JP2981945B2 - Silver halide photographic material - Google Patents

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 material having high sensitivity, high image quality, high covering power, and improved cut-out, cracking, thread-like sensitization and desensitization. And a rapidly processable silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a photosensitive material in which an emulsion containing tabular silver halide grains is coated on both sides in terms of high sensitivity, high image quality, and high covering power is disclosed in, for example, JP-A-61-14636.
And U.S. Patent No. 4,439,226.

[0003] However, the photosensitive material comprising the tabular silver halide grains has a drawback that pressure fog is liable to occur when subjected to mechanical pressure during the manufacturing process or during use.

In recent years, the processing speed of silver halide photographic materials has been increasing more and more, and as a result, opportunities for applying external mechanical stress to the photographic materials have been increasing.

When various mechanical stresses are applied to silver halide grains, pressure fog (hereinafter, fog generated in a portion rubbed by pressure, hereinafter simply referred to as "thread-like sensitization") or pressure desensitization (a portion rubbed by pressure) It is well known that desensitization occurs in the following (hereinafter simply referred to as "thread-like desensitization").

On the other hand, in order to speed up the processing of a light-sensitive material, reducing the amount of gelatin in a layer to form a thin film is one of the effective means for the purpose of reducing the load on drying.

However, when the amount of gelatin, which is a binder for silver halide, is reduced, the above-mentioned thread-like sensitization or desensitization becomes more and more likely to occur, and problems such as cracking of the film occur.

[0008] In medical light-sensitive materials, such a phenomenon is not only a hindrance to diagnosis but also poses a serious problem since there is a risk of inducing misdiagnosis.

A number of proposals have been made to improve the pressure resistance. For example, as a method of alleviating the force transmitted to silver halide grains when an external pressure is applied to an emulsion film, a binder component of a layer is used. A method using a large amount of gelatin, a hydrophilic polymer, or a water-soluble latex, or a method using a polyol or an alkylene glycol as a gelatin plasticizer, and further adding an adsorbable compound to silver halide grains to form a crystal. A method of coating the surface is known. Further, as a recent technique, Japanese Patent Application Laid-Open No. 1-142627 discloses that the Young's modulus of a tabular silver halide emulsion layer is specified to improve the pressure resistance.

However, tabular grains having a large diameter / thickness ratio are generally remarkably weak against external force due to their shape, and the conventional technique as described above cannot provide a sufficient effect. Further, when a polymer latex is added in an amount necessary for obtaining a sufficient effect as an improvement in the thread-like sensitization / desensitization, there is a new problem that the stickiness is deteriorated.

On the other hand, cracks have not yet been improved.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-speed, high-sensitivity, high-image-quality, high-covering power, and improved thread-like sensitization / desensitization without causing crackling and cracking. An object of the present invention is to provide a silver halide photographic light-sensitive material.

[0013]

The object of the present invention has been attained by a silver halide photographic material having the following constitution.

That is, at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer are provided on both sides of the support, and at least one of the emulsion layers has 50% of the projected area.
A shell of crosslinked gelatin grafted to a core polymer is provided on at least one of the emulsion layer and / or the non-photosensitive hydrophilic colloid layer containing tabular silver halide grains having an average aspect ratio of 3 or more. The above object has been attained by a silver halide photographic material characterized by containing polymer particles.

Hereinafter, the present invention will be described specifically.

As the polymer particles of the present invention, any polymer or copolymer which can be covalently bonded directly to gelatin or indirectly using a crosslinking agent can be used.

Monomers which covalently bind to gelatin include, for example, US Pat. Nos. 4,017,442, 4,548,870,
The following compounds described in 3,625,694, 4,161,407 and 3,671,256 are exemplified. Monomers having an active halogen atom such as vinyl chloroacetate, halogenated aromatic vinyl (eg, chloromethylstyrene), chloroalkylacrylic acid or methacrylate (eg, chloroethyl methacrylate, 3-chloro-2-hydroxypropyl-methacrylate) , Chloroethyl acrylate, etc.), a monomer having an isocyanate group (for example,
Isocyanate ethyl acrylate, isocyanate ethyl methacrylate, α, α-dimethylmetaisopropenylbenzyl isocyanate), a monomer having an epoxy group (eg, glycidyl acrylate, glycidyl methacrylate), a monomer having an aldehyde group (eg, vinyl benzaldehyde, acrolein), chloro Monomers containing an ethylsulfone group (eg, chloroethylsulfonylmethylstyrene, vinylsulfonylmethylstyrene), and monomers having an aziridine group (eg, N-acryloylaziridine, 2- (1-aziridinyl))
Ethyl acrylate) and the like.

Monomers whose polymers and copolymers can be covalently bonded to gelatin by using a crosslinking agent include carboxyl group-containing monomers (eg, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride), amine-containing monomers ( Examples thereof include 2-aminoethyl methacrylate, N- (3-aminopropyl) methacrylamide hydrochloride), and an active methylene group-containing monomer (eg, 2-acetoacetoxyethyl methacrylate, diacetone acrylamide).

The polymer particles of the present invention are represented by the general formula [I].

Formula (I)-(A) _X- (B) _100-X -wherein A is a repeating unit composed of one or more monomers which can be covalently bonded to the gelatin directly or via a crosslinking agent. And B represents a repeating unit composed of one or more other ethylenically unsaturated monomers.

As the monomer represented by B, virtually any monomer can be used as long as the monomer can be copolymerized with the above-mentioned monomer A without losing its ability to covalently bind to gelatin. Such monomers include, for example, styrene and styrene derivatives (eg, vinyl toluene, divinylbenzene, 4-t-butylstyrene), acrylic acid and methacrylic esters (eg, methyl methacrylate, methyl acrylate, ethyl methacrylate) Acrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethylene dimethacrylate, methacrylamide, acrylonitrile).

The content X of the monomer A which can be covalently bonded to the gelatin of the present invention directly or via a crosslinking agent is 0.1 mol% to 100 mol%.
mol%, more preferably 1 mol% to 20 mol%.

The glass transition point of the polymer particles of the present invention is about
It is preferably at most 20 ° C, more preferably at most about 10 ° C. As a method of adjusting the glass transition point, the component B of the above general formula [I] may be adjusted, and preferably a monomer such as butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate or propyl acrylate is used in an amount of 40 to 98% by weight of the whole polymer. %.

The polymer particles of the present invention may be of any practical shape. The average particle size of the polymer particle core is about
It is 10 to 10,000 nm, preferably 10 to 500 nm, more preferably 10 to 200 nm. The average particle size of the particles was measured by a light scattering method.

As the gelatin covalently bonded to the polymer particles, any type of gelatin known in the photographic art can be used. That is, for example, alkali-treated gelatin (cattle bone or skin gelatin), acid-treated gelatin (pig skin or bone gelatin), and gelatin derivatives such as partially phthalated gelatin and acetylated gelatin are exemplified.

The polymer particles of the present invention can also cure covalently bound gelatin according to well known techniques,
Crosslinking may be performed with a general crosslinking agent. The thickness of the gelatin layer is affected by the molecular weight of gelatin, pH, and the particle size of the polymer particles, and is usually about 1 to 60 nm, preferably 3 to 40 nm.

Examples of the crosslinking agent for grafting gelatin to the polymer particles or crosslinking the gelatin used in the present invention include free dialdehydes, sulfonic esters, active esters, epoxides and the like described in “Research Disclosure” No. 17643. Aziridine, block activated olefin, vinyl sulfone, dicationic ether, carbodiimide, dialdehyde starch and poly (acrolein
-Methacrylic acid) and carbamoylonium salts described in US Pat. No. 4,421,847.

The polymer particles of the present invention can be obtained by techniques well known in the art, such as polymerization (subsequent milling or grinding to obtain the preferred particles), or a particularly preferred particle size directly as a stable dispersion. It can be adjusted by the emulsion or suspension polymerization method used. According to the emulsion polymerization, a stable water-soluble dispersion which can directly coat gelatin without requiring separation can have a particle size of 0.01 μm to 5 μm (preferably 0.1 to 2.5 μm). In the case of particles of larger diameter, the method of suspension polymerization in an organic solvent system and isolation of the particles, followed by resuspension in water is preferred, and the “critical fusion” method taught in US Pat. No. 3,614,972 is preferred. Is most preferable. Bulk, emulsion and suspension polymerization methods are well known to those skilled in polymerization chemistry,
“Preparation Methods of” by WPSorenson / TWCambell
Polymer Chemistry "2nd edition and other textbooks.

The polymer particles of the present invention can be grafted with gelatin by mixing a gelatin and an aqueous dispersion of the polymer particles as long as the polymer can directly react with gelatin. It is preferable to first react the polymer particles with the crosslinking agent, and then react the gelatin with the polymer particles.

The particles of the present invention are characterized in that, in the gelatin-grafted polymer obtained as described above, the grafted gelatin is crosslinked with a grafting agent or a hardening agent to form a crosslinked gelatin shell.

The gelatin may be in the minimum amount required to cover the surface of the polymer.

The ratio of polymer to gelatin is 1: 2
2: 1 is good.

If gelatin is grafted to the polymer at such a ratio, when cross-linked using a hardener, the gelatin can form a shell of cross-linked gelatin with very little or no gelatin remaining in the aqueous solution.

The thickness of the shell of the crosslinked gelatin is preferably 10 nm or less.

In order to crosslink the gelatin grafted on the core polymer, the grafting agent is added to 6.0 g of gelatin per 1 g of gelatin.
It is sufficient to add 10 ^{-2 to} 10.4 × 10 ^-2 g.

The polymer particles of the present invention may be added to any of the layers constituting the silver halide photographic material, but a layer containing silver halide particles is preferred.

The amount used is preferably 5 to 50% by weight of the total binder, more preferably 20 to 40% by weight.

The silver halide emulsion used in the present invention is:
Tabular grains having a tabular silver halide grain having an average aspect ratio of 3 or more, preferably having an aspect ratio of 3 to 20, more preferably 5 to 15 are used.

The size of the tabular grains is 0.4 μm or more, preferably 0.4 to 4 μm.

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

The proportion occupied by these tabular silver halide grains is preferably at least 50%, more preferably at least 70%, particularly preferably at least 90%, based on the total projected area.

The halogen composition of the tabular grains is silver bromide, silver iodobromide, silver iodochlorobromide and the like. In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably It is at most 20 mol%, more preferably at most 15 mol%.

The production method of these tabular silver halide grains is as follows.
For example, U.S. Patents 4,434,226, 4,439,520, and 4,414,
No. 310, No. 4,425,425, No. 4,399,215, No. 4,435,501
Nos. 4,386,156, 4,400,463, 4,414,306,
4,425,426, EP84,637A2, JP-A-59-99433, RD-
22534 (1983.1) or the like or a method analogous thereto.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention include, for example, those described in "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coting Photographic Emulsion "by Focal Press (1964).

That is, under solution conditions such as an acidic method, an ammonia method, and a neutral method, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
At least 95% of the grains by number or weight are silver halide grains within ± 40%, preferably ± 30% of the average grain size.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a core portion of high silver iodide is covered with a shell layer of low silver iodide may be used.

The method for producing the above-mentioned monodispersed emulsion is known.
J. Phot. Sci, 12.242-251, (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Pat. Nos. 3,574,628, and 3,655,394. The emulsion used in the silver halide photographic light-sensitive material of the present invention is obtained by, for example, using a seed crystal as a method for obtaining the above-mentioned monodispersed emulsion, and supplying and growing silver ions and halide ions using the seed crystal as a growth nucleus. May be used.

The method for preparing the above-mentioned core / shell type emulsion is known, and is described, for example, in J. Phot. Sci, 24.198. (1976), US Pat.
Nos. 250, 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion of the present invention can be prepared, for example, by cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt at the stage of physical ripening or grain preparation. May be used.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons 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 G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 1
7643, (RD) No. 18716 and various kinds of compounds described in (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures 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 Top right Fog inhibitor / stabilizer 24 IV 649 Top right 1006 ~ 7 VI Brightener 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 present invention Examples of the support used for the silver photographic light-sensitive material include those described in the above RD,
A suitable support may be a plastic film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by the above-mentioned RD-17643 XX-XXI, pp. 29-30 or 308119 XX-XX.
I, treatment with a treatment solution as described on pages 1011 to 1012 may be performed.

[0056]

The present invention will now be described in more detail with reference to Examples, but it should be understood that the present invention is by no means restricted to such specific Examples.

[0057] Synthesis Example -1 (Gel-g-latex) of styrene 92.8g and chloromethylstyrene 4.64g were mixed in a vessel, the mixture Aer o sol-OT surfactant (American C
0.74 g of yanamide) was dissolved, followed by 0.49 g of 2,2-azobis (2-methylpropionitrile). 324 ml of nitrogen-substituted distilled water was added, followed by polymerization at 70 ° C. for 22 hours with stirring. Unreacted monomers were distilled off, and the remaining suspension was cooled and filtered to obtain a polymer particle dispersion. The obtained polymer particle dispersion is placed in a one-liter three-
Heated to ° C and adjusted the pH to 8.0. 74.5 g of gelatin in distilled water
The suspension was dissolved in 268 ml, the pH 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 gelatin graft polymer particles. This is referred to as GA-1.

Similarly, instead of the above 92.8 g of styrene, 85.6 g of ethyl methacrylate was used for GA-
2. A product using 68.1 g of vinyl toluene and 27.4 g of methacrylamide is referred to as GA-3.

Synthesis Example-2 (case hardening) [Latex] 800 ml of nitrogen-substituted distilled water is placed in a 1-liter three-necked flask and heated to 60 ° C. Next, 30 g of styrene, 30 g of butyl acrylate, 19 methacrylic acid
g, sodium dodecyl sulfonate 0.08 g, K ₂ S ₂ O ₈ 0.4 g,
0.2 g of K ₂ S ₂ O ₅ are added. Polymerization is performed at 60 ° C. for 20 hours, and the resulting latex is dialyzed against distilled water for 56 hours to obtain a latex having an average particle size of 96 nm.

[Gel graft] 411 g of the obtained latex
In a round bottom flask and adjust the pH to 8.0 with 20% NaOH.
Add 0.41 g of the grafting agent (1) into the latex heated to 60 ° C. and stir for 15 minutes. Then add 16g of gelatin to 164
A substance dissolved in ml of distilled water and adjusted to pH 8.0 was added and reacted for about 15 minutes to obtain a gel graft latex. This is GB-1.

[0061]

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Similarly, a mixture of 58.2 g of 2-hydroxyethyl methacrylate in place of 30 g of styrene and 30 g of butyl acrylate was used to prepare GB-2 and 15.7 g of vinyl toluene.
g, ethylene dimethacrylate 43.6g using GB-3
And

The obtained gelatin graft latex was used as it is or gelatin shell was formed by the following method.

[Gel shelling] 100 g of the obtained Gel graft latex was placed in a beaker and heated to 60 ° C. to adjust the pH to 20% Na.
Adjust to 8.0 with OH. Grafting agent dissolved in water (1) 0.3
g was added at 60 ° C. and stirred for 15 minutes to obtain gelatin-shelled polymer particles.

[Emulsion Preparation 1] (1) Preparation of seed emulsion 1 Controlled at 60 ° C., pAg = 8, pH = 2.0, containing 2 mol of silver iodide having an average grain size of 0.3 μm by a double jet method. Monodispersed cubic grains of silver iodobromide were prepared. The resulting reaction solution was desalted at 40 ° C. using an aqueous solution of Namol and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and then re-dispersed by adding an aqueous solution of gelatin to obtain a seed emulsion.

(2) Growth from Seed Emulsion 1 Using the above-described seed emulsion, grains were grown as follows.
First, the seed emulsion was dispersed in an aqueous gelatin solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, pAg = 7.3 and pH = 9.7 were controlled to form a layer having a silver iodide content of 35 mol%. Next, an aqueous ammonium nitrate solution and an aqueous potassium bromide solution were added by a double jet method. The pAg was maintained at 9.0 until 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Then, adjust to pAg = 11.0 and pH = 8.0
And grown to the target particle size. Then pH with acetic acid
= 6.0, 5.5'-dichloro-9-ethyl-3.3'-di- (3
-Sulfopropyl) oxacarbocyanine sodium salt anhydrous was added at 400 mg / mol AgX, desalted using an aqueous solution of Demol-Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and redispersed by adding an aqueous solution of gelatin.

According to this method, the apexes having an average silver iodide content of 2.0 mol% with rounded vertices, an average grain size of 0.40 μm, and an average grain size of 0.4 mol.
65 μm, 1.00 μm, variation coefficient (δ / r) 0.1
7, 0.16, 0.16 monodispersed silver iodobromide emulsions (A), (B),
(C) was adjusted.

[Emulsion preparation 2] (1) Seed emulsion preparation 2 A silver sulfate aqueous solution and a hydrogen peroxide-treated gelatin were added to a 0.05 N aqueous solution of potassium bromide containing hydrogen peroxide-treated gelatin, which was vigorously stirred at 40 ° C. Of equimolar potassium bromide in water by the double jet method, and after 1.5 minutes, lower the solution temperature to 25 ° C over 30 minutes, and then add
80 ml of aqueous ammonia (28%) was added and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalted using an aqueous solution of Demol Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and redispersed by adding an aqueous solution of gelatin. The obtained seed emulsion has an average particle size of 0.23 μm and a coefficient of variation.
The particles were 0.28 spherical particles.

(2) Growth from Seed Emulsion 2 Using the above-described seed emulsion, grains were grown as follows. 75
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by double jet method to an aqueous solution containing ossein gelatin and propyleneoxy / polyethyleneoxy disuccinate / disodium salt vigorously stirred at ℃. During this time, pH = 5.8 and pAg = 9.0 were maintained. After the addition is completed, adjust the pH to 6.0
And anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt was added at 400 mg / mol AgX. After desalting at 40 ° C. using an aqueous solution of Demol Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., an aqueous solution of gelatin was added and redispersed.

According to this method, a tabular silver iodobromide emulsion (D) having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, and a variation coefficient of 0.25 aspect ratio (projected area diameter / grain thickness) of 4.0 was prepared. Prepared.

[Emulsion Preparation 3] In the same manner as in [Emulsion Preparation 2], except that pAg at the time of growth from the seed emulsion was kept at 8.6, the average silver iodide content was 1.5 mol%, and the projected area diameter was
A tabular silver iodobromide emulsion (E) having a 0.71 μm coefficient of variation and a 0.27 aspect ratio of 1.8 was prepared.

[Preparation of Sample] The obtained emulsion (A),
(B), (C), (D) and (E) at 55 ° C.
5,5-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl)
Anhydrous sodium oxacarbocyanine and 5,5'-di-
Anhydrous (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt at a weight ratio of 200: 1 per mole of silver halide ( A) 975mg, (B) 600mg, (C) 390m
g, (D) and (E) were added in an amount of 500 mg.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out chemical ripening. Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 3 × per mol of silver halide. 10 ^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

Of the five types of ripened emulsions, (A)
(B) and (C) were mixed at a weight ratio of 15:65:20 to prepare Emulsion-I, and (D) and (E) were used alone as Emulsion-II and Emulsion-III.

The following additives and the gelatin graft polymer shown in Table 1 were added to each of Emulsion-I, Emulsion-II, and Emulsion-III. The amount of addition is shown in an amount per mole of silver halide.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 4 g 2-Sodium mercaptobenzimidazole-5-sulfonate 15 mg 1-phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂
1g

[0078]

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Further, 1.2 g of a dye emulsified dispersion shown below
Was added to obtain an emulsion coating solution.

[Preparation Method of Dye Emulsion Dispersion]
10Kg of tricresyl phosphate 28l and ethyl acetate 85l
At 55 ° C. This is called an oil-based solution. On the other hand, 270 l of a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) was prepared. This is called an aqueous solution.

Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C.

An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was added with water.
Finished to 240Kg.

[0083]

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The additives used in the protective layer solution are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Coal-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate, matting agent having an area average particle diameter of 3.5 μm 1.1 g Silicon dioxide particles Area average particle diameter 1.2 μm 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H
2.0g

[0086]

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The emulsion layer had a silver equivalent of 1.7 per side.
g / m ² , and 90 m / min with two slide hopper coaters so that the protective layer becomes 0.99 g / m ^{2 in} terms of gelatin.
At a speed of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate, and 40% by weight of butyl methacrylate, a copolymer consisting of three types of monomers was used.
An emulsion layer and a protective layer were simultaneously coated on both sides of a 175 μm polyethylene terephthalate film base coated with an aqueous copolymer dispersion obtained by dilution to give
After drying for 15 minutes, Sample Nos. 1 to 18 were obtained.

[Sensitometry] The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), and a tube voltage of 90 KVP, 20
X-rays were irradiated for 0.05 seconds at mA, and a sensitometric curve was created by the distance method to determine the sensitivity. The sensitivity value is fog + 1.
It was calculated as the reciprocal of the X-ray dose required to obtain a concentration of 0.
The results were expressed as relative sensitivities when the sensitivity of sample No. 1 was set to 100. The development was performed by an automatic processor SRX-501 (manufactured by Konica Corporation).
Using a developer and a fixer having the following composition at a developing temperature of 35
The fixing temperature was 33 ° C., the washing water was supplied at a temperature of 18 ° C. at a rate of 3.5 l / min, and the drying process was performed at 45 ° C. for 45 seconds.

[Processing step] Step Processing temperature (° C) Processing time (seconds) Replenishment amount Insert --- 1.2 Development + transfer 35 14.6 33cc / 4 cut Fix + transfer 33 8.2 63cc / 4 cut Rinse + transfer 18 7.2 3.51 / Min Squeeze 40 5.7 Dry 45 8.1 Total --45.0 (Developer) Potassium sulfite 70g Hydroxyethylethylenediamine trisodium triacetate 8g 1,4-dihydroxybenzene 28g Boric acid 10g 5-Methylbenzotriazole 0.04g 1-Phenyl-5-mercapto Tetrazole 0.01 g sodium metabisulfite 5 g acetic acid (90%) 13 g triethylene glycol 15 g 1-phenyl-3-pyrazolidone 1.2 g 5-nitroindazole 0.2 g glutaraldehyde
4g potassium bromide
4 g 5-Nitrobenzimidazole 1 g An aqueous solution of 1 liter was prepared and adjusted to pH 10.5 with sodium hydroxide.

(Fixing solution) Sodium thiosulfate-5-hydrate 4.5 g Disodium ethylenediaminetetraacetate 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10-18 water salt 10 g Sulfuric acid (50 wt%) 5 g Citric acid 1 g 7 g of boric acid 5 g of glacial acetic acid An aqueous solution of 1 liter was made to pH 4.2 with glacial acetic acid.

Further, the covering power of the obtained sample was measured.

After the covering power was measured, the sample was exposed to the maximum density, developed with a Kodak D-90 developing solution at 20 ° C. for 5 minutes, and then ace-fix fixing solution (Konica Corporation) fixed for 5 minutes in Etsu Chemical Co., Ltd.),
Washing with 2 l of running water per minute for 10 minutes and natural drying were performed to obtain a developed sample. The amount of silver in the obtained sample was determined by X-ray fluorescence analysis.
(G / dm ² ) was measured, and the covering power was determined by dividing the density by the amount of silver.

Further, the sensitization or desensitization due to the rubbing of the film was evaluated as a thread-like sensitization and a thread-like desensitization, respectively, and evaluated by the following methods.

After the samples were conditioned in an atmosphere of 70% relative humidity for 1 hour in a thread-like sensitized dark room, two samples were placed on a horizontal table and placed on top of each other.
While applying a load of Kg, the upper one of the two samples was pulled at a speed of 5 cm / Sec, and scratches were formed between the samples.

Next, the sample was developed in the same manner as in sensitometry, and visually evaluated according to the following five ranks.

1; thread scratches occur throughout the sample,
High fog density and large fog width 2; Blackening flaws due to threading occur on about half of the sample, fog density is somewhat high and fog width is moderate 3; Fog density is slightly high and fog width is medium 4; fog density is low and fog density is low and fog width is small 5; no fog is generated by thread and thread-like desensitization Same as thread-like sensitization Three minutes after forming the scratches between the samples, the entire surface was uniformly exposed to give a density of 1.0, and developed in the same manner as described above. The obtained sample was visually evaluated in the following five ranks.

1; Thread-like desensitization occurs over about 2/3 of the sample, and the desensitization is large and the density is clearly white. 2; Thread-like desensitization occurs over about 1/3 of the sample. , White spots are somewhat conspicuous; 3; some thread-like desensitization is observed, but the desensitized areas are white and blurred; 4; thread-like desensitization is slightly observed, but little noticeable. No desensitization occurred due to the evaluation of Kutzki films were superimposed on each other, sealed and packaged under the same conditions, and a load was applied so that a pressure of 20 g / cm ² was applied to the film.
After standing at 3 ° C. for 3 days, the degree of tightness between the films was evaluated in five steps as follows.

A: No adhesion at all B: Adhesion within 5% of the entire area C: Adhesion within 10% of the entire area D: Adhesion within 30% of the entire area E: Adhesion cracking at least 31% of the entire area Silica gel 10 completely dried in a desiccator
After 0 g was sealed together with the sample, the sample was left at 45 ° C. for 2 weeks, and then developed using the automatic developing machine described above.

Cracks were observed on the obtained sample using a 10-fold loupe, and the following five-stage evaluation was performed.

1; remarkably cracked, unusable level 2; many occurrences (outside of practical use tolerance) 3; slight occurrence (within practical use allowance) 4; very slight occurrence 5; no occurrence Are shown in Table 1 below.

[0101]

[Table 1]

As is clear from the results shown in Table 1, the sample of the present invention has higher sensitivity, higher image quality and higher covering power than the comparative sample, and has no threading and no cracking and has a thread-like increase. It can be seen that the feeling and the thread-like desensitization were improved.

[0103]

According to the present invention, a halogen which has high sensitivity, high image quality, high covering power, and has improved thread-like sensitization and desensitization without causing crackling and cracking, and which can be rapidly processed. A silver halide photographic light-sensitive material can be provided.

Claims (1)

(57) [Claims] 1. A support comprising at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on both sides of the support, wherein at least one of the emulsion layers has an average projected area of 50% or more. Polymer particles containing tabular silver halide grains having an aspect ratio of 3 or more and having a shell of crosslinked gelatin grafted to a core polymer on at least one of the emulsion layer and / or the non-photosensitive hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising: