JPH11237708A - Silver halide photographic element and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitivity even in the case of low replenished processing, to lower fog, to improve pressure characteristics, to prevent occurrence of roller marks, and to attain high enough film strength by incorporating inorganic fine particles combined with a high-boiling compound in an emulsion layer or a nonphotosensitive hydrophilic colloidal layer. SOLUTION: This photographic element is provided on a support with at least one silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer and at least one of these layers contains the inorganic fine particles combined with the high boiling compound combined on the surfacees of the particles by covalent bond. This compound has a boiling point >=100 deg.C and has a group capable of covalently bonding to the inorganic fine particles, and above all, the ones forming phosphoric and phthalic acid esters are preferable.

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 element and a processing method thereof, and more particularly, to a high sensitivity even when an ultra-rapid processing with a total processing time of 30 seconds or less is performed in an environment in which a replenishing amount of a developer is reduced. The present invention relates to a silver halide photographic element having low fog, excellent pressure characteristics and excellent film strength, and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, advances in electronics have dramatically shortened access times to images, and silver halide photographic elements have been required to be processed more and more rapidly.

In order to impart rapid processing properties, the amount of gelatin, which is a binder which has conventionally dispersed and protected silver halide grains, is reduced, and the developing speed, fixing speed, washing speed and drying speed of photographic processing are increased. The technology is known.
However, as the amount of gelatin used decreases, the high-sensitivity silver halide grains become more and more vulnerable to external pressure, and when processed by an automatic processor, a roller mark, called a roller mark, of a transport roller in a developing tank of the automatic processor is used. There is a problem that a large number of fine spot-like density non-uniformities occur due to the pressure caused by the unevenness. Therefore, as a technique for solving such a problem of handling properties, for example, Japanese Patent Application Laid-Open No. 9-218488 discloses a core / shell composite particle having a colloidal silica core and an organic polymer as a shell. I have. However, in this technology, although the roller mark is improved, since the shelling is performed with an organic polymer having a binder property, the effect of reducing the amount of the binder is poor,
It was found that the effect of improving the photographic performance was insufficient.

[0004] On the other hand, in recent years, global environmental pollution has been taken up as a global problem, and interest in waste has been increasing both in Japan and overseas. Under such circumstances, reduction of photographic processing waste liquid has become an urgent issue.

As means for achieving the above, conventionally, a technique of flattening silver halide grains or performing selenium sensitization on silver halide grains is disclosed in, for example, JP-A-4-29125.
No. 2. Also, when silver chloride is used as silver halide grains, the developability is rapid and the effect of halide ions on the developer is higher than that of Br and I ions.
Since the effect of the accumulation of the developer can be improved at a point where the l-ion is very small, it is advantageous for the low replenishment treatment.

However, in these techniques, the level of the replenishment amount is still insufficient, and if the level is to be further reduced, the level of the above-mentioned pressure resistance tends to deteriorate. Furthermore, even when combined with the above-mentioned composite fine particle technology, the photographic element 1 m ²
High sensitivity in ultra-rapid and low replenishment processing with a total processing time of 30 seconds or less with a development replenisher such as 35-98 ml per solution,
It was found that it was difficult to achieve all of low fog, pressure property and film strength.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high sensitivity, low fog, improved pressure characteristics, no roller marks, and a sufficient film strength even when processing at a low replenishment rate in consideration of the environment. And a method of processing the same.

[0008]

The above objects of the present invention have been attained by the following constitutions.

(1) In a photographic element having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, at least one of the emulsion layer and / or the non-photosensitive hydrophilic colloid layer is used. A silver halide photographic element further comprising inorganic fine particles having a compound having a high boiling point bonded thereto.

(2) The silver halide photographic element as described in (1) above, wherein the compound having a high boiling point has a phosphoric acid or phthalic acid moiety in its structure.

(3) The compound having a high boiling point having a phosphoric acid or phthalic acid moiety in its structure is a compound represented by the following general formula (1) or (2): A silver halide photographic element as described in 1 or 2.

[0012]

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[Wherein X is a halogen atom or OR
Represents _three groups. R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom,
It represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, but R ₁ and R ₂ are not simultaneously hydrogen atoms. ]

[0014]

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Wherein Y ₁ is a halogen atom or O
R _{4 represents a} group, and Y ₂ represents a halogen atom or an OR ₅ group. R ₄ and R ₅ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. n is 1 or 2. (4) The method for processing a silver halide photographic element according to the above item 1, 2 or 3, wherein an automatic developing machine having a total processing time of 10 to 30 seconds is used, and the developer is replenished with the photographic element 1.
A method for processing a silver halide photographic element, wherein the processing is performed at 35 to 98 ml per m < ² >.

The present invention will be described in more detail. The inorganic fine particles having a compound having a high boiling point bonded thereto used in the present invention are those in which a compound having a high boiling point is covalently bonded to the surface of the inorganic fine particles.

The compound having a high boiling point used in the present invention is a compound having a boiling point of 100 ° C. or higher and having a group capable of covalently bonding to the surface of inorganic fine particles. Above all, those which form a phosphoric acid ester or a phthalic acid ester are preferable, and a compound represented by the above general formula (1) or (2) is particularly preferable.

In the general formula (1) or (2), examples of the halogen atom include fluorine, chlorine, bromine, iodine and astatine, and chlorine is preferable. As the alkyl group,
A straight-chain or branched one having 2 to 30 carbon atoms is preferred, but it may form a ring. Examples of the aryl group include a phenyl group, a naphthyl group and an anthracenyl group, and a phenyl group is preferable. Examples of the substituent include an alkyl group, an acyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. Further, it may be further substituted with a halogen group in order to have a binding reactivity.
Among them, an alkyl group or an alkyl-substituted phenyl group is preferably used.

Preferred specific examples of the compound having a high boiling point used in the present invention are shown below.

[0020]

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[0021]

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[0022]

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[0023]

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The molecular weight of these compounds is 100 to 1000
And more preferably 200 to 600. Further, these compounds may be used alone or in combination.

The inorganic fine particles used in the present invention include:
Oxidation whose main component is selected from silicon, aluminum, titanium, indium, yttrium, tin, antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium, alkali metals, alkaline earth metals, etc. Among them, silicon oxide (colloidal silica), antimony oxide, titanium oxide, zinc oxide,
Zirconium oxide, tin oxide, vanadium oxide, yttrium oxide, aluminum oxide, and titanium oxide are preferred. The shape may be a flat shape or a needle shape, in addition to a spherical shape or an amorphous shape. As a flat plate,
Tabular silica is mentioned. The tabular silica means a layered silicate containing an alkali, an alkaline earth metal, aluminum or the like, and is described in detail in JP-A-7-64232. The synthetic clay described in JP-A-7-92606 is also included in this category. Specific examples include kaolinite, deckite, nacrite, halloysite,
Serpentine, pyrophyllite, talc, muscovite, swellable synthetic fluoromica, sericite, chlorite, smectite, vermiculite, swellable synthetic fluorine vermiculite. Their average particle size is from 1 nm to 5 μm.

A specific example will be described below.

CA-1 colloidal silica (average particle size 1
CA-2 Antimony pentoxide sol (average particle size 30 nm) CA-3 Smectite (average particle size 300 nm × 1 n)
m) CA-4 swellable synthetic fluorine mica (average particle size 3 μm ×
CA-5 Tin oxide sol (average particle diameter 30 nm) CA-6 Zinc oxide sol (average particle diameter 10 nm) CA-7 Aluminum oxide sol (average particle diameter 200 n)
m) CA-8 zirconium oxide sol (average particle size 500n)
m) CA-9 Yttrium oxide sol (average particle size 30 nm) CA-10 Niobium oxide sol (average particle size 30 nm) CA-11 Titanium oxide sol (average particle size 20 nm).

The preparation of the inorganic fine particles of the present invention can be obtained by adding a compound having a high boiling point to the inorganic fine particles dispersed in an organic solvent, mixing and stirring, adding a catalyst if necessary, or heating. In this process, both form a chemical bond, but preferably form an ester bond. After the reaction, remove the organic solvent used in the reaction, and in the presence of a dispersion stabilizer, use a homomixer, colloid mill, impeller disperser, etc., and optionally remove a small amount of a volatile organic solvent miscible with water such as alcohols and ethyl acetate. It is added and dispersed at warm or normal temperature to obtain an aqueous dispersion.

The organic solvent used in the reaction of the present invention includes alcohols (eg, methanol, ethanol, isopropanol, 2-methoxy-1-propanol, butanol, t-butanol, pentanol, neopentanol, cyclohexanol, -Methoxy-2-propanol), ethylene glycol, ethylene glycol-mono-n-propyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone,
Examples include methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, dioxolan, ethyl acetate, toluene, xylene and the like. These organic solvents may be used alone or in combination with each other. In some cases, other organic solvents may be mixed and used.

The dispersion stabilizer preferably used in the present invention is an anionic surfactant and / or a polymer dispersion stabilizer. Examples of the anionic surfactant used in the present invention include alkali metal salts of higher fatty acids such as sodium laurate, sodium stearate and sodium oleate, and higher alcohol sodium sulfates such as sodium laurate sulfate and sodium cetyl sulfate. Higher alkyl ether sulfates such as lauryl alcohol ethylene oxide adduct sulfates, sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated olefins, sodium alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, formalin condensed naphthalene sulfonates, α-olefin sulfonates, oleyl (N-methyl) taurides, di-2-sulfosuccinate Sulfosuccinic acid diester surfactants such as sodium tylhexyl ester, higher alcohol phosphate monoester disodium salt, higher alcohol phosphate diester monosodium salt, phosphate alcohol sodium salt of higher alcohol ethylene oxide adduct, zinc dialkyldithiophosphate, etc. Is mentioned. Of these, preferred are sodium salts of alkylbenzenesulfonic acid, alkylarylsulfonates, sulfosuccinic acid diester-type surfactants, and sodium phosphate esters of higher alcohol ethylene oxide adducts.

In the present invention, a polymer dispersion stabilizer may be used or used in combination as a dispersion stabilizer.
Preferred polymer dispersion stabilizers include gelatin, colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, carboxymethylcellulose, cellulose compounds such as hydroxymethylcellulose, polyvinyl alcohol, and terminal long-chain alkyl. Modified polyvinyl alcohol, N-vinylpyrrolidone, acrylic acid, methacrylic acid, maleic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, p-styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropane Constructs ethylenically unsaturated monomers such as sulfonic acid, vinyl alcohol, methyl vinyl ether, acrylamide, methacrylamide, diacetone acrylamide, vinylimidazole, and styrene Examples thereof include a homopolymer or copolymer having an element, and a synthetic hydrophilic polymer such as polyoxyethylene, polyoxypropylene, and poly-2-methyloxazoline. Further, as the polymer dispersion stabilizer, a graft polymer or a block polymer in which an anchor group and a dispersion stabilizing group are separated may be used. Among them, gelatin is particularly preferred.

The preferred molecular weight range of the high molecular weight dispersion stabilizer is 2,000 to 800,000, and the preferred concentration is 0.1 to 0.8.
It is from 05 g / liter to 50 g / liter.

The weight ratio of the compound having a high boiling point to the inorganic fine particles is preferably from 0.1% by weight to 100% by weight. The desired effect cannot be obtained with more or less than this.
The compounds having a high boiling point may be used alone or in combination of two or more.

The average particle size of the composite of the present invention is 0.005.
It is from 5 μm to 5 μm, preferably from 0.01 μm to 1 μm. If it is smaller or larger, the pressure resistance is insufficient.

The amount added to the photographic element is 0.1 g /
m ² ~10g / m ^2, preferably 0.1 g / m ² to 1.5
g / m ² .

In preparing the aqueous dispersion, it may be dispersed together with a compound having a high boiling point described below. In that case, it is necessary to pay attention to the addition amount so that the compound having a high boiling point is adsorbed on the surface of the inorganic fine particles of the present invention and the compound having the high boiling point alone does not form droplets. In that case, although it depends on the particle diameter of the inorganic fine particles of the present invention, 0.1% by weight to 100% by weight based on the weight of the inorganic fine particles.
Is preferably within the range.

The compound having a high boiling point has a boiling point of 100 ° C.
As described above, the compound used when dispersing a hydrophobic compound such as a coupler is dibutyl phthalate, di-N-
Phthalic acid esters such as octyl phthalate;
Trimetates such as 2-ethylhexyl trimellitate, aliphatic dibasic esters such as dibutyl adipate, phosphates such as tributyl phosphate and tricresyl phosphate, and ricinoleates such as methylacetyl ricinoleate; Examples thereof include acetates such as 2-ethylhexyl acetate and sulfonamides such as N-butylbenzenesulfonamide. Of these, phthalic esters and phosphoric esters are preferred.

An example of the synthesis of the inorganic fine particles of the present invention to which the compound having a high boiling point is bonded is described below.

(Synthesis of K-1) In a 500 ml three-necked glass flask equipped with a stirrer, a thermometer and a reflux condenser, 270 CA-1 dispersed in dimethylacetamide was added.
g (the solid concentration of CA-1 was 20% by weight) and 2.28 g of triethylamine. P while stirring under nitrogen stream
6.0 g of A-17 was added and heating was continued for 7 hours. After cooling to room temperature, the reaction product was added to distilled water to precipitate a reaction product, and further washed with distilled water to remove solvents. Distilled water 24
After adding 0 g of the obtained reaction product and 0.5 g of sodium dodecylbenzenesulfonate as a dispersion stabilizer to adjust the pH to 6.5, a high-speed stirrer (ULTRA-TURRRA) was added.
X T25 JANKE & KUNKEL IKA La
b. And 290 g of a dispersion having a solid content of 19.5% by weight was obtained. (Yield 93.5%) (Synthesis of K-2) CA-1 and P
The reaction product of A-17 was obtained. The reaction product obtained in 280 ml of distilled water, 6.0 g of tricresyl phosphate, and 0.1 g of sodium dodecylbenzenesulfonate as a dispersion stabilizer.
After adding 4 g and adjusting the pH to 6.5, a high-speed stirrer (UL
TRA-TURRAX T25 JANKE & KUNK
EL IKA Lab. And 340 g of a dispersion having a solid content of 18.5% by weight. (Yield 94.7%) (Synthesis of K-13) 300 g of CA-11 dispersed in acetonitrile (solid content of CA-11) was placed in a 500 ml glass three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. (A concentration of 20% by weight) and 0.5 g of concentrated sulfuric acid. While stirring under a nitrogen stream, 240.0 g of PA was added,
Heating was continued for 5 hours. After cooling to room temperature, the reaction product was added to distilled water to precipitate a reaction product, and further washed with distilled water to remove solvents. The obtained reaction product and 400 g of sodium di-2-ethylhexyl sulfosuccinate as a dispersion stabilizer were added to 400 ml of distilled water, the pH was adjusted to 6.5, and then a high-speed stirrer (ULTRA-TURRAX T25) was added.
JANKE & KUNKEL IKA Lab. And 490 g of a dispersion having a solid content of 19.0% by weight was obtained. (Yield 92.5%) (Synthesis of K-14) CA-1 was prepared in exactly the same manner as K-13.
The reaction product of 1 and PA-2 was obtained. 20. The reaction product obtained in 380 ml of distilled water and di-2-ethylhexyl phthalate.
After adding 0 g, 0.6 g of sodium sulfosuccinate di-2-ethylhexyl ester as a dispersion stabilizer and 10.0 g of alkali-treated gelatin, adjusting the pH to 6.5, a high-speed stirrer (ULTRA-TURRAX T25 JAN) was added.
KE & KUNKEL IKALab. And 490 g of a dispersion having a solid content of 23.0% by weight. (Yield 93.9%) Table 1 lists specific examples of the inorganic fine particles to which the compound having a high boiling point of the present invention is bound, but the present invention is not limited to these.

[0040]

[Table 1]

Gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids may be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, cellulose derivatives such as cellulose sulfate, sodium alginate, starch derivatives, dextran, dextrin, etc. Synthetic hydrophilic high-molecular substances such as sugar derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As the gelatin, an acid-treated gelatin may be used in addition to the alkali-treated gelatin, and a gelatin hydrolyzate and a gelatin enzyme-decomposed product may also be used. Gelatin amount of all the hydrophilic colloid layer is preferably from support per side 1.3~2.5g / m ^2, in particular 1.5~2.3g / m ² is preferred.

The silver halide used in the photographic element of the present invention is not limited, but tabular grains are preferably used in order to obtain high sensitivity. AgBr, AgCl, AgClBr, AgClBrI,
AgBrI, AgClBrI, etc. can be used arbitrarily, but AgBr or AgClBr is preferred.

Tabular grains are described in US Pat. No. 4,439,5.
No. 20, 4,425, 425, 4,414,30
No. 4, etc., and target tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. In order to control the photosensitive nuclei, a transition line may be provided on the surface or inside of the tabular grains.

The tabular grains are preferably tabular grains having an aspect ratio of 2 or more at least 50% of the total projected area of all grains in the emulsion layer in which the tabular grains are used. In particular, the proportion of tabular grains is from 60% to 70%, further 80%
The more favorable the result, the better the result. The aspect ratio here indicates the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. In the present invention, the aspect ratio is 2 or more and less than 20, 3 or more and 16 or less.
It is preferably less than.

The tabular grains preferably have a thickness of 0.5 micron or less, preferably 0.3 micron or less. The distribution of tabular grains has a coefficient of variation (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle) divided by the diameter D of 30% or less, particularly 2%.
It is preferable that the emulsion is a monodispersed emulsion having 0% or less. Further, two or more kinds of tabular grains and non-tabular grains of normal crystals may be mixed.

In order to control the growth of the grains during the formation of the tabular grains, for example, ammonia, a thioether compound, a thione compound or the like can be used as a silver halide solvent. In addition, metal salts such as zinc, lead, thallium, iridium, and rhodium can coexist during physical ripening or chemical ripening.

When at least 50% of the total projected area of the silver halide grains are tabular grains satisfying the following conditions, favorable results can be obtained in terms of low replenishment processing.

A) The parallel main plane is the (100) plane,
And the aspect ratio is 2 or more. b) The silver chloride content is 2
0 mol% or more. More preferably, the silver chloride content is 30 mol% or more and 70 mol% or less. More preferably, tabular grains satisfying the above conditions account for 80% of the total projected area.
That is all.

The term "principal plane" as used herein means a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains. Means the ratio of the thickness between the main planes to the edge length of the

The average edge length of the main plane can be determined, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the edge length of the particle on the print or the area at the time of projection. It is obtained by doing. (The number of measured particles is 100 indiscriminately.
It is assumed that there are zero or more. Also, the particle thickness can be obtained by actually measuring an electron micrograph.

The fact that the main plane is the (100) plane can be determined by an electron diffraction method or an X-ray diffraction method. According to electron micrograph observation, particles having a (100) principal plane have an orthogonal square (square or rectangular).
It can be checked because it is a surface.

The silver halide photographic emulsion of the present invention comprises (a)
A step of introducing a silver salt and a halide salt into a dispersion medium to form nuclei of tabular grains; (b) following nucleation, Ostwald ripening is performed under conditions that maintain the (100) major surface of the tabular grains. The step (c) is performed by a step of growing grains so as to have a desired particle size and silver chloride content.

It is preferable to use a double jet method (simultaneous mixing method) as a method of reacting a silver salt and a halide salt during nucleation.

The double-jet method is also used during grain growth. One type of double-jet method is a method of keeping pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method. It can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion, a part or all of the steps during grain formation may be grain forming steps by supplying fine silver halide grains.

Since the particle size of the fine particles governs the supply rate of the halide ions, the preferred particle size varies depending on the size and the halogen composition of the silver halide grains of the host, but those having an average sphere equivalent diameter of 0.3 μm or less are preferred. Used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the size of the fine particles is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/10 or less of the equivalent sphere diameter.

The silver halide emulsion to be used is subjected to a Nudel washing method, flocculation sedimentation method or the like in order to remove soluble salts after completion of the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or Exemplified G which is a polymer flocculant described in JP-A-2-7037 And desalting method using G-8 and the like. Also, Research Disclosure (RD) Vol. 102, 1972, October issue,
Item 10208 and Vol. 131, 1975, 3
Desalting may be performed by using an ultrafiltration method described in Monthly Date, Item 13122.

It is preferable to perform selenium sensitization or tellurium sensitization as chemical sensitization of the emulsion. The selenium sensitizer used in the present invention includes a wide variety of selenium compounds. For example,
Regarding this, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, JP-A-4-109240, No. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N
-Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. That is, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447 and 3,320,069, Nos. 3,408,196, 3,408,197, 3,442,653, 3,420,670, 3,591,385 and French Patent No. 2693038
No. 2093209, Japanese Patent Publication No. 52-34491,
Nos. 52-34492, 53-295, 57-2
No. 2090, JP-A-59-180536 and JP-A-59-1
Nos. 85330, 59-181337, 59-18
Nos. 7338, 59-192241, 60-150
No. 046, No. 60-151637, No. 61-2467
No. 38, JP-A-3-4221 and JP-A-3-24537,
3-1-111838, 3-116132, 3-
148648, 3-237450, 4-168
No. 38, No. 4-25832, No. 4-32831, No. 4-96059, No. 4-109240, No. 4-14
No. 0738, No. 4-140739, No. 4-14725
No. 0, No. 4-149337, No. 4-184331,
4-190225, 4-191729, 4-
No. 195035, British Patent Nos. 255,846 and 8619
No. 84. In addition, H. E. FIG. Journa by Spencer et al.
l of Photographic Science
Journal, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 mol to 10 mol per mol of silver halide.
^Use about ^-4 moles. Depending on the properties of the selenium compound to be used, the addition method may be a method of dissolving in water or an organic solvent such as methanol, ethanol or ethyl acetate alone or in a mixed solvent, or a method of preliminarily mixing with a gelatin solution. Also, the method of adding
No. 9, that is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The temperature of chemical ripening using a selenium sensitizer is as follows:
A range from 40 to 90C is preferred. More preferably 45 ° C
Not less than 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferred.

For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, UK Patent No. 235,21
No. 1, No. 1, 121, 496, No. 1, 295, 462
No. 1,396,696, Canadian Patent No. 800,9
No. 58, JP-A-4-204640, JP-A-4-3330
No. 43 and the like. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl). -N'phenyltellurourea), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides (e.g., , Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.
The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

Further, selenium sensitization or tellurium sensitization may be used in combination with sulfur sensitization, reduction sensitization, and noble metal sensitization.

As the sulfur sensitizer, US Pat. No. 1,57
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
Nos. 1,313 and 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-249.
Nos. 37 and 55-45016 can be used. As a specific example,
1,3-diphenylthiourea, triethylthiourea, 1
Preferred examples thereof include thiourea derivatives such as -ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

It is also preferable to use reduction sensitization in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains.

Examples of gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amount of the selenium sensitizer, tellurium sensitizer, sulfur sensitizer, reduction sensitizer and gold sensitizer depends on the type of silver halide emulsion, the type of compound used and the ripening conditions. Usually, it is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The selenium sensitizer, tellurium sensitizer, sulfur sensitizer, reduction sensitizer and gold sensitizer can be added by dissolving them in water or alcohols, or other inorganic or organic solvents, and adding them in the form of a solution. It may be added, or may be added in the form of a dispersion obtained by emulsifying and dispersing using a solvent such as water-insoluble solvent or gelatin.

The silver halide photographic emulsion of the present invention can be spectrally sensitized with a sensitizing dye, but any sensitizing dye can be used. For example, a cyanine dye can be preferably used. In that case, the compounds of S-1 to S-124 represented by the general formulas (I) to (III) described in JP-A-1-100533 can be preferably used.

When the above sensitizing dye is added, 2
More than one species may be used in combination. In this case, two or more sensitizing dyes may be mixed and added simultaneously, or may be added separately at different times. The amount of addition is 1 mg to 1000 mg, preferably 5 mg to 50 mg per mol of silver.
0 mg is good. Further, it is preferable to add potassium iodide before adding these sensitizing dyes and then add them.

The sensitizing dye may be added at the time of silver halide grain formation and at any time after the formation and before coating, but is preferably before the end of the desalting step.

The pH of the reaction solution (usually in a reaction vessel) at the time of addition is preferably in the range of 4 to 10. More preferably, the pH is in the range of 6 to 9. The pAg in the reaction solution (reaction vessel) is preferably 5 to 11.

The sensitizing dye can be directly dispersed in the emulsion. They can also be dissolved in a suitable solvent, for example, methanol, ethanol, acetone, water, pyridine or a mixed solvent thereof, and added in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, the water-insoluble sensitizing dye may be added as a fine particle dispersion by high-speed impeller dispersion without dissolving in water.

In the present invention, as matting agents, US Pat. Nos. 2,992,101 and 2,701,245
No. 4,142,894, No. 4,396,70
No. 6, a homopolymer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, amorphous silica,
Fine particles of an inorganic compound such as titanium dioxide, strontium sulfate, and barium sulfate can be used. The particle size is preferably 0.6 to 10 μm, particularly preferably 1 to 5 μm.

In the surface layer of the photographic element of the present invention, US Pat. Nos. 3,489,576 and 4,047,
No. 958, etc., JP-B-56-2
In addition to the colloidal silica described in JP-A-3139, paraffin wax, higher fatty acid esters, starch derivatives and the like can be used.

In the constituent layers of the photographic element of the present invention, trimethylolpropane, pentanediol, butanediol,
Polyols such as ethylene glycol and glycerin can be added as plasticizers.

Further, the constituent layers of the photographic element of the present invention include:
A polymer latex can be included 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 or styrene, a styrene-butadiene copolymer, a polymer or copolymer comprising a monomer having an active methylene group, a water-soluble group or a crosslinkable group with gelatin is preferred. Can be used. In particular, in order to increase the affinity with gelatin as a binder, an alkyl ester of acrylic acid, a copolymer with a monomer having a water-soluble group mainly composed of a hydrophobic monomer such as styrene or a crosslinkable group with gelatin is most preferable. Used. Preferred examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid, and preferred examples of the monomer having a crosslinkable group with gelatin. Examples thereof include glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, and the like.

When the photographic element of the present invention is used as a medical double-sided emulsion X-ray sensitive material, it is preferable to provide a transverse light blocking layer for the purpose of improving image sharpness. The transverse light blocking layer contains a solid fine particle dispersion of a dye for the purpose of absorbing transverse light. Such a dye is not particularly limited as long as it has a structure that is soluble in an alkali having a pH of 9 or more and has a structure that is hardly soluble at a pH of 7 or less. The compound of the general formula (1) described in JP-A-308670 is preferably used.

Preferred developers for developing the photographic element of the present invention include, as developing agents, JP-A-4-15641,
Examples of dihydroxybenzenes described in JP-A-4-16841, for example, hydroquinone, paraaminophenols, for example, p-aminophenol, N-methyl-p-aminophenol, 2,4-diamiphenol, etc.
Examples of the pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone,
It is preferable to use phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and to use these in combination.

The above-mentioned paraaminophenols, 3-aminophenols
The preferred amount of the aminopyrazolidones used is 0.004 mol / l, more preferably 0.04 to 0.1.
2 mol / l.

The total mole number of dihydroxybenzenes, paraaminophenols, and 3-pyrazolidones contained in all the components of the developing solution is preferably 0.1 mol / liter or less.

Preservatives may include sulfites, such as potassium sulfite, sodium sulfite, reductones, such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Furthermore, a buffer such as borate described in JP-A-61-28708 and saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 may be used. Good. The content of these chemicals should be adjusted to a pH of the developer of 9.0 to 13, preferably p.
H10 to 12.5.

Examples of the dissolution aid include polyethylene glycols and esters thereof. Examples of the sensitizer include:
For example, a development accelerator, a surfactant and the like such as a quaternary ammonium salt can be contained.

The silver sludge inhibitor is disclosed in
No. 106244, silver stain inhibitor, JP-A-3-
The sulfide and disulfide compounds described in the specification of Japanese Patent Application No. 51844, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used. Chelating agents for concealing calcium ions mixed in tap water used in the treatment liquid include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-193853 as an organic chelating agent. It is preferably used.
Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The replenishment in the present invention replenishes the processing fatigue and the oxidative fatigue equivalent, but 35 to 9 per m ^{2 of} the photographic element.
Perform with a replenishment volume of 8 ml. Examples of the replenishment method include replenishment by width and feed speed described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area controlled by the number of continuously processed sheets described in JP-A-1-149156. It may be supplemented.

Preferred fixing solutions may include fixing materials commonly used in the art. pH3.
8 or more, preferably 4.2 to 5.5.

As the fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferred in view of the fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l.

The fixing solution of the present invention may be one that forms an acidic film. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

The fixing solution of the present invention may further contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid or oxalic acid). ,
Various acids such as malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium), and chelating agents having water softening ability can be contained.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

The silver halide emulsion layer of the present invention preferably has a swelling ratio of 150 to 250% during the development process, and a film thickness after swelling of 70 μm or less. 250% water swelling
If the temperature exceeds the limit, drying failure occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. On the other hand, when the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling ratio is the difference between the film thickness after swelling in each processing solution and the film thickness before development processing,
This is a value obtained by dividing 100 times the film thickness before processing.

The photographic element of the present invention has a total processing time of 10 to 3 times.
It shows excellent performance in rapid development processing by an automatic developing machine at 0 seconds. In the rapid processing of the present invention, the temperature and time for development, fixing and the like are each about 25 ° C. to 50 ° C. for 15 seconds or less, preferably 30 ° C. to 40 ° C. for 2 seconds to 10 seconds.
In the present invention, the photographic element is washed after being developed and fixed. Here, in the rinsing step, water can be conserved by using a two- or three-stage countercurrent rinsing method. When washing with a small amount of washing water, a squeeze roller washing tank is preferably provided. The temperature and time of the water washing step are preferably 5 ° C to 50 ° C for 2 seconds to 10 seconds. In the present invention, the developed, fixed and washed photographic elements are dried through a squeeze roller. As a drying method, any one or a combination of hot air convection drying, radiation drying with a far-infrared heater, and heat transfer drying with a heat roller can be used. The drying temperature and time are from 40 ° C to 100 ° C for 4 seconds to 15 seconds. The total processing time in the present invention means that after inserting the leading end of the film into the insertion opening of the automatic developing machine, the developing tank, the transition portion, the fixing tank,
This is the total time from when the film passes through the transfer section, the washing tank, the transfer section, and the drying section until the film tip comes out of the drying outlet. Since the silver halide photographic element of the present invention can reduce the amount of gelatin used as a binder for the emulsion layer and the protective layer without impairing the pressure characteristics, the development speed can be increased even in a rapid processing of 10 to 30 seconds. The developing process can be performed without impairing the fixing speed and the drying speed.

Hereinafter, embodiments of the present invention will be described. Note that, needless to say, the present invention is not limited to the embodiments described below.

[0098]

EXAMPLES Example 1 (Preparation of Tabular Grain Emulsion of Silver Chlorobromide (Br / Cl = 45/55)) First, a seed emulsion was prepared as follows.

Preparation of EM-C (Pure Silver Chloride Tabular Seed Emulsion) A1 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water B1 Silver nitrate 1500 g Make up 2500 ml with distilled water 4 g of C1 KI NaCl 140 g Make up to 684 ml with distilled water D1 NaCl 375 g Make up to 1816 ml with distilled water At 40 ° C., JP-B-58-58288, 58-58
No. 58289, solution A1 in a mixing stirrer
684 ml of solution B1 and the total amount of solution C1 were added thereto over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the remaining amount of solution A1 and solution D
1 was added over 40 minutes. Meanwhile, EAg is 1
Controlled to 49 mV.

Immediately after the addition was completed, desalting and washing were performed to obtain a seed emulsion EM-C. Seed emulsion EM-C thus prepared
Means that at least 60% of the total projected area of silver halide grains is (1
00) a tabular grain having a plane as a main plane, an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a variation coefficient of 25.
% By electron microscope observation.

[0102] A2 ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) 10 % D2 1.75 N NaCl aqueous solution to 2240Ml 0.98 mole equivalent of distilled water in methanol solution 1.25ml seed emulsion EM-C silver amount B2 3.50N AgNO ₃ solution 2240ml C2 NaCl 455g KBr 473g distilled water to 3000ml At the following silver potential control amount of 40 ° C., JP-B-58-58288 and 58-58288
Using a mixing stirrer described in the specification of Japanese Patent No. 58289, the total amount of the solution B2 and the solution C2 is added to the solution A2 by a simultaneous mixing method (double jet method) so that the flow rate at the end of addition is three times the flow rate at the start of addition. It took 110 minutes to perform additional growth. During this time, the silver potential was increased by +10 using solution D2.
It controlled so that it might be set to 0 mV.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate in order to remove excess salts.

When about 3,000 of the obtained emulsions were observed and measured by an electron microscope and analyzed for their shapes, 80% or more of the total projected area had a (100) plane as the main plane, an average diameter of 1.17 μm, and an average diameter of 1.17 μm. The particles were tabular grains having a thickness of 0.12 μm, and the coefficient of variation was 24%.

(Preparation of silver iodide fine particles) A3 ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water B3 AgNO ₃ 360 g Make up to 605 ml with distilled water C3 KI 352 g Make up 605 ml with distilled water Solution A3 in a reaction vessel , And the solution B3 and the solution C3 were added at a constant speed over 30 minutes by a simultaneous mixing method while stirring at 40 ° C.

The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide has an average grain size of 0.06.
It was a mixture of μm β-AgI and γ-AgI. This emulsion is called a silver iodide fine grain emulsion.

(Preparation of solid fine particle dispersion of spectral sensitizing dye) The following spectral sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) was added. ) At 3,500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine salt Anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 '-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride (chemical sensitization) Next, the obtained emulsion was subjected to spectral sensitization and chemical sensitization according to the following method to give chemical sensitization. An emulsion was obtained.

After the emulsion was heated to 60 ° C., the solid fine particle dispersion was added so that the sensitizing dye (A) was 460 mg per mol of silver, and then ammonium thiocyanate was added to the emulsion at 7.0 per mol of silver. × 10 ^-4 mol, potassium chloroaurate, sodium thiosulfate, and triphenylphosphine selenide were added at 3.0 × 10 ^-6 mol per mol of silver to perform optimal chemical ripening. 3 emulsion
× 10 ^-3 mol / Ag mol was added, and then 4-hydroxy-6 was added.
-Methyl-1,3,3a, 7-tetrazaindene (TA
I) Stabilized at 3 × 10 ^-2 mol.

Next, the emulsion thus sensitized was
Additives described below were added to obtain an emulsion layer coating solution. At the same time, a coating solution for the transverse light shielding layer and a coating solution for the protective layer were prepared.

<Preparation of Sample> The following transverse light-shielding layer coating solution, emulsion layer coating solution, protective lower layer coating solution, and protective upper layer coating were applied to both sides of a polyethylene terephthalate support provided with an undercoat layer containing tin oxide sol. The solution was simultaneously and sequentially coated from the bottom so as to have a predetermined coating amount described below, followed by drying.
The following numerical values are the coating amounts per 1 m ² .

First layer (transverse light-shielding layer (AHL)) Gelatin 0.2 g Solid fine particle dispersion dye (AH) 20 mg Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1 5,3,5-Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Latex (L) 0.1 g Potassium polyethylenesulfonate 50 mg Second layer (emulsion layer (EML)) Potassium tetrochloropalladate (II) with various additives 100 mg Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 5 mg Polyvinylpyrrolidone (molecular weight 10,000) 20 mg styrene Maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 50 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 1 mg 1,3-Dihydroxybenzene-4-ammonium ammonium sulfonate 50 mg 2-Mercaptobenzimidazole-5-sulfonic acid sodium 5mg compound _{(H) 0.5mg n-C 4} H 9 OCH 2 CH (OH) CH 2 n (CH 2 COOH) 2 20mg compound (M) 5mg compound (n) 5mg latex (L) 0.2 g invention (See Table 2) Dextran (average molecular weight: 40000) 0.2 g Sodium styrenesulfonate (molecular weight: about 500,000) 7 mg However, the total weight of one side of gelatin is 1.8 g / m.
Adjusted to be ² .

Third Layer (Protective Layer Lower Layer (EPD)) Gelatin 0.2 g Dioctyl phthalate 0.1 g Latex (L) 0.2 g Sodium polyacrylate (average molecular weight 50,000) 30 mg Sodium styrene sulfonate (molecular weight about 500,000) 7 mg Fourth layer (protective layer upper layer (EPU)) Gelatin 0.28 g Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 27 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine Sodium salt 10 mg Latex (L) 0.1 g Colloidal silica (average particle size 0.014 μm) 50 mg Polyacrylamide (average molecular weight 10,000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (S1) 50 mg Compound of the present invention (see Table 2) ) Compound (I) 30 m Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg Compound (F-1) 3 mg Compound (F-2) 2 mg Compound (F-3) 1 mg Compound (F-4) 10 mg Compound (P) 50 mg The amount of the raw material was one side, and the amount of applied silver was adjusted to be 1.0 g / m ² as one side. The structure of the compound used in the above sample is shown below.

[0113]

Embedded image

[0114]

Embedded image

[0115]

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The obtained samples were evaluated as described below, and the results are shown in Table 2. 1) Evaluation of sensitivity The coated and dried samples were stored at 23 ° C. and 55% RH for 3 days, and then intensified screen KO for X-ray photography was used. -250 scissors, after X-ray irradiation through penetrometer B type, using a roller transport type automatic developing machine (SRX-501: manufactured by Konica Corporation) modified to increase the transport speed, using a developer having the following composition And a fixing solution.

[0117] Developing solution formulation Part-A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to make 5000 ml.

Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to finish to 1.0 L .

Fixer Formulation Part-A (for finishing 18 liters) Ammonium thiosulfate (70 wt / vol%) 6000 g sodium sulfite 110 g sodium acetate trihydrate 450 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18 g Part-B 800 g of aluminum sulfate To prepare a developer, add Part A and Part B simultaneously to about 5 l of water, add water while stirring and dissolving, add 12 l of water, and adjust the pH to 10.40 with glacial acetic acid. It was adjusted. This is used as a development replenisher.

The starter described above was added at 20 ml / l to 1 liter of the replenisher for development to adjust the pH to 10.26 to obtain a working solution.

The fixer was prepared by adding Part A, P to about 5 l of water.
ArtB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The sensitivity was expressed as a relative value with the reciprocal of the amount of exposure energy required to give the sample 1 a density of fog +1.0 as 100. The fog value was shown as a net value after subtracting the base density.

2) Evaluation of brittleness The coated and dried sample was stored at 23 ° C. and 55% RH for 3 days, seasoned at 40 ° C. and 0% RH for 1 hour or more, and then subjected to ISO 6077 “Wedge brittle”.
In the same manner as in the “essence test”, the average value of the points where cracks first occurred was determined. The higher the value,
It is brittle, indicating that cracking is easy to occur.

3) Evaluation of Roller Mark The sample was uniformly exposed to a size of 10 × 12 inches so as to have a blackening density of 1.0, and then subjected to the above processing. However, the developing rack and the transition rack from the development to the fixing used at this time were intentionally fatigued. That is,
Due to the fatigue of the rollers of each rack, irregularities of about 10 μm were formed on the entire surface. Due to the pressure caused by the unevenness in the sample after the treatment, many fine spot-like density unevennesses occurred in the sample having poor pressure resistance. This level was visually evaluated according to the following ranks.

5 No spots were generated 4 Levels where spots were slightly generated but did not cause a problem in practice 3 Permissible limit level where small spots were generated but not normally generated on racks 2 Spots were generated and Occasionally occurring on racks 1 Spots frequently occur. It is always occurring even in normal racks.

[0126]

[Table 2]

Comparative a is Snowtex C manufactured by Nissan Chemical Co., Ltd., and Comparative b is composite fine particle P-2 described in Synthesis Example 1 of JP-A-9-218488.

As is evident from Table 2, the present invention provides excellent photographic elements having high sensitivity, low fog, roller marks and sufficient film strength.

Example 2 Sample No. 1 prepared in Example 1 was used. 2,5,9,12,1
6, 18, and 20 were subjected to X-ray exposure, and the developing solution of Example 1 was used.
Using the fixing solution, the automatic developing machine used in Example 1 was used, and each sample was processed under the following conditions until the running equilibrium was reached.

[0130] Replenishment conditions Running 1 equilibrium solution 1 Running equilibrium solution 2 per 4 slices (10 × 12 inches) Development replenishment amount 14.0 ml 7.0 ml (180 ml / m ² ) (90 ml / m ² ) Fixing replenishment amount 14.0 ml 7.0ml (180ml / m ²⁾ sample prepared in (9Oml / m ²⁾ example 1 No. 2,5,9,12,1
6, 18, and 20 were used as the running equilibrium solution 1 (condition 1).
Using the running equilibrium solution 2 (condition 2) under the above conditions, the sensitivity and the roller mark were evaluated. Table 3 shows the results.

[0131]

[Table 3]

As is evident from Table 3, it can be seen that the present invention can provide an excellent photographic element having a small decrease in sensitivity, a low fog, and no occurrence of roller marks even in ultra-rapid processing at a low replenishment rate.

[0133]

As described above, according to the present invention, an excellent photographic element which has a small decrease in sensitivity even in ultra-rapid processing at a low replenishing rate, has low fog, and does not generate roller marks, and a processing method therefor can be obtained.

Claims (4)

[Claims] 1. A photographic element having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, at least one of said emulsion layer and / or non-photosensitive hydrophilic colloid layer. A silver halide photographic element characterized by further comprising inorganic fine particles having a compound having a high boiling point bonded thereto. 2. A silver halide photographic element according to claim 1, wherein the compound having a high boiling point has a phosphoric acid or phthalic acid moiety in its structure. 3. The compound having a high boiling point having a phosphoric acid or phthalic acid moiety in its structure is a compound represented by the following general formula (1) or (2). A silver halide photographic element as described in 1 or 2. Embedded image [In the formula, X represents a halogen atom or an OR ₃ group.
R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, but R ₁ and R ₂ are not simultaneously hydrogen atoms. [Chemical formula 2] Wherein, Y ₁ is a halogen atom, or an OR ₄ group, Y ₂
Represents a halogen atom or an OR ₅ group. R ₄ and R ₅
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. n is 1 or 2. ] 4. A method for processing a silver halide photographic element according to claim 1, wherein the total processing time is from 10 to 30.
Using an automatic developing machine is seconds, and method for processing a silver halide photographic element the replenishment of developer and performing in the photographic elements 1 m ² per 35～98Ml.