JPS6048025B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved color reproducibility and image sharpness.

In silver halide photographic materials, it is known that a colored layer such as an antihalation layer, a filter layer, or a backing layer is provided in order to improve image sharpness and, in the case of color, color reproducibility. ing.

For such colored layers, dyes and pigments such as carbon black, colloidal silver, manganese colloids, etc. added to alkali-soluble resins or hydrophilic colloids are used. It goes without saying that it must be completely decolored in post-exposure processing steps, such as development processing steps, etc., and it is also required to have excellent spectral absorption and be photochemically inert. Therefore, the selection of colorants is extremely limited. For example, conventional carbon black is black, and the only way to remove it is to remove it together with the binder. use. There is no other option, and in the case of colloidal silver, not only is it not always possible to obtain sufficiently favorable spectral properties, but also it is not completely inert from a photographic chemical perspective, so it has the disadvantage of causing undesirable fog in the emulsion layer. . Therefore, recently, a method using a colored layer in which a mordant and an acidic dye are combined has been adopted.

Many patents have been filed regarding these basic polymer mordants and acid dyes, such as British Patent No. 7865.
9, No. 906083, No. 1162214, U.S. Patent No. 3445231, West German Patent (OLS) No. 19
No. 14361 and No. 191408, etc., but in these techniques, the mordant cannot completely retain the acidic dye, and the acidic dye diffuses into the adjacent layer, resulting in a decrease in sensitivity and the formation of fog. This may cause deterioration in storage performance, deterioration of storage performance, etc. In order to improve these drawbacks, searches have been made for basic polymeric mordants that are chemically inert and have strong mordanting power.

A method using a mordant obtained by reacting aminoguanidine with a polymeric oxo compound as a compound to achieve the above object is described in British Patent No. 850281 and West German Patent No. 2009498. A particularly preferred mordant is U.S. Pat.
No. 6 and No. 3,706,563, the condensation products of polyvinyl alkyl ketone or poly N-oxoalkyl (meth)acrylamide and aminoguanidine are mentioned. Most of the disadvantages of the mordants described above are avoided when using the mordant described in the above-mentioned U.S. patent, which is a condensation product of polyvinyl alkyl ketone or poly N-oxoalkyl (meth)acrylamide and aminoguanidine. It was found that it is possible to compensate for

However, even when this mordant was used, the following drawbacks were pointed out. That is, so-called desilvering failure development, which is known to those skilled in the art, occurs. Generally, antihalation layers and filter layers are used in silver halide color photographic materials for the purpose of improving sharpness and improving spectral sensitivity distribution, but these must be completely removed at the end of the development process.

As mentioned above, it is also necessary to completely remove metallic silver generated during development. However, a portion of this metallic silver is not completely removed and remains in the color image, which may cause color turbidity and make it impossible to achieve the initial purpose. . In this development, due to the use of basic polymer compounds as mordants in silver halide photographic light-sensitive materials, desilvering defects occur in large numbers, regardless of the amount or type of compound used. The use of basic polymer mordants with such strong mordant power tends to further increase desilvering defects. This desilvering failure is thought to be caused by physical development, and in order to solve this problem, a patent application was filed in
21 specification, JP-A No. 50-25217) for details [wherein R9 is a hydrogen atom or a lower alkyl group, R
IO and Rll represent a lower alkyl group.

[Detailed Description of the Invention] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved color reproducibility and image sharpness.

In silver halide photographic materials, it is known that a colored layer such as an antihalation layer, a filter layer, or a backing layer is provided in order to improve image sharpness and, in the case of color, color reproducibility. ing.

For such colored layers, dyes and pigments such as carbon black, colloidal silver, manganese colloids, etc. added to alkali-soluble resins or hydrophilic colloids are used. It goes without saying that it must be completely decolored in post-exposure processing steps, such as development processing steps, etc., and it is also required to have excellent spectral absorption and be photochemically inert. Therefore, the selection of colorants is extremely limited. For example, conventional carbon black is black, and the only way to remove it is to remove it together with the binder. use. There is no other option, and furthermore, the combination of colloidal silver does not necessarily provide sufficiently favorable spectral characteristics, and is not completely inert from a photographic chemical standpoint, so it has the disadvantage of causing undesirable fog in the emulsion layer. Ta. Therefore, recently, a method using a colored layer in which a mordant and an acidic dye are combined has been adopted.

Many patents have been filed regarding these basic polymer mordants and acid dyes, such as British Patent No. 7865.
9 Trowel, 906083, 1162214, U.S. Patent No. 3445231, West German Patent (0LS) No. 19
No. 14361, No. 191436? However, in these technologies, the mordant cannot completely retain the acidic dye, and the acidic dye diffuses into the adjacent layer, causing a decrease in sensitivity, fogging, and desensitization. , or deterioration of storage performance. In order to improve these drawbacks, searches have been made for basic polymer mordants that are chemically inert and have strong mordanting power.

A method of using a mordant obtained by reacting aminoguanidine with a polymeric oxo compound as a compound to achieve the above object is described in British Patent No. 850281 and West German Patent No. 9 (0LS) No. 2009498. A particularly preferred mordant is U.S. Pat.
No. 6 and No. 3706563, the condensation products of polyvinyl alkyl ketone or poly N-oxoalkyl (meth)acrylamide and aminoguanidine are mentioned. Most of the disadvantages of mordants mentioned above are avoided when using the mordant described in the above-mentioned US patent, which is a condensation product of polyvinyl alkyl ketone or poly N-oxoalkyl (meth)acrylamide and aminoguanidine. It was found that it is possible to compensate for

However, even when this mordant was used, the following drawbacks were pointed out. That is, so-called desilvering failure development, which is known to those skilled in the art, occurs. Generally, antihalation layers and filter layers are used in silver halide color photographic materials for the purpose of improving sharpness and improving spectral sensitivity distribution, but these must be completely removed at the end of the development process.

As mentioned above, it is also necessary to completely remove metallic silver generated during development. However, a portion of this metallic silver is not completely removed and remains in the color image, which may cause color turbidity or the like, making it impossible to achieve the initial objective. In this development, due to the use of basic polymer compounds as mordants in silver halide photographic light-sensitive materials, desilvering defects occur in large numbers regardless of the amount or type of compound used. The use of basic polymer mordants with such strong mordant power tends to further increase desilvering defects. This desilvering failure is thought to be caused by physical development, and in order to solve this problem, a patent application was filed in
21, JP-A No. 50-25217), a heterocyclic mercapto compound, e.g. - There are methods such as adding mercaptobenzothiazole, etc., but when a heterocyclic mercapto compound such as 2-mercaptobenzothiazole is added for the purpose of suppressing physical development by the method described here, silver halide In order to prevent defective desilvering in color photographic materials, the reduction in sensitivity was large and it was not sufficient.

There is also a method of adding vinylpyrrolidone homopolymer or a copolymer with other monomers to a so-called photosensitive layer containing silver halide, as described in Japanese Patent Publication No. 42-705. Desilvering defects cannot be completely prevented no matter the method used, and desilvering defects can be improved to some extent by adding large amounts of such compounds for this purpose, but at the same time desilvering defects may deteriorate. This results in negative effects on photographic performance, such as

Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material containing a basic polymer mordant and an acidic dye, which does not cause desilvering defects and has excellent image sharpness. provides silver halide photographic materials with excellent color reproducibility. A second object of the present invention is to provide a silver halide photographic material that prevents desilvering defects while maintaining good sensitivity.

The above objects of the present invention and other objects described below are achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a basic polymer mordant, an acidic dye, and a vinylpyrrolidone polymer.

That is, the present inventor has decomposed a vinyl pyrrolidone homopolymer or a copolymer with other monomers into a hydrophilic colloid solution containing a colored layer in which an acidic dye is bonded to a basic polymer mordant. It has been discovered that silver defects can be eliminated.

The present invention is characterized in that a vinylpyrrolidone homopolymer or a copolymer with other monomers coexists in a hydrophilic colloid aqueous solution having a mordant layer obtained by adding an acidic dye to a basic polymer mordant. However, even if a vinyl pyrrolidone homopolymer or a copolymer with other monomers was present in a layer adjacent to the mordant layer, it had little or no effect. The vinyl pyrrolidone polymer used in the present invention includes not only homopolymers but also copolymers thereof.

The copolymerization form of this copolymer is not particularly limited, and any polymerization form can exhibit similar effects. Typical monomers as other copolymerization components of the pyrrolidone copolymer used in the present invention include saturated aliphatic vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl acrylate, and ethyl acrylate. , acrylic acid n
-butyl, methacrylic acid, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate,
Acrylic acid or acrylic acid esters such as methyl α-chloroacrylate, 2-hydroxyethyl acrylate, 2-N-,N-dimethylaminoethyl acrylate, etc., olefins such as ethylene, propylene, isobutylene, etc., vinyl chloride , halogenated olefins such as vinylidene chloride, dienes such as butadiene, isoprene, nitriles such as acrylonitrile, methacrylnitrile, etc., aromatic unsaturated hydrocarbons such as styrene, methylstyrene, acrylamide, methacrylamide, Acrylamides such as N-methylacrylamide, N,N-diethylacrylamide, diacetone acrylamide, etc., vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, etc., N-vinylpyrrolidone, etc., CF2=CF2, CH2=CF2, etc. These include fluorinated vinyl compounds such as.

The degree of polymerization of the pyrrolidone polymer used in the present invention may be determined by dissolving it in water or a water-soluble organic solvent such as methanol.
The preferred average degree of polymerization is 10 to 300 degrees. As the basic polymer mordant used in the present invention, various mordants conventionally known as mordants in the photographic field can be used, for example, U.S. Pat.
No. 675316, No. 2882156 and No. 37
Among them, polymers having repeating units represented by the following general formulas [1], [■], [■], or [■] are preferably useful.

General formula [■] [In the formula, R1 represents a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, etc.), and R2 represents a lower alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.) or a substituted or unsubstituted aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), and A represents a simple bond or a divalent group. organic groups (e.g. arylene groups such as phenylene groups, methylene groups, ethylene groups,
(alkylene group such as trimethylene group), m is O
Or 1, X represents an anion.

] General formula [■] [In the formula, R3 represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), and R4 represents a substituted or unsubstituted alkyl group.
kill group (e.g. methyl group, ethyl group, octyl group, phenylmethyl group, vinylmethyl group, chloromethyl group, etc.),
XO is an anion (e.g. chloride ion, bromide ion, p-
toluenesulfonic acid ion, etc.).

] General formula [■] [In the formula, R5 represents a hydrogen atom or a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), and R6
, R7 and R8 each represent a lower alkyl group (for example, methyl group, ethyl group, propyl group, etc.) or a substituted or unsubstituted aryl group (for example, phenyl group, tolyl group, naphthyl group, etc.), and B is a divalent organic group. represents a group (e.g., methylene group, alkylene group such as ethylene 7 group, arylene group such as phenylene group, arylene alkylene group such as carbonyloxymethylene group, phenylenemethylene group, etc.), and Xθ represents an anion (e.g., chlorine ion, bromide ion, etc.). ).

] General formula [■] [In the formula, R9 represents a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), and RlO and Rll each represent a lower alkyl group (e.g., methyl group, ethyl group, n -propyl group, t-butyl group, etc.), and XO represents an anion (for example, p-toluenesulfonic acid ion, etc.).

゛The basic polymer mordant used in the present invention may have a degree of polymerization of 20 to 20 as long as it does not substantially diffuse from the coating layer.
A value of about 10(1) is practical. The typical basic polymer compound preferably has a secondary amino group, a tertiary amino group, or a nitrogen atom constituting ammonium in its main chain or side chain. Further, the basic polymer compound may be a homopolymer, a copolymer, or a graft polymer.
Also, general formulas [1], [■], [■] used in the present invention
Alternatively, the polymer having the repeating unit represented by [■] may contain other copolymer components shown below.

Typical monomers having vinyl bonds as copolymerization components include, for example, styrene, metastyrene, vinyl chloride, vinylidene chloride, isobutylene, ethyl acrylate, methyl methacrylate, butyl methacrylate, acrylamide, N,N -dimethylacrylamide, diacetone acrylamide, vinyl acetate, N-vinylpyrrolidone,
Examples include diethylamino-ethyl methacrylate, 4-vinylpyridine, 2-methyl-N-vinylimidazole, and acrylonitrile.

Typical specific examples of basic polymer mordants used in the present invention include the following.

[Specific examples of basic polymer mordants]

Any acidic dye can be used as the acidic dye used in the present invention, but acidic dyes having a sulfonyl group or a carboxyl group are preferred, such as azo dyes, triphenylmethane dyes, anthraquinone dyes, and styryl dyes. , benzylidene-based, merocyanine-based, oxonol-based, and other acidic dyes can be used.

Next, typical examples of acid dyes used in the present invention are listed.

[Specific examples of acidic dyes]

The hydrophilic colloid used in the present invention is preferably gelatin, but other hydrophilic colloids may be used depending on the purpose.

Other examples of hydrophilic colloids include gelatin derivatives, cellulose derivatives, polysaccharides, water-soluble synthetic polymer compounds, and water-insoluble synthetic polymer compounds, which may be used alone or in combination of two or more. The weight ratio of the hydrophilic colloid and the basic polymer mordant used in the present invention is arbitrary, but considering the stability of the coating solution, etc.
The amount of the basic polymer mordant is 1 to 200 parts by weight, particularly preferably 10 to 15 parts by weight.
In addition, the amount of vinyl pyrrolidone polymer used varies depending on the type and amount of basic polymer mordant used, but
The range commonly used is basic polymer mordant 10
It can be used in an amount of 1 to 1000 parts by weight, preferably in a range of 10 to 500 parts by weight. Furthermore, the amount of acidic dye used in the present invention is arbitrary depending on the purpose, but the range usually used is 20 to 100% by weight based on 10% by weight of the basic polymer mordant. The basic polymer mordant, acid dye, and pyrrolidone polymer used in the present invention are usually added by adding the basic mordant and acid dye to a hydrophilic colloid solution by any method (for example, an aqueous solution), and then adding the basic mordant and acid dye to a hydrophilic colloid solution before or after adding the basic mordant and acid dye. At the same time, add the pyrrolidone polymer.

The hydrophilic colloid solution prepared by the above-described method according to the present invention is coated on a support by the method described below.

Further, when the layer containing the basic polymer mordant, acidic dye and vinylpyrrolidone polymer of the present invention is a silver halide emulsion layer, the hydrophilic colloid solution may be added to the silver halide emulsion. The basic polymer mordant of the present invention,
The hydrophilic colloid layer containing an acid dye and a vinylpyrrolidone polymer may be any layer constituting the silver halide photographic light-sensitive material, but if the light-sensitive material is for color use, it may be an antihalation layer or a filter. Although it is generally a layer or an intermediate layer, it may be an emulsion layer if necessary.

Other photographic additives may be added to the silver halide photographic material of the present invention having a hydrophilic colloid layer containing the basic polymer mordant, acidic dye and vinylpyrrolidone polymer of the present invention.

Examples of hardeners that can be optionally added include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, and acyloyl-based hardeners. Contains membrane agents.

Antifoggants or stabilizers that can be optionally used include, for example, imidazole-based, oxazole-based, thiazole-based, triazole-based, tetrazole-based, mercapto-based, azaindene-based compounds, and wetting agents include, for example, dihydroxyalkanes. Examples of film property improvers include copolymers of alkyl acrylates or alkyl methacrylates and acrylic acid or methacrylic acid, styrene-maleic acid copolymers,
Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as styrene maleic anhydride half alkyl ester copolymers are suitable.

Other photographic additives include gelatin plasticizers, ultraviolet absorbers, PH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, brighteners, development rate adjusters, matting agents,
The use of stabilizers and the like is optional. Furthermore, it is useful to use the silver halide photographic light-sensitive material of the present invention for color applications, and in this case, it is preferable to include cyan, magenta and yellow couplers in the silver halide photographic emulsion.

These coloring agents include phenols, 5-pyrazolones,
A ketomethylene compound is effective, and it is preferable to use it in combination with an active site substitution type coupler, a strong lard coupler, or a development inhibitor release type coupler. The silver halide photographic emulsion used in the silver halide photographic light-sensitive material of the present invention may be of any type depending on the application and purpose, but examples include silver chloride, silver iodide, and silver bromide. All kinds of silver halides such as silver iodobromide, silver chloroiodide, and silver chloroiodobromide can be used as photosensitive components.
Ruthenium, rhodium,
Salts of noble metals such as palladium, iridium, platinum, gold, etc., or noble metal sensitization with e.g. ammonium chlorovaladate, potassium chloroplatinate, potassium chloropaladite, potassium chloroaurate, etc., or sulfur sensitization with sulfur compounds, or e.g. It is optional to perform various chemical sensitizations such as reduction sensitization using stannous salts, polyamines, etc., and sensitization using polyalkylene oxide compounds.

Optical sensitizers that can be optionally added to the silver halide photographic emulsion of the present invention include cyanines, merocyanines,
These optical sensitizers include trinuclear or tetranuclear cyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols, and hemioxonols, and these optical sensitizers have nitrogen-containing heterocyclic nuclei. As part of its structure, it contains basic groups such as thiazoline and thiazole, or cordanine, thiohydantoin, oxazolidine di. Preferably, those containing a nucleus such as on, barbituric acid, thiobarbituric acid, pyrazolone, etc., and such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl, cyano, or alkoxy, and can be substituted with carbocyclic or heterocyclic ring. Condensation is optional.

Furthermore, the silver halide photographic emulsion used in the present invention includes:
Gelatin is preferably used as the hydrophilic colloid, but
Other hydrophilic binders may be included depending on the purpose.

Suitable binders include the gelatin derivatives mentioned above and others. Any support can be used for the silver halide photographic light-sensitive material of the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, cellulose acetate film, and glass, if necessary. , baryta paper, polyethylene laminate paper, etc.

The basic polymer mordant, acidic dye, and vinylpyrrolidone polymer of the present invention are particularly preferably applied to antihalation layers, intermediate layers, filter layers, silver halide emulsion layers, etc. of color films and photographic papers. In addition, it can be applied to the hydrophilic colloid layer of various silver halide photographic materials such as general black and white negatives, x-rays, direct positives, printing, and infrared. When applied to the anti-halation layer formed between the support and the emulsion layer, a microfilm with extremely excellent resolution can be obtained.

A conventional liquid coating method is used to coat the hydrophilic colloid layer containing the basic polymer mordant, acidic dye, and vinylpyrrolidone polymer of the present invention on the support together with other constituent layers of the silver halide photosensitive material. It will be done.

For example, various coating methods can be employed, such as a dip method in which the coating roller is immersed in the coating liquid, a bead method using a slide hopper, and a curtain method in which the coating liquid is dropped in a curtain shape. Generally, in these coatings, hydrophilic colloid layers containing basic mordants and acidic dyes often cause problems such as uneven coating and streaks. The reason for this is presumed to be the influence of the large amount of salt that is thought to be contained in these hydrophilic colloid layers.
Removal of such harmful salts is preferable for improving the stability of production and the stability of the quality obtained, and various methods can be used for desalting, and there are no particular limitations. EXAMPLES Hereinafter, the effects of the present invention will be illustrated with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A first layer coating liquid and a second layer coating liquid having the following compositions were applied onto a subbed triacetyl cellulose film support using a slide hopper from the support side to a dry film thickness of 3 μm.
Two types of samples were prepared by simultaneous multilayer coating and drying to give a thickness of 0.8μ.

1 kg of red-sensitive silver iodobromide gelatin B emulsion (silver amount 0.35 mol/KdL agent) containing 4 mol% silver iodide in the first layer coating solution
4-hydroxy-6-methyl-1,3,3a,7-
100 ml of a 0.5% solution of tetrazaindene, 700 mg of 1,3,5-triacryloylhexahydro-8 triazine as a hardening agent, and hexamethylene bis(N, IN
- 1 da of ethylene urea) was added, and a mixed solution of 20 V of cyan coupler, 10 q of tricresyl phosphate, and 60 y of ethyl acetate was added to 20 d of a 10% gelatin solution.
Add a dispersion aid to 0f1 with Alkanol XC (manufactured by DuPont)
A coating liquid prepared by adding 1 emulsified dispersion obtained by adding 1.

60 ml of a 5% aqueous solution of specific example 1 of the mordant described above was added to 600 ml of a 5% gelatin solution of the second layer coating solution, and then 150 ml of a 1% aqueous solution of specific example 7 of the dye described above was added while stirring. Two coating solutions were used: one containing 40 ml of a 5% aqueous solution of pyrrolidone (degree of polymerization 90) and the other containing no polyvinylpyrrolidone, and 5y of sodium p-dodecylbenzenesulfonate, an activator, was added to each as a coating aid. 2 coating liquids prepared by

The above two types of samples were subjected to the following development treatment, and defective desilvering was confirmed.

The results are shown in Table 1. The treatment steps and treatment liquid composition used are as follows. Treatment process (38°C
) Processing time First development
6 minutes Wash with water 2 minutes
Reversal bath 2 minutes Color development
6 minutes. conditioner
2 minutes bleaching bath 6 minutes fixing bath 4 minutes washing with water
4 minutes stable bath
3 Box 2 [First developer] Water
600ml water softener (NO-4)
1Tn1 potassium sulfite (45% solution)
44ml sodium bromide
22q Rodin Soda 1.
0 Dayodokari 4.5f
Potassium hydroxide (45% solution) 7 ml diethylene glycol 12 ml Kodak, Day Maison-Sl. 4g potassium carbonate
14g sodium bicarbonate 1
2q Kodak developer (DA-1) 22y Add water to make 1'.

Inversion bath〕Water 900
ml propionic acid 12ml Kodak, reversal liquid (RA-4) 1.65q bulk
Aminophenol 0.5m9 Sodium hydroxide 4.8mg Water softener (N
O-4) Add 15ml of water to make 1e.

[Color developer] Water 800ml Hard water softener (NO-4) 5.0TrLL phosphoric acid (85% aqueous solution) 7.0ml Sodium bromide 0.70y Potassium iodide 30mg Potassium hydroxide (
45% solution) 31ml sodium sulfite
4.5q citradinic acid
1.25g Kodatsu color developer (CD-3
) 11g Kodatsu (HS-104)
Add 1q water to make 1'.

[Conditioner liquid]

Water 800 ml Potassium sulfate (45% aqueous solution) 20 mL Ethylene diamine 8q Kodak, Condectioner (CA-2) Add 0.4 ml water to make 1e.

[Bleach solution]

Water 500mt Potassium nitrate 30g Potassium bromide
100g Kodatsu, bleach (B
L-1) 270mL hydrobromic acid (48%)
40mt ethylenediaminetetraacetic acid iron ammonium salt
Add 4y of water to make 1'.

[Fixer]

Water 500ml ammonium thiosulfate (58%) 120ml ethylenediaminetetraacetic acid (EDTA) 1y sodium metasulfate 10y sodium hydroxide
Add 2y of water to make 1'.

[Stability bath]

Water 900ml, Stabilizer 0.20ml formalin (37.5%) Add 6ml water to make 1f.

Note 1 Optical red density (DB) is the logarithm of the reciprocal of transmittance (T) measured through a red filter (DB='
0g101/T), (the same applies hereinafter).

). It should be noted that when measuring using DB, it is easy to detect desilvering defects, and it can be seen that the higher the concentration, the more desilvering defects occur. As is clear from Table 1, poor desilvering was observed in the samples coated with a mordant layer containing no polyvinylpyrrolidone, which was easily detected visually. It can be seen that no defective desilvering was observed in the samples of the present invention.

In addition, it was confirmed that the desilvering treatment for the sample according to the present invention had the same effect as the present example even when the following bleaching treatment was performed.

[Bleach solution-A] (38°C for 11 minutes) Hydrogen peroxide (35%) 50ml Glacial acetic acid (98%)
30ml 1-Hydroxyethylidene diphosphonic acid 5ml Adjust pH with sodium hydroxide and finish to 1e with water.

[Bleach solution-B] (processed at 38°C for 2 minutes) [Translation☆↑Special: 9ya ”X: [? ((; Tan, 6.

"i: Bleach solution-C" (processed at 38°C for 2 minutes) EDTA monoferrous sodium salt 100yEDT
A-2-Sodium salt 5y Ammonium iodide 200q PVT (K-30) Finish to 1e with water.

a [Bleach solution-D] (processed at 38°C for 15 minutes) EDTA monoferrous sodium salt 100y Sodium sulfite
10y ammonium thiosulfate
90y sodium thiocyanate 3
Finish to 1f with 0q ammonium bromide and 150q water.

The results are shown in Table 2.

Example 2 The first and second layers of the coating solution were prepared in exactly the same manner as in Example-1, but the mordant in the second layer used the one with the specific example number shown in Table 3. .

The sample was treated in the same manner as in Example 1, and the optical red density was measured. The results are shown in Table 3. Example 4 A first layer coating liquid and a second layer coating liquid having the following compositions were applied onto a subbed triacetylcellulose film support using a slide hopper from the support side to a dry film thickness of 3 μm.
and 0.8μ, and dried.

1st layer coating liquid 1kg of 3% gelatin solution containing 3g of black colloidal silver
A coating solution prepared by adding a coating aid to.

60 mL of a 5% aqueous solution of mordant No. 1 described above was added to 600 ml of a 5% gelatin solution of the second layer coating solution, and then 150 mL of a 1% aqueous solution of acid dye No. 9 described above was added while stirring.
t, and further polyvinylpyrrolidone (polymerization degree 90
A coating solution prepared by adding 40 mL of a 5% aqueous solution of ).

Next, using the same slide hopper, a third layer coating liquid and a fourth layer coating liquid having the following compositions were simultaneously applied by heavy wound injection so that the dry film thicknesses were 3.5μ and 0.8μ, respectively. I
llO/. ;Seqζ Example 3 The first and second layers of the coating solution were prepared in exactly the same manner as in Example-1, but the polyvinylpyrrolidone polymer in the second layer was replaced with the vinylpyrrolidone (co)polymer shown in Table 4. Used instead of combination.

It was treated in the same manner as in Example-1, and the optical blue density was measured. The results are shown in Table 4. A layer was applied and dried.

Red-sensitive silver iodobromide gelatin emulsion containing 4 mol% silver iodide in the third layer coating solution (
100 mt of a 0.5% solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and a hardener 1,3,5-triacryloyl were added to 1k9 containing 0.35 moles of silver/Kg emulsion). Hexahydro s-triazine 700mg
, hexamethylene bis(N,N-ethyleneurea) 1g
Further, a mixed solution of 20 g of cyan coupler, 10 da of tricresyl phosphate, and 60 g of ethyl acetate was added to a solution of 200 q of 10% gelatin solution and 40 TfL1 of 5% aqueous dispersion aid. A coating liquid prepared by adding the obtained emulsified dispersion.

Fourth Layer Coating Liquid A coating liquid prepared in the same manner as the second layer coating liquid of Example-1 except that the dye number 7 was used instead of the dye number 1.

Next, using the same slide hopper, a fifth layer coating liquid and a sixth layer coating liquid having the following compositions were simultaneously coated in a multilayer manner so that the dry film thicknesses were 3.5 μm and 0.8 μm, respectively, and dried. Green-sensitive silver iodobromide gelatin emulsion containing 4 mol% silver iodide in the fifth layer coating solution (
100 ml of 0.5% solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and hardener 1,3,5-triacryloylhexa Hydro s-triazine 700m9
, 1 da of hexamethylene bis(N,N-ethylene urea) was added, and a mixed solution of 36 y of magenta coupler, 10 y of tricresyl phosphate, and 10 y of ethyl acetate was added to 300 ml of a 10% gelatin solution as a dispersion aid. A coating liquid prepared by adding an emulsified dispersion obtained by adding 60 ml of a 5% aqueous solution of

6th layer coating liquid A coating liquid prepared in the same manner as the 4th layer coating liquid, except that dye number 6 was used instead of dye number 7 in the 4th layer coating liquid.

Furthermore, using the same slide hopper, a 7th layer coating liquid and an 8th layer coating liquid having the following compositions were simultaneously coated in layers so that the dry film thicknesses were 3.5μ and 0.8p, respectively, and dried. Sample A was obtained.

2 7th layer coating solution 4-hydroxy-6-methyl-1,3
,3a,7-tetrazaindene 0.5% solution 100W
Lt and hardener 1,3,5-triacryloylhexahydro s-triazine 700m9, hexamethylene bis(
1y of yellow coupler, 20y of dibutyl phthalate, and 244g of ethyl acetate was added to 10% gelatin solution 6.
A coating liquid prepared by adding an emulsified dispersion obtained by adding 130 mL of a 5% aqueous solution of a dispersion aid to 00 mL of a solution.

8th layer coating liquid Coating liquid consisting of 5% gelatin solution with addition of coating aids.

Separately, in the sample A, the second layer and the fourth layer
Sample B was prepared having the same structure as Sample A except for the mordant and dye in the layer. Sample C was prepared having the same structure as Sample B except that yellow colloidal silver 1y was used in place of the mordant and dye in the sixth layer.

In addition, in the samples A, B, and C, samples A'', B'', and C'' were prepared at the same time, in which the second layer, fourth layer, and sixth layer did not contain polyvinylpyrrolidone at all.

In addition, the following couplers and sensitizing dyes were used in each of the above samples.

[Third Layer] Sensitizing Dye Sensitizing Dye [Seventh Layer] Coupler Sensitizing Dye Each sample was treated in the same manner as in Example 1, and its photographic performance was measured.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material comprising a hydrophilic colloid layer containing a basic polymer mordant, an acidic dye, and a vinylpyrrolidone polymer. 2 The basic polymer mordant has the following general formula [I], [II
The silver halide photographic material according to claim 1, which is a polymer having a repeating unit represented by ], [III] or [IV]. General formula [I]▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is a hydrogen atom or lower alkyl group, R_
2 represents a lower alkyl group or a substituted or unsubstituted aryl group, A represents a simple bond or a divalent organic salt, m represents 0 or 1, and X represents an anion. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_3 is a hydrogen atom or a lower alkyl group, R_
4 represents a substituted or unsubstituted alkyl group. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_5 is a hydrogen atom or a lower alkyl group, R_
6, R_7 and R_8 represent a lower alkyl group, a substituted or unsubstituted aryl group, and B represents a divalent organic group. ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_9 is a hydrogen atom or a lower alkyl group, R_
1_0 and R_1_1 represent a lower alkyl group. ]