JPH05281652A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material restrained from variation of sensitivity with the lapse of time after applying a coating fluid containing a mold-preventive agent and adapted to rapid processing by incorporating a specified compound. CONSTITUTION:The silver halide photographic sensitive material has on a support at least one silver halide emulsion layer containing silver chlorobromide comprising 90mol% or more of silver chloride and at least one of the compounds represented by formulae I and II and the like and at least one of the compounds represented by formula III, and in formulae I-III, R<1> is lower alkylene; M is H, an alkali metal, or the like; X is H, halogen, or the like; m is an integer of 1-5; n is 0 or 1; R<2> is H, alkyl, or the like; each of R3 and R<4> is H, halogen, or the like; Ar is an aromatic group; R1-OR2, COOM2, or the like: R2 is a >=2C hydrocarbon group; and each of M1 and M2 is an H or alkali metal atom or ammonium or the like.

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 silver halide photographic material in which a variation in sensitivity with time of a coating solution containing a mildew-proofing agent is improved and which is suitable for rapid processing. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In recent years, in order to shorten the delivery time of photographic prints and to improve the productivity, rapid development using photographic light-sensitive materials for prints using silver halide having a high development rate and a high silver chloride content, Also, a method of shortening the printing time by increasing the sensitivity has been adopted. However, it has been found that the silver chloride emulsion is apt to cause fog, and fog-like spot defects frequently occur due to propagation of microorganisms in the coating solution. In particular, when performing long-distance coating using a batch production system, such a failure occurs due to mold in the latter half of the coating, and the coating length is currently limited.

As a countermeasure against such mold generation, various antifungal agents have been studied so far. For example, Japanese Patent Laid-Open No. 59-2
No. 2857, No. 59-131929, No. 60-119547, No. 63-274944
The compounds and the like described in the publications are useful and have been put to practical use.

However, it has been found that when an effective amount of these antifungal agents is used, the sensitivity decreases with the lapse of time in the coating solution. This phenomenon is particularly remarkable when the silver halide emulsion is a high silver chloride emulsion, and it is a major obstacle when producing a silver halide photographic light-sensitive material containing a high silver chloride emulsion having high rapid processability. Improvement was awaited. In particular,
In the case of multi-layer color light-sensitive materials, if the sensitivity and gradation between layers are changed, the desired performance cannot be obtained because the color balance is disturbed. Since the print quality is not uniform, printing with different exposure conditions in advance when printing in a lab will result in different print results for each roll, resulting in problems such as a significant drop in yield. Become.

In order to prevent the performance variation of this coating solution over time, for example, a method of adding an azole or an azaindene compound known as a stabilizer, a method of adding a reducing agent such as hydroquinone or sulfinic acid, or JP-A As described in JP-A-49-11629, a method of using a specific copolymer in combination with a fluorescent whitening agent, a method of adding a sensitizing dye described in JP-A-58-7629 to a coating solution, etc. Although proposed, even if these techniques are used alone or in combination, a sufficient improvement effect cannot be obtained.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have found that when the compounds represented by the general formulas (I), (II), (III) and (IV) are added to such an extent that mold generation can be prevented, a problem occurs. As for the sensitivity variation with time of the coating solution, as a result of extensive studies, by containing the compound represented by the general formula (V), the sensitivity variation with the passage of time can be remarkably improved, and further the general formula (I), (II ), (III) and (IV), the present invention has been completed by finding that coating failure due to mold can be reduced at the same time without hindering the effects of the compounds.

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material which is improved in sensitivity variation with time of a coating solution containing a mildew-proofing agent and is suitable for rapid processing.

[0008]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide content is 90%. More than mol% of silver chlorobromide or silver chloride having the following general formulas (I), (II), (III) and (I
A silver halide photographic light-sensitive material characterized by containing at least one compound selected from the compounds represented by the formula (V) and at least one compound selected from the compounds represented by the following general formula (V): It

[0009]

[Chemical 6]

In the formula, R ¹ represents a lower alkylene group, and M
Represents a hydrogen atom, an alkali metal or an alkyl group. X represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carboxyl group, an amino group, a hydroxyl group, a sulfo group, a nitro group or an alkoxycarbonyl group.
m represents an integer of 1 to 5, and n represents 0 or 1.

[0011]

[Chemical 7]

In the formula, R ² is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, -CONHR (R is a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group. Represents an alkylsulfonyl group or an arylsulfonyl group)
Alternatively, it represents a heterocyclic group. R ³ and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfonyl group or an alkylsulfinyl group. Represent Further, R ³ and R ⁴ may be bonded to each other to form a benzene ring which may have a substituent.

[0013]

[Chemical 8]

In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 5 carbon atoms or a hydroxymethyl group, and R ⁷ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. Represents a group.

[0015]

[Chemical 9]

In the formula, R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁹ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxyl group, a halogen atom, Represents an alkoxy group or a thiazolyl group. Z represents an atom group forming a thiazole ring, and m ′ represents 0 or 1.

[0017]

[Chemical 10]

In the formula, Ar represents an aromatic group and R ₁ is -O.
R _2, represents a _{-N (R 3) SO 2 R} 4 or -COOM _2. R ₂ represents a hydrocarbon group having 2 or more carbon atoms, R ₃ represents a hydrogen atom or a hydrocarbon group, and R ₄ represents a hydrocarbon group. M ₁ and M ₂ are respectively
It represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group.

The present invention will be specifically described below.

First, the compounds represented by formulas (I), (II), (III) and (IV) will be described.

In the general formula (I), examples of the lower alkylene group represented by R ¹ include methylene, ethylene and propylene. Examples of the alkali metal represented by M include sodium and potassium, and examples of the halogen atom represented by X include chlorine, bromine, iodine and the like. The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 8 carbon atoms. The cycloalkyl group represented by X is
Preferred is a cycloalkyl group having 4 to 8 carbon atoms, and the aryl group is a phenyl group, a naphthyl group or the like.
The preferred carbon number of the alkoxycarbonyl group is 1 to 5
Is.

Further, each of the above groups may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, a cyano group, a carboxyl group, a phenyl group and the like.

In the general formula (II), the alkyl group and alkenyl group represented by R ² preferably has 1 to 36 carbon atoms, and more preferably 1 to 18 carbon atoms. The cycloalkyl group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. These alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group and heterocyclic group may have a substituent, and the substituent may be a halogen atom or nitro, cyano, thiocyano, aryl, alkoxy, aryl. Oxy, carboxyl, sulfoxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido,
Thioureido, urethane, thiourethane, sulfonamide, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialkylamino, anilino, hydroxyl, mercapto, heterocyclic group, etc. Chosen from.

The number of carbon atoms of the alkyl group represented by R ³ and R ⁴ is 1.
-18 is preferable, and 1-9 is more preferable. The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. These alkyl group, cycloalkyl group and aryl group may have a substituent, and examples of the substituent include a halogen atom and nitro, sulfo, aryl and hydroxyl groups. R ³ ,
When R ⁴ forms a benzene ring with each other, examples of the group substituted on the benzene ring include a halogen atom, an alkyl group, an alkoxy group, a cyano group and a nitro group.

In the general formula (III), R ⁵ , R ⁶ and R ⁷
The lower alkyl group having 1 to 5 carbon atoms represented by may have a substituent.

In the general formula (IV), R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ is preferably a nitro group, a sulfo group, a halogen atom or a hydroxyl group. m'is preferably 1.

Specific examples of the compounds represented by the above general formulas (I), (II), (III) and (IV) (hereinafter referred to as the compound of the present invention) are shown below, but the invention is not limited thereto.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

In the present invention, one kind or two or more kinds can be selected from these exemplified compounds. These compounds are generally well known, such as IC Japan Co., Ltd., Dainippon Ink and Chemicals Co., Ltd., Rohm and Haas Japan Co., Ltd., Sanai Petroleum Co., Ltd., etc. Is commercially available from.

The amount of these compounds used is not particularly limited, but is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-2 g / m ² , and is added to either the silver halide emulsion layer or the non-emulsion layer. May be. The addition method is not particularly limited.

Next, the compound represented by the general formula (V) will be described.

In the general formula (V), Ar represents an aromatic group, and examples thereof include a phenyl group, a naphthyl group and a pyridyl group. These aromatic groups may have a substituent.
When Ar is a phenyl group, the effect of the present invention is remarkably obtained, which is preferable.

In the general formula (V), R ₁ is --OR ₂ or --N
It represents a (R ₃₎ SO ₂ R ₄ or -COOM _2. Here, R ₂ has ₂ carbon atoms
Representing the above hydrocarbon groups, for example, an alkyl group such as an ethyl group, a hexyl group, a dodecyl group, a phenyl group, a p- (t) -butylphenyl group, an m-methoxyphenyl group, an aryl group such as an o-methoxyphenyl group. Is mentioned. When R ₂ is an alkyl group, the effect of the present invention is remarkably obtained, which is preferable. In addition, R ₁ is preferably —N (R ₃ ) SO ₂ R ₄ or —OR ₂ , and particularly preferably —N (R ₃ ) SO ₂ R ₄ .

R ₃ represents a hydrogen atom or a hydrocarbon group, and examples of the hydrocarbon group include a methyl group and groups similar to those represented by R ₂ . When R ₃ is a hydrogen atom, the effect of the present invention is remarkably obtained, which is preferable.

R ₄ represents a hydrocarbon group, and examples thereof include the same groups as the hydrocarbon group represented by R ₃ . When R ₄ is an alkyl group, the effect of the present invention is remarkably obtained, which is preferable.

In the general formula (V), M ₁ and M ₂ represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group, and examples of the metal atom include sodium, lithium, potassium and calcium. Is mentioned. When the metal atom has a valence of 2 or more, an anion is bonded to neutralize the charge. When M ₁ is a hydrogen atom, the effect of the present invention is remarkably obtained, which is preferable.

Specific examples of the compound represented by the general formula (V) are shown below. Of course, the present invention is not limited to these exemplified compounds.

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044] The above compounds, Journal of Chemical Society (J.Chem.Soc.) 49 .1748 (1927 ), Journal of Organic Chemistry (J.Org.Che
m.) 39 .2469 (1965) , JP-A-50-89034, An'naren Chemie (Ann.Chim.), 44-3,1954, JP-B-40-2849
No. 6, Chemical Berichte (Chem.Ber.) 20 .231 (1887),
It can be synthesized with reference to USP.3,259,976.

The compound represented by the general formula (V) is preferably added to the coating solution preparation step, but the chemical sensitization step,
It can also be used at the end of the chemical sensitization step.

When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ^{−5 to} 5 × ⁵ mol per mol of silver halide.
It is preferably used in an amount of about 10 ⁻⁴ mol. When added at the end of chemical sensitization, 1 × 1 per mol of silver halide
The amount is preferably about 0 ^-6 mol to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-5 mol to 5 × 10 ^-3 mol. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, and 1 × 10 ^-5 mol to 1 mol per 1 mol of silver halide. 1 × 10 ⁻² mol is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention contains silver chloride in an amount of 90 mol% or more, and is preferably silver chlorobromide containing substantially no silver iodide. The content of silver chloride is more preferably 97 to 99.9 mol%, and more preferably 99.0 to 99.9 mol% in order to reduce the amount of development and replenishment of the color developing solution in a shorter time. The silver halide grains may be used alone or as a mixture 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 90 mol% or less. Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the proportion of all silver halide grains contained in the emulsion layer is 60% by weight or more, preferably Is 80% by weight or more. The composition of the silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The silver halide grains used in the light-sensitive material of the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. In addition, U.S. Pat.Nos. 4183756, 4225666, JP-A-55-26589, JP-B-55-42737 and The Journal of Photographic Science (J. Photogr.
Sci.) 21, 39 (1973) and the like, particles having an octahedron, tetradecahedral, dodecahedron, etc. shape can be prepared and used. Further, grains having twin planes may be used.

The silver halide grains used in the light-sensitive material of the present invention may be grains of a single shape,
It may be a mixture of particles having various shapes.

The grain size of the silver halide grains used in the light-sensitive material of the present invention is not particularly limited, but it is preferably 0 in view of other photographic properties such as rapid processing property and sensitivity.
It is in the range of 1 to 1.2 μm, and more preferably 0.2 to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's "particle size analysis method" (A.
STM Symposium on Light Microscopy, pp. 94-122, 1955) or "The Theory of Photographic Process"
Third Edition "(Mies and James, co-authored, Chapter 2, published by Macmillan, 1966).

This particle size can be measured using the projected area of the particle 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 used in the light-sensitive material of the present invention may be polydisperse or monodisperse. The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method of making 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 halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor as described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, etc., and taking out the reaction mother liquor outside the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

In the present invention, a metal ion is added using a cadmium salt (including complex salt) or an iron salt (including complex salt) in the process of forming and / or growing the silver halide grain, and the inside of the grain is added. And / or on the grain surface, and by placing it in a reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be kept contained.

In the present invention, the silver halide grain used in the emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside. Grains whose latent image is mainly formed on the surface are preferable.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound. Sensing methods and the like can be used alone or in combination. Of these, the sulfur sensitization method, the gold sensitization method, and the gold / sulfur sensitization method in which the both are combined are preferably used.

Examples of the sulfur sensitizers include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The silver halide emulsion used in the present invention is for the purpose of preventing fogging occurring during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Antifoggant known in
Stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific compounds thereof include: 8 of the publication
(IIa-1) to (IIa-8) and (IIb-1) to
Examples thereof include the compound (IIb-7) and 1- (3-methoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of spectral sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-51 is used.
BS-1 to BS-8 described in No. 124, pages 108 to 109 can be preferably used alone or in combination. Examples of the green-sensitizing sensitizing dye include GS-
1 to 5 are preferably used, and RS-1 to 8 described on pages 111 to 112 of the same specification are preferably used as the red photosensitive sensitizing dye. When exposing the silver halide photographic light-sensitive material according to the present invention by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, The dyes of IRS-1 to 11 described in Japanese Patent Application No. 3-73619, pages 12 to 14 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used, but especially as a dye having absorption in the visible region,
AI-1 to 1-1 described on pages 117 to 118 of Japanese Patent Application No. 2-51124
The dye of 1 is preferably used, and as the infrared absorbing dye, the compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column, have preferable spectral characteristics. And has no effect on the photographic characteristics of the silver halide photographic emulsion, and is free from contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same specification.

The coupler used in the silver halide photographic light-sensitive material of the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength region of 600 to 750 nm.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (YI) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned.
Specific compounds are described in YC-1 to YC on pages 9 to 11 of the same specification.
Those listed as -9 can be mentioned.
Among them, YC-8 and YC-described on page 11 of the same specification.
No. 9 is preferable because it can reproduce a preferable yellow color.

The magenta coupler preferably used in the silver halide photographic light-sensitive material of the present invention is described in JP-A-
No. 62-166339 Exemplified compounds 1-223 described on pages 18-32,
Exemplified compound M-described on pages 5 and 6 of JP-A No. 2-100048
1 to M-29, Exemplified Compounds M-1 to M-30 described on pages 9 to 12 of JP-A-3-214155, and JP-A-62-215272 104 to
Exemplified compounds M-1 to M-47 described on page 114 may be mentioned.

A cyan coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 on pages 18 to 21 of the specification.
To those described as CC-9.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, If necessary, a low boiling point and / or a water-soluble organic solvent is used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution.
As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. Examples of the high boiling point organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate, but the phthalic acid ester is an effect of the present invention. To be exhibited more effectively.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-
11) and compounds such as the compound (A′-1) described on page 35 of the same specification can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in 774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ³ mol per mol of silver halide. Used in the range of ^-2 to 1 mol.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support of the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used.
For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silica such as synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation. Zinc, talc,
Examples include clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the water resistant resin layer, and further, The content is preferably 13% by weight or more, and particularly preferably 15% by weight or more. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention is as described in JP-A-2-
It can be measured by the method described in No. 28640, when it is measured by this method, the dispersion degree of the white pigment is preferably 0.20 or less as the coefficient of variation described in the above publication, 0.15
It is more preferably at most 0, and still more preferably at 0.10.

The silver halide photographic light-sensitive material according to the present invention may be directly or undercoated (adhesiveness of the surface of the support, after the surface of the support is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. It is applied through one or more undercoat layers) for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional property and / or other properties. Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention are aminophenol and p-phenylenediamine which are widely used in various color photographic processes. A compound is used. In particular, aromatic primary amine type color developing agents are preferably used.

Examples of the aromatic primary amine developing agent include (1) N, N-diethyl-p-phenylenediamine hydrochloride (2) N-methyl-p-phenylenediamine hydrochloride (3) 2-amino-5- ( N-ethyl-N-dodecylamino) toluene sulfate (4) N-ethyl-N- (β-methanesulfonamidoethyl) -3-
Methyl-4-aminoaniline sulfate (5) N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-aminoaniline sulfate (6) 4-amino-3-methyl-N, N,- Diethylaniline sulfate (7) 4-Amino-N- (β-methoxyethyl) -N-ethyl-3-methylaniline p-toluenesulfonate (8) 4-Amino-N-ethyl-N- (γ- Hydroxypropyl) -3-
Methylaniline p-toluenesulfonate These color developing agents are used in an amount of 1 × per liter of developing solution.
It is preferable to use it in the range of 10 ^{−3 to} 2 × 10 ⁻¹ mol,
It is more preferable to use it in the range of 5 × 10 ^{−3 to} 2 × 10 ⁻¹ mol.

To the color developing solution, a known developer component compound can be added in addition to the color developing agent. Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent and the like are used.

As the alkaline agent used in the color developing solution for the silver halide photographic light-sensitive material according to the present invention, potassium carbonate, potassium borate, trisodium phosphate and the like are used, and water is mainly used for the purpose of adjusting pH and the like. Sodium oxide, potassium hydroxide or the like is used. The pH of the color developer is 9-
It is generally 12 and preferably between 9.5 and 11.

For the purpose of suppressing development, halide salt ions are often used, but in the image forming method according to the present invention, it is necessary to finish development in a very short time, so that chloride ions are mainly used. Used are potassium chloride, sodium chloride and the like. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more per liter of color developing solution,
It is preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol. Bromide ion can be used within a range that does not impair the effects of the present invention, but has a large effect of suppressing development, and is approximately 1.0 × 10 ⁻³ mol or less per liter of color developing solution,
It is preferably 5.0 × 10 ⁻⁴ or less.

As preservatives, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids,
Hydrazines, hydrazide aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic compounds. It is a preservative. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroxyamine and alkanolamines such as triethanolamine are preferably used.

As the chelating agent used in the color developing solution according to the present invention, compounds such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. Especially, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid is preferably used.

The color developing temperature is usually 15 ° C. or higher, and generally 20 to 50 ° C. Also, for quick processing, 30
It is preferable to carry out at a temperature of not less than ° C.

Color development processing time is generally 10 seconds to 4
Although it is a minute, for the purpose of speeding up, it is preferably carried out in the range of 10 seconds to 1 minute, and when further speeding up is required, it is preferably carried out in the range of 10 to 30 seconds.

Further, in the image forming method according to the present invention, the running process is carried out while continuously replenishing the color developing solution. At that time, the replenishment amount of the color developing solution is preferably substantially free of overflow at the time of running in consideration of environmental pollution caused by the recent developer waste solution, and specifically, the replenishing amount of the developing solution is preferably 20 to 60 cc. ..

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching processing and fixing processing after color development processing. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative of a washing process. The development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed to the belt and conveyed, but in particular, the processing tank may be formed in a slit shape so that the processing liquid is supplied to the processing tank and the photosensitive material is conveyed.

[0094]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high To 6.67 g of a boiling point organic solvent (DNP), 60 cc. Of ethyl acetate was added and dissolved, and this solution was 9.5 cc. Of 15% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 cc. Of a 10% gelatin aqueous solution containing the above using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions, and a 5% aqueous solution of the anti-irradiation dye AI-3 was added to 6.7 cc.
In addition, each of the compounds shown in Table 3 was added 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. The second layer and the fourth layer are hardeners.
(H-1) was added to the layer and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (SU-
3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0098]

[Table 1]

[0099]

[Table 2]

The additives used in each layer are as follows.

H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfo Succinic acid di (2-ethylhexyl) ester sodium SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester sodium DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HBS-1: 1-dodecyl-4- (p-toluenesulfonamido) benzene HBS-2: 2: 1 of tri (2-ethylhexyl) phosphate and tricresyl phosphate (Volume ratio) HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2-hexadecyl-5-methylhydroquinone

[0102]

[Chemical 18]

[0103]

[Chemical 19]

[0104]

[Chemical 20]

(Preparation of Blue-Sensitive Silver Halide Emulsion) The following (solution A) was added to 1000 cc. Of a 2% gelatin aqueous solution kept at 40 ° C.
And (B solution) were simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (C solution) and (D solution) were added to pAg.
= 7.3, pH = 5.5, and simultaneous addition over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 cc. (Solution B) Silver nitrate 10 g Water was added to 200 cc. (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water was added 600 cc. (Liquid D) 300 g of silver nitrate Water is added to 600 cc. After the addition is complete, desalting is performed using a 5% aqueous solution of Demol N and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution. Thus, a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-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 (preparation of green-sensitive silver halide emulsion) (solution A) and solution (B)
The average particle size is 0.43 μm in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
A monodisperse cubic emulsion EMP-2 having a variation coefficient (S / R) of 0.07 and a silver chloride content of 99.0 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as in EMP-1, except that the average particle size is 0.50 μm.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation (S / R) of 0.08, and a silver chloride content of 99.0 mol% was obtained.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB- 1 1- (3-acetamido) phenyl-5-mercaptotetrazole

[0113]

[Chemical 21]

[Coating Solution Stability] In the preparation of Sample 101, after the coating solution was prepared, the solution was kept at 40 ° C., the sample applied for the second hour and the sample for which the solution had been aged for 10 hours were prepared. The stagnation property of the coating liquid was examined. The sample was wedge-exposed by a conventional method, processed according to the following processing steps, and subjected to sensitometry to obtain a sensitivity change ΔS = (S10 / S2) × 100.
Here, S10: sensitivity of the sample applied 10 hours after the adjustment,
S2: The sensitivity of the sample applied 2 hours after the adjustment was determined.
The smaller ΔS indicates the better stagnation of the coating liquid.

[Bacterial resistance] 36
After being left open for 2 days in an atmosphere of ℃ heating and 75% relative humidity, the presence or absence of bacteria was examined by a microscope. The results were evaluated in three grades: ◯: no occurrence, Δ: slightly generated, and x occurred frequently.

(Processing step) Processing step Processing temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleach fixing 35.0 ± 0.5 ° C 45 seconds Stability 30-34 ° C 90 seconds Dry 60-80 ° C 60 seconds Composition of developing solution Is shown below.

Color developer Pure water 800 cc. Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline sulfate 6.0g N, N-diethylhydroxylamine 6.8g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g Potassium carbonate 30g Add water Adjust the total volume to 1 liter and adjust the pH to 10.10.

Bleach-fixing solution Diethylenetriamine pentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc. 5-Amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc. Add water to bring the total volume to 1 liter, and adjust the pH to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing solution o-Phenylphenol 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g BIC13 (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g PVP ( polyvinylpyrrolidone) 1.0 g of ammonia water (ammonium hydroxide 25% aqueous solution) 2.5g Nitrilotriacetic acid / trisodium salt 1.5g Add water to make the total volume 1 liter and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The blue density of the obtained sample was measured using a PDA-65 densitometer (Konica Corporation). Sensitivity is density 0.
It was defined based on the reciprocal of the exposure dose giving 75. The results are shown in Table 3 below.

[0121]

[Table 3]

As is clear from Table 3, the addition of the mildew-proofing agent alone has the effect of preventing the generation of bacteria, but the emulsion coating solution stagnation property deteriorates, which is a major obstacle in practical use. On the other hand, it is clear that the addition of the compound represented by the general formula (V) of the present invention significantly improves the stagnation property of the coating solution and prepares a stable coating solution without generation of bacteria. is there.

Example 2 In the preparation of the blue-sensitive emulsion of Example 1, the Y coupler was changed to Y.
The stagnation property of the coating solution and the bacterial resistance of the coating solution were examined in the same manner as in Example 1 except that -1 was replaced with Y-2.

As a result, it was confirmed that the effect of Example 1 could be reproduced regardless of the type of Y coupler.

[0125]

[Chemical formula 22]

Example 3 The same experiment as in Example 1 was conducted on a green-sensitive emulsion and a red-sensitive emulsion. As a result, it was found that the improvement of the bacterial resistance of the emulsion coating solution and the stabilization of the photographic performance were similarly achieved by adding the compound of the present invention.

[0127]

Industrial Applicability According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has improved sensitivity fluctuation with time of a coating solution containing a mildew-proofing agent and is suitable for rapid processing.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide contained is silver chlorobromide or silver chloride having a silver chloride content of 90 mol% or more, and is represented by the following general formula (I), (I
A halogen containing at least one compound selected from the compounds represented by I), (III) and (IV) and at least one compound selected from the compounds represented by the following general formula (V): Silver halide photographic light-sensitive material. [Chemical 1] [In the formula, R ¹ represents a lower alkylene group, and M represents a hydrogen atom, an alkali metal or an alkyl group. X is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carboxyl group, an amino group, a hydroxyl group, a sulfo group,
Represents a nitro group or an alkoxycarbonyl group. m is 1
Represents an integer of 5, and n represents 0 or 1. ] [Chemical 2] [In the formula, R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, -CONHR (R represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkyl group. Represents a sulfonyl group or an arylsulfonyl group) or a heterocyclic group. R ³ and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfonyl group or an alkylsulfinyl group. Represent Further, R ³ and R ⁴ may be bonded to each other to form a benzene ring which may have a substituent. ] [Chemical 3] [In the formula, R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom,
It represents a lower alkyl group having 1 to 5 carbon atoms or a hydroxymethyl group, and R ⁷ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. ] [Chemical 4] [In the formula, R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group,
It represents a hydroxyl group, a halogen atom, an alkoxy group or a thiazolyl group. Z represents an atom group forming a thiazole ring, and m ′ represents 0 or 1. ] [Chemical 5] [In the formula, Ar represents an aromatic group, R ₁ is -OR ₂ , and -N (R ₃ ) SO.
₂ R ₄ or —COOM ₂ is represented. R ₂ represents a hydrocarbon group having 2 or more carbon atoms, R ₃ represents a hydrogen atom or a hydrocarbon group, and R ₄ represents a hydrocarbon group. M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. ]