JPH07128796A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material substantially short in cross-linking reaction and stable in performance by controlling the steam permeability of the resin layer of the silver halide photographic sensitive layer composed of a hydrophilic colloidal layer to be a specific value. CONSTITUTION:This silver halide photographic sensitive material is provided with the silver halide photographic sensitive layer comprising mainly at least one hydrophilic colloidal layer on the resin layer constituting a support together with a support base and at least one resin layer is formed on the support. The steam permeability of the resin layer is regulated to >=0.04g/100cm<2>, preferably 0.06-0.50g/100cm<2>, and for obtaining an effect, >=0.04g/100cm<2> steam permeability is required. The steam permeability is measured by covering the side not coated with an emulsion and the cut sides of the support with a metallic tape and only exposing the surface not coted with the emulsion, leaving this sample at 23 deg.C in a relative humidity of 80% for 3 days, and then, leaving it at 23 deg.C and in a relative humidity of 20% for 2 hours, and measuring its weight drop per 100cm<2> of the exposed surface.

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 specifically, a halogen having a silver halide light-sensitive layer provided on a support having a support base and a resin layer, the performance of which is stabilized. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material uses a hydrophilic binder mainly containing gelatin. on the other hand,
Development processing of a silver halide photographic light-sensitive material is usually carried out with an aqueous processing solution. Therefore, in order to prevent the hydrophilic binder from flowing out into the processing solution and to ensure the mechanical strength of the binder in the processing step, the binder used in the silver halide photographic light-sensitive material is usually crosslinked using a crosslinking agent. It is being appreciated. However, this crosslinking reaction is easily influenced by the manufacturing conditions of the light-sensitive material, and it is necessary to manage storage conditions sufficiently until the crosslinking is completed.

In particular, in a silver halide photographic light-sensitive material containing couplers which react with a color developing agent, a cross-linking agent having no reactivity with a coupler is used, but such a cross-linking agent is generally used until the end of the cross-linking reaction. Takes time. A photosensitive material using such a cross-linking agent may have a variation in performance depending on its storage conditions. JP-A-52-48311,
No. 60-225148, No. 61-240236, and the like, a cross-linking agent having a fast cross-linking reaction is studied in order to solve such a problem.
Although these cross-linking agents have a fast cross-linking reaction and do not affect couplers, they have a practical limitation because they affect the storage stability of the silver halide emulsion. As described above, it was difficult to obtain the desired performance only by examining the crosslinking agent.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having a substantially short crosslinking reaction and stable performance.

[0005]

The object of the present invention is to provide a halogenated compound comprising at least one hydrophilic colloid layer on a resin layer of a support having a support substrate and at least one resin layer. A silver halide photographic light-sensitive material provided with a silver photographic light-sensitive layer, wherein the water vapor permeability of the resin layer is 0.04 g.
This can be achieved by a silver halide photographic light-sensitive material characterized by having a size of / 100 cm ² or more.

The present invention will be described in detail below.

The base material for the support used in the present invention is preferably selected from base papers, which are made from materials commonly used for photographic printing paper such as natural pulp and synthetic pulp. Is. Thickness is usually 80-250 μm
It is of a degree. Such base materials include various ordinary paper additives such as dry paper strengthening agents (cationized starch, cationized polyacrylamide, anionic polyacrylamide, etc.), sizing agents (fatty acid salts, rosin, and rosin maleate cationized). Sizing agent, reactive sizing agent, etc.), filler (clay, kaolin, etc.), wet paper strengthening agent (melamine resin, epoxidized polyamide resin, etc.), fixing agent (aluminum sulfate, cationized starch, etc.), pH adjusting agent ( Caustic soda, sodium carbonate, etc.) and the like. Further, the base paper may be tabsized or size-pressed with a treatment liquid containing one or more of a water-soluble polymer additive, a sizing agent, an inorganic electrolyte, a hygroscopic substance, a pigment, and a pH adjusting agent.

The water content of the support of the present invention depends on the weight (W1) of the support before coating the emulsion, and the water content of the support is 8 in a constant temperature bath at 120 ° C.
The value obtained by subtracting the weight (W2) when dried for days is divided by the value obtained by subtracting the weight of the resin layer from W1
It is represented by.

The water content can be controlled by controlling the water content of the base material before forming the resin layer.

A water content of 3% or more is preferable from the viewpoint of the effect of the present invention, and if it is too large, on the contrary, the effect of the present invention, particularly the effect of improving the storage stability of the emulsion, is reduced. It is particularly preferably 3 to 11%. The resin layer of the present invention does not substantially permeate the developing solution within the developing time within the developing time, and the component of the resin layer is not particularly limited as long as it has the water vapor transmission amount of the present invention.
Examples thereof include polyolefins such as low-density polyethylene and high-density polyethylene as disclosed in JP-A-48-9963, and electron-curable resins such as those disclosed in US Pat. No. 3,864,133, with polyolefin resins being preferred. The polyolefin resin is preferably polyethylene, and may be low density polyethylene or high density polyethylene, or a mixture thereof.

The water vapor permeability of the resin layer of the present invention is measured as follows.

To prevent water from permeating, a metal tape (Shine tape manufactured by Sekisui Chemical Co., Ltd.) is applied and covered on the side not coated with the emulsion and the cut surface of the support so that only the surface coated with the emulsion is exposed. The exposed surface when this sample was left at 23 ° C and 80% RH for 3 days and then left at 23 ° C and 20RH% for 2 hours.
The amount of weight reduction per 100 cm ^{2 is} defined as the amount of water vapor transmission.

The method of controlling the amount of water vapor transmission is not particularly limited, but there are methods such as changing the film thickness and using resins having different water vapor transmission rates.

The amount of water vapor permeation is required to be 0.04 g / 100 cm ² or more in order to obtain the effects of the present invention, but it is preferable.
It is 0.06 to 0.50 g / 100 cm ² .

From the viewpoint of the effect of the present invention, the larger the amount of water vapor permeation, the better. However, if it is too large, the developing solution permeates to cause poor drying, which is not preferable.

As the binder (or protective colloid) for the silver halide emulsion layer and the non-photosensitive layer of the silver halide photographic light-sensitive material according to the present invention, it is advantageous to use gelatin, but gelatin derivatives, gelatin and others. Other hydrophilic colloids such as high molecular weight graft polymers, other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, Bulletin of Society of Science of Photography of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, p. 30. The enzyme-treated gelatin as described in (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used.

Examples of the gelatin derivative include gelatin such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, epoxy compounds and the like. Those obtained by reacting various compounds are used. Specific examples thereof are U.S. Pat.No. 2,614,928,
Nos. 3,132,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, 1,005,784, and Japanese Patent Publication No. 42-26845.

Proteins include albumin, casein,
Preferred cellulose derivatives are hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, and sugar derivatives are sodium alginate and starch derivatives.

As the graft polymer of the above gelatin and other polymers, gelatin is a homopolymer or homopolymer of acrylic acid, methacrylic acid derivatives thereof such as esters and amides, acrylonitrile, styrene and other vinyl monomers. What grafted the coalescence can be used. In particular, a polymer having a certain degree of compatibility with gelatin, for example, a graft polymer with a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are U.S. Patents 2,763,625, 2,831,767, 2,956,88.
It is described in No. 4 etc.

Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. A copolymer or the like, for example, West German patent application (OLS) 2,312,708
No. 3, U.S. Pat.No. 3,620,751, No. 3,879,205, Japanese Patent Publication No. 43-7
561.

The curing agent used for crosslinking the hydrophilic colloid layer in the present invention is preferably a vinyl sulfone type curing agent,
The S-triazine-based curing agent is mentioned in terms of its effect.

As the S-triazine type curing agent, compounds represented by the following general formulas [HI] and [H-II] are preferable.

[0024]

[Chemical 1]

In the formula, R ₁ is chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, --OM ₁ group (M ₁ is a monovalent metal atom), --NR ₅ R ₆ group (R ₅ and R _{5 6} is a hydrogen atom, an alkyl group, an aryl group) or-
NHCOR ₇ group (R ₇ is hydrogen atom, alkyl group, aryl group)
And R ₂ represents a group having the same meaning as R ₁ above except a chlorine atom.

[0026]

[Chemical 2]

In the formula, R ₃ and R ₄ each represent a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or a —OM ₁ group (M ₁ is a monovalent metal atom). Q ₁ and Q ₂ each represent a linking group selected from —O—, —S—, and —NH—, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1.

The vinyl sulfone type hardener used in the present invention is described in, for example, aromatic compounds as described in German Patent 1,100,942, Japanese Patent Publication Nos. 44-29622 and 47-25373. Heteroalkyl-bonded alkyl compounds, such as sulfonamides as described in JP-B-47-8736, ester compounds, 1,3,5-tris [as described in JP-A-49-24435] β- (vinylsulfonyl)
-Propionyl] -hexahydro-s-triazine or an alkyl compound as described in JP-A-51-44164.

Representative compounds thereof are shown below, but the invention is not limited thereto.

[0030]

[Chemical 3]

[0031]

[Chemical 4]

[0032]

[Chemical 5]

In addition to the above-exemplified compounds, the vinyl sulfone-based hardener in the present invention is a compound having at least three vinyl sulfone groups in the molecular structure, such as exemplified compounds [H-5] to [H-22]. It includes a reaction product obtained by reacting a compound having a group reactive with a vinyl sulfone group and a water-soluble group, such as diethanolamine, thioglycolic acid, sodium salt of sarcosine, sodium salt of taurine.

Next, the compound represented by the above general formula [HI] or [H-II] according to the present invention will be described in detail.

In the general formulas [HI] and [H-II], examples of the alkyl group, alkoxy group and alkylthio group represented by R ₁ include alkyl groups having 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group and an ethylthio group.

Examples of M ₁ representing a monovalent metal atom of the —OM ₁ group represented by R ₁ include sodium, potassium and ammonium, and R ₅ and R of the —NR ₅ R ₆ group.
_The alkyl group represented by _{6 includes} an alkyl group having 1 to 3 carbon atoms, such as a methyl group and an ethyl group, and the aryl group includes a phenyl group.

Further, the alkyl group and aryl group represented by R _{7 of the} —NHCOR ₇ group represented by R ₁ are the same groups as the alkyl group and aryl group represented by R ₅ and R ₆ , respectively.

R ₂ is a group having the same meaning as R ₁ except the above-mentioned chlorine atom.

Next, the groups represented by R ₃ and R ₄ are the above-mentioned R ₁
Represents the same group as the group represented by.

As the alkylene group represented by L,
An alkylene group having 1 to 3 carbon atoms, for example, a methylene group,
For example, ethylene group. Examples of the arylene group include a phenylene group.

Next, the above general formulas [HI] and [HI]
Representative specific examples of the hardener according to the present invention represented by I] will be described.

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

To add the vinyl sulfone type hardener according to the present invention and the hardeners represented by the general formulas [HI] and [H-II] to a silver halide emulsion layer and other constituent layers. , Water or a solvent miscible with water (eg methanol,
It may be dissolved in ethanol or the like) and added to the coating liquid for the above-mentioned constituent layers. The addition method may be either a batch method or an in-line method. The addition time is not particularly limited, but it is preferably added just before coating.

The vinyl sulfone type hardener according to the present invention and the hardeners represented by the general formulas [HI] and [H-II] are particularly preferably vinyl sulfone type hardener and general formula [H-
I] or a vinyl sulfone type hardener and a general formula [H-II]
Is preferred. The layer to be added may be the same layer or a different layer, but it is particularly preferable to add it to another layer.

These hardeners are added per 1 g of coated gelatin.
0.5 to 100 mg, preferably 5.0 to 50 mg is added.

These hardeners according to the present invention, after coating and drying, are heated at a temperature of 30 to 55 ° C. and a humidity of 30 to 80% RH for 15 to 15
The hardener according to the present invention and the addition amount thereof are selected so that the surface pH of the light-sensitive material specified in the present invention is reached when left for 180 hours.

The silver halide grains of the silver halide photographic light-sensitive material according to the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less, and a silver iodide content. The ratio is preferably 0.5 mol% or less. More preferably, it is a silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 10 mol% or less.

In the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the chloride content in all silver halide grains contained in the emulsion layer is The proportion of silver halide grains having a silver content of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain,
The composition inside and outside the particle may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains of the present invention is not particularly limited, but considering other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. Is the range. The particle size is
It can be measured by various methods generally used in the art. A typical method is Loveland's “Particle Size Analysis Method” (ASMTM Symposium on Light Microscopy, 1955, 94).
~ 122) or "The Theory of Photographic Process" (co-authored by Mies and James, 3rd edition, published by Macmillan, Inc. (1966)
Year 2) Chapter 2).

The grain size can be measured by using the projected area of the grain or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

[0056]

[Equation 1]

Here, ri represents the particle size of each particle, and ni represents the number thereof. The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a cubic image or a grain having a non-spherical shape when the projected image is converted into a circular image of the peripheral area. .

The silver halide grains used in the emulsion of the silver halide photographic light-sensitive material according to the present invention are prepared by the acidic method, neutral method,
It may be one obtained by any of the ammonia methods. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. . Further, the pAg-controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation. The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.Nos. 4,183,756 and 4,225,666.
Issue, JP-A-55-26589, JP-B-55-42737 and The Journal of Photographic Science (J.Ph.
otgr.Sci.), 21 , 39 (1973) and the like, particles having an octahedron, a tetradecahedral shape, a dodecahedron shape, etc. can be prepared and used. Further, grains having twin planes may be used. The silver halide grains according to the present invention may use grains having a single shape,
It may be a mixture of particles of various shapes.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt during the grain forming process and / or the growing process. , An iron salt or a complex salt may be used to add a metal ion to the inside of the particle and / or the surface of the particle so that the metal ion can be incorporated into the particle. Nucleus can be imparted.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic carbon-hydrogen ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus,
That is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxozar nucleus, a naphthoxozar nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketone methylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus are used. , 5 to 6-membered heterocyclic nuclei such as Rhodanine nucleus and thiobarbituric acid nucleus can be applied.

As a method of adding a sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes include pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of the above solvents).
Dissolved in a water-soluble solvent of, in some cases diluted with water,
In some cases, they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibration for this dissolution. Further, the sensitizing dye used in the present invention, as described in U.S. Pat.No. 3,469,987,
A method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added, JP-B-46-2.
As described in Japanese Patent No. 4185 etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding the dispersion is also used. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method. Other addition methods, U.S. Pat.
No. 345, No. 3,342,605, No. 2,996,287, No. 3,42
The method described in 5,835, etc. is also used.

The sensitizing dye contained in the silver halide emulsion of the present invention is dissolved in the same or different solvent, and these solutions are mixed or added separately prior to addition to the silver halide emulsion. May be. When they are added separately, their order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion production process, but is preferably added during or after chemical ripening, and more preferably during chemical ripening.

As the dye which is used together with the sensitizing dye and has no spectral sensitizing effect, or the substance which does not substantially absorb visible light and exhibits supersensitization,
For example, aromatic organic acid formaldehyde condensate (for example,
Those described in US Pat. No. 3,437,510), cadmium salt,
Azidene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (see, for example, US Pat. No. 2,933,390,
Those listed in No. 3,635,721). US Patent 3,61
5,613, 3,615,641, 3,617,295, 3,635,721
The combinations described in item No. are particularly useful.

Various photographic additives can be added to the silver halide photographic light-sensitive material of the present invention in addition to the above compounds.

As such examples, for example, couplers, ultraviolet absorbers (for example, benzophenone compounds, benzotriazole compounds, etc.), development accelerators (for example, 1-aryl-3-pyrazolidone compounds, etc.), surfactants ( For example, alkyl naphthalene sulfonate, alkyl succinate sulfonate, itaconic acid salt, polyalkylene oxide compound, etc.), water-soluble anti-irradiation dye (eg, azo compound, styryl compound, oxonol compound, anthraquinone compound) Compounds and triphenylmethane compounds, etc.), film physical property improvers (eg glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin etc.), color turbidity inhibitors (diffusion resistant hydroquinone compounds etc.), dye image stabilization Agents (eg hydroquinone derivation , Gallic acid derivatives, phenol compounds, hydroxychroman compounds, polyalkylpiperidine compounds, aromatic amine compounds, etc.), water-soluble or oil-soluble fluorescent whitening agents, ground color regulators (oil-soluble coloring dyes, etc.) Etc.

In the present invention, known couplers can be used.

As the yellow dye-forming coupler, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazolotriazole type couplers and open chain acylacetonitrile type couplers can be preferably used.

As the cyan dye-forming coupler, known naphthol type couplers and phenol type couplers can be preferably used.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, ultraviolet absorbers, optical brighteners, etc. which are not required to be adsorbed on the surface of silver halide crystals, hydrophobic The compound is a solid dispersion method, a latex dispersion method, an oil-in-water emulsion dispersion method, or the like.
Various methods can be used, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied with various methods of dispersing a hydrophobic additive such as a coupler, and usually has a boiling point of about
If necessary, a low boiling point organic solvent having a boiling point of 150 ° C. or higher, and / or a water-soluble organic solvent may be dissolved in combination, and a stirrer, a homogenizer using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, It may be added to the target hydrophilic colloid layer after emulsifying and dispersing using a dispersing means such as a colloid mill, a flow jet mixer, and an ultrasonic device.
A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

The ratio of the high-boiling organic solvent to the low-boiling organic solvent is preferably 1: 0.1 to 1:50, more preferably 1: 1 to 1:20.

As the high-boiling point oil agent, a phenol derivative, a phthalic acid alkyl ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester, etc. having a boiling point of 150 ° C. or higher which does not react with the oxidized product of the developing agent is used. The organic solvent of is used.

High boiling organic solvents that can be used include US Pat. Nos. 2,322,027, 2,533,514 and 2,835,57.
No. 9, No. 3,287,134, No. 2,353,262, No. 2,852,383,
3,554,755, 3,676,137, 3,676,142, 3,7
00,454, 3,748,141, 3,779,765, 3,837,86
3, British Patent 958,441, 1,222,753, OLS 2,53
8,889, JP-A-47-1031, 49-90523, 50-23823
No. 51, No. 51-26037, No. 51-27921, No. 51-27922, No. 51-27922
-26035, 51-26036, 50-62632, 53-1520
53-1521, 53-15127, 54-119921, 54
-119922, 55-25057, 55-36869, 56-19049
No. 56-81836, and Japanese Patent Publication No. 48-29060.

Low-boiling or water-soluble organic solvents that can be used with or instead of high-boiling solvents are described in US Pat. No. 2,801,17.
Examples thereof include those described in No. 1 and No. 2,949,360. The low-boiling substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and the water-soluble organic solvent includes acetone, Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.

Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and Anionic surfactants such as sulfoalkyl polyoxyethylene alkylphenyl ethers, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkyl sulfonic acids, and alkyl betaines It is preferable to use amphoteric surfactants such as the above, and cationic surfactants such as quaternary ammonium salts.

Specific examples of these surfactants are described in "Surfactant Handbook" (Industrial Books, 1966) and "Emulsifier / Emulsifier Research and Technical Data Collection" (Kagakugenron, 1978). .

Examples of the latex dispersion method include US Pat. Nos. 4,199,363, 4,214,047, 4,203,716 and 4,2.
47,627, JP-A-49-74538, 51-59942, 51-599
The methods described in No. 43, No. 54-32552 and the like are preferable.

The silver halide photographic light-sensitive material of the present invention can form an image by performing color development processing known in the art.

The color developing agent used in the color developing solution in the present invention includes known ones which are widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds generally have a concentration of about 0.1 g to about 30 g per liter of color developing solution, preferably about 1 g to about 1.5 g per liter of color developing solution.
Use at the concentration of.

As the color developing agent used in the color developing solution, aromatic primary amine compounds, particularly p-phenylenediamine type compounds are typical, and preferred examples are:
N, N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-
p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-
p-toluenesulfonate, N, N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N- (β-hydroxyethyl) -3-
Methyl-4-aminoaniline and the like can be mentioned.

These color developing agents may be used alone or in combination of two or more kinds, and one or more color developing agents and other black and white developing agents such as hydroquinone and 1-phenyl- 3-pyrazolidone, N-methyl-p-
It may be used in combination with aminophenols. In this case, the addition amount of this color developing agent is 0.
It is in the range of 2 mol to 2 mol, preferably 0.4 mol to
It is in the range of 0.7 mol.

When the silver halide photographic light-sensitive material of the present invention is subjected to color development processing, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-, among the above-mentioned compounds, is particularly used as a color developing agent. 4-Aminoaniline sulfate is particularly preferred.

In the color developing solution, in addition to the above color developing solution,
For example, an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, N, N-diethylhydroxylamine, N, N-bis (methoxyethyl) hydroxylamine,
Preservatives such as triethanolamine, diethanolamine glycose, potassium sulfite, organic solvents such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol, development regulators such as citrazinic acid and polyethylene glycol, and heavy metal ion masking agents, development accelerators. If desired, various photographic additives known in the photographic field can be contained. Further, sulfite ions such as sodium sulfite and potassium sulfite as a preservative of the color developing solution are relatively large (for example, color developing solution 1 when the color developing solution contains benzyl alcohol which is a color developing agent). Addition of about 0.01 mol or more per liter) causes a small decrease in color developability, but when benzyl alcohol in the color developer contains only 0 to about 5 ml per liter of color developer, the sulfite ion concentration is It is necessary that the amount is about 0.004 mol or less per liter of the color developing solution.

The silver halide photographic light-sensitive material of the present invention is developed with a color developing solution containing no or very small amount of water-soluble bromide. When the content of the water-soluble bromide is excessive, the developing rate of the silver halide photographic light-sensitive material is drastically reduced and the object of the present invention cannot be achieved. The bromide ion concentration in the color developing solution is approximately 0.1 g per liter of the color developing solution in terms of potassium bromide.
The following is preferably 0.05 g or less.

When the light-sensitive material of the present invention is continuously processed while continuously replenishing the color-developing replenisher, when a slight amount of bromide ion is eluted from the light-sensitive material as a result of development, color-developing is performed. Although a small amount of bromide ion accumulates in the solution, even in this case, the replenishment ratio of the color developing solution replenishing solution is appropriately selected with respect to the total amount of bromide contained in the light-sensitive material. It is preferable that the bromide ion is within the above range.

The effect of the present invention becomes particularly remarkable when a water-soluble chloride is used as a development modifier in the color developing solution.

The water-soluble chloride used is in the range of 0.5 g to 5 g, preferably 1 g to 3 g per liter of the color developing solution in terms of potassium chloride.

Further, in the above color developing solution, JP-A-58-95345 is used.
The organic development inhibitors described in JP-A No. 1994-154 can be used within a range not impairing the present invention. Adenine and guanine are preferably used in the color developer in an amount of 0 to 0.02 g / liter.

The pH of the developer of the present invention is preferably 9.5 or more, more preferably 13 or less. Conventional developer p
It is known that the development is promoted by increasing H, but in the silver halide photographic light-sensitive material of the present invention, sufficient rapid developability can be obtained even if the pH is 11 or less.

The temperature of the color developing solution is 15 to 45 ° C., preferably
It is carried out between 20 and 40 ° C.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as bleaching agents, among which iron (III), cobalt (II
I), copper (II) and other polyvalent metal compounds, especially complex salts of these polyvalent metal cations with organic acids, for example aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotritriacetic acid, N-hydroxyethylethylenediaminediacetic acid, A metal complex salt of malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid or the like, or ferricyanates, dichromates or the like may be used alone or in an appropriate combination.

As the fixing agent, a soluble complexing agent which solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.

After the fixing process, a washing process is usually performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjusting agent, a chelating agent, an antifungal agent and the like. For these specific conditions, reference can be made to JP-A-58-134636.

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EXAMPLES Specific examples of the present invention will be described below.
Embodiments of the present invention are not limited to these.

Example 1 (Manufacture of Support) A polyethylene resin coating layer was extrusion-coated on a paper base material made of a natural pulp material having a thickness of 160 μm, the humidity of which was adjusted to the water content shown in Table 1. Formed by. The back side is formed with high density polyethylene with a density of 0.955 and low density polyethylene with a density of 0.924 to a thickness of 28 μm with a polyethylene resin coating layer with a mixing ratio such that the former is 40 wt%, and the surface on which the emulsion is applied. A high density polyethylene containing 12 wt% of titanium oxide and a low density polyethylene with a density of 0.920 and a low density polyethylene with a density of 0.920 were formed with a mixing ratio such that the former is 7 wt% and the thickness is as shown in Table 1. did.

Corona discharge was applied to the surface of the support thus prepared, and each layer having the constitution shown below was coated on this surface to prepare a multilayer silver halide photographic light-sensitive material.

First layer coating liquid 26.7 g of a yellow coupler (as shown in the table), 10.0 g of a dye image stabilizer (ST-1), a dye image stabilizer (ST-
2) To 6.67 g, add 60 ml of ethyl acetate to dissolve and dissolve this solution.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was prepared under the following conditions to produce a blue-sensitive silver halide emulsion (silver
(Containing 10 g) to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, a mixture of H-2 and HI-2 in a molar ratio of 3: 1 was added to the ^second , fourth and seventh layers at 30 mg / m ² and 40 mg / m ² , respectively. ² , 50 mg / m ^{2 was} added. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The second layer, the fourth layer, the sixth layer
After coating and drying the layers and the seventh layer, the pH of the coating solution was adjusted using 0.2 M nitric acid so that the pH of the surface was 5.85.

Layer component Addition amount (g / m ² ) 7th layer Gelatin 1.00 (Protective layer) Anti-stain agent (HQ-2) 0.002 Anti-stain agent (HQ-3) 0.002 Anti-stain agent (HQ-4) 0.004 Anti-stain (HQ-5) 0.02 DIDP 0.005 Sixth layer Gelatin 0.40 (UV absorber layer) UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.04 UV absorber (UV- 3) 0.16 Anti-stain agent (HQ-5) 0.04 DNP 0.20 PVP 0.03 Anti-irradiation dye (AI-2) 0.02 Anti-irradiation dye (AI-4) 0.01 Fifth layer Gelatin 1.30 (Red-sensitive layer) Red-sensitive salty odor Silver halide emulsion (Em-R) 0.21 Cyan coupler (C-1) 0.17 Cyan coupler (C-2) 0.25 Dye image stabilizer (ST-1) 0.20 Stain inhibitor (HQ-1) 0.01 HBS-1 0.20 DOP 0 .20 4th layer Gelatin 0.94 (UV absorber layer) UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Anti-stain (HQ-5) 0.10 DNP 0.40 Third layer Gelatin 1.40 (Green-sensitive layer) Green-sensitive silver chlorobromide emulsion (Em-G) 0.17 Magenta coupler (M-1) 0.23 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST -4) 0.17 DIDP 0.13 DBP 0.13 Anti-irradiation dye (AI-1) 0.01 Second layer Gelatin 1.20 (Intermediate layer) Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.03 Stain Inhibitor (HQ-4) 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.06 Compound (F-1) 0.002 First layer Gelatin 1.20 (Blue sensitive layer) Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow Coupler (Y-1) 0 .80 Dye image stabilizer (ST-1) 0.30 Dye image stabilizer (ST-2) 0.20 Anti-staining agent (HQ-1) 0.02 Anti-irradiation dye (AI-3) 0.01 DNP 0.20 Support polyethylene laminated paper The amount of silver halide emulsion added is shown in terms of silver.

(Preparation method of blue-sensitive silver chlorobromide emulsion) In 1000 ml of 2% gelatin aqueous solution kept at 40 ° C., the following (solution A) and solution (B) were adjusted to pAg = 6.5 and pH = 3.0. Simultaneously add over a minute, and then add the following (C liquid) and (D liquid)
Simultaneous addition was carried out over 180 minutes while controlling Ag = 7.3 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver sulfate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added 600 ml (Solution D) 300 g of silver nitrate Water was added and after 600 ml was added, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. As a result, a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 μm, a coefficient of variation (σ / r) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-1.
After chemical ripening at 50 ° C for 90 minutes, a blue-sensitive silver chlorobromide emulsion (E
m-B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (Method for preparing green-sensitive silver chlorobromide emulsion) (solution A) and solution B
Except that the addition time of (C liquid) and the addition time of (D liquid) are changed, the average particle size is 0.43 μm in the same manner as EMP-1.
A monodisperse cubic emulsion EMP-2 having a variation coefficient (σ / r) of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver chlorobromide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Preparation Method of Sensitive Silver Chlorobromide Emulsion) (Solution A) and (Solution B)
Except that the addition time of (C liquid) and the addition time of (D liquid) were changed, the average particle size was 0.50 μm, as in EMP-1.
A monodisperse cubic emulsion EMP-3 having a variation coefficient (σ / r) of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The above EMP-3 was chemically ripened for 90 minutes at 60 ° C. using the following compound to give a red-sensitive silver chlorobromide emulsion (E
m-R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 1 × 10 ⁻⁴ mol / mol AgX

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[Chemical 9]

[0115]

[Chemical 10]

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[Chemical 11]

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[Chemical 12]

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[Chemical 13]

<< Preservation property over time >> A part of the sample prepared above was stored for 3 weeks under the conditions of 40 ° C. and 40% relative humidity, exposed through an optical wedge, and processed according to the following processing steps. With respect to the obtained sample, the reflection density of the yellow dye image was measured with a PDA-65 densitometer, and the sensitivity (density
The reciprocal of the amount of exposure giving 1.0) was determined. The sensitivity variation ΔS was compared with the sample that was not stored with time, and the results are shown in Table 1.

The storage stability ΔS is expressed by the following equation.

ΔS = (sensitivity after the storage condition) / (sensitivity before the storage condition) × 100-100 “processing step” temperature (° C.) time (second) replenishment amount (ml / m ² ) color development 38.0 ± 0.3 45 120 Bleach-fixing 35.0 ± 0.5 45 54 Stabilization 30-40 90 250 Dry 50-75 60 Color development tank solution Replenisher Potassium bromide 20mg 8.0mg Potassium chloride 2.0g-Kalous sulfite (50% solution) 0.6ml 1.0ml N-ethyl-N- (β-methanesulfonamidoethyl) 4.5 g 9.2 g -3-methyl-4-aminoaniline sulfate N, N-diethylhydroxylamine 5.0 g 9.0 g triethanolamine 10.0 g 15.0 g potassium carbonate 27.0 g 30.0 g Ethylenediaminetetraacetic acid sodium salt 1.0 g 2.0 g Optical brightening agent (diaminostilbene disulfonic acid derivative) 1.0 g 2.2 g After finishing to 1 liter with water, pH = 1 for tank liquid
Adjust to 0.10 and 10.60 for replenisher with sodium hydroxide or sulfuric acid.

Bleach-fixing (common to tank solution and replenisher) ethylenediaminetetraacetic acid ferric ammonium dihydrate 20 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 200 ml ammonium sulfite (40% aqueous solution) 85 ml 1 with water Finish to liters and use ammonia water or glacial acetic acid
Adjust to pH 5.0.

Stabilization (common to tank liquid and replenisher) 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g 2- octyl-4-isothiazolin-3-one 0.01 g 1-hydroxy-1,1-disulfonic acid 3.0 g (60% aqueous solution) BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} (25% aqueous solution) 0.20 g Ammonium hydroxide (25% aqueous solution) 2.5 g Nitrilotriacid trisodium salt 1.5 g Water to 1 liter, p with ammonia water or sulfuric acid
Adjust to H7.0.

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[Table 1]

As is clear from Table 1, the storage stability is excellent when the water vapor transmission rate of the resin layer is 0.04 g / 100 cm ² or more, and when the water content of the support base material is 3% or more, It turns out to be excellent.

Claims (2)

[Claims] 1. A halogenation in which at least one silver halide photographic light-sensitive layer mainly composed of a hydrophilic colloid layer is provided on a resin layer of a support having a support base material and at least one resin layer. A silver photographic light-sensitive material, wherein the water vapor transmission amount of the resin layer is 0.04 g / 100 cm ² or more. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the crosslinking agent used in the hydrophilic colloid layer is a vinyl sulfone-based curing agent and / or a halogen-substituted s-triazine-based curing agent.