JPH08211535A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material using a laser beam source having high sensitivity and prevented from deterioration of silver tone in rapid processing and occurrence of roller marks. CONSTITUTION: The silver halide photographic sensitive material has, no one side of a transparent support, at least one photosensitive silver halide emulsion layer containing silver halide grains having an average iodine content of <=0.5mol% spectrally sensitized in a wavelength of >=600nm, and hardened with a pyrrolidinocarbonylpyridinium compound, and the method for processing this photosensitive material is included in this invention.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also referred to as "sensitive material"), and more specifically, a silver halide photographic light-sensitive material having suitable sensitivity to a laser light source and capable of rapid processing. The present invention relates to a material and a processing method thereof.

[0002]

2. Description of the Related Art Images for radiation diagnosis such as MRI (Magnetic Resonance Imaging), X-ray CT (Computed Tomography), and digital X-ray diagnosis are captured as a digital or video signal and scanned with a laser beam. Generally, a means for visualizing it on a silver halide photographic light-sensitive material and providing it as a transmission photographic image for diagnosis is used.

As the light source of these scanning laser exposure apparatuses, coherent light sources such as argon, helium-neon, helium-cadmium, and semiconductor lasers are used. A silver halide photographic light-sensitive material sensitive to the infrared region is required.

As a means for spectrally sensitizing silver halide to the near infrared, for example, The Theory of the Photograph process
icProcess) A method using a long-chain cyanine dye as described in the third edition (Macmillan Co. 1966) pp. 198-201 is known.

With the widespread use of light-sensitive materials for laser imaging, market demand for image quality has increased. Especially, when the color tone of a silver image becomes a warm black tone, it becomes difficult to diagnose fine shadows and the structure of capillaries. Is required to improve.

Further, it is generally connected directly to an automatic developing machine which automatically conveys a laser-exposed light-sensitive material and carries out a developing process. Therefore, the shortening of the processing time accelerates the diagnosis, The efficiency of the device is required.

It is known to increase the film hardness of the light-sensitive material in order to make the color tone of the image cold black. However, if the film hardness is increased, the maximum density decreases and the density of the shoulder portion on the characteristic curve increases. There is a problem that the background density of the border portion of the photographed image is lowered due to the deterioration (softening), and the missing characters are deteriorated.

In speeding up the processing, fixing and drying in the processing step are rate-determining. To improve dryness,
The amount of gelatin applied may be reduced, but simply reducing the amount of gelatin may deteriorate the pressure resistance of the light-sensitive material or cause black spots called roller marks during processing by an automatic processor. Also, instead of reducing the amount of gelatin, if the amount of hardener that is normally used is further increased to suppress the swelling of the gelatin film, the drying property is improved, but as described above, the maximum concentration decreases and the softening It is not preferable because it has become In particular, in a silver halide photographic light-sensitive material exposed by a laser imager, the amount of coated silver per one side of the light-sensitive material is large, and the above-mentioned points are a problem.

Japanese Patent Laid-Open Nos. 5119419 / 5-119420 disclose a technique in which a water-soluble polymer is used in place of a gelatin binder to elute the polymer during processing and reduce the load of drying. However, there is a problem in that the polymer accumulates in the processing liquid and stains are attached to the film.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks, and for a laser imager capable of rapid processing without deterioration of image quality due to temperature control of silver images, generation of roller marks and the like. A photosensitive material and a processing method thereof are provided.

[0011]

The above object of the present invention is achieved by any of the following (1) to (4).

(1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a transparent support, the silver halide emulsion layer has an average iodide content of 0.5 mol%. Halogenation characterized by comprising a silver halide emulsion containing silver halide grains spectrally sensitized to a wavelength of 600 nm or more and further hardened using a pyrrolidinocarbonylpyridinium compound Silver photographic light-sensitive material.

(2) The silver halide photographic light-sensitive material described in (1), wherein the pyrrolidinocarbonylpyridinium compound is represented by the general formula [1].

(3) The silver halide grains are at least 1
The silver halide photographic light-sensitive material as described in (1) or (2), which is chemically sensitized with one kind of selenium compound.

(4) The total processing time of the silver halide photographic light-sensitive material described in (1), (2) or (3) is 15 in a processing step containing a developer containing substantially no hardener.
A method for processing a silver halide photographic light-sensitive material, which comprises processing for 30 seconds to 30 seconds.

The present invention will be described in detail below.

The average grain size of the silver halide grains according to the present invention is preferably 0.1 to 2.0 μm, particularly preferably 0.2 to 1.0 μm.
Is.

The grain size of the silver halide grain in the present invention is defined as the diameter of a sphere having a volume equal to the volume of the grain (sphere equivalent diameter) from the observation of an electron micrograph of the silver halide grain.

The emulsion used in the present invention may be a single emulsion or a mixture of two or more kinds of emulsions.
The emulsions to be mixed may be emulsions according to the present invention, or may be normal crystals or twinned grains or tabular grains having an aspect ratio (grain size / thickness) of less than 2.

As the silver halide emulsion of the present invention, those which are monodisperse are preferably used, and the variation coefficient of the grain size distribution ((standard deviation of grain size distribution / average grain size) × 100%) is 25% or less,
It is more preferably 20% or less.

Silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide are used in the silver halide emulsion of the present invention.
Particularly, silver bromide, silver iodobromide and silver chloroiodobromide are preferable.

The iodine content is 0.5 mol% or less. Silver iodobromide having an iodide content of 0.3 mol% or less is preferable, and silver iodobromide having an iodide content of 0.1 mol% or less is more preferable.

At this time, the iodine may be present uniformly in the grains, but it is preferable that the iodide is localized on the surface of the grains.

The size of the silver halide grain can be controlled by the temperature at the time of grain formation and the addition rate of the silver salt and halide aqueous solution. The grain growth may be carried out by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. As silver halide fine particles, silver iodide, silver iodobromide, silver bromide, silver chlorobromide, and silver chloride fine particles can be used, and they may be supplied in combination with an aqueous solution containing silver ions or halogen ions. .

The silver halide grains according to the present invention include
A core / shell type or multi-structure type grain having a silver halide composition having different compositions inside and outside the grain is also preferably used.

Regarding the core / shell type particles, JP-A-59-1
The particles can be prepared by the method described in 77535, 59-178447, 60-35726, 60-147727 and the like.

Further, tabular silver halide grains can be used as the silver halide grains according to the present invention. A method for producing a tabular silver halide emulsion is described, for example, in JP-A-58-1.
13926, 58-113927, 58-113934, 62-1855
Nos. 219,849 and 219,850 can be referred to. Further, as a method for producing a monodisperse tabular silver halide emulsion, reference can be made to JP-A-61-6643.

The emulsion may be washed with water by a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. For example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086,
Alternatively, G3 as an example of an aggregating polymer agent described in JP-A-63-158644,
A particularly preferable desalting method is a method using G8 or the like.

In the present invention, the silver halide photographic emulsion can be chemically sensitized. There are no particular restrictions on the conditions of the chemical ripening, that is, the steps of chemical sensitization, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method to be used, gold and other noble metal sensitization methods using a noble metal can be used alone or in combination.
It is preferable to use the selenium sensitization method alone or in combination with the above chemical sensitization method.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. For example, in this regard, U.S. Pat.Nos. 1,574,944, 1,602,592, 1,62.
3,499, JP 60-150046, JP 4-25832, 4-1
09240, 4-147250, etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenoate). Urea, N, N, N′-trimethyl-N′-heptafluoroselenourea, N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea, N, N, N′-trimethyl-N′- 4-nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg , 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg,
Tri-p-triselenophosphate and the like) and selenides (diethyl selenide, diethyl diselenide and the like). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The temperature of the chemical ripening using the selenium sensitizer is
The range of 40 to 90 ° C is preferable. More preferably 45 ° C or higher
It is below 80 ℃. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

The silver halide photographic light-sensitive material according to the present invention is subjected to a reduction treatment, so-called reduction sensitization method, in which a reducing compound is added, and a silver ion excess state of pAg = 1 to 7 called silver aging is passed. Method, p called high pH aging
It may be applied to the silver halide emulsion by a method of allowing a high pH state of H = 8 to 11 to pass. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable in that the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfite. Examples thereof include salts and the like, and particularly preferable are thiourea dioxide, stannous chloride, and dimethylamine borane. The addition amount of these reducing compounds varies depending on the reducing property of the compound, the type of silver halide, the emulsion production conditions such as the dissolution conditions, and is 1 × 10 ⁻⁸ per mol of silver halide.
A range of up to 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization from the viewpoint of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group and compounds having a benzene ring.

In the present invention, the sensitizing dyes for spectrally sensitizing to wavelengths of 600 nm or more include the following general formulas [2] and [3].
Alternatively, the compound represented by [4] is useful.

[0038]

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In the formula, Z ¹ and Z ² represent a non-metal atomic group necessary for forming a benzthiazole nucleus, a benzselenazole nucleus, a naphthothiazole nucleus or a naphthoselenazole nucleus which may have a substituent.

R ¹ and R ² represent a lower alkyl group or a substituted lower alkyl group.

X ₁ represents a counter ion, and n represents 1 or 2. However, n is 1 when the dye represented by the general formula [2] forms an inner salt.

Typical examples of the sensitizing dye represented by the general formula [2] include, for example, Exemplified Compounds II-1 to 9 and 11 to 30 described on pages 4 to 5 of JP-A-2-284136. And the following compounds, but the present invention is not limited thereto.

[0043]

Embedded image

The compound represented by the general formula [3] will be described.

[0045]

[Chemical 4]

In the formula, Z ³ and Z ⁵ represent a nonmetallic atom group necessary for forming a benzthiazole ring, a naphthothiazole ring, a benzoxazole ring and a naphthoxazole ring which may have a substituent. Z ⁴ represents a 5- to 6-membered carbon atom ring which may have a substituent, and R ³ and R ⁴ each represent an alkyl group or a substituted alkyl group. X ₂ represents a counter ion, and n represents 1 or 2.

When Z ⁴ of the above general formula [3] of the present invention is a 5-membered carbon atom ring, it can be represented by the following general formula [3-a].

[0048]

Embedded image

R ⁵ and R ⁶ are each a hydrogen atom and a carbon number of 1 to
An alkyl group having 4 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a chlor atom, a bromine atom, etc.), and R ⁷ and R ⁸ each have an alkyl group having 1 to 12 carbon atoms and a substituent. A phenyl group (for example, a phenyl group,
m-tolyl group, p-tolyl group, m-chlorophenyl group, p-chlorophenyl group, for example, p-methoxyphenyl group substituted with an alkoxy group having 1 to 4 carbon atoms), alkoxycarbonylalkyl group having 1 to 4 carbon atoms (For example, an ethoxycarbonylmethyl group etc.) can be mentioned. R ⁹ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms. Z
³ , Z ⁵ , R ³ , R ⁴ , X ₂ and n have the same meanings as in the general formula [3].

When Z ⁴ of the above general formula [3] of the present invention is a 6-membered carbon atom ring, it can be represented by the following general formula [3-b].

[0051]

[Chemical 6]

In the formula, R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
Z ³ , Z ⁵ , R ³ , R ⁴ , X ₂ and n have the same meanings as in formula [3].

Specific examples of the compound represented by the general formula [3] are shown below, but the invention is not limited thereto.

[0054]

[Chemical 7]

The compound represented by the general formula [4] will be described.

[0056]

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Z ⁶ represents a non-metal group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole ring, a selenazole ring, an oxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, An imidazole ring etc. can be mentioned.

Of these, a thiazole ring or an oxazole ring is preferred, and a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring,
Examples thereof include a naphthoxazole ring.

Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxy group, or a halogen atom (eg, chlorine atom, fluorine atom).

R ¹² and R ¹³ are each a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and examples of the substituent to these alkyl groups include a carboxyl group, a sulfone group, a cyano group, a halogen atom ( For example, chlorine atom, bromine atom, fluorine atom, hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms), alkoxy group (preferably having 7 or less carbon atoms), aryloxy group, acyloxy group (preferably having 8 or less carbon atoms) ), A carbamoyl group,
Examples thereof include a sulfamoyl group and an aryl group.

R ^{14 represents} a hydrogen atom, a lower alkyl group having 1 to 8 carbon atoms, a lower alkoxy group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. Preferably 1 to 4 carbon atoms
Is an alkyl group or a benzyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group. X ₃ represents an acid anion, and m, n and p represent 1 or 2. N is 1 when the compound forms betaine.

Specific examples of the compound represented by the general formula [4] are shown below, but the invention is not limited thereto.

[0063]

[Chemical 9]

The above general formulas [2] and [3] according to the present invention.
Dyes are, for example, FM Chemer, The Chemistry of Het
The dye of the general formula [4] can be synthesized in erocyclic compound Vol. 18, for example, by the method described in JP-A-59-192242 or by a method similar thereto.

The spectral sensitizing dyes represented by the general formulas [2], [3] and [4] are preferably used per mol of silver halide.
It is preferable to add 0.003 g to 0.3 g, and more preferably 0.005 g to 0.15 g. The addition method can be carried out by dissolving in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, or a mixed solvent thereof, and then adding. An ultrasonic method may be used as the dissolution method.

The method of adding the spectral sensitizing dye to the emulsion is described in, for example, US Pat. Nos. 3,469,987, 3,822,135, JP-B-46-24185, JP-A-50-80826, and JP-A-51-74624. The described method may be used.

Although each of these spectral sensitizing dyes can obtain the desired spectral sensitivity even when used alone, two or more of them may be combined if necessary, and the mixing ratio in that case is arbitrarily determined. To be Further, other known spectral sensitizing dyes may be combined.

In the silver halide photographic light-sensitive material, the silver halide grains are reduced and converted into metallic silver in the state where the gelatin layer has sufficiently absorbed water and swollen during development. Therefore, even after drying, the emulsion layer does not return to its original state and the dimensions are different, and a pressure effect (in-liquid pressure) occurs in the developing solution. For this reason, a technique in which a polymer latex is contained in a silver halide emulsion layer, a backing layer or the like to improve the physical properties of a light-sensitive material and the photographic processing performance is well known.

The silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention contains an inorganic or organic hardener. The hardener of the present invention is preferably a pyrrolidinocarbonylpyridinium compound represented by the following general formula [1].

[0070]

[Chemical 10]

In the formula, R ^11a represents a hydrogen atom or an optionally substituted alkyl group or alkoxy group, and R ^11a
12a represents an alkyl group which may have a substituent, an acyl group or an acylamino group, X ^11a- represents an anion, and y ^11a
Is 1 or 2 and forms an inner salt when y ^11a is 1.

In the general formula [1], R ^12a is-(-
CH ₂ −) m ^11a −SO ₃ ⁻ , −NR ^13a COR ^14a , − (− CH ₂ −) p−CON
R ^17a R ^18a , − (− CH ₂ −) q−NR ^19a R ^110a , − (CH ₂ −) s−CH
-(LR ^112a ) -R ^111a , R ^13a represents a hydrogen atom or an alkyl group which may have a substituent, and R ^14a represents an alkyl group which may have a substituent, an alkoxyl group, -O- (−CH _{2
^{-) n 11a -SO 3 -,}} -NR 15a R 16a, - (- CH 2 -) n 11a -SO 3 -
R ^15a and R ^{16a each} represent a hydrogen atom or an alkyl group which may have a substituent, — (— CH ₂ —) n ^11a —SO ₃ ^— , and R ^17a
Represents a hydrogen atom, or an alkyl group or aryl group which may have a substituent, R ^18a represents a hydrogen atom, an alkyl group which may have a substituent, or R ^17a and a 5- or 6-membered aliphatic ring. R ^19a represents a hydrogen atom or an alkyl group which may have a substituent or -COR ^14a , and R ^110a represents a hydrogen atom or an alkyl group which may have a substituent or -COR ^14a.
_{(-CH 2 -) r-SO} 3 - represents, L is represents -O- or -NR ^113a, R ^111a represents an alkyl group which may have a hydrogen atom or a substituent, R ^112a is hydrogen Or an alkyl group which may have a substituent, -COR ^114a , -CONHR ^115a ,
R ^113a , R ^114a and R ^115a represent a hydrogen atom or an alkyl group which may have a substituent, and m ^11a is 0 or 2 to 4, n ^11a.
Is 1-3, p is 0-2, q and r are 1-3, and s is 2-3.
Is.

In the above general formula [1], R ^11a is a hydrogen atom or an alkyl group or an alkoxy group which may have a substituent, and R ^12a is — (— CH ₂ —) m—SO ₃ ^— or NR ^13a. COR ^14a
Is.

Typical compounds are shown below, but the present invention is not limited thereto.

[0075]

[Chemical 11]

[0076]

[Chemical 12]

[0077]

[Chemical 13]

[0078]

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Although gelatin is preferably used as the hydrophilic colloid or binder used in the light-sensitive material of the present invention, other hydrophilic colloid layers can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfate, sugar derivatives such as sodium alginate, dextrin and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5,000 to 100,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-624748,
No. 2-44445, No. 1-66031, JP-A No. 64-65540, No. 63-1
No. 01841, 63-153538, etc.

Examples of the gelatin include lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin as described in Bull. Soc. Phot. Japan, No. 16, p. Halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, those obtained by reacting various compounds such as epoxy compounds) Included.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) 17643 (December 1978), (RD) 18716 (1
(November 979) and (RD) 308119 (December 1989). The types of compounds shown in these three (RD) and the places where they are described are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 right 1006 to 7 XIII plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008 to 9 XVI binder 26 XXII 1003 to 4 IX support 28 XVII 1009 XVII according to the present invention Examples of the support that can be used in the light-sensitive material include those described in the above RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer or subjected to corona discharge or ultraviolet irradiation in order to improve the adhesion of the coating layer.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308,119, XX to XX.
Treatment with a treatment solution as described in XXI, pp. 1011-1012 may be performed. This process may be a black and white photographic process that forms a silver image. Processing temperature is usually 18 ℃ ~ 50
It is processed in the range of ℃.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol).
Etc. can be used alone or in combination.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a solubilizing agent, a viscosity imparting agent and the like may be used if necessary. However, for rapid processing, it is preferable that the hardener is contained in the light-sensitive material as described above and caused to act, rather than caused to act in the development processing step.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

When the light-sensitive material of the present invention is developed using a roller-conveying type automatic processor, the effect of the present invention can be fully exhibited by a rapid processing such that the total processing time is 15 seconds or more and 30 seconds or less. . Here, the total processing time means that after the photosensitive material of the present invention is imagewise exposed, it is inserted into the first roller, which is the photosensitive material insertion port of the automatic developing machine, and then passes through the developing tank, the fixing tank and the washing tank, and the outlet of the drying section. The time it takes to reach the final roller.

[0088]

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

Example 1 Using a silver bromide seed emulsion having an average grain size of 0.1 μm, an ammoniacal silver nitrate aqueous solution, potassium bromide and an aqueous solution of potassium iodide were appropriately mixed and then added by the double jet method. A cubic monodisperse emulsion having a silver iodide content and an average grain size of 0.25 μm described in 1 was grown.

After the completion of the addition, the pH was adjusted to 6.0, and then desalting and desalting were performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, followed by washing with water.

Further, a gelatin solution containing 23 g of ossein gelatin was added and the above emulsion was redispersed. The emulsion had a potential of 50 mV at 50 ° C and a pH of 5.85.

The 200 particles thus obtained were arbitrarily selected, and the particle size was measured with an electron microscope. The coefficient of variation of the particle size was determined to be 15%.
Met.

To the above emulsion, 5.2 ml of 1% ammonium thiocyanate per 0.7 mol of silver, 0.78 ml of 0.2% chloroauric acid, 0.25
A chemical sensitizer consisting of 5.6 ml of% sodium thiosulfate and 3.5 ml of 0.6% triphenylphosphine selenide was added. Immediately before the addition of these additives, the spectral sensitizing dye was added to 40 mg of 2-5 and 30 mg of 3-2 per mol of silver, respectively.
mg and 4-1 (10 mg) were added and chemically sensitized at 48 ° C.

When the increase in fog reached 0.02, 2.4 g of 4-hydroxy-6-methyl-1,3.3a, 7-tetrazaindene, which was 1 mol of silver halide, was added, and the temperature was lowered to carry out chemical reaction. Aging was stopped.

Further, this emulsion was mixed with an unchemically sensitized emulsion prepared as described below so that the ratio with the chemically sensitized emulsion was 9: 1.

Preparation of unchemically sensitized emulsion A silver bromide seed emulsion having an average grain size of 0.3 μm was used to grow a monodisperse emulsion having an average grain size of 1.1 μm by the ammonia method. Coefficient of variation of grain size of this emulsion grain When measured in the same manner as above, 0.
It was 15.

The following compounds were added to 1 mol of silver in the emulsion prepared above to prepare an emulsion coating solution.

1-phenyl-5-mercaptotetrazole 10 mg 1-trimethylolpropane 14 g t-butylcatechol 68 mg polyvinylpyrrolidone (molecular weight 10.000) 850 mg styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl-phosphonium chloride 50 mg 1 , 3-Dihydroxybenzene-4-sulfonic acid 1.7g 1,1 Dimethylol-1-bromo-1-nitromethane
_{6.2mg n-C 4 H 9 OCH} 2 CH (OH) CH 2 N (CH 2 COOH) 2
700 mg

[0099]

[Chemical 15]

The additives used in the protective layer of the emulsion are as follows. The added amount is shown as an amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 21 mg Matting agent composed of polymethylmethacrylate having an average particle size of 3 μm 28 mg Hardener shown in Table 1

[0102]

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Preparation of backing layer 100 g gelatin Anti-halation dye 4 g below Potassium nitrate 1 g Glyoxal 2 g Water

[0104]

[Chemical 17]

Preparation of protective layer for backing layer Using the binders and hardeners shown in Table 1, the following additives were added per 1 m ² for each formulation.

Matting agent consisting of polymethylmethacrylate having an average particle size of 6 μm 30 mg C ₁₃ H ₂₃ CONH (CH2 ₂ O) ₅ H 0.1 g Emulsion coating solution, emulsion protective layer solution, backing layer solution, backing protection prepared as described above The film solution was simultaneously applied to the undercoated base.

The amount of silver on the emulsion layer side was 2.0 g / m ² ,
The amount of gelatin on the emulsion layer side was 1.8 g / m ² of the emulsion layer,
The emulsion protective layer is 0.8 g / m ² . The amount of gelatin attached to the backing layer was 2 g / m ^{2 of} the backing layer, and the protective layer of the backing was the amount shown in Table 1.

The obtained sample was cut into four pieces and left in an atmosphere of 40% RH and 40 ° C. for 12 hours.
In the environment of ℃, 50% RH, 100 sheets of packaging is used to make a no-interleaf package, and the thickness is 100 μm and the density is 1.0 g.
/ Cm ³ , a moisture-proof polyethylene polyethylene bag in which carbon black was dispersed as a light-shielding agent was vacuum-sealed under a depressurized pressure of 50 mmHg for light-tight packaging.

The obtained sample was evaluated by processing with the developing solution and fixing solution shown below.

Developer formulation Part-A (for finishing 10.8 liters) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetriamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 5-Methylbenzotriazole 150 mg 1-Phenyl-5-mercaptotetrazole 15mg Hydroquinone 280g Part-B (10.8L for finishing) Glacial acetic acid 158g Triethylene glycol 114g 1-Phenyl-3-pyrazolidone 19.5g 5-Nitroindazole 0.32g n-Acetyl-D, L-penicillamine 0.11g Part-A and B Were mixed and water was added to make 10.8 liters.

Starter liquid formulation (for finishing 1 liter) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Water was added 1 Finish to liters.

The amount of the starter added was 20 ml per liter of the developing solution.

Fixer Formulation Part-A (for finishing 16.4 liters) Ammonium thiosulfate (70 wt / vol%) 3460 g Sodium sulfite 150 g Sodium acetate trihydrate 350 g Sodium citrate 43 g Gluconic acid 33 g Boric acid 26 g Glacial acetic acid 120 g Part-B (16.4 (For liter finishing) Aluminum sulfate 56 g Sulfuric acid (50 wt%) 91 g Part-A and B were mixed, and finished to 16.4 liters with water.

Processing Step Processing Temperature (° C) Processing Time (sec) Insertion-0.7 Development + Crossover 35 8.0 Fixing + Crossover 33 5.8 Washing + Crossover 18 5.6 Squeeze 40 2.5 Dry 50 4.3 Total-24.9 Each of the automatic processors used The tank capacity is 16 liters for the developing tank, 10 liters for the fixing layer, and 10 liters for the washing tank.
200 g of Clinker 205 (manufactured and sold by NIPPON R & D Laboratories, Inc.) was filled in a bag sewn with a 20-mesh polyethylene woven fabric, and immersed in the vicinity of the flush water supply section of the flush tank. For drying, an infrared heater (heater temperature 220 ° C) and warm air (60 ° C) were used together.

The amount of replenishment was an area replenishment system using an infrared sensor detection mechanism, and the area of 10 sheets cut in four was detected and replenished.

Replenishing amount of developer and fixer is 300 ml each
/ M ² .

(Evaluation of silver tone) The obtained sample (half-cut size) was left in an environment of 30 ° C. and 40% RH for 24 hours to obtain a density of 1.2.
After the exposure, the development treatment was performed and the visual evaluation was performed. Rank 1 is a level that is not suitable for practical use because the film is yellowish and the silver tone is not black but brown. Rank 3 represents the lowest level allowed in the market, and rank 5 represents the cold tone level.

(Evaluation of Drying Property) The same sample as used for the evaluation of silver tone was continuously processed on an automatic processor in an environment of 25 ° C. and 80% RH for 50 sheets, and then 5 sheets were further processed. The dryness was evaluated by touch.

Rank 1 indicates a level at which the film is tight, and when two films are stacked, they stick to each other, which is completely unsuitable for practical use. Rank 3 indicates the lowest level at which the film is cold but does not stick to practical use. Rank 5 indicates the level at which the film is completely dry.

(Measurement of maximum density) For samples used for silver tone
The maximum density was measured by irradiating 100 lux of white light for 10 seconds.

The results are shown in Table 1.

[0122]

[Table 1]

From the results shown in Table 1, the samples of the present invention have excellent rapid processability and good images can be obtained. That is, by using the silver halide and the hardener according to the present invention, the drying property was improved and an image with sufficient maximum density and good color tone was obtained.

Example 2 The film used in Example 1 was developed as in Example 1.
Processing with the automatic developing machine of Example 1 using the solution and the fixing solution
Replenishment rate of developer and fixer is 200cc / m ², 100
cc / m²Developing process in the same manner as in Example 1 except that
Was done.

When the replenishment amounts of the developing solution and the fixing solution are reduced, both the drying property and the silver tone deteriorate, but the hardener of the present invention,
And the level using Agl composition is 200cc / m ²
At that time, the deterioration is only about 1/4 rank, and the level of comparison is deteriorated by 3/4 rank. Also, when the replenishment rate is 100 cc / m ² , the level of the present invention is half the deterioration
In contrast to the rank, the level of comparison is deteriorated by 1 to 1.5 ranks, and it can be seen that the effect of the present invention is more exerted when the processing in which the replenishment amount of the developing solution and the fixing solution is small is performed.

[0126]

According to the present invention, a silver halide photographic light-sensitive material for a laser light source, which has high sensitivity and is free from deterioration of silver color tone and generation of roller marks, and which can be rapidly processed, was obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/20 5/26

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on one side of a transparent support, wherein at least one of the silver halide emulsion layers is provided.
One layer has an average iodine content of 0.5 mol% or less and 600 nm
A silver halide photographic light-sensitive material comprising silver halide grains spectrally sensitized to the above wavelengths and further hardened with a pyrrolidinocarbonylpyridinium compound. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the pyrrolidinocarbonylpyridinium compound is represented by the following general formula [1]. Embedded image In the formula, R ^11a represents a hydrogen atom or an optionally substituted alkyl group or alkoxy group, and R ^12a represents an optionally substituted alkyl group, an acyl group or an acylamino group, X ^11a- Represents an anion, y ^11a is 1 or 2, and when y ^11a is 1, it forms an inner salt. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains are chemically sensitized with at least one selenium compound. 4. The total processing time of the silver halide photographic light-sensitive material according to claim 1, 2 or 3 in a processing step containing a developer containing substantially no hardener is from 15 seconds to 30 seconds. A method of processing a silver halide photographic light-sensitive material, which comprises processing.