acid esters, and starch derivatives can be used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, a styrene-butadiene copolymer, and a polymer or copolymer consisting of a monomer having an active methylene group can be preferably used.

The photographic emulsions and non-light-sensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (1,3,5-triacryloyl-hexahydro-s -triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-
[β-(vinylsulfonyl)propionamide], etc.)
, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids, etc. can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, JP-A-5
Preferred are the active vinyl compounds described in US Pat. No. 9-162,546 and US Pat. No. 60-80,846 and the active halogen compounds described in US Pat.

When the photosensitive material of the present invention is used as an X-ray photosensitive material, the hydrophilic colloid layer is hardened with these hardening agents so that the swelling ratio in water is 200% or less, particularly 150% or less. Preferably. As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the 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; sodium alginate; polyvinyl alcohol, polyvinyl alcohol partial acetal, and A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of -N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and hydrolysates of gelatin may also be used.

In addition to the light-sensitive silver halide emulsion layer, the silver halide photographic material of the present invention may have non-light-sensitive layers such as a surface protective layer, an intermediate layer, and an antihalation layer. There may be two or more silver halide emulsion layers, and the two or more silver halide emulsion layers may have different sensitivities, gradations, etc. Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

Cellulose triacetate film is preferred as a support for general light-sensitive materials, and may be colored or uncolored for antihalation purposes. Also preferably used is a support made of a sheet of baryta paper, synthetic paper, paper, etc. whose both sides are covered with a polymer film. The support for X-ray photography is preferably a polyethylene terephthalate film or a cellulose triacetate film, and is particularly preferably colored blue. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment, or is made of styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer. Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

For photographic processing of the light-sensitive material of the present invention, for example, research disclosure
ISCIOSURE) No. 176, pages 28-30 (RD-
Any of the known methods and known treatment liquids, such as those described in 17643), can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.

For example, the developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. may be used alone or in combination. It can be used as The photographic processing of the light-sensitive material of the present invention can also be carried out using a developer containing imidazoles as a silver halide solvent as described in JP-A-57-78535. Also, JP-A-58-376
It can be processed with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in No. 43. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc.
Furthermore, it may contain a solubilizing agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent (for example, glutaraldehyde), a viscosity imparting agent, etc., if necessary. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

[0046]

[Example] The present invention will be illustrated by giving examples below.
The present invention is not limited to this. Example 1 Preparation of amorphous (twinned plate) silver halide emulsion In 1 liter of water, 25 g of potassium bromide, 24 g of potassium iodide,
While maintaining the temperature of a container containing 1.9 g of potassium thiocyanate and 24 g of gelatin at 60°C and stirring vigorously, a silver nitrate aqueous solution and a potassium bromide aqueous solution were added using the usual ammonia method and a potassium bromide aqueous solution using the double jet method. Finally, a relatively amorphous thick plate-like silver iodobromide emulsion with an iodine content of 8 mol % and an average grain size of 1.0 μm was prepared. Soluble salts were removed by conventional sedimentation and 83 g of gelatin was added. After this, 230 mg/mol Ag of dye (a) and 5.4 g of a 35% methanol solution of phenoxyethanol were added, followed by chemical sensitization using sodium thiosulfate and chloroauric acid to make photosensitive silver iodobromide. Emulsion (A) was obtained. Same as emulsion (A), except that the amount of potassium iodide in the initial solution was 18 g, the temperature was 40°C, and the iodine content was 6 mol%.
A photosensitive silver iodobromide emulsion (B) having an average grain size of 0.6 μm was obtained. Furthermore, a photosensitive silver iodobromide emulsion (C) was obtained in the same manner as emulsion (B), but without chemical sensitization. Pigment (a):

[0047]

[Chemical formula 15]

Preparation of Coated Samples Coated samples 1 to 13 were prepared by coating the following layers on a cellulose triacetate support which had been subbed on both sides in advance. (Back side) Bottom layer gelatin

0.45g/m2

[0049]

[Chemical formula 16]

2nd layer gelatin

5g/m2

[0051]

[Chemical formula 17]

Top layer (surface protective layer) Gelatin

0.7g/m2 Polymethyl methacrylate fine particles (average particle size 3μm)
35mg/m2 Polypotassium-p-vinylbenzenesulfonate 51m
g/m2 Bis-(vinylsulfonylacetamido)ethane 470mg/m2
C8 F17SO3 K

6mg/m2

[0053]

[Chemical formula 18]

(Side having emulsion layer) First layer (emulsion layer) Emulsion (C) was used. Ag amount

0.8g/m2 gelatin

1.1g/m2 polyethylene glycol (average molecular weight 1000)
4mg/m2 4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene
8.5mg/m2
Polypotassium-p-vinylbenzenesulfonate 17mg/m2

[0055]

[Chemical formula 19]

Second layer (emulsion layer) Emulsion (B) was used. Ag amount

1.4g/m2 gelatin

2
g/m2 Polyethylene glycol (average molecular weight 1000) 7mg/
m2 4-hydroxy-6-methyl-1,3,3
a,7-tetrazaindene

15mg/m2 polypotassium-p-vinylbenzenesulfonate
50mg/m2

[0057]

[C20]

Third layer (emulsion layer) Emulsion (A) was used. Ag amount

4.5g/m2 gelatin

8.3g/
m2 Polyethylene glycol (average molecular weight 10
00) 27mg/m2
4-hydroxy-6-methyl-1,3,3a,7
− Tetrazaindene

45mg/m2 CH3 CH2 C
(CH2OH)3
210mg/m2 Polypotassium-p-vinylbenzenesulfonate
63mg/m2 Top layer (surface protective layer) Gelatin

0.9g/m2 Polymethyl metaglycol fine particles (average particle size 2μm)
24mg/m2 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene

15mg/m2
Polypotassium-p-vinylbenzene sulfonate
6mg/m2

[0059]

[C21]

and the compounds listed in Table 1

[0061]
Evaluation of Coated Samples After storing the coated samples at a temperature and humidity of 25° C. and 60% RH for 7 days, the following evaluations were performed.

Evaluation of static marks After the coated sample was left at a temperature and humidity of 25°C and 10%RH for 2 hours,
A nylon rod and a rotatable rubber roller were attached to the coating sample for 30 minutes.
After rubbing at a speed of 1 m/sec while pressing at a pressure of 0 g/cm2, development was performed, and the frequency of static marks was evaluated. The evaluation of static marks was based on the following five-level criteria. A: No static marks were observed. B: Some static marks occur. C: Static marks occur considerably. D: Significant static marks occur. E: Static marks appear on the entire surface.

Evaluation of adhesion with adhesive tape: 6 coated samples
Process the sample to a size of 1 mm x 850 mm, overlap one short end of the sample with the leader, and use registered trademark Scotch photographic splice tape #250 with a width of 25 mm to adhere the emulsion layer side of the coated sample to the leader. did. With the leader at the top, development was performed using a roller conveyance type automatic processor. The processing conditions are as follows. Treatment Treatment liquid Treatment temperature
Processing time Development
HPD 26
．． 5℃ 2 minutes Fixation Super Fuji Fix DPII 26.5℃
2 minutes wash with water
flowing water
Dry at 15℃ for 3 minutes
−
50℃
Both 2-minute HPD and Super Fuji Fix DPII are manufactured by Fuji Photo Film Co., Ltd. After processing, the length of the part where the developer had penetrated between the sample and the adhesive tape was measured. 1
The experiment was performed 0 times and the average length was taken.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[C22]

[0067] As is clear from Table 1, among the fluorine-containing surfactants, only the combination of the present invention has improved adhesion to adhesive tapes and also produces fewer static marks. .

Example 2 Coated samples 14 to 19 were prepared in the same manner as in Example 1, except that the compounds added to the surface protective layer were changed as shown in Table 2.
It was created. Adhesiveness to the static mark and adhesive tape was evaluated in the same manner as in Example 1, and water droplet unevenness was further evaluated in the following manner. Evaluation of water droplet unevenness Under the same processing conditions as in the adhesion test with adhesive tape in Example 1, 30 sheets of each sample were developed in succession, and the condition of unevenness after processing of the 30th sample was visually observed. evaluated. ○ No uneven water droplets are observed. △ Some water droplet unevenness is observed. × Significant uneven water droplets are observed. The results are summarized in Table 2.

[0069]

[Table 3]

As is clear from Table 2, Samples 16 to 18 of the present invention do not produce static marks, have good adhesion to adhesive tapes, and have small uneven water droplets.

Claims (2)

[Claims] Claim 1: In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support, the uppermost layer on the side having the silver halide emulsion layer has the following general formula: Compounds represented by (I) and general formula (I
A silver halide photographic material containing a compound represented by I). General formula (I) [Formula 1] General formula (II) [Formula 2] 2. A claim characterized in that at least one of the photographic constituent layers on the side having the silver halide emulsion layer of the silver halide photographic light-sensitive material contains a surfactant having a (poly)glycerol group. 1. The silver halide photographic material described in 1.