JPH04328737A - Silver halide photographic sensitive material and development processing method thereof - Google Patents

Abstract

PURPOSE:To improve the development progressability of a silver halide photosensitive material for an IR laser printer and covering power and to impart rapid development processability to the material by using an emulsion formed by gold sensitization of silver chlorobromide particles consisting of hetero layers varying in intra-particle halogen compsn. CONSTITUTION:This photosensitive material has a base and at least one layer of hydrophilic colloidal layers including silver halide emulsion layers. The silver halide emulsion has the silver chlorobromide particles consisting of the hetero layers varying in the intra-particle halogen compsn. and is subjected to gold sensitization. More preferably the amt. of the silver to be applied on one surface of the silver halide emulsion is <=2.8g/m<2> and the total amt. of the gelatin applied on the base on the same surface side as the silver halide emulsion is 3g/m<2>.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and in particular, it has fast developability and fast fixability when processed using an automatic processor (hereinafter referred to as automatic processor). The present invention also relates to a photographic material with high sensitivity and high covering power.

0002

[Prior Art] In recent years, high-temperature rapid processing has rapidly become popular in the development process of silver halide photographic materials (hereinafter referred to as "sensitized materials"), and even in the automatic processing of various kinds of photosensitive materials, the processing time is It has been significantly shortened. In order to achieve rapid processing, a sensitive material that can provide sufficient blackening density in a short period of time and characteristics that allow fixing, washing, and drying to be completed in a short period of time are required. In particular, various methods have been studied to quickly complete drying, but one method that is commonly used to improve the drying properties of sensitive materials is to apply a sufficient amount of hardness in advance during the coating process of the sensitive material. There is a method of adding a membrane agent (gelatin crosslinking agent) to reduce the amount of swelling of the emulsion layer and surface protective layer during the development, fixing, and water washing processes, thereby reducing the water content in the sensitive material before drying begins. be. In this method, the drying time can be shortened by using a large amount of a hardening agent, but the swelling becomes smaller, which delays development, resulting in lower sensitivity and lower covering power.

Furthermore, a high temperature rapid processing method using a processing agent in which the developing solution and the fixing solution do not substantially have a gelatin hardening effect is described, for example, in JP-A-63-136043. Although these methods speed up development and improve fixing properties, they end up slowing drying properties and cannot be said to be sufficiently effective methods.

On the other hand, as a method of accelerating development and increasing covering power, it is known to use various additives to silver halide. For example, polyacrylamides are used as polymers in US Pat. No. 3,271,158.
No. 3,514,289, No. 3,514,28
No. 9, etc., and dextran compounds as sugars are disclosed in US Pat. No. 3,063,838, US Pat. No. 3,272,631, etc. However, these compounds have drawbacks such as slow drying and deterioration of film strength when used in amounts sufficient to achieve their purpose.

Furthermore, on the other hand, there are also known methods for increasing the developing activity of the processing solution, such as increasing the amount of the main agent or auxiliary developing agent in the developer, raising the pH of the developer, and raising the processing temperature. However, all of these methods have drawbacks such as damaging the preservative in the processing solution, softening the tone even if the sensitivity is increased, and being prone to fogging.

[0006] Apart from the viewpoint of rapid processing, further increasing the sensitivity of photosensitive materials and improving the covering power are issues that have been continuously investigated. If higher sensitivity is achieved by increasing the particle size, the covering power generally decreases. It is meaningless unless higher sensitivity is achieved with the same size particles, or higher covering power is achieved with the same sensitivity.

[0007]

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide particles of the same size (diameter of projected area) that have excellent development progress and sensitivity, and that have high covering power and fixing properties.
It is an object of the present invention to provide a silver halide photographic material in which the burden of rapid processing of washing and drying steps is reduced.

[0008]

[Means for Solving the Problems] The object of the present invention is to provide a silver halide photographic light-sensitive material for infrared laser printers, which has a support and at least one hydrophilic colloid layer including at least one silver halide emulsion layer. Achieved by a silver halide photographic light-sensitive material, characterized in that the silver halide emulsion contains silver chlorobromide grains consisting of multiple layers with different intra-grain halogen compositions, and is gold sensitized. I found out that it can be done.

Further, the present invention provides a support and at least one
A method for processing a silver halide photographic light-sensitive material for an infrared laser printer having at least one hydrophilic colloid layer including a silver halide emulsion layer in an automatic processor, wherein the silver halide emulsion layer has grains. A silver halide photographic material characterized by containing silver chlorobromide grains consisting of multiple layers with different inner halogen compositions and being gold sensitized is represented by the following general formula [a] 3 - It has been found that the present invention can be carried out more effectively by a method for processing silver halide photographic materials, which is characterized by developing using a developer containing a pyrazolidone-based developing agent.

General formula [a]

[0011]

[Case 2]

(Here, R represents an aryl group. R1
, R2, R3, and R4 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. However, when R represents an unsubstituted phenyl group, R1, R2, R3 and R4
are not all hydrogen atoms at the same time)

A further object of the present invention is to provide a support and at least one silver halide emulsion layer comprising at least one silver halide emulsion layer.
In a silver halide photographic light-sensitive material for infrared laser printers comprising a hydrophilic colloid layer,
The silver halide emulsion contains silver chlorobromide grains consisting of multiple layers with different intra-grain halogen compositions, and the grain surfaces are modified by conversion with silver bromide or silver iodide, and then gold sensitized. This can be more preferably achieved by using a silver halide photographic material which is characterized by being treated with the following.

The photosensitive silver halide used in the present invention is a halogen consisting of chlorine, bromine and/or iodide, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. In the case of silver iodobromide or silver chloroiodobromide, silver iodide is 0 to 3 mol%, preferably 0 to 1 mol%, and silver chloride is 0 to 70 mol%, preferably It is 0 to 50 mol%. In the case of silver chlorobromide, the content of silver chloride is 1 to 95 mol%, preferably 10 to 70 mol%. The crystal structure of silver halide grains preferably has a layered structure in which the inside and outside are different. For example, in the case of silver chlorobromide grains, it is preferable that the silver chloride content of the inner and outer shells differ by 10 mol% or more. preferable.

Further, the ratio of (100) plane/(111) plane of the silver halide grains used in the present invention is preferably 3 or more, particularly preferably 4 or more, and still more preferably 5 or more. The above ratio may be 100% for the (100) plane. It is preferable to contain silver halide grains having a (100) plane/(111) plane ratio of 3 or more, preferably 5 or more in an amount of 50 wt% or more, particularly preferably 80 wt% or more. The silver halide grains of the present invention having a (100) plane/(111) plane ratio of 3 or more can be prepared by various methods. The most common method is to reduce the pAg value to 8 during particle formation.
．． This is a method in which a silver nitrate aqueous solution and an alkali halide aqueous solution are simultaneously added at a rate faster than the dissolution rate of the particles and at a rate that does not cause re-nucleation (so-called controlled double jet method) while maintaining a constant value of 1 or less. More preferably, the pAg value is 7.8 or less, and even more preferably 7.6 or less. Although there is no particular restriction on the pAg value during nucleation of silver halide, the pAg value during grain growth is preferably 8.1 or less, preferably 7.8 or less, and more preferably 7.6 or less. Furthermore, although a one-sided mixing method may be used as the format for reacting the silver nitrate aqueous solution and the alkali halide aqueous solution, a simultaneous mixing method is preferred in order to obtain good monodispersity.

These emulsions may have coarse grains, fine grains, or mixed grains thereof, but preferably have an average grain size of about 0.5 mm (as measured by projection photography or number average method).
Emulsion grains of 0.4 to 1.0 micron, preferably 0.2 to 0.7 micron are preferred. The grain shape is preferably cubic, but as long as it satisfies the surface index conditions of the present invention, it may be spherical, potato-like, plate-like, or tabular grains with an aspect ratio of 5 or more (see Research Disclosure for details).
Item No. 22534 p. 20-p. 58) may have an irregular crystal form. These photosensitive silver halide emulsions may be mixed with a substantially non-photosensitive silver halide emulsion (for example, an internally fogged fine grain emulsion). Of course, emulsions with different grain sizes may be applied in separate layers in order to expand the exposure latitude. As for the particle size distribution, a narrow so-called monodisperse particle size distribution is preferably used. More specifically, as a monodisperse emulsion, ±
90% or more of all particles within 40%, preferably ±20%
An emulsion in which 90% or more of all grains are contained within the range is preferred.

The sensitive material of the present invention may contain iridium. In order to contain iridium ions, it is common to add an aqueous iridium compound (for example, hexachloroiridate (IV) salt, etc.) in the form of an aqueous solution during the preparation of a silver halide emulsion. It may be added in the same aqueous solution form as the halide for grain formation, it may be added before grain formation, it may be added during grain formation, or it may be added between grain formation and chemical sensitization, but it is particularly preferred. is added during particle formation. The iridium ion is preferably used in an amount of 10-8 to 10-5 mol, more preferably 10-7 to 10-6 mol, per mol of silver halide.

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (for example, US Pat. No. 3,271,15) are used as silver halide solvents to control grain growth.
No. 7, No. 3,574,628, No. 3,704,1
No. 30, No. 4,297,439, No. 4,276,
No. 374, etc.), thione compounds (e.g., JP-A-53-1
No. 44,319, No. 53-82,408, No. 55
-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.), etc. can be used. In addition to the silver halide solvent, compounds that control crystal habit by adsorbing onto the grain surface, such as cyanine-based sensitizing dyes, tetrazaindene-based compounds, and mercapto compounds, can be used during grain formation.

The emulsion used in the present invention can be prepared by a commonly used chemical sensitization method, such as sulfur sensitization (US Pat. No. 1,
No. 574,944, No. 2,278,947, No. 3
, No. 021,215, No. 3,635,717, etc.)
, reduction sensitization (U.S. Pat. No. 2,518,698, Research Disclosure)
osure ) Vol. 176 (1978.12) 17
No. 643, Section 3), sensitization with thioether compounds (for example, U.S. Pat. No. 2,521,926, No. 3,0
No. 21,215, No. 3,046,133, No. 3,
No. 165,552, No. 3,625,697, No. 3
, No. 635,717, No. 4,198,240, etc.)
, or a combination of various sensitization methods. More specific chemical sensitizers include sodium thiosulfate and allyl thiocarbamide.
sulfur sensitizers such as thiourea, thiosulfate, thioether and cystine; and reduction sensitizers such as tin chloride, phenylvidrazine and reductone.

Furthermore, the emulsion used in the present invention is preferably gold-sensitized (eg, US Pat. No. 2,540,085, US Pat. No. 2,399,083). Specific gold sensitizers include potassium chlorooleate,
These include aura thiosulfate and potassium chloroparadate. These gold compounds may be added before or after the sulfur sensitizer. It can also be added at the same time as a sulfur sensitizer. The amount of gold sensitizer used in the present invention is 10-7 to 10 per mole of silver halide.
It is preferable to use it in a proportion of -3 mol, and more preferably 10-6 mol.
It is particularly preferred to use it in a proportion of 10-4 mol.

In the present invention, as spectral sensitization,
At least one of tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes as described in No. 3-89838 can be used. The above-mentioned spectral sensitizing dye used in the present invention is 10-7 to 10-2 mol, preferably 10-2 mol per mol of silver halide.
It is contained in a silver halide photographic emulsion in a proportion of 6 to 10-3 moles. The above-mentioned spectral sensitizing dyes used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent, such as methyl alcohol, ethyl alcohol,
It can also be dissolved in methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution. The dye is usually added after chemical sensitization in many cases, but it may be added either during grain formation or before chemical sensitization. Ultrasonic waves can also be used for dissolution. For addition to emulsions, U.S. Pat.
No. 42,605, No. 2,996,287, No. 3,
The method described in eg No. 429,835 can also be used. The above spectral sensitizing dyes may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but as mentioned above, the spectral sensitizing dyes may be dispersed uniformly in the silver halide emulsion at any stage of preparation. Can be dispersed. Furthermore, other sensitizing dyes can also be used in the present invention. For example, U.S. Patent No.
No. 703,377, No. 2,688,545, No. 3
, No. 397,060, No. 3,615,635, No. 3,628,964, British Patent No. 1,242,588
No. 1,293,862, Special Publication No. 43-4936
No. 44-14030, No. 43-10773, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930
No. 3,615,613, U.S. Patent No. 3,615
, No. 632, No. 3,617,295, No. 3,63
The spectral sensitizing dyes described in No. 5,721 and the like may be used, and the above-mentioned infrared sensitizing dyes and these spectral sensitizing dyes can also be used together.

In the present invention, the compounds described in JP-A-63-89838 can be used together with the above-mentioned sensitizing dyes for the purpose of further enhancing the supersensitizing effect. Furthermore, together with the above-mentioned sensitizing dye, JP-A No. 63-89838
Preservability improvers such as those described in the above may be used in combination in an amount of about 0.01 to 5 g per mole of silver halide in the emulsion. The supersensitizer or storage improver used in the present invention may be directly dispersed into the emulsion,
It can also be dissolved in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a mixed solvent containing two or more of these solvents and added to the emulsion. In addition, it can also be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. The supersensitizer and storage improver may be added to the emulsion before or after the addition of the above-mentioned spectral sensitizing dye. Further, these may be dissolved separately from the spectral sensitizing dye and added separately to the emulsion at the same time, or they may be mixed and then added to the emulsion.

The photographic light-sensitive material of the present invention includes a manufacturing process thereof,
Various compounds can be added to prevent a decrease in sensitivity or the occurrence of fog during storage or processing. These compounds include nitrobenzene imidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene, 1-phenyl-
A large number of compounds have been known for a long time, including 5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. An example of a compound that can be used is C. E. K. “The
Thoery of the Photographic
Process” (3rd edition, 1966) 344~
The original document is listed on page 349. For example, U.S. Patent Nos. 2,131,038 and 2,6
Thiazolium salts described in US Pat. No. 94,716, etc.; US Pat. No. 2,886,437 and US Pat.
Azaindenes described in US Pat. No. 5, etc.; urazoles described in US Pat. No. 3,287,135, etc.; sulfocatechols described in US Pat. No. 3,236,652, etc.; UK Patent No. 623,448
Oximes described in US Patent Nos. 2 and 4
No. 03,927, No. 3,266,897, No. 3,
Mercaptotetrazoles, nitrones, and nitroindazoles described in US Pat. No. 397,987, etc.; Polyvalent metal salts described in US Pat.
); Thiuronium salt described in U.S. Patent No. 3,220,839 etc.
s) ; U.S. Patent No. 2,566,263, U.S. Patent No. 2,5
Examples include salts of palladium, platinum, and gold, as described in No. 97,915.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (such as development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. As an antistatic agent, in particular, US Pat. No. 4,201,586, JP
-80,849, 59-74,554, patent application No. 1983
Fluorine-containing surfactants or polymers described in No. 0-249,021 and No. 61-32,462, JP-A-60-7
No. 6,742, No. 60-80846, No. 60-808
No. 48, No. 60-80,839, No. 60-76,74
No. 1, No. 60-58-208,743, Patent Application No. 1988-1
No. 3,398, No. 61-16,056, No. 61-32
, 462, etc., or conductive polymole or latex (nonionic amphoteric, anionic, cationic, amphoteric) can be preferably used. As the inorganic antistatic agent, conductive tin oxide or zinc oxide described in JP-A-57-118242, or a composite oxide doped with antimony or the like described in these metal oxides can be preferably used.

Hardeners used in the present invention include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy- 1,
4-dioxane, 2,3-dihydroxy-5-methyl-
Aldehyde compounds such as 1,4-dioxane, succinic aldehyde, 2,5-dimethoxytetrahydrofuran, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1, 3,5-Triacryloyl-hexahydro-s-triazine, 1,3
, 5-trivinylsulfonyl-hexahydro-s-triazine bis(vinylsulfonylmethyl)ether,
1,3-bis(vinylsulfonylmethyl)propanol-2-bis(α-vinylsulfonylacetamide)
Active vinyl compounds such as ethane; 2,4-dichloro-
6-hydroxy-s-triazine sodium salt, 2,
4-dichloro-6-methoxy-s-triazine, 2,4
-dichloro-6-(4-sulfonilino)-s-triazine sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-s-triazine, N,N'-bis(2-chloroethyl Active halogen compounds such as carbamyl) piperazine; bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate, 1,4-bis(2',3'-epoxypropyloxy)butane, 1 , 3,5-triglycidyl isocyanate, 1,3-diglycidyl-5-(γ-acetoxy-β-oxypropyl) isocyanate; 2,4,6-triethyleneimino-s-
Ethyleneimine compounds such as triazine, 1,6-hexamethylene-N,N'-bisethyleneurea, and bis-β-ethyleneiminoethylthioether; 1,2,-di(
Methanesulfonic acid ester compounds such as methanesulfonoxy)ethane 1,4-di(methanesulfoneoxy)butane and 1,5-di(methanesulfoneoxy)pentane; furthermore, carbodiimide compounds; isoxazole compounds; and chromium Mention may be made of inorganic compounds such as alum.

In the present invention, as matting agents, US Pat. Nos. 2,992,101, 2,701,245,
Homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid as described in 4,142,894 and 4,396,706, organic compounds such as starch, silica, titanium dioxide, strontium sulfate , fine particles of an inorganic compound such as barium can be used. The particle size is 1 to 10 μm,
In particular, it is preferably 2 to 5 μm.

The surface layer of the photographic light-sensitive material of the present invention contains as a slipping agent US Pat. No. 3,489,576 and US Pat.
Silicone compounds described in No. 7,958 etc., Japanese Patent Publication No. 1983
In addition to the colloidal silica described in -23,139, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. The hydrophilic colloid layer of the photographic material of the present invention may contain a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include homopolymers of alkyl esters of acrylic acid or copolymers with acrylic acid, styrene-butadiene copolymers, and polymers or copolymers of monomers having active methylene groups.

In addition to gelatin, acylated gelatin such as phthalated gelatin or malonated gelatin is used as a binder in the silver halide photographic emulsion layer, intermediate layer, protective layer, antihalation layer, back layer, etc. used in the present invention; Cellulose compounds such as hydroxyethylcellulose and carboxymethylcellulose; soluble starches such as dextrin; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid can be added. Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

The silver halide photographic material of the present invention may have non-photosensitive layers such as a surface protective layer, an intermediate layer, an antihalation layer, and a back layer in addition to the photosensitive silver halide emulsion layer. There may be two or more silver halide emulsion layers, and the two or more silver halide emulsion layers may have different sensitivities, gradations, etc. Further, the support may have one or more silver halide emulsion layers or non-photosensitive layers on both sides.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film, and is particularly preferably colored blue. The surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment in order to improve adhesion to the hydrophilic colloid layer. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex, etc. may be provided, and a gelatin layer may be provided on top of the undercoat layer. Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

The antihalation dye and/or antiirradiation dye used in the present invention is 750
A dye having substantial absorption at long wavelengths of nm or longer is used. Here, the antihalation dye is used for the intermediate layer, undercoat layer, antihalation layer, back layer, emulsion layer, etc., and the anti-irradiation dye is used for the intermediate layer, etc. in addition to the emulsion layer. Moreover, these dyes are preferably 1
0-3 to 1 g/m2, more preferably 10-3 to 0.5
It is used in a dosage of g/m2. For example, U.S. Pat.
, No. 895,955, No. 3,177,078, No. 4,
581,325, the dyes described in JP-A-50-100,116, and JP-A-63-23148, JP-A-63-898.
Dyes such as those described in No. 38 are preferably used. These dyes may be used alone or in combination of two or more. Further, other dyes may be used in place of the above dyes or in combination with these dyes. Dyes that can be used instead or in combination include, for example, the pyrazolone oxonol dyes described in US Pat. No. 2,274,782, the diarylazo dyes described in US Pat. No. 2,956,879, and the diarylazo dyes described in US Pat. No. 3,423,207, styryl dyes and butadienyl dyes described in No. 3,384,487, merocyanine dyes described in U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897,
Merocyanine dyes and oxonol dyes described in U.S. Pat. .

[0033]

[Example] Example 1

1. Preparation of silver halide emulsion (A)

00
35] Dissolve 40 g of gelatin in 1 liter of H2O, and add 3 g of potassium bromide and compound [I] in a container heated to 55°C.

[0036]

[Chemical formula 3]

After adding 60 mg of
While keeping the value at 7.0, add 1000 ml of an aqueous solution containing 200 g of silver nitrate and hexachloroiridium(III).
1080 ml of an aqueous solution of 140 g of potassium bromide containing potassium chloride at a molar ratio of 10-7 to silver was added by a double jet method to prepare cubic monodisperse silver bromide particles having an average particle size of 0.4 μm. After desalting this emulsion, 75 g of gelatin was added, and 3 mg of sodium thiosulfate and 4 mg of chloroauric acid were added to adjust the pH to 6.0 and pAg to 8.5, and chemical sensitization was performed at 60°C (emulsion A). .

2. Preparation of silver halide emulsion (B) H2
Dissolve 40 g of gelatin in 1 liter of O, and add 5 g of sodium chloride and 0 potassium bromide to a container heated to 55°C.
．． After adding 4 g and 60 mg of the compound [I],
1000 ml of an aqueous solution containing 200 g of silver nitrate, 1080 ml of an aqueous solution containing potassium hexachloroiridate(III), 21 g of sodium chloride, and 100 g of potassium bromide so that the molar ratio of iridium to silver is 10-7.
ml by the double jet method to prepare cubic monodisperse silver chlorobromide particles with an average particle size of 0.35 μm. After desalting this emulsion, 40g of gelatin was added,
2 mg of triethylthiourea, 4 mg of chloroauric acid and 4-hydroxy-6 to adjust pH 6.0 and pAg 8.5.
-Methyl-1,3,3a,7-tetrazaindene 0.2
Chemical sensitization was carried out at 60° C. (emulsion B).

3. Preparation of silver halide emulsion (E) H2
Dissolve 40 g of gelatin in 1 liter of O, and add 6 g of sodium chloride and 0 potassium bromide to a container heated to 53°C.
．． After adding 4 g and 60 mg of the compound [I],
600 ml of an aqueous solution containing 100 g of silver nitrate, and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride.
ml by double jet method to obtain 20 ml of silver chloride.
After that, 500 ml of an aqueous solution containing 100 g of silver nitrate, 40 g of potassium bromide, 14 g of sodium chloride, and hexachloroiridium (III) was prepared.
) aqueous solution containing potassium acid (10-7 mol/mol silver) 5
00 ml was added by double jet method to form a shell portion containing 40 mol% of silver chloride, and the average grain size was 0.00 ml.
So-called core/shell type cubic monodisperse silver chlorobromide grains of 35 μm were prepared. After desalting this emulsion, 40 g of gelatin was added, and the pH was adjusted to 6.0 and pAg to 8.5. 2 mg of triethylthiourea, 4 mg of chloroauric acid and 4-
Chemical sensitization was performed at 60°C by adding 0.2 g of hydroxy-6-methyl-1,3,3a,7-tetrazaindene (
Emulsion E). Similarly, emulsions C, D, and F to I were prepared so that the silver chloride contents in the core and shell parts were as shown in Table 1.

4. Preparation of emulsion coating solution A container in which 850 g of emulsion A was weighed out was heated to 40° C., and additives were added in the following manner to prepare an emulsion coating solution.

(Emulsion coating liquid formulation A)

[0042]B. Emulsion A

850g lo. Spectral sensitizing dye [II]

1.2 x 10-4 molha. Supersensitizer [II
I]
0.8 x 10-3 molni. Preservation improver [IV]
1 x 10-3 morpho. Polyacrylamide (molecular weight 40,000)
7.5g f. trimethylolpropane
1.
6g. Sodium polystyrene sulfonate
2
．． 4g chi. Poly(ethyl acrylate/methacrylic acid)
16g latex. N,N'-ethylenebis-(vinylsulfoneacetamide) 1
．． 2g

[0043]

[C4]

5. Preparation of coating solution for surface protective layer of emulsion layer A container was heated to 40° C., and additives were added according to the formulation shown below to prepare a coating solution.

(Formulation of coating solution for surface protective layer of emulsion layer) a. gelatin

100g lo. Polyacrylamide (molecular weight 40,000)
10g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6
gni. N,N'-ethylenebis-(vinylsulfoneacetamide) 1.5g e. Polymethyl methacrylate fine particles (average particle size 2.0μm)


2.2g f. Sodium t-octylphenoxyethoxyethanesulfonate


1.2g. C16H33O-(CH2CH2
O) 10-H
2.7g chi. Sodium polyacrylate

4g ri. C8F17SO3K

70mg Nu. C8F1
7SO2N(C3H7)(CH2CH2O)4(CH2
)4-SO3Na
70mg le. NaOH (1N)

4ml. methanol

60ml

6. Preparation of back layer coating solution A container was heated to 40° C., and additives were added according to the following formulation to prepare a back layer coating solution.

(Back layer coating liquid formulation) a. gelatin

80g lo. Dye [V]

3.1g c. Sodium polystyrene sulfonate
0.6g ni. Poly(ethyl acrylate/methacrylic acid) latex
15g e. N,N'-ethylenebis-(vinylsulfoneacetamide) 4.3g

0048
]

[C5]

7. Preparation of a coating solution for the surface protective layer of a bag A container was heated to 40° C., and additives were added according to the formulation shown below to prepare a coating solution.

(Formulation of coating solution for surface protective layer of bag) a. gelatin

80g lo. Sodium polystyrene sulfonate
0.3g c. N,N'-ethylenebis-(
vinyl sulfone acetamide) 1.7 g. Polymethyl methacrylate fine particles (average particle size 4.0μm)

4g ho. t-Octylphenoxyethoxyethane
sodium sulfonate

3.6g f. NaOH (1N)

6ml Sodium polyacrylate
2g chi. C16H
33O-(CH2CH2O)10-H

3.6g li. C8F17SO3K

50mg Nu. C8F17SO2N (C3H7) (CH2CH2O)
4(CH2)4-SO3Na
50mg le. methanol

130ml

8. Preparation of Coated Sample The above-mentioned back layer coating solution was coated on the polyethylene terephthalate support side together with the back layer surface protection layer coating solution so that the total gelatin coating amount was 3 g/m2. Subsequently, the above-mentioned emulsion coating solution and surface protective layer coating solution were applied to the opposite side of the support so that the coating amount of Ag was 2.5 g/m2 and the coating amount of gelatin for the surface protective layer was 1 g/m2. (Coating sample 1-1). Furthermore, Samples 1 to 9 were prepared in exactly the same manner except that Emulsions B to I were used instead of Emulsion A.

9. Method of sensitometry Using the samples 1 to 9 thus prepared, sensitometry was carried out in the following manner to measure sensitivity. Samples 1 to 9 at 25℃60%
Leave it for 7 days after application at a temperature and humidity of 780 nm at room temperature.
Scanning exposure was performed for 10-7 seconds using a semiconductor laser, and development processing was performed using the following processing solution. The development time was carried out in two stages, 5 seconds and 25 seconds, and the initial development start-up and the final sensitivity were compared. The sensitivity was compared at a concentration of 1.0.

Developer [I] Composition Potassium hydroxide

29g sodium sulfite

31g potassium sulfite

44g ethylenetriaminetetraacetic acid

1.7g boric acid

1g
hydroquinone

30g diethylene glycol

29g 1-phenyl-
3-pyrazolidone
1.5g glutaraldehyde
4.9g
5-methylbenzotriazole
60
mg potassium bromide

7.9g acetic acid

1
8g 5-nitroindazole

0.25g

upto 1000ml

pH
10.3

Fixer [I] Composition Ammonium thiosulfate

140g sodium sulfite

15g Ethylenediaminetetraacetic acid disodium dihydrate
20mg sodium hydroxide

7g aluminum sulfate

10g boric acid

10g sulfuric acid

3.9g acetic acid

15g


upto 1000ml

pH 4
．． 310. Method for Measuring Fixing Removal Speed Each coated sample was immersed in the fixing solution [I], and the time until it became transparent was measured using a spectrophotometer manufactured by Hitachi (Type U-3210). 11. Test results Table 1 shows the results of sensitometry and fixing removal rate.

[0055]

[Table 1]

Example 2

Photographic properties were evaluated in exactly the same manner as in Example 1, except that Samples 1, 2, and 5 of Example 1 were used, and the following developer solution [II] and fixer solution [II] were used as processing solutions. I did it. Table 2 shows the comparison results of sensitivity and fog.

[0058]

[Table 2]

It is clear that the present developer [II] is more effective in terms of sensitivity than the results obtained with the developer [I] used in Example 1.

Developer [II] Composition Potassium hydroxide

24g sodium sulfite

40g potassium sulfite

50g diethylenetriaminepentaacetic acid

2.4g boric acid

10g hydroquinone

35g diethylene glycol

11g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone
6g
5-methylbenzotriazole
60
mg potassium bromide

2g acetic acid

1
．． 8g

upto 1000ml

pH
10.5

Fixer [II] Composition Ammonium thiosulfate

140g sodium sulfite

15g Ethylenediaminetetraacetic acid disodium dihydrate
25mg sodium hydroxide

6g

upt
o 1000ml

pH 5.10
Example 3

1. Preparation of silver halide emulsion (J) H2
Dissolve 40 g of gelatin in 1 liter of O, and add 6 g of sodium chloride and 0 potassium bromide to a container heated to 53°C.
．． 4g, and compound [I]

[0063]

[C6]

After adding 60 mg of [0064], 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride were added by a double jet method to create a core portion containing 20 mol% of silver chloride. , then 500 ml of an aqueous solution containing 100 g of silver nitrate
, 40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridate(III) (10
500 ml of an aqueous solution containing -7 mol/mole of silver) was added by double jet method to form a shell portion of 40 mol% silver chloride, and a so-called core/shell type cubic monodisperse salt with an average particle size of 0.35 μm was added. Silver bromide particles were prepared. Furthermore, after that, an aqueous solution 6 containing 0.6 g of potassium iodide
0 ml is added to convert some of the silver chlorobromide on the grain surface into silver iodide. After desalting this emulsion, 40 g of gelatin was added, and the pH was adjusted to 6.0 and pAg to 8.5. 2 mg of triethylthiourea, 4 mg of chloroauric acid and 4-
Chemical sensitization was performed at 60°C by adding 0.2 g of hydroxy-6-methyl-1,3,3a,7-tetrazaindene (
Emulsion J). Similarly, emulsions K and L were prepared using 1.2 g and 1.8 g of potassium iodide, respectively.

2. Preparation of coating sample

Coating samples 10 to 12 were prepared in the same manner as in Example 1 using emulsions J to L, respectively. This was processed using the developer [II] and fixer [II] shown in Example 2. The results of sensitometry and fixability are shown in Table 3.

[0067]

[Table 3]

It can be seen that Samples 10 to 12 of the present invention are more advantageous in terms of sensitivity than the results of Examples 1 and 2. Example 4

Using coated sample-1 (comparison) and coated sample-5 (invention), FCR7000 manufactured by Fuji Photo Film KK was used.
Laser Image Printer (Type C
R-LP 414), and the drying properties, fixing properties, and silver staining of the developer were evaluated. The processing speed is
Modify the electric circuit to adjust the rotation speed of the roller,
The test was conducted under two conditions: Dry-to-Dry for 68 seconds and 30 seconds. The results are shown in Table 4.

[0070]

[Table 4]

Comparative sample 1 shows good drying, fixing and silver staining when processed for 68 seconds, but does not give satisfactory results due to poor drying and fixing when processed for 30 seconds. On the other hand, the present invention sample-5
68 second processing is not sufficient to remove silver stains, and 30 second processing is suitable.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material for infrared laser printers, comprising a support and at least one hydrophilic colloid layer including at least one silver halide emulsion layer, wherein the silver halide emulsion comprises: 1. A silver halide photographic material, characterized in that it contains silver chlorobromide grains consisting of a plurality of layers having different intra-grain halogen compositions, and is gold sensitized. Claim 2: The amount of silver coated per side of the silver halide emulsion is 2.8 g/m2 or less, and the total amount of gelatin coated on the same side of the support as the silver halide emulsion is 3 g.
2. The silver halide photographic material according to claim 1, wherein the silver halide photographic material has a particle size of /m2 or less. 3. A silver halide photographic light-sensitive material for infrared laser printers containing a support and at least one hydrophilic colloid layer including at least one silver halide emulsion layer is processed using an automatic processor. In the method of A method for processing a silver halide photographic light-sensitive material, the method comprising developing a silver halide photographic material using a developer containing a 3-pyrazolidone developing agent represented by (a). General formula [a] [Formula 1] (Here, R represents an aryl group. R1 , R2 , R
3 and R4 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. However, when R represents an unsubstituted phenyl group, R1, R2, R3 and R4 are not all hydrogen atoms at the same time) 4. A silver halide photographic material for infrared laser printers, comprising a support and at least one hydrophilic colloid layer including at least one silver halide emulsion layer, wherein the silver halide emulsion comprises: It contains silver chlorobromide grains consisting of multiple layers with different intra-grain halogen compositions, and the grain surface has been modified by conversion with silver bromide or silver iodide, and then gold sensitized. Characteristic silver halide photographic materials.