JPH0980665A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the sharpness of character with high sensitivity, and prevent deteriorations of flaw resistance and white pin by containing a specified compound in a silver halide emulsion layer and a specified latex (Lx) in a hydrophilic colloid layer adjacent thereto. SOLUTION: In a silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer on a base, at least one of compounds represented by the formulae I, II is contained in the silver halide emulsion layer, and a polymer latex (L) stabilized with gelatin or a latex (Lx) having a glycizyl methacrylate or glycizyl acrylate unit having an opening ratio of epoxy ring of 35 mole % or more. In the formulae I, II, Y11 -represents a nonmetal atom group required to complete a 5-membered or 6-membered nitrogenous heterocyclic ring, R11 , R12 , R21 , R22 represent alkyl group, aryl group or the like, R13 -R15 , R23 -R26 represent hydrogen atom, aralkyl group, or the like, and X11 <-> , S21 <-> represent anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for printing plate making which has high sensitivity, good character sharpness, scratch resistance and white pin.

[0002]

2. Description of the Related Art In recent years, a scanner method has been widely used in the field of printing plate making. As a recording light source of a recording apparatus that has put this image forming method using the scanner system into practical use,
Glow lamp, xenon lamp, tungsten lamp,
There are LEDs, He-Ne lasers, semiconductor lasers, and the like. Especially in recent years, LED, H
The e-Ne laser and the semiconductor laser are becoming mainstream. Further, in the printing and plate making industry, there is a great need to speed up the development process from the viewpoint of shortening the delivery time and improving the work efficiency by shortening the waiting time in the development.

In order to adjust the spectral sensitivity to the emission wavelength of the light source, it becomes necessary to adsorb the spectral sensitizing dye onto the silver halide grains. In addition, when the amount of gelatin is reduced for rapid processing, there is a problem that the white pin deteriorates due to scratches and sinking of the matting agent.

[0004]

In contrast to the problems described above, the object of the present invention is to provide high sensitivity, good character sharpness, and scratch resistance (scratch resistance) due to reduction of gelatin accompanying rapid processing. Another object of the present invention is to provide a silver halide photographic light-sensitive material with improved deterioration of white pins.

[0005]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide emulsion layer having the above-mentioned general structure. Polymer latex (L) or epoxy amount containing at least one compound represented by the formula [Ia] or [Ib] and stabilized with gelatin in at least one of adjacent hydrophilic colloid layers. (Lx) having a glycidyl methacrylate or glycidyl acrylate unit having a ring opening ratio of 35 mol% or more
It is achieved by a silver halide photographic light-sensitive material characterized by containing

The above photosensitive emulsion is chemically sensitized with an inorganic sulfur and / or selenium compound and has a density of 0.3 to
It is a preferred embodiment that the gamma (γ) between 3.2 is 8 or more.

The present invention will be specifically described below.

First, the infrared spectral sensitizing dye used in the present invention will be described.

The infrared spectral sensitizing dye used in the present invention may be any, for example, US Pat. Nos. 3457078 and 358.
No. 2344, No. 3695888, No. 4011086, JP-A-61-116351
61, 133-942, 61-138251, 62-56953, 62-56953
Examples thereof include those described in JP-A Nos. 62-106452 and 64-86136, and more preferably, the cationic di- or tricarbocyanine infrared sensitizing dyes shown below.

As the cationic di- or tricarbocyanine infrared sensitizing dye used in the present invention, the compounds represented by the above formulas [Ia] and [Ib] are preferable.

Next, specific examples of the sensitizing dye used in the present invention (hereinafter referred to as the sensitizing dye of the present invention) are shown, but the present invention is not limited thereto. In addition, I-1 ~ 13
Is the above general formula [Ib], and I-14 to 21 are the general formula [Ia].
Is a compound represented by.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

[Chemical 6]

The sensitizing dye of the present invention is preferably 1 mg to 2 g, and more preferably 3.5 mg to 1 mol per mol of silver halide.
It is contained in the silver halide emulsion in the range of 1 g.

The sensitizing dye of the present invention can be directly dispersed in a silver halide emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The time of addition may be any time during the production process of the silver halide photographic light-sensitive material, but preferably any time from physical ripening to immediately before coating.

The sensitizing dyes of the present invention may be used alone or in combination of two or more kinds. Further, sensitizing dyes other than the present invention can be used in combination. When other sensitizing dyes are used in combination, the total content is preferably the above content.

The sensitizing dye of the present invention is the same as US Pat. No. 250377.
6, US Patent 742112, French Patent 2065662, JP40
It can be easily synthesized with reference to No. 2346.

The gelatin-stabilized polymer latex (L) that can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex are dispersion-stabilized with gelatin. It is particularly desirable that the polymer constituting the latex and the gelatin have some kind of bond. In this case, the polymer and gelatin may be directly bonded, or may be bonded via a crosslinking agent.

The gelatin-stabilized polymer latex of the present invention is prepared after the polymerization reaction of the polymer latex is completed.
It can be obtained by adding a gelatin solution to the reaction system and reacting. It is preferred that the polymer latex synthesized in the surfactant is reacted with gelatin using a crosslinking agent. Further, it can be obtained by a method in which gelatin is present during the polymerization reaction of the polymer. Further, in this case, it is preferable not to use a surfactant during the polymerization reaction of the polymer, but when the surfactant is used, its addition amount is 0.1 to 3.0%, particularly preferably 0.1 to 1.5% with respect to the polymer component.
%.

The ratio of gelatin to polymer at the time of synthesis is 1:
100 to 2: 1 is preferable, and 1:50 to 1: is particularly preferable.
2 and 1:20 to 1: 5.

The preferred range of average particle size of the gelatin-stabilized polymer latex used in the present invention is 0.00
It is 5 to 1 μm, preferably 0.02 to 0.5 μm.

Examples of the gelatin-stabilized polymer latex of the present invention include those described in US Pat. No. 2,772,166.
3,325,286, 3,411,911, 3,311,912, 3,52
No. 5,620, Research Disclosure
DISCLOSURE) No. 19551 (July 1980) and the like include hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters and styrene.

The polymer latex portion of the gelatin-stabilized polymer latex (L) preferably used in the present invention is a homopolymer of a metaalkyl acrylate such as methyl methacrylate or ethyl methacrylate,
Homopolymer of styrene, or copolymer of methacryl acrylate or styrene with acrylic acid, N-methylol acrylamide, glycidol methacrylate, etc., homopolymer of alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or alkyl acrylate Copolymer of acrylic acid, N-methylol acrylamide, etc. (preferably 30% by weight of copolymerization components such as acrylic acid), homopolymer of butadiene or one of butadiene and styrene, butoxymethyl acrylamide, acrylic acid Examples thereof include copolymers with the above, vinylidene chloride-methyl acrylate-acrylic acid terpolymer, and the like.

When binding to gelatin via a crosslinking agent, the monomers constituting the polymer latex include:
Carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, active ester group, methylol group, cyano group, acetyl group,
It is desirable to include those having a reactive group such as an unsaturated carbon bond. When a cross-linking agent is used, those used as a general gelatin cross-linking agent can be used. For example, aldehyde type, glycol type,
Crosslinking agents of triazine type, epoxy type, vinyl sulfone type, oxazoline type, methacryl type, acrylic type and the like can be used. Furthermore, in order to further enhance the dispersion stability of the gelatin-stabilized polymer latex of the present invention, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof can be used as a monomer constituting the polymer latex. The amount of the above-mentioned monomer added is preferably 0.5 to 20% by weight based on the total weight of the constituents.

As the gelatin used for stabilizing the latex of the present invention, gelatin and gelatin derivatives, cellulose derivatives, and graft polymers of gelatin and other polymers, which are generally used for silver halide photographic light-sensitive materials described below, and Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

The gelatin-stabilized polymer latex used in the present invention may be added to at least one hydrophilic colloid layer, but it may be added to all hydrophilic colloid layers on one side having a support. A preferable result is obtained when it is added. It may be contained on only one side of the support, or may be contained on both sides. The amount of the latex added is preferably 30% or more, and particularly preferably 30% to 30% with respect to the gelatin in each hydrophilic colloid layer.
200%. A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When the polymer latex is contained on both sides of the support, the type of the polymer latex contained on each side and / or
Or the amounts may be the same or different.

Next, some specific examples of the latex which can be used in the present invention will be described. The specific examples of the latex shown in the present specification represent a latex having any composition ratio of the latex composed of its constituent components. Of course, the specific examples of the latex shown here are typical examples of the latex that can be used, and it goes without saying that the constituent components (not only the composition ratio) of the latex used in the present invention are not limited to these specific examples. Yes.

[0033]

[Chemical 7]

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

[Chemical 12]

[0039]

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[0040]

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The amount of epoxy used in the present invention is 3 during ring opening.
Latex (Lx) having 5 mol% or more glycidyl methacrylate or glycidyl acrylate units
Is characterized by having no or very little adverse effect in the following points even when used in a silver halide emulsion. The latex surface is photographically inert and has very little interaction with various photographic additives. As one example, it is difficult for the silver halide photographic light-sensitive material to be color-contaminated by adsorbing a dye or pigment. Further, it is difficult to adsorb a development accelerator, a development inhibitor, and the like, which affect the speed of development, and hardly affect sensitivity and fog.

When a silver halide photographic light-sensitive material is produced, the silver halide emulsion liquid in which the latex of the present invention is dispersed has little pH dependence and is less susceptible to ionic strength, and therefore is less likely to aggregate and precipitate.

The fact that the latex (Lx) of the present invention has the above-mentioned properties is considered to be greatly influenced by the monomer composition and properties of this latex.

An index called a glass transition point is often used for the latex (Lx). The higher the transition point is, the harder it becomes and cannot serve as a buffer. Therefore, the selection of the composition and the amount used are not simple considering the photographic characteristics. Latex using monomers such as styrene, butadiene, and vinylidene is well known, but none of them gave satisfactory performance. Also,
It is said that introduction of a monomer having a carboxylic acid group such as acrylic acid itaconic acid and maleic acid during the synthesis of a latex reduces the influence on photographic properties, and such a synthesis is often attempted. However, such a method also does not guarantee good performance. In the present invention, the latex obtained by such a combination has a surprising effect by containing a glycidyl methacrylate or glycidyl acrylate monomer unit having a ring opening ratio of at least 35 mol% of epoxy. It was unexpected.

JP-A-2-135335 describes a latex comprising tabular grains and a methacrylate polymer.
It is stated in the specification that methacrylates with glycidyl groups can be used as cure sites therein. However, this example is not taken up in the examples, and does not suggest the configuration effects of the present invention. There is no mention of ring opening of this epoxy. The present invention proposes a novel invention in which the characteristics of tabular grains can be sufficiently exhibited by positively using a methacrylate or acrylate having a glycidyl group.

The amount of glycidyl methacrylate or glycidyl acrylate methacrylate unit having a ring-opening ratio of the epoxy amount in the latex (Lx) of 35 mol% or more is preferably 0.01 or more and 30 wt% or less in the latex solid content. The method for synthesizing latex is described in, for example, Japanese Patent Publication No. 60-15935.
Can be synthesized by the method described in No. The latex synthesis method is not limited because there are numerous synthesis methods other than this patent.

It is preferable to select an alkyl acrylate, an alkyl methacrylate, or a styrene type monomer as a monomer used in the synthesis of the latex (Lx). As the alkyl group of alkyl acrylate or alkyl methacrylate, methyl group, ethyl group, butyl group, hexyl group,
Cyclic saturated rings such as octyl group, nonyl group, dodecyl group, hexadecyl group, etc., which may be substituted, straight or branched, aliphatic groups, cyclohexyl groups, etc., phenyl groups, pyridyl groups, furan groups, etc. Examples thereof include those in which the aromatic group is directly substituted and those in which a linking group is interposed.

The monomer can be selected from the exemplified monomers described in JP-B-60-15935. The blending of these monomers is preferably selected as appropriate by setting the glass transition point which is an index of the hardness of the latex. The glass transition point of the latex is greatly affected by the selection of the alkyl group, but the glass transition point can be controlled by selecting 20% by weight or more of the alkyl acrylate component.
The temperature is preferably 60 ° C or lower, more preferably 50 ° C or lower, and further preferably 40 ° C.

The latex (Lx) of the present invention contains an epoxy base as a monomer unit, but it does not necessarily have to be copolymerized in the latex. This is because a part of the polymerization proceeds as a homopolymer, which may act as a dispersion medium at the time of forming the latex to stabilize the polymerization. Therefore, it is also possible to polymerize a monomer containing an epoxy group in advance and polymerize other monomers in this homopolymer.

If the epoxy ring-opening rate of the glycidyl group of the latex (Lx) having the glycidyl methacrylate or glycidyl acrylate monomer unit of the present invention is too low, the pressure resistance will be deteriorated, and if it is too large, the stickiness upon storage with time will be deteriorated. Become. Therefore, the epoxy ring-opening rate of the glycidyl group is 20 mol% or more, preferably 35 mol% or more, and more preferably 45% or more.

The ring-opening rate of the glycidyl group referred to in the present invention is
Journal of Polymer Science, Vol. 34, No. 8, pp. 571-576 (August 1977)
It is a value measured by the hydrochloric acid-pyridine method as described in 1. and can be obtained by the following calculation formula.

Glycidyl group ring-opening rate = [(A−B) / A] × 100 (mol%) In the above formula, A is the number of moles of the glycidyl group-containing monomer used at the time of polymerization, and B is the synthesized weight. It is the number of moles of the glycidyl group-containing monomer unit in the united body.

The glycidyl methacrylate or the glycidyl acrylate of the present invention is characterized in that the ring-opening rate of the epoxy amount is 35 mol% or more. As a method for setting the ring-opening rate of the glycidyl group to a desired value, polymerization temperature, A method of appropriately selecting the polymerization reaction time or lowering or increasing the pH to forcibly hydrolyze with an acid or alkali to open the ring,
There is a method of adding a compound that reacts with an epoxy group such as amines and aldehydes to open a ring. The choice of these compounds is arbitrary and does not limit the invention.

The stability of the latex can be imparted by using a surfactant for dispersing the monomer during the synthesis of the latex (Lx). The type of activator can be arbitrarily selected from anionic, nonionic, cationic and amphoteric. Nonionic or anionic activators, alone or in combination, give good results. Further, the pH during the polymerization can be selected from neutral, alkali and acid. In the case of an acid monomer, when it is polymerized under acidic condition, it is easily incorporated into the polymer and gives good results. However, acid (pH 1 to 6) or alkali. When it is polymerized at (pH 8-14), it is preferable to add it after returning it to neutrality. Further, for the polymerization, it is preferable to use a dispersion obtained by emulsion polymerization in an aqueous solution, but the solvent may be distilled and used after the polymerization in alcohol or an organic solvent.

As the dispersion medium for the latex, natural amphoteric gelatin may be used. When gelatin is used, it can be incorporated into a latex to obtain a latex having good crosslinkability. There are two methods of using gelatin: one is to add gelatin instead of the active agent, and the other is to use it in combination with the active agent. The gelatin may be either one obtained by alkali decomposition or one treated with an acid. Further, the molecular weight can be controlled depending on the degree of decomposition to improve the dispersibility of the monomer, and the monomer can be used.

Glycidyl methacrylate latex having a ring-opening ratio of epoxy of 15 mol% or more is optionally copolymerized with glycidyl methacrylate in which epoxy of glycidyl group is not ring-opened and other unsaturated vinyl monomer,
After that, the ring can be opened. However, the epoxy may be opened before the polymerization and then polymerized. The unsaturated monomers to be copolymerized are described in JP-A-51-114120
It can be selected with reference to page 8. Particularly, the vinyl monomer as a partner for copolymerization is preferably a methacrylate or acrylate type. However, this is not a limitation and may be a non-acrylate type such as styrene or acrylonitrile.

In order to enhance the stability of the latex (Lx), a monomer having a carboxylic acid group such as acrylic acid, itaconic acid, maleic acid or the like is introduced, or 2-acrylamido-2-methylpropanesulfonic acid or styrene is introduced. Introduction of a sulfonic group such as sulfonic acid or isoprene sulfonic acid is optional. As these acid monomers,
You can refer to page 6 of 2-135335.

The molecular weight of the copolymerization product can be set from 1,000 to 1,000,000 depending on the degree of polymerization. The preferred molecular weight is 1500 to 600,000 but is not limited to this molecular weight.

The particle size of the latex (Lx) is 0.001 to 1
It can be arbitrarily selected up to 0 μm. If the particle size is large, the haze of the film deteriorates. On the other hand, if it is small, a large amount of emulsifier is required, which deteriorates photographic performance and film physical properties. The preferable particle size is 0.01 to 1 μm, and the narrower the particle size distribution is, the more preferable. The index showing the distribution of grains can be expressed by a statistical coefficient of variation, as in the case of silver halide grains. Usually used within 40%. It is preferably within 30%, more preferably within 20%, within 10%, and within 5%. The method of narrowing the distribution may be to eliminate the heterogeneity of the polymerization reaction. For example, the reaction vessel should be sufficiently stirred (stirring under Reynolds' complete stirring and mixing conditions) and the addition of monomers should be controlled (flow rate control, pH
Control).

Specific examples of the latex (Lx) are shown below. Here, GMA is glycidyl methacrylate, GA is glycidyl acrylate, St is styrene, and α-methylstyrene is glycidyl methacrylate having an epoxy content of 35 mol% or more. α-St, MA for methyl acrylate, MMA for methyl methacrylate,
EA for ethyl acrylate, BA for butyl acrylate, HA for hexyl acrylate, IN for isononyl acrylate
A, cyclohexyl methacrylate CA, hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA, acrylic acid AA, itaconic acid IA, maleic acid MA, acrylamide AAm, styrene sulfonic acid S
tS, acrylamido-2-methylpropanesulfonic acid amide are abbreviated as AMPS, and 2-propenyl-4-nonylphenoxyethylene oxide (n = 10) sulfonic acid ester is abbreviated as PFS. The accompanying small letters indicate the composition weight composition ratio.

Specific Examples of Latex Lx Monomer Species Molecular Weight (10,000) Average Particle Size Ring-Opening Rate (%) 1) St ₂₅ MA ₂₅ EA ₄₀ GMA ₁₀ 2 0.20 63 2) St ₃₅ MA ₁₅ EA ₄₀ GMA ₁₀ 1 0.20 62 3 ) St ₃₅ MA ₁₅ EA ₄₀ GMA ₁₀ 2 0.20 63 4) [Activator change in (2)] 2 0.20 70 5) St ₂ CA ₅₀ NA ₃₈ GMA ₁₀ 2 0.20 62 6) St ₄₀ MMA ₁₀ EA ₄₀ GMA ₁₀ 2 0.20 42 7) St ₂ MMA ₁₀ NA ₄₀ GMA ₁₀ 3 0.10 43 8) AN ₂₅ MMA ₁₀ EA ₄₀ GMA ₁₀ 3 0.10 42 9) α-St ₂₅ MMA ₁₀ EA ₄₀ GMA ₈ 2 0.20 53 10) St ₂₀ MMA ₃₀ EA ₄₀ BA ₈ GMA ₂ 2 0.20 51 11) St ₁₀ MMA ₃₀ EA ₅₀ GMA ₁₀ 2 0.20 55 12) EA ₉₀ GMA ₁₀ 5 0.10 58 13) MMA ₁₀ EA ₈₈ GA ₂ 0.2 0.10 63 14) St ₃₀ MMA ₂₀ EA ₄₀ BA ₅ GMA ₅ 0.8 0.20 72 15) CA ₆₀ INA ₃₀ GMA ₁₀ 3 0.10 83 16) MMA ₅₀ EA ₄₀ GMA ₁₀ 4 0.10 70 17) MMA ₅₀ EA ₄₀ GMA ₁₀ 10 0.10 62 18) EA ₉₀ GMA ₁₀ 50 0.10 92 19) MMA ₅₀ EA ₄₀ GMA ₁₀ 20 0.10 93 20) St ₂₀ MMA ₃₀ EA ₅₀ GMA ₁₀ 10 0.20 82 21) St ₁₀ MMA ₃₀ EA ₅₀ HEMA ₅ GMA ₅ 10 0.20 83 22) BA ₄₀ MMA ₂₀ EA ₃₀ AA ₅ GMA ₅ 10 0.10 71 23) CA ₆₀ INA ₃₀ MA ₁₀ GMA ₂ 20 0.10 65 24) CA ₆₀ INA ₃₀ AMPS ₈ GMA ₂ 4 0.10 60 25) CA ₅₀ INA ₃₀ EA ₁₀ GMA ₁₀ 3 0.08 52 26) EA ₉₅ AA ₃₂ GMA ₂ 10 0.06 63 27) EA ₉₁ BA ₃ GMA ₆ 13 0.05 52 28) EA ₄₂ BA ₄₇ AA ₃ GMA ₈ 20 0.03 63 29) EA ₈₀ MMA ₅ GMA ₁₅ 2 0.02 70 30) St ₂₀ MMA ₂₉ EA ₃₉ BA ₈ AA ₃ GMA ₁ 5 0.01 82 31) St ₁₅ IPS ₅ INA ₃₀ GMA ₅₀ 0.2 0.20 92 32) EA ₆₅ GMA ₃₅ 0.8 0.05 63 33) MMA ₂ EA ₈₈ AMPS ₁₀ GA ₃ 3 0.06 62 34) St ₃₂ MMA ₂₀ EA ₄₀ BA ₅ AA ₃ GA ₃ 4 0.30 63 35) CA ₅₀ INA ₃₀ GA ₂₀ 10 0.15 71 The silver halide photographic light-sensitive material using the latex of the present invention can also be used for medical and printing color light-sensitive materials. Here, the case for X rays is taken as an example, but the present invention is not limited to this. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is preferably used by stirring the emulsion at 40 ° C. or higher for a certain period of time. As a labile selenium compound, Japanese Patent Publication No. 44
It is preferable to use the compounds described in JP-B-15748 and JP-B-43-13489. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides,
(For example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. Further, examples of the non-labile selenium compound include selenite, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, and 2-selenazolidine. Examples include dione, 2-selenooxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formulas (I) and (I
I) can be mentioned.

[0062]

[Chemical 15]

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, , Vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoyl) Phenyl group, α-naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group,
Furyl group, imidazolyl group), -NR ₁ (R ₂ ), -OR ₃ or -SR ₄ . R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents an alkyl group, an aralkyl group,
It represents an aryl group or a heterocyclic group. Alkyl group, an aralkyl group, the aryl group or heterocyclic group include the same examples as Z _1. However, R ₁ and R ₂ are each a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group,
Benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group). In general formula (I), Z ₁ preferably represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (I), more preferably
N, N-dialkylselenourea, N, N, N′-trialkyl-N ′
-Acyl selenoureas, tetraalkyl selenoureas, N, N-
Represents dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different, and are an aliphatic group, an aromatic group, a heterocyclic group, —OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ represents --SeR ₁₁ , X, and a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (II), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁
The aliphatic group represented by is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n- Butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, aryl group, 2-butenyl group, 3-pentenyl group,
A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group). In the general formula (II), Z ₃ , Z ₄ , Z
_The aromatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (eg, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3-sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (II), Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Represents a group (for example, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (II), the cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In formula (II), preferably Z ₃ , Z ₄ or Z ₅ is an aliphatic group,
It represents an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (II), it is more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

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[0070]

[Chemical 21]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and are added at the time of chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like. 1x per mole
It is 10 ^-8 mol or more. More preferably, it is 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 ° C or higher and 80 ° C or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9. Selenium sensitization is more effective when performed in the presence of a silver halide solvent.

The inorganic sulfur used in the present invention is a compound of S ₈ .

The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, but silver chloride, silver chlorobromide or silver chloroiodobromide is preferable.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For more information on how to determine the average particle size, see: The Theory of the Photographic Process (CEMees & T.H.Ja).
mes: The theory of the photographic process),
3rd edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Gives a silver halide emulsion having a substantially uniform grain size.

The silver halide grains used in the silver halide emulsion may be cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or any of these in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing the element.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear
ch Disclosure) No. 176, 17643, pp. 22-23 (December 1978)
Or cited in the literature cited.

The silver halide emulsion may or may not be chemically sensitized. As methods for chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these methods may be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization, and as the sulfur sensitizer, various sulfur compounds other than the sulfur compound contained in gelatin, such as thiosulfates, thioureas, rhodanins, and polysulfide compounds, are used. Although it can be used, inorganic sulfur is preferable.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts of selenium, platinum, palladium, rhodium, etc. may be contained. Selenium sensitization is preferred.

Examples of reduction sensitizers include stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The silver halide photographic light-sensitive material used in the present invention contains various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be made. That is, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazain Denes, tetrazaindenes (particularly 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzene Luffin acid, can be added to many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide.

The silver halide emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-
Triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), Mucohalogen acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc. can be used alone or in combination.

The silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention include a coating aid, an antistatic agent,
Various known surfactants may be used for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties.

Gelatin is advantageously used as the binder or protective colloid of the silver halide emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The silver halide emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, Methacrylic acid,
A polymer having a monomer component of a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

The silver halide emulsion of the present invention is preferably spectrally sensitized with various sensitizing dyes. A preferred sensitizing dye is Research Disclosure Vol. 176 1
Issued in 978 (17643), pages 23-24, and 346, published in 1993 (3468
5) Those described can be used.

Various other additives are used in the silver halide photographic light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes, etc.

Regarding these additives and the above-mentioned additives, specifically, those described in Research Disclosure No. 176 (supra), pages 22 to 31 can be used.

In the silver halide photographic light-sensitive material used in the present invention, the emulsion layer and the protective layer may be a single layer or a multi-layer composed of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the silver halide photographic light-sensitive material of the present invention, a silver halide emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for silver halide photographic light-sensitive materials. Those useful as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing after exposure by various methods, for example, a commonly used method.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone and 2,5-dimethylhydroquinone). 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3- Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc., aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2 , 4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (tato) If 1
-(p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-
Methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) alone or Although they can be used in combination, it is preferable to use them in a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / l.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a silver sludge inhibitor (for example, JP-B-62-4702, JP-A-03-51844).
No. 04-26838, No. 04-362942, No. 01-319031, etc.), pH buffer (for example, carbonate, phosphate, borate, boric acid, acetic acid, citric acid) , Alkanolamines, etc., dissolution aids (eg polyethylene glycols, their esters, alkanolamines etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.), surface active agents Agents, antifoaming agents, antifoggants (for example, halogens such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, Ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetate,
Polyphosphate, etc., development accelerator (eg US Pat. No.
2,304,025, compounds described in Japanese Patent Publication No. 47-45541, etc.), hardeners (eg glutaraldehyde or
The bisulfite adduct, etc.), or an antifoaming agent can be added. The pH of the developer is less than 11.0, 9.
It is preferably adjusted to 5 to 10.5.

In the present invention, as a special form of development processing, an activator processing solution which contains a developing agent in a light-sensitive material, for example, an emulsion layer, and processes the light-sensitive material in an alkaline aqueous solution to perform development may be used. . Such a development process, in combination with a thiocyanate silver salt stabilization treatment,
It is often used as one of the methods for rapid processing of a light-sensitive material, and the effects of the present invention can be obtained even when rapid processing is performed with such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and others, and the pH is usually from 3.8 to 5.8. Sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, and organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents Can be.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

If desired, the fixer contains a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. And the like.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity in a semi-kneaded state. Further, it may be used after being diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set in the normal temperature range of 20-30 ° C,
It can be set in the range of high temperature treatment of 30 to 40 ° C.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At this time, the processing is performed while replenishing a fixed amount of a developing solution proportional to the area of the photosensitive material. The development replenishment amount is 200 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 ml or more and 180 ml or less per 1 m ² . Particularly preferably, it is 75 ml or more and 160 ml or less per 1 m ² . 75 ml per 1 m ²
If the replenishment amount of the developing solution is less than the above, satisfactory photographic performance cannot be obtained due to desensitization, softening, and the like.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is carried out by using the automatic developing machine is demanded in order to shorten the developing time. It is preferably 20 to 60 seconds. The term "total processing time" as used herein includes the total processing time required for processing a black-and-white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilizing processing, and drying required for processing. Time including all the time of process such as Dr
It is y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 20 to 48 seconds.

[0106]

The present invention will be specifically described with reference to the following examples. It should be understood that the present invention is not limited to the examples described below.

Example 1 (Emulsion 1) Solution A Water 1000 ml Propylene oxide-ethylene oxide copolymer 0.15 g NaCl 20 g Gelatin 2 g Nitric acid (3.7N) 8 ml Solution B 440 ml Propylene oxide-ethylene oxide copolymer 0.10 g NaCl 42.0g Gelatin 10.8g KBr 51.8g K ₃ IrCl ₆ 0.2mg K ₃ RhBr ₆ 0.01mg To make 490cc C liquid Water 443ml Nitric acid (3.7N) 8.2ml AgNO ₃ 170ml To make 490ml. While maintaining pH 3.5 and pAg 8.0 in the above solution A kept at 38 ° C, 1/10 each of the above solutions B and C were simultaneously added to 11.0.
The solution was added at a constant rate of ml / min, and 2 minutes after that, the remaining solution B and solution C were added functionally over 90 minutes, and stirring was continued for another 10 minutes. Then, the pH was adjusted to 5.8 with CaCO ₃ aqueous solution. , Mg
Using SO ₄ and polynaphthalene sulfonic acid, ordinary desalting was performed, and silver bromide 35 mol%, silver chloride 65 mol%, and average particle size of 0.
36 μm silver chlorobromide grains were obtained.

(Preparation of coating sample) To the obtained emulsion, 0.12 g of citric acid and 0.25 g of KBr were added per mol of silver, and the pH was adjusted to 5.5.
After adjusting to pAg7, 8.5 mg of chloroauric acid and 1.2 mg of inorganic sulfur were added, and chemical aging was performed at 60 ° C. so that the maximum sensitivity was obtained. Then 1-phenyl-5-mercaptotetrazole 35mg, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2
g, and after lowering the temperature to 50 ° C., the sensitizing dye I-3 was added to 23
Spectral sensitization was carried out by adding 0 mg and 140 mg of I-4.

Further, the following amounts of additives were added per mol of silver halide.

Compound 1.4 g 0.5 N NaOH 2.8 ml Phenidone 0.14 g Hydroquinone 5.94 g Polystyrene sulfonic acid 2.4 g Styrene-maleic acid copolymer 2.4 g In addition, the polymer latex shown in Table 1 was adjusted to 500 mg / m ^2. Was added.

Further, a non-photosensitive colloid layer as an upper layer of the emulsion layer was prepared as follows.

Gelatin 60 g Amorphous silica 42.5 g Bis (2-ethylhexyl) sulfosuccinate 2.4 g Also, a backing layer prepared as follows and its protective layer were coated before coating the above emulsion.

Backing layer liquid Gelatin 72g Compound 0.72g Compound 2.90g Sodium dodecylbenzenesulfonate 5.3g Citric acid 0.50g Polystyrene sulfonic acid 0.67g Backing protective layer Gelatin 42g Ethyl bis (2-ethylhexyl) sulfosuccinate 0.58g Sodium chloride 0.2g Polymethylmethacrylate (average particle size 18μm) 0.72g Polysiloxane 2.5g

[0114]

Embedded image

A polyethylene terephthalate base on which both liquids had been subbed was used, and the amount of gelatin in the backing layer was 1.6 g.
/ m ² , the amount of gelatin in the backing protective layer was 0.7 g / m ² , and glyoxal 30 mg / m ² as a hardener was added and simultaneously coated.

Then, on the side opposite to the backing layer, the amount of silver was
3.6 g / m ^2, the amount of gelatin 1.2 g / m ^2, the amount of gelatin light-insensitive layer
It was applied at 0.8 g / m ² . Also, as hardeners, triazine and formalin are added to 14 g each per 1 g of gelatin.
mg was added. The samples thus obtained were evaluated as follows.

(Sensitivity, gamma) The obtained sample was passed through an optical wedge to pass light passing through an interference filter of 780 nm for 10 minutes.
^-Exposure for ⁶ seconds, and use CDM-671 (Konica Corp.) 38
Development processing was carried out at 10 ° C for 10 seconds. The fixing solution at this time was CFL-871 (manufactured by Konica Corporation) at 36 ° C, and the automatic processor was Konica Corporation.
Adjust the line speed and rack length of GR-26SR made by Dry t
o Dry Processed in 35 seconds. The replenishment rates of the developing solution and the fixing solution were 300 cc / ml and 400 cc / ml. After processing the sample
It was measured with a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is density
It is the reciprocal of the exposure dose required to obtain 3.5 and is expressed as relative sensitivity with sample No. 1 as 100.

Gamma is represented by the tangent between densities 0.3 and 3.2. In the present invention, 8 or more is required.

(White pin failure) The highest density portion of the developed sample used for the sensitivity evaluation was visually evaluated.

(Scratch) After controlling the humidity of the obtained sample for 2 hours under the condition of 30 ° C. and 80% Rh, two samples were overlaid, and 1 sample was placed thereon.
Place a weight of kg and slowly pull the sample above. Then, the above-mentioned development processing was performed, and the degree of blackening was visually evaluated.

The results are shown in Table 1.

[0122]

[Table 1]

[0123]

Embedded image

As described above, it can be seen that the sample of the present invention has high sensitivity even after rapid processing, and scratches and white pin failures are improved.

[0125]

According to the present invention, there is provided a silver halide photographic light-sensitive material having high sensitivity, good character sharpness, and improved scratch resistance (scratch resistance) and deterioration of white pins due to reduction of gelatin accompanying rapid processing. I was able to offer.

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer has the following general formula [Ia] or [Ia]
-B] containing at least one of the compounds represented by the formula (b) and having at least one of the adjacent hydrophilic colloid layers stabilized with gelatin a polymer latex (L) or an epoxy compound having a ring-opening rate of 35 mol% or more. A silver halide photographic light-sensitive material containing a latex (Lx) having a glycidyl methacrylate or glycidyl acrylate unit. Embedded image [In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are each 5 members or 6 members.
Represents a group of non-metal atoms necessary for completing a nitrogen-containing heterocycle of a member, for example, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring, quinoline ring, Examples thereof include a 3,3-dialkylindolenine ring, a benzimidazole nucleus, and a pyridine ring. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom. R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂
Each represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ ,
R ₂₄ , R _25, and R ₂₆ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, or —N <W ₁ W ₂ . Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms in the alkyl portion, preferably 1 to 4) and an aryl group, and W ₁
And W ₂ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Also, R ₁₃ and R ₁₅ and R ₂₃ and R
₂₅ can be connected to each other to form a 5- or 6-membered ring. X ₁₁ ^- and X ₂₁ ^- is an anion. n ₁₁ , n ₁₂ , n
₂₁ and n ₂₂ represent 0 or 1. ] 2. A silver halide emulsion is chemically sensitized with an inorganic sulfur and / or selenium compound, and has a concentration of 0.3-.
2. The silver halide photographic light-sensitive material according to claim 1, wherein gamma (γ) between 3.2 is 8 or more.