JPH09211765A - Silver halide photographic element and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic element having aptitude to ultrahigh speed processing, such as keeping sensitivity high and improving pressure characteristics and preventing occurrence of roller marks even in the case of processing in a small amount of a replenishing solution considering environmental problems. SOLUTION: This photographic element has, on a support, silver halide emulsion layers and at least each one nonphotosensitive hydrophilic colloidal layer on one of this emulsion layer, and at least one of the emulsion layers contains flat silver halide grains occupying >=50% of the projection areas of the total silver halide grains and having an aspect ratio of >=2, and the emulsion layer or the nonphotosensitive hydrophilic colloidal layer contains minute truely spherical particles having an average particle diameter of 1.1-10μm and composed mainly of silicon, and all the hydrophilic colloidal layers on one side of the support contains gelatin in an amount of 1.3-2.5g/m<3> .

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 method for processing the same, and particularly to high sensitivity even when subjected to ultra-rapid processing in a total processing time of 30 seconds or less in an environment in which the replenishment amount of a developing solution is reduced. The present invention provides a silver halide photographic element having excellent pressure characteristics and a processing method thereof.

[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.

Therefore, silver halide grains are also required to have high sensitivity, and tabular silver halide grains are often used. This is because flattening increases the projected area, increases the amount of received light per unit grain, and allows a large amount of sensitizing dye or the like to be adsorbed, so that higher spectral sensitization is expected. Regarding the use of the tabular silver halide grains described above in a silver halide photographic light-sensitive material having gelatin as a binder, U.S. Pat. Nos. 4,386,156 and 4,3,4 are disclosed.
No. 99,215, No. 4,414,304, No. 4,42
No. 5,425, etc., the description is found.

On the other hand, in order to provide rapid processing, the amount of gelatin, which is a binder which has conventionally been used to disperse and protect silver halide grains, is reduced, and the developing speed of photographic processing is reduced.
Techniques for increasing a fixing speed, a washing speed, and a drying speed are known. However, as the amount of gelatin used decreases, the high-sensitivity silver halide grains become more and more vulnerable to external pressure,
When processed by an automatic developing machine, there arises a problem that a large number of fine spot-like density unevenness occurs due to the pressure caused by the unevenness of the transport roller in the developing tank of the automatic developing machine, which is called a roller mark. This problem is prominent in highly sensitive tabular silver halide grains. Therefore, as a technique for solving this problem, for example, Japanese Patent Laid-Open No.
No. 159634 discloses a combination of the regulation of the elution amount of an organic substance at the development processing and the inclusion of a matting agent in the emulsion layer, but the effect is not sufficient, and the total processing time is 30 seconds. The effect was slight when the following ultra-rapid treatment was performed.

[0005] 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 abroad, and corporate responsibilities have been questioned. Under such circumstances, reduction of photographic processing waste liquid has become an urgent issue.

As means for achieving the above, there have heretofore been known techniques for flattening silver halide grains or performing selenium sensitization on silver halide grains.
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, it has been found that with these techniques, the level of replenishment amount reduction is still insufficient, and if further reduction is attempted, the level of pressure resistance deteriorates.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic element having an ultra-rapid processing suitability in which sensitivity is improved and pressure characteristics are improved even when processing in a low replenishing amount in consideration of environment, and roller marks are not generated. It is to provide the processing method.

[0009]

The above objects of the present invention are as follows: 1) At least one silver halide emulsion layer on a support, and at least one non-photosensitive hydrophilic colloid above and below the silver halide emulsion layer. In a photographic element having a layer, at least one of the emulsion layers contains tabular grains having an aspect ratio of 2 or more in at least 50% of the total projected area of silver halide grains, and the emulsion layer and / or the supporting layer. The non-photosensitive hydrophilic colloid layer between the body and the emulsion layer has an average particle size of 1.1 μm to 10 μm, contains true spherical particles containing silicon as a main component, and is a hydrophilic colloid layer on one side of the support. A silver halide photographic element characterized in that the amount of gelatin in the range from 1.3 to 2.5 g / m < ² > is 2) two parallel main planes of the tabular silver halide grains are (100) planes, And silver chloride content 20 % Or more, 1) The silver halide photographic element according to 1), 3) The tabular silver halide grains are chemically sensitized with a selenium or tellurium compound, and 1) or 2) is described. 4) A silver halide photographic element according to any one of 1) to 3) above, wherein the silver halide photographic element is 35 to 98 ml per 1 m ^{2 of the} photographic element.
And a processing method for silver halide photographic elements characterized by processing in an automatic processor having a total processing time of 10 to 30 seconds.

The present invention will be described in detail below.

The average particle size of the present invention is 1.1 μm to 10 μm.
The true spherical particles containing silicon as the main component will be described with reference to m. The true spherical shape means that the particle has a spherical shape, and the particle diameter ratio of the major axis to the minor axis is 0.98 to 1.00 in any cross section through the center point of the particle. The average particle size is in the range of 1.1 μm to 10 μm,
It is preferably 3 μm to 6 μm. If it is smaller or larger, the pressure resistance is insufficient. The main component is silicon, but titanium, zirconia, aluminum,
It may be combined with cerium or yttrium. Examples of the compound include inorganic compounds such as silicon dioxide, silicon nitride, calcium silicate, barium silicate, magnesium silicate, silica-titania composite oxide, silica-zirconia composite oxide, silica-cerium composite oxide, and silica-tin composite oxide. The organic crosslinked silicone resin particles described in the general formula (1) of JP-A-63-237054 can be mentioned.

Of these, silicon dioxide and organic crosslinked silicone resin particles are preferably used. Further, when it is an inorganic compound, it may be non-porous or porous and may have voids inside. The added amount is 5 mg / m ^{2 to} 200 m
g / m ² , preferably 20 mg / m ^{2 to} 100 mg / m ²
It is.

A specific example will be shown below.

K1 silicon dioxide average particle size 1.1 μm non-porous K2 silicon dioxide average particle size 2.0 μm non-porous K3 silicon dioxide average particle size 4.0 μm non-porous K4 silicon dioxide average particle size 10.0 μm non-porous Quality K5 Silicon dioxide average particle size 4.0 μm Porous (average pore size 60 Å) K6 Silicon dioxide average particle size 4.0 μm Porous (average pore size 100 Å) K7 Silicon nitride average particle size 4.0 μm Non-porous K8 calcium silicate Average particle size 4.0 μm non-porous K9 barium silicate average particle size 4.0 μm non-porous K10 magnesium silicate average particle size 4.0 μm non-porous K11 silica-titania composite oxide (composite ratio silica / titania 70/30) Average particle size 3.0 μm Non-porous K12 silica-zirconia composite oxide (composite ratio silica / zirconia 95/5) Average particle size 4 0μm porous (average pore diameter 60 Å) K13 silica - cerium composite oxide (composite ratio silica / cerium 90/10) Average particle diameter 6.0μm nonporous K14 organic crosslinked silicone resin particles (CH ₃ -SiO _{1.5) n} Mean Particle size 3.0 μm K15 organic crosslinked silicone resin particles (CH ₃ —SiO _1.5 ) _n average particle size 4.5 μm K16 organic crosslinked silicone resin particles (C ₆ H ₅ —SiO _1.5 ) _n average particle size 4.5 μm The fine particles are added to the emulsion layer and / or the non-photosensitive hydrophilic colloid layer between the support and the emulsion layer. Even if it is placed in a layer located farther from the support than the emulsion layer such as a protective layer, the desired effect cannot be sufficiently obtained.

In the present invention, the amount of gelatin in the total hydrophilic colloid layer including the emulsion layer on one side of the support is preferably 1.3 to 2.5 g / m ² per one side of the support, and particularly 1.5 to.
2.3 g / m ² is preferred. Examples of gelatin include alkali-treated gelatin and acid-treated gelatin.

As the silver halide used in the photographic element of the present invention, tabular grains are used in order to obtain high sensitivity.
AgBr, AgCl, AgCl as the silver halide composition
Although Br, AgBrI, AgClBrI and the like can be arbitrarily used, AgBr or AgClBr is preferable.

Tabular grains are described in US Pat. No. 4,439,5
20, No. 4,425,425, No. 4,414,304, 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 of the present invention are preferably tabular grains having an aspect ratio of 2 or more in 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used. Particularly, as the proportion of tabular grains increases from 60% to 70%, and more preferably to 80%, more favorable results are obtained. Here, the aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes. In the present invention, the aspect ratio is 2 to less than 20, 3
It is preferably at least 16 and less than 16.

The tabular grains of the present invention preferably have a thickness of 0.5 micron or less, preferably 0.3 micron or less. The distribution of tabular grains is such that the coefficient of variation often used (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter D) is 30% or less, particularly 20% or less. It is preferably a monodisperse emulsion.
Further, two or more tabular grains and non-tabular grains of normal crystals may be mixed.

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

When the silver halide grains of the present invention are tabular grains satisfying the following conditions in an amount of 50% or more of the total projected area, preferable results can be obtained from the viewpoint of low replenishing treatment.

A) The parallel principal planes are (100) planes,
And the aspect ratio is 2 or more.

B) The silver chloride content is 20 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% or more of the total projected area.

The principal plane here is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the aspect ratio is the average forming the principal plane of grains. The ratio of the thickness between the main planes to the edge length of the.

The average edge length of the main plane is obtained by, for example, photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the edge length of the particles on the print or the area at the time of projection. It is obtained by doing. (The number of measured particles is 100 indiscriminately.
There shall be 0 or more. The particle thickness can also be obtained by actually measuring an electron micrograph.

The fact that the principal plane is the (100) plane can be examined 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 is preferably (a) a step of introducing a silver salt and a halide salt into a dispersion medium to form nuclei of tabular grains, and (b) following nucleation, a tabular grain. Prepared by the step of performing Ostwald ripening under the condition of maintaining the (100) major surface of the granular particles, and (c) the step of growing the grains so that the desired grain size and silver chloride content are obtained.

A double jet method (simultaneous mixing method) is preferably used as a method of reacting a silver salt and a halide salt during nucleation.

The simultaneous mixing method is also used at the time of grain growth. One of the methods of the simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, 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 of the present invention, part or all of the steps during grain formation may be a grain formation step by supplying fine silver halide grains.

Since the grain size of fine grains controls the supply rate of halide ions, the preferred grain size varies depending on the size and the halogen composition of the silver halide grains of the host, but those having an average equivalent spherical diameter of 0.3 μm or less are preferable. 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 used in the practice of the present invention comprises the Nudel water washing method and flocculation so as to remove the soluble salts after the growth of the silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. A precipitation method or the like may be used, and a preferable washing method is, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-2-
Illustrative G-3, G-, which is a polymer flocculant described in No. 7037
8 and the like. Also, Research Disclosure (RD) Vol. 102,
1972, October issue, Item 10208 and Vol.
131, 1975, March issue, Item 13122, may be used for ultrafiltration.

The silver halide emulsion of the present invention is preferably subjected to selenium sensitization or tellurium sensitization as chemical sensitization.
The selenium sensitizer used in the present invention includes a wide variety of selenium compounds. For example, in this regard, U.S. Pat.
574,944, 1,602,592, 1,6
23,499, JP-A-60-150046, JP-A-4-25832, JP-A-4-109240, and JP-A-4-14
No. 7250 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'-heptafluoropropylcarbonyl selenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonyl selenourea, etc.), selenoketones (eg, selenacetone, selenacetophenone, etc.), selenamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosate). Fate, etc.) and selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, 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, 3,320,069, No. 3,408,196, No. 3,408,197, No. 3,442,653, No. 3,420,670, No. 3,591,385, and French Patent No. 2693038.
No., 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. 4-149437, No. 4-184331,
4-190225, 4-191729, 4-
195035, British Patent 255846, 8619
No. 84. In addition, H. E. FIG. Spencer et al. Journa
l of Photographic Science
It is also disclosed in scientific literatures such as Journal, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer which may be used in the silver halide emulsion of the present invention varies depending on the selenium compound used, the silver halide grains, the chemical ripening conditions and the like, but is generally 10 ⁻ per mol of silver halide. ^{About 8} to 10 ^-4 mol is preferable. In addition, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol, ethanol, and ethyl acetate alone or in a mixed solvent depending on the properties of the selenium compound to be used, or by previously mixing with a gelatin solution. Alternatively, a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer is
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 preferable.

Regarding the tellurium sensitizer and the sensitizing method, US Pat. Nos. 1,623,499 and 3,320,069 are cited.
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
58, JP-A-4-204640, and 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 combined with sulfur sensitization, reduction sensitization and noble metal sensitization.

As the sulfur sensitizer, US Pat.
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.
The sulfur sensitizers described in Japanese Patent No. 37, No. 55-45016, etc. can be used. As a specific example,
1,3-diphenylthiourea, triethylthiourea, 1
Preferred examples include thiourea derivatives such as -ethyl, 3- (2-thiazolyl) thiourea, rhodamine derivatives, dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

In the present invention, it is also preferable to use reduction sensitization together. 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.

As the gold sensitizer used in the present invention, in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like, gold complexes of thioureas, rhodanines and other various compounds can be mentioned. .

The amount of the selenium sensitizer, tellurium sensitizer, sulfur sensitizer, reduction sensitizer and gold sensitizer used depends on the kind of silver halide emulsion, the kind of compound used and the ripening conditions. Although it is not so, usually, it is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the present invention, the selenium sensitizer, tellurium sensitizer, sulfur sensitizer, reduction sensitizer and gold sensitizer are added by dissolving them in water or alcohols, other inorganic or organic solvents, and dissolving them. Or in the form of a dispersion obtained by emulsification and dispersion using a water-insoluble solvent or a medium such as gelatin.

The sensitizing dye used in the present invention is optional. For example, a cyanine dye can be preferably used. In that case, S-1 to S-124 represented by the general formulas (1) to (3) described in JP-A-1-100533.
Can be preferably used.

When the above-mentioned 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 used in the present invention may be added at any time during the formation of silver halide grains and after the formation, but before the desalting step is preferable.

The pH of the reaction liquid (usually in the reaction kettle) 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 used in the present invention can be directly dispersed in the emulsion. They can also be dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, 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 a matting agent, US Pat. Nos. 2,992,101 and 2,701,245 are used.
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.

The surface layer of the photographic element of the present invention can be used as a slip agent in US Pat. Nos. 3,489,576 and 4,047.
No. 958, etc .;
In addition to the colloidal silica described in Japanese Patent No. 3139, paraffin wax, higher fatty acid ester, starch derivative and the like can be used.

The constituent layers of the photographic element of the present invention include 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 enhance the affinity with gelatin as a binder, a copolymer with a monomer having a water-soluble group mainly composed of an alkyl ester of acrylic acid, 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 double-sided emulsion X-ray sensitive material for medical use, a transverse light-shielding layer is preferably provided 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 which is soluble in an alkali having a pH of 9 or more and has a structure which is hardly soluble at a pH of 7 or less. The compound of the general formula (I) described in 5-119113 is preferably used.

As a preferable developing solution for developing the light-sensitive material of the present invention, as a developing agent, JP-A-4-15641,
Dihydroxybenzenes such as those described in JP-A-4-16841, such as hydroquinone, para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol, and 2,4-diamiphenol, and 3-
Examples of the pyrazolidones include 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like are preferably used in combination.

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

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in the components of all the development processing solutions 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.

As the solubilizing agent, polyethylene glycols and their esters, and as the sensitizing agent,
For example, a development accelerator, a surfactant and the like such as a quaternary ammonium salt can be contained.

As a silver sludge preventive agent, Japanese Patent Laid-Open No. 56-
No. 106244, a silver stain preventive agent, JP-A-3-
The sulfides and disulfide compounds described in Japanese Patent No. 51844 and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type or a thiadiazole type compound is used.

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

A dialdehyde compound may be used as the development hardener. In this case, glutaraldehyde is preferably used.

The replenishment in the present invention replenishes the amount corresponding to processing fatigue and oxidation fatigue, but 35 to 9 per 1 m ^{2 of} the photographic element.
It is preferable to carry out the replenishment amount of 8 ml. The replenishment method includes replenishment by width and feed rate 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.

A preferable fixing solution can contain a fixing material generally used in the art 1. pH
It is 3.8 or more, preferably 4.2 to 5.5.

As a fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable in terms of 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 used in the present invention may be one that performs acidic hardening. 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.

Others In the fixing solution of the present invention, if desired, preservatives such as sulfites and bisulfites, pH buffering agents such as acetic acid and boric acid, mineral acids (sulfuric acid and nitric acid) and organic acids (citric acid and 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 fixing accelerators include Japanese Patent Publication No. 45-
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 during development of 150 to 250% and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing. Further, if 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.

Photographic elements of this invention have total processing times of 10 to 3
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 the tip of the film is inserted into the insertion port of the automatic developing machine, the developing tank, the transition portion, the fixing tank,
It is the total time until the leading edge of the film comes out of the drying outlet after passing through the crossing portion, the washing tank, the crossing portion, and the drying portion. 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, so that the development speed can be increased even in the rapid processing for a total processing time of 10 to 30 seconds. The developing process can be performed without impairing the fixing speed and the drying speed.

[0074]

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

Example 1 (Preparation of seed emulsion EM-A) Seed emulsion EM was prepared as follows.
-A was prepared.

A1 ossein gelatin 100 g potassium bromide 2.05 g distilled water to 11500 ml B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml distilled water to 2600 ml C1 ose In-gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Distilled water to 3000 ml D1 Silver nitrate 95 g Distilled water to 2700 ml E1 Silver nitrate 1410 g Distilled water to 3200 ml A1 solution kept at 60 ° C. in a reaction kettle and B1 solution The D1 liquid was added by the control double jet method over 30 minutes, and then the C1 and E1 liquids were added by the control double jet method over 105 minutes. Stirring is 5
It was carried out at 00 rpm. The flow rate was such that no new nuclei were generated with the growth of the particles and so-called Ostwald ripening was performed, and the flow rate was such that the particle size distribution did not spread. At the time of adding the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then in order to remove excess salts, JP-B-35-1608 was used.
A desalting treatment was performed by the method described in No. 6.

When this seed emulsion was observed by an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution with a width of 17%.

Preparation of Em-1 A monodisperse core / shell type emulsion was prepared by using the seed emulsion EM-A and the following seven kinds of solutions.

A2 ossein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Emulsion EM-A 0.119 mol equivalent Finish to 600 ml with distilled water B2 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g Distillation Make up to 110 ml with water C2 ossein gelatin 2 g Potassium bromide 90 g Make up to 240 ml with distilled water D2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Make up to 110 ml with distilled water E2 Silver nitrate 130 g Ammonia water (28%) 100 ml Make up to 240 ml with distilled water F2 Potassium bromide 94 g Make up to 165 ml with distilled water.

G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Make up to 110 ml with distilled water.

Liquid A2 was kept warm at 40 ° C. and stirred with a stirrer for 800 r
Stirring was performed at pm. The pH of solution A2 was adjusted to 9.9 using acetic acid.
The solution was adjusted to 0, the seed emulsion EM-A was collected, dispersed and suspended, and then the G2 solution was added at a constant speed over 7 minutes to adjust the pAg to 7.3.
I made it. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. At this time, pAg was kept constant at 7.3. PH with potassium bromide solution and acetic acid over a further 10 minutes
= 8.83, pAg = 9.0, C2 solution, E
The two solutions were added simultaneously over 30 minutes.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
Also, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. When the C2 solution and the E2 solution were added in only 2/3 of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg was from 9.0 to 11.0.
Up. Further, acetic acid was added to adjust the pH to 6.0.

After the addition, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas Co.) and an aqueous solution of magnesium sulfate to obtain pAg8.
5, an emulsion having an average silver iodide content of about 2 mol% at pH 5.85 was obtained at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.55 μm and the grain size distribution was 14%.
A rounded tetradecahedral monodisperse core / shell emulsion was obtained.

(Preparation of hexagonal tabular seed emulsion EM-B) A hexagonal tabular seed emulsion EM-B of pure silver bromide was prepared by the following method.

[0087] A3 ossein gelatin 60.2g Distilled water _{20000ml 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% methanol aqueous solution 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml B3 silver nitrate 1487.5 g distilled water to 3500 ml C3 KBr 1050 g distilled water to 3500 ml D3 1.75N KBr aqueous solution Volume 35 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Using a mixing stirrer described in the specification of Japanese Patent No. 58289, 64.1 ml of each of the solution B3 and the solution C3 was added to the solution A3 by a simultaneous mixing method over a period of 2 minutes to form nuclei.

After stopping the addition of the solution B3 and the solution C3, it took 60 minutes to raise the temperature of the solution A3 to 60 ° C., and the solution B3 and the solution C3 were mixed again by the simultaneous mixing method.
Each was added at a flow rate of 68.5 ml / min for 50 minutes.
During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. After completion of the addition, p is added with 3% KOH.
H was adjusted to 6 and immediately desalted and washed with water to give seed emulsion EM-
B. The seed emulsion EM-B thus prepared is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 at least 90% of the total projected area of the silver halide grains, and the average thickness of the hexagonal tabular grains. 0.07 μm, average diameter (converted to circular diameter) is 0.
It was found by electron microscope observation that the variation coefficient was 5 μm and the variation coefficient was 25%.

(Preparation of Pure Silver Bromide Emulsion Em-2) The following 4
Tabular pure silver bromide emulsions were prepared using the various solutions.

[0090] A4 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 % Methanol aqueous solution 1.25 ml seed emulsion EM-B 2.65 mol equivalent distilled water to make 3000 ml B4 3.50N AgNO ₃ aqueous solution 1760 ml C4 KBr 737 g distilled water to 1760 ml D4 1.75N KBr aqueous solution Silver potential control amount below At 60 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Using a mixing stirrer described in the specification of Japanese Patent No. 58289, the total flow rate of the solution B4 and the solution C4 to the solution A4 is doubled by the simultaneous mixing method (double jet method), and the flow rate at the end of the addition becomes three times the flow rate at the start of the addition. In this way, 110 minutes were required to perform the additive growth.

During this period, the silver potential was +40 using the solution D4.
It controlled so that it might be set to mV.

After the addition is completed, in order to remove excess salts,
Precipitation and desalting were performed by the following method.

1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
20 g / AgX1 mol of Exemplified Aggregated Gelatin Agent G-3 is added, the pH is lowered to 4.30 by adding 56 wt% acetic acid, the mixture is allowed to stand, and decantation is performed.

1.8 liters of pure water at 2.40 ° C./AgX
After adding 1 mol and stirring for 10 minutes, the mixture is left standing and decanted.

3. The above step 2 is repeated once.

4. Thereafter, 15 g of gelatin / 1 mol of AgX, sodium carbonate and water were added, and the mixture was dispersed to pH 6.0.
Finish to 450 cc / AgX1 mol.

Approximately 3000 grains of the obtained emulsion Em-2 were observed and measured by an electron microscope to analyze the shape. The average equivalent circle diameter was 0.59 μm and the average thickness was 0.17 μm.
It was a hexagonal tabular grain of m and had a coefficient of variation of 24%.

(Preparation of Pure Silver Chloride Tabular Seed Emulsion EM-C) A5 ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g distilled water to 7500 ml B5 silver nitrate 1500 g distilled water to 2500 ml C5 KI 4 g NaCl 140 g made up to 684 ml with distilled water D5 NaCl 375 g made up to 1816 ml with distilled water At 40 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Solution A5 in a mixing stirrer as described in US Pat.
To this, 684 ml of solution B5 and the total amount of solution C5 were added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the remaining amount of solution A5 and solution D
The total amount of 5 was added over 40 minutes. Meanwhile, EAg is 1
Controlled to 49 mV.

Immediately after the completion of the addition, desalting and washing were carried out 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.

(Preparation of Pure Silver Chloride Emulsion Em-3) The following 4
Tabular pure silver chloride emulsions were prepared using the various solutions.

[0102] A6 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 % Methanol aqueous solution 1.25 ml seed emulsion EM-C 0.98 mol equivalent distilled water to 3000 ml B6 3.50N AgNO ₃ aqueous solution 2240 ml C6 NaCl 455 g distilled water to 2240 ml D6 1.75N NaCl aqueous solution silver potential control amount below At 40 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Using the mixing stirrer described in the specification of Japanese Patent No. 58289, the total flow rate of the solution B6 and the solution C6 to the solution A6 is doubled by the simultaneous mixing method (double jet method) when the flow rate at the end of the addition is three times the flow rate at the start of the addition. In this way, 110 minutes were required to perform the additive growth.

During this period, the silver potential was +12 using the solution D6.
It controlled so that it might be set to 0 mV.

After the addition is completed, in order to remove excess salts,
Precipitation desalting was performed in the same manner as EM-1.

Approximately 3,000 grains of the obtained emulsion EM-3 were observed and measured by an electron microscope to analyze the shape, and 80% or more of the total projected area had a (100) plane as a main plane and an average diameter of 1 It was a tabular grain having an average thickness of 0.12 μm and a coefficient of variation of 24%.

(Silver chlorobromide emulsion Em-4 (Br0.45 /
Preparation of Cl0.55 tabular grains) In the preparation method of EM-3, 473 g of potassium bromide was added to the solution C6,
Tabular grain EM- was prepared in exactly the same manner except that the silver potential during addition of solution B6 and solution C6 was controlled to +100 mV.
Adjusted 4.

Approximately 3,000 emulsions EM-4 thus obtained were observed and measured by an electron microscope to analyze the shape, and 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

(Preparation of silver iodide fine particles) A7 ossein gelatin 100 g KI 8.5 g Made to 2000 ml with distilled water B7 AgNO ₃ 360 g Made to 605 ml with distilled water.

C7 KI 352 g Distilled water to 605 ml.

The solution A7 was added to the reaction vessel, and the solution B7 and the solution C7 were added at a constant rate over 30 minutes by the simultaneous mixing method while maintaining the temperature at 40 ° C. and stirring.

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 sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water preliminarily adjusted to 27 ° C., and a high speed stirrer (dissolver) was used. ) 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 <Gold-sulfur sensitization> Next, the obtained emulsions Em-1 to Em-
No. 4 was subjected to spectral sensitization and chemical sensitization by the following methods to obtain chemically sensitized emulsions A-1 to A-4.

After the emulsion was heated to 50 ° C., the solid fine particle dispersion was added so that the amount of the sensitizing dye (A) was 460 mg per mol of silver, and then ammonium thiocyanate was added to 7.0 per mol of silver. X 10 ^-4 mol was added, and potassium chloroaurate and sodium thiosulfate were added to perform optimum chemical ripening, and the above silver iodide fine grain emulsion was added with 3 x 10 ^-3 mol / Ag.
After adding 1 mol, 4-hydroxy-6-methyl-1,3,3
Stabilized with 3a, 7-tetrazaindene (TAI) 3 × 10 ^-2 mol.

<Selenium sensitization> Emulsions Em-1 to Em-4
Was subjected to spectral sensitization and chemical sensitization in the following manner to obtain chemically sensitized emulsions B-1 to B-4.

After the emulsion was heated to 60 ° C., the above 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 7.0 per mol of silver. × 10 ^-4 mol was added, and potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide were added in an amount of 3.0 × 10 ^-6 mol per mol of silver,
After the addition of the silver iodide fine grain emulsion, 3 × 10 ⁻³ mol / Ag mol was added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added. ) Stabilized at 3 × 10 ^-2 mol.

<Tellurium sensitization> Emulsions Em-1 to Em-4
Was subjected to spectral sensitization and chemical sensitization in the following manner to obtain chemically sensitized emulsions C-1 to C-4.

After the emulsion was heated to 60 ° C., the solid fine particle dispersion described above was added so that the sensitizing dye (A) was 460 mg per mol silver, and then the thiocyanic acid ammonium salt was added to 7.0 per mol silver. The above silver iodide was prepared by adding 10 × 10 ^-4 mol of potassium chloroaurate, sodium thiosulfate and the tellurium sensitizer shown below at 3.0 × 10 ^-6 mol per 1 mol of silver for optimum chemical ripening. Fine grain emulsion 3 × 10 ^-3 mol /
After adding 1 mol of Ag, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene (TAI) 3 × 10 ^-2
Stabilized on a molar basis.

Next, Emulsion A-sensitized in this manner was used.
Additives described below were added to 1 to A-4, B-1 to B-4, and C-1 to C-4 to prepare emulsion layer coating solutions. At the same time, a coating solution for the protective layer was prepared.

<Preparation of Subbed Substrate> Concentration 0.17
On one side of a polyethylene terephthalate film base for X-rays having a blue color of 0 (thickness: 175 μm), a styrene-butadiene undercoating latex (solid content: 20
%) Of the undercoating latex liquid, and on the other side of the lower layer, a coating solution obtained by mixing SnO ₂ sol and styrene-butadiene undercoating latex is applied to the upper layer so that the film thickness after drying is 0.1 μm. Gelatin was simultaneously applied so as to have a thickness of 0.1 μm, and dried at 120 ° C. for 1 minute. Before coating, a corona discharge treatment of 0.5 kV · A · min / m ² was performed.

<Preparation of Sample> The following transverse light-shielding layer, emulsion layer coating solution, protective lower layer coating solution and protective upper layer coating solution were applied to the respective surfaces of each of the above supports in the following prescribed coating amounts. Simultaneous multilayer coating from the bottom, dried, and sample No.
1 to No. 24 was created.

First layer (transverse light shielding layer (AHL)) Solid fine particle dispersion dye (AH) 50 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Fine particles of the present invention (see Table 1) Latex (L ) 0.2 g / m ² potassium polystyrene sulfonate 50 mg / m ² second layer (emulsion layer (EML)) The following various additives were added to each emulsion obtained above.

Potassium tetrachloropalladium (2) ate 100 mg / m ² compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / M ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-ammonium sulfonate 500 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² compound (H) _{^{.5mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (M) 5mg / m ² Compound (N) particles of 5 mg / m ² the invention (See Table 1) Latex (L) 0.4 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² sorbitol 0.1 g / m ² However, the total amount of gelatin on one side is shown in Table 1. The amount was adjusted.

Third Layer (Protective Lower Layer) Gelatin 0.2 g / m ² latex (L) 0.2 g / m ² sodium polyacrylate (average molecular weight 50000) 30 mg / m ² compound (K) 15 mg / m ² dioctyl phthalate Dispersion 0.2 g / m ² 4th layer (protective upper layer) Gelatin 0.4 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 50 mg / m ² colloidal silica (average particle size) Diameter 0.014 μm) 200 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² polyacrylamide (Average molecular weight 10000) 0.1 g / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² compound (F-1) 3 mg / m ² compound ( F-2) 2 mg / m ² compound (F-3) 1 mg / m ² compound (P) 50 mg / m ^{2 In} addition, the coating amount of the material is for one side and the coated silver amount is 1.0 g / m for one side. Adjusted to ² .

The structural formulas of the materials used are shown below.

[0126]

Embedded image

[0127]

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[0128]

Embedded image

1) Evaluation of Sensitivity The coated and dried sample was stored at 23 ° C. and 55% RH for 3 days, then pinched with an intensifying screen KO-250 for X-ray photography and irradiated with X-ray through a penetrometer B type. Processing was performed using a roller-conveying type automatic developing machine (SRX-501: manufactured by Konica Corporation) with a developing solution and a fixing solution having the following compositions.

[0130] Developer formulation Part-A (for 12 liter finish) 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-mercapto Tetrazole 0.2 g Hydroquinone 340 g Water is added to make 5 liters.

Part-B (for 12 l finishing) 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 Water is added to make 1 liter.

Fixer formulation Part-A (for 18 liter finish) 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 Aluminum sulphate 800 g The developer was prepared by adding Part A and Part to about 5 liters of water.
B was added at the same time, water was added while stirring and dissolving, and the mixture was adjusted to 12 liters and the pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher.

To 1 liter of this development replenisher, 20 ml / liter of the above starter was added to adjust the pH to 10.2.
Adjust to 6 to make the working solution.

The fixing solution was prepared by adding Part to 5 liters of water.
A and Part B were added simultaneously, and water was added while stirring and dissolving to make up to 18 liters.
Was adjusted to 4.4. This is used as a fixing replenisher.

The sensitivity was expressed as a relative value with the reciprocal of the exposure energy amount required for the sample 1 to give a density of fog + 1.0 as 100. The maximum density is the blackening density obtained when the sample is exposed to light.

2) Evaluation of Roller Mark The sample was uniformly exposed in a size of 10 × 12 inches so that the blackening density was 1.0, and then the above-mentioned treatment was performed. However, the developing rack and the transition rack from the development to the fixing used at this time were intentionally fatigued. That is,
Since the rollers of each rack were fatigued, unevenness of about 10 μm was 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 by the following ranks.

5 No spots are generated 4 A few spots are generated, but they are not a problem in practical use 3 A few spots are generated but an allowable limit level 2 which is not usually generated in a rack 2 spots are usually generated Occasionally occurs on racks 1 Many spots occur. It is always occurring even in normal racks.

The results are shown in Table 1.

[0140]

[Table 1]

Incidentally, the elution amount of the organic substance in the developing treatment was 3 to 8% by weight based on the total amount of the organic substance before the treatment.

As is apparent from Table 1, according to the present invention, it is possible to obtain a photographic element having high sensitivity and excellent pressure characteristics without generation of roller marks.

Example 2 Sample No. prepared in Example 1 4 to 7 and No. 15 ~
24 was exposed to X-rays, and the developing solution and fixing solution of Example 1 were used, and the automatic developing machine was the SRX-501 used in Example 1.
(Manufactured by Konica Co., Ltd.) with an improved transport speed was used to treat each sample under the following conditions until running equilibrium was reached to prepare running equilibrium liquid 1 and running equilibrium liquid 2.

[0144] Replenishment Conditions Running Equilibrium Solution 1 Running Equilibrium Solution 2 Per four-sided size (10 × 12 inch) Development replenishment amount 14.0 ml 7.0 ml (180 ml / m ² ) (90 ml / m ² ) Fixing replenishment amount 14.0 ml 7 0.0 ml (180 ml / m ² ) (90 ml / m ² ) Sample No. prepared in Example 1 4 to 7 and No. 15 ~
24 was treated with the above running equilibrium 1 (condition 1) and running equilibrium 2 (condition 2) under the above conditions,
The sensitivity and roller mark were evaluated.

[0145]

[Table 2]

As is clear from Table 2, according to the present invention, it is possible to obtain a photographic element excellent in pressure characteristics without causing a roller mark even when the replenishment rate is extremely rapid and the rapid decrease in sensitivity is small.

[0147]

EFFECTS OF THE INVENTION A photographic element having excellent pressure characteristics without generation of roller marks can be obtained with a small decrease in sensitivity even in an ultra-rapid processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 5/26 G03C 5/26 5/31 5/31 (72) Inventor Shinichi Okamura Hino, Tokyo Sakura-cho 1 Konica Stock Association In-house

Claims (4)

[Claims] 1. A photographic element having at least one silver halide emulsion layer on a support and at least one non-photosensitive hydrophilic colloid layer above and below said silver halide emulsion layer, at least one layer of said emulsion layer. 50% or more of the total projected area of the silver halide grains contains tabular grains having an aspect ratio of 2 or more, and the emulsion layer and / or
The side of the support having the emulsion layer, which has a non-photosensitive hydrophilic colloid layer between the support and the emulsion layer and which contains spherical particles having an average particle size of 1.1 μm to 10 μm and containing silicon as a main component. The total amount of gelatin in the hydrophilic colloid layer is 1.3 to 2.5
A silver halide photographic element characterized in that it is in g / m ² . 2. The tabular silver halide grains have two parallel main planes (100) planes and a silver chloride content of 20.
A silver halide photographic element according to claim 1, wherein the silver halide photographic element is at least mol%. 3. A silver halide photographic element according to claim 1, wherein said tabular silver halide grains are chemically sensitized with a selenium or tellurium compound. Wherein 35 per said photographic element 1 m ² of the silver halide photographic element according to any one of claims 1 3
A method for processing a silver halide photographic element, wherein the processing is carried out with an automatic developing machine having a total processing time of 10 to 30 seconds using 98 ml of a developing replenisher.