JPH06258762A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which has no trouble of roller mark and grazing fault causing at the time of development processing of the silver halide photographic sensitive material, is high in sensitivity and has high covering power. CONSTITUTION:In the silver halide photographic sensitive material, a silver halide emulsion layer is incorporated with the plane table like silver halide particles having >=2 average aspect ratio, and the photosensitive material is incorporated with the compd. expressed by the general formula, further, the polymer particles of the photosensitive material covered with gelatin by covalent bond and the gelatin layer of the photosensitive material is bonded by covalent bond. In the formula, each of A1 and A2 is the group having >=2 valency formed by being bonded along or plural group selected from among an aliphat., an arom. and a heterocyclic ring. Each of R1, R2 and R3 is hydrogen atom or an alkyl group and may be the same or different with each other. M is hydrogen atom, an alkali metal atom or ammonium group. Z is an inorg. acid or an org. acid, (n) is 1 or 2.

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 having high sensitivity and excellent covering power, which prevents roller marks and scratches from being generated during development or handling of the silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, a photosensitive material is easily subjected to mechanical stress such as pulling or bending when it is loaded into a cassette, a camera or the like, including cutting and processing.

Particularly, since sheet-shaped photosensitive materials such as X-ray films and printing films are often handled directly by hand, there are many chances of pressure on the films and scratches are apt to occur. Further, during development processing, roller conveyance of an automatic developing machine is apt to cause fog failures called roller marks.

It is well known that mechanical stress on silver halide grains causes pressure fog or pressure desensitization. Since such an unfavorable phenomenon also causes a misdiagnosis in the case of an X-ray film, for example, its prevention is considered to be extremely important.

A number of techniques have been proposed as methods for preventing the sensitivity of photographic light-sensitive materials to external pressure. For example, JP-A 61-255337 or JP-A 61-255337 using a binder component such as latex polymer has been proposed. U.S. Pat.
No. 13583 is disclosed.

It is also well known to use a matting agent such as polymer beads in order to prevent the films from sticking to each other and to prevent static marks and scratches due to peeling charging.

However, all of the above-mentioned conventional techniques have a problem that the preventive effect is insufficient, and it is difficult to improve particularly when the silver halide grains are tabular silver halide emulsions having high sensitivity and high covering power. .

[0008]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to prevent roller marks and scratches that may occur during development or handling when a tabular silver halide emulsion is used, and to provide high sensitivity and covering power. To provide an excellent silver halide photographic light-sensitive material.

[0009]

The above problems have been solved by the present invention described below. That is, in a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on at least one side of a support, the silver halide emulsion layer is a tabular halogen having an average aspect ratio of 2 or more. Polymer particles containing silver halide grains and containing at least one of the compounds represented by the following general formula [1], wherein the photosensitive material is covered with gelatin by covalent bonds:
A silver halide photographic light-sensitive material characterized by being covalently bonded to a gelatin layer of the light-sensitive material.

[0010]

[Chemical 2]

In the formula, A ₁ and A ₂ each represent a divalent or higher valent group formed by a single or a plurality of groups selected from an aliphatic group, an aromatic group and a heterocyclic group, and R ₁ , R ₂ and And R ₃ ,
R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group, Z represents an inorganic acid or an organic acid, and n represents 1 or 2.

The present invention will be described in detail below.

In the formula [1], the aliphatic group represented by A ₁ or A ₂ is a divalent or higher valent residue derived from a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, It has 1 to 20 carbon atoms, and preferably 1 to 10. Specific examples of such groups include residues derived from ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl groups and the like. Examples of the aromatic group include a divalent or higher valent residue derived from a monocyclic or bicyclic aryl group, for example, a residue derived from a phenyl group, a naphthyl group or the like and having 6 to 20 carbon atoms.
And preferably 6-10. A divalent or higher valent residue derived from a benzyl group is also preferred.

Examples of the heterocyclic group include a saturated or unsaturated divalent or higher valent heterocyclic group having a 3- to 10-membered ring containing at least one of nitrogen, oxygen and sulfur atoms, which may be a monocyclic ring. May form a condensed ring with an aromatic ring or a heterocycle. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group, and is derived from, for example, a pyridyl group, an imidazolyl group, a triazolyl group, a pyrazolyl group, or a pyrimidyl group.
It is a residue having a valency or higher. The alkyl group of R _{1 to} R ₄ may be linear, branched or cyclic and has 1 to 6 carbon atoms.
Are preferred. Further, this alkyl group may be substituted, for example, alkoxy, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen atom, cyano, sulfo. , Acyl, carboxyl, phosphoric acid amide, phosphono group and the like.
R _{1 to} R ₄ may be the same or different.

Examples of the alkali metal atom represented by M include sodium and potassium atoms, and examples of the ammonium group include trimethylammonium and dimethylbenzylammonium groups.

In the general formula [1], A ₁ and A ₂ are preferably divalent or higher-valent residues derived from an alkyl group, and R _{1 to} R ₄ are preferably alkyl groups.

The inorganic and organic acids represented by Z are, for example, hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, p-
Toluenesulfonic acid, oxalic acid and the like can be mentioned, with hydrochloric acid being particularly preferred.

Specific examples of the compound represented by the general formula [1] of the present invention are shown below, but the present invention is not limited thereto.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

Next, the polymer particles of the present invention will be described.

The polymer particles referred to in the present invention are polymer particles in which each polymer particle is covered with gelatin, and the polymer particles and gelatin are covalently bonded.

Polymer particles useful in the present invention include:
Included are any polymers to which gelatin can be covalently bonded, either directly or through a crosslinking agent. Monomers with which the polymer or copolymer is covalently bonded to gelatin include the following compounds.

Monomers containing active halogen atoms such as vinyl chloroacetate, halogenated aromatic vinyls (eg,
Chloromethyl styrene), chloroalkyl acrylic acid or methacrylic acid ester (eg, chloroethyl methacrylate, 3-chloro-2-hydroxypropyl-methacrylate, or chloroethyl acrylate), isocyanate (eg, isocyanate ethyl acrylate,
Isocyanate ethyl methacrylate, or α, α-
Dimethyl metaisopropenyl benzyl isocyanate), epoxides (eg glycidyl acrylate or glycidyl methacrylate), and compounds containing aldehyde groups (eg vinyl benzoate and acrolein), and monomers containing chloroethyl sulfone groups (chloroethylsulfonylmethylstyrene and Vinylsulfonylmethylstyrene), which are described in US Pat. No. 4,161,407.

Monomers whose polymers and copolymers can be covalently bound to gelatin by the use of cross-linking agents include carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, and maleic acid or maleic anhydride), amine-containing monomers (eg , 2-aminoethyl methacrylate and N- (3-aminopropyl) methacrylamide hydrochloride), and monomers containing active methrene groups (eg, 2-
Acetoacetoxyethyl methacrylate, and diacetone acrylamide).

Polymers particularly useful in the present invention are from monomer-bonded polymers or copolymers in which at least 0.1 mol%, and more preferably at least 1 mol% of the monomer can be covalently bonded to gelatin either directly or via a cross-linking agent. Become.

In one aspect of the invention, useful polymers are represented by the general formula:

-(A) _x- (B) _{100-x-wherein} A represents a repeating unit derived from one or more of the above monomers capable of covalently bonding to gelatin, and B represents one or more ethylene. The repeating units resulting from associatively unsaturated monomers are shown.

The monomer represented by B includes virtually any monomer capable of covalently bonding with gelatin and copolymerizable with the above-mentioned monomer. Examples of such monomers include styrene and ethylenically unsaturated monomers such as styrene derivatives (eg, vinyltoluene, vinylbenzene, divinylbenzene, 4-t-butylstyrene, and 2-chloromethylstyrene), and acrylic acid and Methacrylic acid ester (eg, methyl methacrylate, methyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-
Ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethylene dimethacrylate, methacrylamide, and acrylonitrile). In such copolymers, the amount of copolymer capable of covalently bonding with gelatin should be sufficient to bond the contact layer of gelatin to the surface of the polymer particles.

In the above formula, x represents 0.1 to 100 mol, preferably 1 to 20 mol.

The polymer particles of the present invention can be of any size or shape, depending on the intended use.

The average diameter of the particles used is 1 to 15 μ
A range of m is preferred. Particles with an average diameter of 4 to 8 μm
Particularly preferred. The average diameter of particles is defined as the diameter of spherical particles of the same mass. In some embodiments of the invention, beaded polymer particles having a diameter in the above range may be preferred.

Next, a method for preparing polymer particles will be described.

The polymer particles of the present invention can be prepared by techniques well known in the art, such as polymerization (followed by milling or polishing to obtain a desired particle size) or direct stable dispersion of a particularly preferred particle size. It can be prepared by an emulsion or suspension polymerization method obtained as a liquid. According to emulsion polymerization, 0.01 to 5 μm (preferably 0.1 to 5 μm) is obtained as a stable water-soluble dispersion that can be directly coated without separation.
A particle size of 2.5 μm) can be formed. Particles of larger size (eg, greater than 3 μm) are often prepared by suspension polymerizing in an organic solvent system to isolate the particles and then resuspending in water as the most economical coating method, or US Pat. Most preferred is the preparation by the "marginal fusion" method taught in 3,614,972. Bulk, emulsion and suspension polymerization methods are well known to those skilled in the field of polymerization chemistry, for example, "Prepar
"Methods of Polymer Chemistry", Second Edition, and "Polymer Chemistry-An Introduction", Addison W
It is described in textbooks such as esley publication (1975).

The polymer particles can be covalently bound to gelatin by simply contacting the particles with gelatin under the following conditions, provided that the polymer is of the above-mentioned type capable of directly polymerizing with gelatin.

If the polymer is of a type that uses a cross-linking agent to bind to gelatin, it is first contacted with the cross-linking agent and then with gelatin, and instead of gelatin-gelatin cross-linking formation, gelatin forms polymer particles. It is preferable to react selectively. In the practice of the present invention, it is beneficial to use a pyridinium carbamoyl crosslinker because the crosslinker first binds to carboxyl groups on the polymer particles and subsequently to amino groups on gelatin molecules. is there.

The contact between the polymer particles and gelatin is preferably carried out in an aqueous dispersion of particles. The polymer particle concentration in the aqueous dispersion is preferably less than 25% by weight, particularly preferably 15% by weight, and the gelatin concentration in the same liquid is also the same.

The pH of the aqueous dispersion and the concentration of particles and gelatin should be adjusted to prevent crosslinking or agglomeration of gelatin molecules between polymer particles. The pH of gelatin is preferably maintained at its isoelectric point or above (for example, 5.8 or above, especially 8 to 10 for lime-treated bone gelatin). Under such conditions,
Both particles and gelatin should have the same charge (especially negative charge) to minimize aggregation.

Polymer particles having covalently bound gelatin, or "gel-grafted polymer particles," are generally known to be useful as matting agents in photographic elements, but in accordance with the present invention. It was found that it was extremely effective in preventing scratches on the film.

The polymers of the present invention provide the size, hardness and inertness necessary to effectively function against scratches, while the gelatin shell allows the particles to crosslink with the gelatin layer of the composition. Is not spilled during processing.

When used as a cross-linking agent, the gel of the present invention
-The grafted polymer particles can be cross-linked with another gelatin in which gelatin is covalently bonded to the particles and can be applied anywhere in the photographic element.

The polymer particles of the present invention are incorporated in the outermost layer of the photographic element, the overcoat layer, or in the lower layer, such as an emulsion layer.

In a preferred embodiment of the present invention gel-
Graft polymer particles are utilized on the outermost surface of the photographic element, as shown in FIG.

In the element of FIG. 1, there is a support 1 on which is located a gelatin-containing layer 2, which may be, for example, a silver halide emulsion layer. Overlying layer 2 are polymer particles 4, with gelatin 3 covalently bound to the outside. Gelatin 4 is cross-linked to gelatin in layer 2. In a further preferred embodiment of the invention, the photographic element as shown in FIG. 1 comprises a gelatin-containing layer on a support to form a crosslink between gelatin in the layer and gelatin covalently bound to polymer particles. Coating, at least partially drying the layer, gel on the surface of the layer
It is prepared by coating the graft polymer particles and hardening the gelatin in the layer.

Gelatin-containing layers and other layers in the element can be flow coated, roller coated, bead coated, knife coated,
It can be applied by any known coating method such as gravure coating or reverse gravure coating. In general, the layer can be dried by simple evaporation by known methods such as convection heating to accelerate the layer formation.

Known coating and drying methods are described in detail, for example, in Research Disclosure (RD) No. 17643. Also, the polymer particles can be coated on the surface of the gelatin-containing layer by various methods such as air jet or dripping.

The method of applying polymer particles to the gelatin-containing layer is to coat the gelatin-containing layer with a dispersion liquid of particles dissolved in a liquid solvent such as an organic solvent or water. The liquid medium contains a small amount of gelatin (for example,
It may optionally contain the same weight concentration dimension as the polymer particles, in particular less than 25%, based on the total amount of the dispersion. If the coating dispersion is such, the ratio of polymer particles to liquid is usually 1:99 to 5:95.

The gelatin in the gelatin-containing layer and the gelatin covalently bonded to the polymer particles can be cross-linked by using any of the compounds known as a cross-linking agent, or a hardening agent or a gelling agent. These include, for example, free dialdehydes, sulfonates, active esters, epoxides, aziridines, block-active olefins, carbodiimides, carbamoylpyridinium, vinyl sulfones, dialdehyde starches or polymer hardeners such as poly (acrolein-methacrylic acid). Is mentioned. Crosslinking is usually accomplished by simply applying a solution of the above curing agents to the photographic element.

The cross-linking agent can be applied to the grain or gelatin-containing layer. It should be noted that when such particles come into contact with a layer, if such contact occurs while there is sufficient residual cross-linking agent to cross-link the gelatin on the gelatin layer on the particle with the gelatin in the layer, the particles will be Apply before contact with layers. Also,
The cross-linking agent can also be applied after the particles have come into contact with the gelatin-containing layer. For a detailed disclosure of cross-linking hardeners, see
Found in (RD) No. 17643 above.

The amount of the gelatin-grafted polymer particles used in the present invention is preferably 0.01 g to 1.0 g / m ² , particularly 0.05
The range from g to 0.2 g / m ² is preferred.

The gelatin layer covalently bonded to the polymer particles may be any type of gelatin well known in the photographic art. For example, alkali-treated gelatin
(Pig skin or bone gelatin) and gelatin derivatives such as partially phthalated gelatin and acetylated gelatin, and others. Gelatin may be hardened according to well known techniques and may be crosslinked by the use of common crosslinkers.

The size of the gelatin layer may vary depending on the conditions under which it is covalently bonded to the polymer particles, but is usually 20 to 60 nm in the hydrated state and 2 to 6 nm in the dried state.

The covalently bonded polymer grains according to the present invention may be used in a hydrophilic colloid layer such as a silver halide emulsion layer, the same protective layer and an intermediate layer, and a protective layer on the emulsion layer is particularly preferable. The gelatin layer containing the polymer particles may contain, as a binder, a known binder material described in JP-A-2-135335, in addition to gelatin.
The gelatin content at this time is preferably 20% or more by weight. Next, the silver halide emulsion according to the present invention will be described.

The silver halide emulsion used in the present invention is
It contains tabular silver halide grains having an average aspect ratio of 2 or more, preferably tabular grains having an aspect ratio of 3 to 30, and more preferably 5 to 20.

The grain size of the silver halide grain of the present invention is 0.2 to 1
0 μm, preferably 0.3-5 μm, more preferably
It is 0.4 to 2.0 μm. However, the particle size referred to here is represented by the side length when converted to a cube having the same volume with the particle size obtained by the centrifugal sedimentation method. Further, the silver halide grain of the present invention is preferably so-called monodisperse with a narrow grain size distribution. The definition of monodispersity is described in JP-A-60-162244, and a preferable coefficient of variation of particle size is 5% to 25%.

The aspect ratio mentioned here is represented by the ratio of the diameter to the thickness of the tabular grains. The grain diameter refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed under a microscope, and the thickness is indicated by the distance between two parallel planes constituting a tabular grain.

The halogen composition of the silver halide photographic light-sensitive material of the present invention may be silver chloride silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide.

The silver halide grain of the present invention may have a multilayer coating layer having an arbitrary halogen composition as a shell layer, preferably 1 to 5 layers. The iodide content of the shell layer is 0 to 40 mol%, preferably 0 to 20 mol%. The halogen composition of the core, which is the inner core of the grain, is 0
Has an iodide content of -40 mol%, more preferably 5-20
It has an iodide content of mol%.

The average iodide content of the entire silver halide grain of the present invention may be 10 mol% or less, preferably 6 mol% or less. It is more preferably 3 mol% or less.

The method for producing silver halide grains having a multilayer structure in which the silver halide composition of the inner core of the silver halide grains and the coating layer thereof as in the present invention is changed is widely known.
For example, U.S. Patents 2,592,250, 3,505,068, 4,210,
450, 4,444,877, JP-A-60-143331 and J. Pho
t.Sci. 24 .198 (1976) can be referred to the method described, for example.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, (RD)
No.17643 (Dec. 1978), pages 22-23, 1. Emulsion Preparation and types, and (RD) No.187
16 (November, 1979) -It can be prepared by the method described on page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described in, for example, "The theory of the phot" by TH James.
"graphic process" 4th edition, published by Macmillan (1977) 3
Method described on pages 8 to 104, "Photographic Emulsion Chemistry" by GF Daufin, Focal pres
s Company (1966), P. Glafkides "Physics and Chemistry of Photography""Chimie et physique photographique" Paul Mon
Published by tel (1967), VL Zelikman et al. "Making and Coating photographic Emul"
It is prepared by the method described in “sion” Focal press, Inc. (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the controlled double jet method under the solution conditions such as the neutral method, the acidic method and the ammonia method, the conversion method, the core / shell method. It can be produced using the particle preparation conditions such as and the like and a combination method thereof.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is a tabular grain having an aspect ratio of 2 or more.

The advantages of such tabular grains are that they can improve spectral sensitization efficiency and image graininess and sharpness. For example, British Patent No. 2,112,157 and US Patent
4,439,520, 4,433,048, 4,414,310, 4,43
4,226, JP-A-58-113927, 58-127921, 63-13
No. 8342, No. 63-284272, No. 63-305343, etc., and the emulsion can be prepared by the method described in these publications.

These emulsions may be prepared by using a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts, and a preferable water washing method is, for example, an aromatic hydrocarbon containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

In the silver halide emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening.

Examples of the compound used in such a step include (RD) No. 17643 (December 1978) and No. 18716 (197).
(November 9) and No. 308119 (December 1989). The types and locations of the compounds described in these three (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the Invention Examples of the support used for the silver photographic light-sensitive material include those described in RD above,
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or subjected to corona discharge or ultraviolet irradiation.

[0071]

The present invention will be further described below with reference to examples, but the present invention is not limited to the examples described below.

Example 1 A seed emulsion T-1 having high monodispersity was prepared by the following method.

[0073] A liquid B _{1 and a} liquid C ₁ were added to a liquid A ₁ which was vigorously stirred at 40 ° C. by a double jet method to generate nuclei. 30 ml after addition
Water was added, the temperature of the mixed solution was lowered to 20 ° C., the potential was adjusted to 40 mv, D ₁ was added in 20 seconds, and the mixture was aged for 5 minutes.

Thereafter, the pH was adjusted to 6.0, and desalting was carried out using a formaldehyde resin of sodium naphthalenesulfonate and an aqueous magnesium sulfate solution. When the seed emulsion was observed with an electron microscope, it was a monodisperse silver bromide emulsion having an average grain size of 0.28 μm and a broad distribution of 30%. This emulsion was designated as seed emulsion T-1.

(Preparation of T-2) A seed emulsion T-2 was prepared in the same manner as in T-1, except that the ripening time after the addition of D-1 in the preparation of T-1 was 3 minutes. Observation of this seed emulsion with an electron microscope revealed that it was a monodisperse silver bromide emulsion having an average grain size of 0.25 μm and a distribution of 30%.

Preparation of Tabular Grain Emulsion (Preparation of Em-1) A silver halide emulsion mainly composed of tabular twin crystals was prepared by using the seed emulsion T-1 described above and the following solution.
(Em-1) was prepared.

E ₁ Hydrogen peroxide treated ossein gelatin 37 g Polypropyleneoxy-polyethyleneoxy-di-succinate-disodium salt (10% methanol solution) 10 ml Equivalent to 1.14 mol of the seed emulsion (T-1) 4000 ml with water F to 1103Ml G ₁ ossein gelatin 96.5g said E ₁ solution was stirred vigorously at 6248ml 75 ℃ potassium bromide 624g water at 4096Ml H ₁ Silver nitrate 1132g water at ₁ ossein gelatin 26g potassium bromide 151g potassium iodide 23g water, Solution F _{1 and} solution H ₁ were added by the double jet method. During this time, the pH was kept at 6.5 throughout.

After the completion of the addition, the pH was adjusted to 6.0 and then 5,5'-di-chloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) oxacarbocyanine sodium salt anhydride [sensitizing dye (A)] per mol of silver halide
After 300 mg was added for sufficient adsorption, desalting was carried out in the same manner as in the above seed emulsion. The emulsion has a pAg of 8.5 and 40 ° C.
PH was 5.85. Observation of the resulting emulsion with an electron microscope revealed that the average grain size was 0.85 μm and the distribution was 2
0% tabular silver halide grains with an aspect ratio of
At 2.4, the average particle thickness was 0.35 μm.

Em-2 was grown in the same manner as described above except that when grains were grown in the same manner as described above using the seed emulsion T-2, the pAg was grown to 9.0. Em-2 is the average particle size
The silver halide grains were 0.85 μm, the width of distribution was 20%, the aspect ratio was 7, and the average grain thickness was 0.12 μm.

Normal Crystal Grain Emulsion (Preparation of Em-3) 2 mol% of silver iodide having an average grain size of 0.3 μm was obtained by the double jet method while maintaining the conditions of the reaction vessel at 60 ° C., pH = 8, and pH = 2. A monodisperse cubic emulsion of silver iodobromide containing was obtained. According to the electron microscope observation, the occurrence rate of twins is 1 in number.
It was other than%. This emulsion was used as a seed crystal and further grown as follows.

The gelatin aqueous solution was kept at 40 ° C. in the reaction vessel to disperse the seed crystals, and ammonia water and acetic acid were further added to adjust the pH.
I adjusted it to 9.5.

After adjusting the pH to 7.3 with an ammoniacal silver ion solution, a solution containing ammoniacal silver ions, potassium iodide and potassium bromide was added by the double jet method while keeping the pH and pAg constant, and the iodide was added. A silver iodobromide layer containing 30 mol% of silver was formed.

PH = 9, pH = 9.0 using acetic acid and silver bromide
After that, an ammoniacal silver ion solution and potassium bromide were added at the same time, and the grains were grown to 90% of the grain size after growth. At this time, the pH gradually decreased from 9.0 to 8.20.

After adding potassium bromide solution to adjust pAg = 11, further adding ammoniacal silver ion solution and potassium bromide to obtain p
Gradually reduce H to pH 8 and grow to obtain an average particle size
A silver iodobromide emulsion containing 1.23 μm and 2 mol% of silver iodide was obtained.

When preparing the emulsion, the sensitizing dye (A) is used.
200 mg per mol of silver was added to the emulsion to obtain an emulsion.

Next, as shown below, a desalting step for removing excess salt was carried out.

The silver halide emulsion solution was kept at 40 ° C., a formalin condensate of sodium naphthalenesulfonate was added to precipitate silver halide grains, and the supernatant was discharged, and then pure water at 40 ° C. was added. Then, magnesium sulfate is added and the silver halide grains are allowed to settle again, and the supernatant is removed. Do this again and add gelatin to add pH 6.0, pAg
An emulsion of 8.5 was obtained. This emulsion was designated as Em-3.

Each of the emulsions Em-1, 2 and 3 of the obtained emulsion was treated with 150 mg and 5 mg of the above (A) as a spectral sensitizing dye immediately before the addition of the chemical sensitizer consisting of hypo and chloroauric acid. ,Five'-
Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-
Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride [sensitizing dye (B)] was added at a rate of 15 mg per mol of silver halide, and after chemical ripening, potassium iodide was added per mol of silver halide. 300 mg was added to stop the chemical ripening. Further, 2.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added per mol of silver halide.

The emulsions that had been chemically ripened were mixed as shown in Table 1 below, and then the following various additives were added to prepare coating solutions.

To the emulsions of Em-1 to 3 above, t-butyl-catechol 400 mg, styrene maleic anhydride copolymer 2.5 g, nitrophenyl-triphenylphosphonium chloride 50 mg per mol of silver halide as an additive. Ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1,1-Dimethylol-1-bromo-1-nitromethane 20 mg Table 1 and The compound of the general formula [1] described in 2 and the addition amount thereof

[0091]

[Chemical 5]

The above was added to prepare an emulsion coating solution.

Further, as a protective layer solution, the following amounts of additives were added per 1 g of gelatin to prepare a protective layer coating solution.

Glyoxal 25 mg Matting agent listed in Table 1 (a) Amount listed in Table 1 Matting agent listed in Table 1 (b) Amount listed in Table 1

[0095]

[Chemical 6]

Next, preparation examples of gel-grafted polymer particles used in the examples of the present invention will be shown.

Step 1. Preparation of gel-graft polymer particles (A) Styrene (928g) and chloromethylstyrene (46.4g)
g) was mixed in a container. 7.4 g of Aerosol-OT surfactant (American Cyanamide) were dissolved in the mixture, followed by 4.92 g of 2,2-azobis (2-methylpropionitrile).
Nitrogen-purged distilled water (3240 g) was added to the mixture, which was then mixed for 30 seconds and left under nitrogen in a 70 ° C. constant temperature bath for 22 hours. Unreacted monomer was then removed by evaporation and the remaining suspension was cooled and filtered through cheesecloth to give a bead suspension containing 21.7% by weight solids.

Step 2. Covalent binding of gelatin to particles The suspension obtained in step 1 was placed in a 12 liter three-way flask equipped with a gas flow stirrer and condenser. The suspension was heated to 60 ° C and the pH was adjusted to 8.0. Lime-treated bone gelatin (dry weight 745 g) was added to distilled water 2683 g and heated to 60 ° C. to dissolve. The pH of the gelatin solution was adjusted to 8.0, the solution was added to the flask containing the suspension, and the mixture was stirred for 2 hours to obtain a suspension of gel-grafted polymer particles (A).

The average diameter of the polymer particles was 2 μm.

Step 3. Preparation of gel-graft polymer particles (B) Sodium chloride (2888 g), potassium dichromate (11
g), diethanolamine adipate (49.5 g), and
Ludox AM Sio ₂ particles (550 g) were sequentially added to 8690 g of distilled water to prepare an aqueous solution. Add styrene (5940
g), methacrylic acid (330g), divinylbenzene (330
g), and a mixture of 2,2'-azobis- (2,4-dimethylvaleronitrile) (69.3g). 2 this mixture
Stir vigorously for hours and emulsify using a homogenizer at 5000 psi. The obtained emulsion was enclosed in a reaction tube. The emulsion was heated to 50 ° C. with stirring at 80 rpm and kept at this temperature for about 20 hours. The mixture was subsequently heated to 75 ° C., kept at this temperature for 3 hours, cooled to room temperature and filtered through a double layer of cheesecloth. The polymer particles were then filtered from the dispersion with a grade 230 filter paper using a Buchner funnel, redispersed in a solution of 11.5 kg distilled water, 1200 g 50% sodium hydroxide, and 8.34 g sodium dodecyl sulfate, and Stir vigorously for 15 minutes. The polymer particles were filtered using the same filtration device and distilled water 11.6
Redispersed in 6 kg and 600 g of 50% sodium hydroxide solution, filtered again and washed with distilled water. The average diameter of the polymer particles was 6.4 μm.

Step 4. Covalent binding of gelatin to particles A gelatin solution was prepared by dissolving 1099 g of lime-treated bone gelatin in 6 g of distilled water. 2N sodium hydroxide 67g
Was added to this lysis and then filtered. The particles of step 1 were dissolved in distilled water at pH 9 to 9 to give a solids content of 29.
1035 g of a weight% dispersion was obtained. The dispersion was diluted with 1 kg of distilled water and the pH was adjusted to 8-9 with 2N sodium hydroxide. Then, this was stirred and heated to 60 ° C., and 10.4 g of 1- (4-morpholinocarbonyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt was added. The mixture was stirred for 15 minutes and then 2343 g of the above gelatin solution heated to 60 ° C. was added. After stirring for 20 minutes, almost all gelatin was covalently bonded to the particles (polymer:
Weight ratio 1: 1 of gelatin, average diameter 6.9 μm) Step 5. Preparation of gel-graft polymer particles (C) Methyl methacrylate (380 g), methacrylic acid (20
g), sodium di (2-ethylhexyl) sulfosuccinate (5 g), and distilled water (800 g) were mixed for 90 minutes. The mixture was deoxygenated with a nitrogen purge and held at 62 ° C for 20 minutes with stirring at 100 rpm. The resulting dispersion of polymer particles was found to have a solids content of 33.2%.

Step 6. Covalent binding of gelatin to particles 1140 g of aqueous dispersion from step 1, pH with sodium hydroxide
Adjusted to 8.0 and heated to 60 ° C. with stirring. continue,
1- (4-morpholinocarbonyl) -4- (2-sulfoethyl) pyridinium hydroxide inner salt dissolved in 200 g of distilled water (13.2
g) was added to the dispersion and stirred for 15 minutes. A 12.5% by weight lime-treated bone gelatin solution dispersion in this mixture was filtered through a coarse screen to give a solids content of
It turned out to be 19.2%. Average particle diameter is 5.5μ
m, polymer: gelatin weight ratio was 2: 1.

The above coating solution was uniformly applied to both surfaces of a blue-colored polyethylene terephthalate film base as an undercoating agent having a thickness of 180 μm. The emulsion layer was coated on both sides such that the amount of silver on one side was 2.1 g / m ^2, and the protective layer was coated on both sides so that the amount of gelatin on one side was 0.98 / m ² .

The sample was glyoxal cured, chill-cured and dried.

Then, a reverse gravure roll coating was applied on the coated material so that the aqueous solutions of the gel-grafted polymer particles (A), (B) and (C) were adjusted to the amounts shown in Tables 1 and 2. Overcoated.

The reverse gravure roll coating was not applied to the comparative sample.

The following tests were conducted on the obtained sample Nos. 1 to 25.

[Sensitivity] The sample was sandwiched between two intensifying screens, KO-250, exposed through an aluminum wedge at a tube voltage of 80 KVp, a tube current of 100 mA, and an irradiation time of 50 msec, and then an SRX-1001 automatic developing machine was used. With XD-SR developer at 33 ℃ and XF-SR fixer at 33 ℃.
It was treated for 45 seconds. (Both manufactured by Konica Corporation) For the obtained sample, the reciprocal of the exposure amount required to obtain the density of the base density + fog density + 1
It was expressed as the relative sensitivity of fitting when the sensitivity of No. 1 was 100.

[Scratch resistance] Each sample was conditioned under the condition of 23 ° C. and 70% for 2 hours, and then each sample was placed on top of a table and placed on a desk, and a 1 kg weight was placed on it. Pull the upper film while touching the lower film. A second film from above was developed without being exposed. When the second film is rubbed with the first film, thin linear black streaks are generated. This degree was evaluated by the following criteria.

1. No thin black streaks occur 1. A slight black streak failure has occurred 3. 3. A thin black streak has occurred. 4. A lot of thin black streaks have occurred. Thin black streaks occur on the entire film A rating of 2 or less is an acceptable level for the product.

[Evaluation of Roller Mark Resistance] The pressure mark (roller mark) by the roller of the automatic processor was evaluated as follows. That is, it was processed in an unexposed state with an automatic developing machine having a facing roller. The roller marks generated at that time were visually evaluated and classified into the following 5 grades. The obtained results are shown in Tables 1 and 2.

1: No occurrence of roller marks 2: Very slight occurrence 3: Some occurrence (within practical use permit) 4: Many occurrences (outside practical use permit) 5: Very many occurrences

[0113]

[Table 1]

[0114]

[Table 2]

As is apparent from the table, the sample containing the compound represented by the general formula [1] according to the present invention in the silver halide emulsion layer and overcoating the gel-graft polymer particles according to the present invention was It can be seen that the scratch resistance and the roller mark resistance are improved, and the effect is particularly remarkable when the silver halide emulsion is tabular grains. With the matting agent in the protective layer according to the conventional method, the curability is not obtained, so that the sensitivity is suppressed to a small extent, but the physical properties are not improved at all.

[0116]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which has a high sensitivity and a high covering power, while preventing roller marks and scratch defects which may occur during the development processing of the silver halide photographic light-sensitive material. .

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of gel-grafted polymer particles of the present invention covalently bonded to the gelatin layer surface of a photographic element.

[Explanation of symbols]

 1 Support 2 Gelatin-Containing Layer 3 Polymer Particles 4 Gelatin

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on at least one side of a support, wherein the silver halide emulsion layer has an average aspect ratio of 2 or more. Polymer particles containing tabular silver halide grains and containing at least one compound represented by the following general formula [1], wherein the photosensitive material is covered with gelatin by covalent bonds, A silver halide photographic light-sensitive material characterized by being covalently bonded to a gelatin layer. [Chemical 1] In the formula, A ₁ and A ₂ are each a group selected from an aliphatic group, an aromatic group and a heterocyclic group, which is formed alone or in combination with 2
It represents a group having a valency or more, and R ₁ , R ₂ , and R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group. Z represents an inorganic acid or an organic acid, and n
Represents 1 or 2.