JPH02302752A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material small in color stains due to residual dyes and excellent in shelf life with time by spectrally sensitizing an emulsion layer with a specified sensitizing dyestuff and incorporating a specified dye in at least one of hydrophilic colloidal layers. CONSTITUTION:The emulsion layer is spectrally sensitized by one of the sensitizing dyestuffs represented by formula I in which each of Y1 and Y2 is a benzothiazole or benzoselenazole ring or the like; each of R1 and R2 is lower alkyl or the like; R3 is methyl or the like; and X1 is an anion; each of n1 and n2 is 1 or 2; and m1 is 1 or when it is an intramolecular salt, m1 is 0. At least one of the emulsion layers contains the dye represented by formula II in which Q is an aliphatic or aromatic group; R is H r same as Q; M is a cation; L is methine; n is 0, 1, or 2; and p is 1 or 2, thus permitting the obtained red- sensitized silver halide photographic sensitive material to be high in sensitivity, small in color stains caused by residual dyes and deterioration of performances during a storing period.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material spectrally sensitized in the red region, and more specifically to a silver halide photographic material that has little residual color and has excellent storage stability over time. This invention relates to silver oxide photographic materials.

[Background of the invention]

A so-called scanner is one of the exposure methods for photographic light-sensitive materials, in which an original image is scanned, and the silver halide photographic light-sensitive material is exposed to light based on the image signal to form a negative or positive image corresponding to the image on the original image. One type of image forming method is known, and a semiconductor laser, a He-Ne laser, an argon laser, or an LED is used as a recording light source in this method.

In silver halide photographic materials, photographic emulsion layers or other layers are often colored in nine colors for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on a photograph, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a single filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

It is based on the fact that the light that is scattered when passing through the photographic emulsion layer or after being transmitted is reflected at the interface between the emulsion layer and the support or the surface of the light-sensitive material on the opposite side of the emulsion layer and enters the photographic emulsion layer again. For the purpose of preventing image blurring or halation, a colored layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multilayer color photosensitive materials, each.

An anti-haleyon layer may be placed between the layers.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, oxonol dyes described in U.S. Pat. There are merocyanine dyes as typified by No. 1, cyanine dyes as typified by U.S. Pat. No. 2,843,486, and the like. However, if all the above conditions are satisfied,
The reality is that there are very few good dyes that can be used in silver halide photographic materials.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that is highly sensitive to red light and has little residual color after processing.

Still another object of the present invention is to provide a silver halide photographic material that forms good images and has excellent stability over time.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, in which the emulsion layer is sensitized by at least one type of sensitized material selected from the following general formula CI). This is achieved by a silver halide photographic material characterized by containing at least one hydrophilic colloid layer that is spectrally sensitized with a dye and contains at least one dye represented by the following general formula [■,]. Ru.

General formula CI) (x+9　　　) Praise.

[In the formula, Yll and Y each represent a nonmetallic atomic group necessary to form a benzothiazole ring, benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, or quinoline ring, and these heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.

R, , R, each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R1 represents a methyl group, an ethyl group, or a propyl group. X represents an anion.

nl and nl represent 1 or 2. m represents l or 0, and when it is an inner salt, m=o. ] General formula (n) [In the formula, Q represents an aliphatic group or an aromatic group, R represents a hydrogen atom, an aliphatic group, or an aromatic group, M represents a cation, and L represents a methine group. , n is 0. 1 or 2, and p is 1 or 2. ] The details of the present invention will be explained below.

General formula (1) will be explained.

In the above general formula CI), Y and Y2 are each a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring,
The naphthothiazole ring or t; represents a group of nonmetallic atoms necessary to form a quinoline ring, and these heterocycles include lower alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.). etc.), a hydroxyl group, an aryl group (eg, phenyl group), an alkoxycarbonyl group (eg, tomexycarbonyl group), a halogen atom (eg, chlorine atom, bromine atom, etc.), or the like. Rr and Rs are lower alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), alkyl groups having a sulfo group (e.g., β-sulfoethyl group, γ-
sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (e.g. sulfoethoxyethyl group, sulfopropoxyethyl group),
It represents an alkyl group having a carboxyl group (eg, β-carboxylethyl group, γ-carboxypropyl group, γ-carboxybutyl group, δ-carboxybutyl group, etc.).

R1 represents a methyl group, an ethyl group, or a propyl group. X,
represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.). m represents ■ or 0, and when it is an inner salt, m=0.

Next, the configuration of the present invention will be explained in more detail.

First, specific examples of the compound represented by the above general formula (1) used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula CI).

Summer-3 I-7 ■ -10 Clh C1h(nil1zJ
! 503- CI+3! -18 (C1li) asOseCalls I -22 (C1h)ssO3e C! 11% (Clb
) 5sOsθ ■ -26 03e (CI+ri IC0OII 1lx to C
)! UIJ”!-32 ells [:I13 The sensitizing dye of the present invention is preferably used in an amount of 1 m/mole of silver halide.
It is contained in the silver halide photographic emulsion in the range of g to 2 g, more preferably 5 mg=1 g.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. They can also be first dissolved in a suitable solvent, such as evaporative methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention can be easily synthesized with reference to US Pat.

General formula (II) where q represents an aliphatic group or an aromatic group, R represents a hydrogen atom, an aliphatic group or an aromatic group, M represents a cation, L represents a methine group, n is 0.1 or 2, and p is 1 or 2.

Below, each substituent Q1R1 in the above general formula (If)
Specific examples of M and L are shown below.

Specifically, the aliphatic group represented by Q includes an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n
-propyl group, n-butyl group, etc.), aromatic groups include aryl groups (e.g., phenyl group, naphthyl group, etc.)
These aliphatic groups and aromatic groups further include halogen atoms (e.g., fluorine atoms, chlorine atoms, etc.), alkyl groups (e.g., methyl groups, ethyl groups, etc.),
Hydroxy group, alkoxy group (e.g. methoxy group)
It may have a substituent other than a sulfo group such as.

The aliphatic group represented by R includes an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.)
, aromatic groups include aryl groups (e.g. phenyl group,
Naphthyl group, etc.), and these aliphatic groups and aromatic groups further include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g.
methyl group, ethyl group, etc.), aryl group (e.g., phenyl group, etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (e.g., methoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.). It's okay.

Specifically, the cation represented by M includes a hydrogen atom, an alkali metal (e.g., sodium, potassium, etc.), an alkaline earth metal (e.g., calsulam, etc.), ammonia, or an organic base (e.g., triethylamine, pyridine, piperidine, etc.). Examples include cations such as morpholine, etc.).

The methine group represented by L may be substituted with an alkyl group, an aryl group, or a halogen atom, and examples of the alkyl group include a methyl group, an ethyl group, etc.
Examples of the aryl group include phenyl group,
Examples of the halogen atom include a chlorine atom and a bromine atom.

Next, typical examples of the oxonol dye represented by the general formula (II) will be shown, but the oxonol dye according to the present invention is not limited thereto.

Exemplary dye l.

-8-1・' 5.

CH3L;H3 6.

11゜17゜L; tl, L; tl! b(J3jL Utl, U
tl,) LJ31L23゜24゜rishi tl3 lishi113
.

26. In the silver halide photographic material of the present invention, the dye represented by the general formula (I[) can be incorporated into the silver halide photographic emulsion and used as an irradiation-preventing dye. It can also be incorporated into a non-photosensitive hydrophilic colloid layer and used as a filter dye or antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion or other hydrophilic colloid layer by a conventional method. Generally, an aqueous solution of a dye or an organic or inorganic alkali salt of a dye is added to a coating solution for coating, thereby making it possible to incorporate the dye into the silver halide photographic light-sensitive material. The content of these dyes varies depending on the purpose of use, but generally the area on the photosensitive material is 1m! 1.0~
It is used by applying it to a total area of 1000m9.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used material can be used, but 50 mol% silver chloride
The particle size is preferably 0.2 μm or more, and 0.2 μm or more.
The thickness is preferably 5 μm or less.

In addition, the amount of gelatin on the emulsion layer side is 2.89/m” or less,
Preferably it is 2.59/m'' or less.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of 7 Autographic Science (J, Photogr., S.
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As for monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r accounts for 60% of the total weight of silver halide grains. It is preferably at least 70%, particularly preferably at least 70%, and even more preferably at least 80%.

Here, the average particle size 7 is the frequency of particles with particle size ``l''
Product old X of and r13 Particle size r when ri3 is maximum
Define i.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical /% silver halide grains, or the projection of the grain in the case of grains with shapes other than spherical. This is the diameter when the image is converted into a circular image with a circumferential area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikIIIan et al. or H. Frlese.
r edition de grundlagen der 7 otographisien prozesse mid zilpel halogennieden (Di
e Grundlagen der Photogra
phischen Prozesse wit Sil
Berhalogeniden, ^kade! n1cc
he Verlagsgesellschaft, 1
968) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

In addition, there are no particular restrictions on the conditions such as pH% pAg and temperature during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the pAg value is maintained at 5 to 11, especially 7 to 9. is preferable. Also, the temperature is 40 to 90°C, especially 45 to 90°C.
75°C is preferred.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a halogenated solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
' to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of capri during the manufacturing process, storage, or processing of the silver halide photographic light-sensitive material.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411.911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 1 tea
17643 (December 1978) and Volume 187 It
ea18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type RD 17643 RD 187
161, chemical sensitizer page 23 6
Page 48, right column 2, Sensitivity enhancer
Same as above 4. Brightener page 24 7. Anti-stain agent page 25 right column page 650 left ~
Right column 8, dye image stabilizer page 25 9, hardener page 26 page 651 left column 10
, binder page 26 Same as above 1
1. Plasticizer/Lubricant Page 27 650
Right column 12, coating aids/surfactants pages 26-27
Same as above 13, static inhibitor page 27
In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and baryta layers. Alternatively, it may be paper coated or laminated with a σ-olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally subjected to a subbing treatment to improve adhesion with emulsion layers and the like. Undercoat treatment is JP-A-52-1049
Preferably, the treatments described in Publications No. 13, No. 59/18949, No. 59-19940, and No. 59-1994 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the development, fixing, washing, and drying processes that take less than seconds.

The developing agent used in the black and white developer used in the present invention has dihydroxybenzene chains and l-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-
Examples include dichlorohydroquinone, 2,3-dichlorohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

The developing agent for l-722-3-pyrazolidone or its derivative used in the present invention is l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3- Examples include pyrazolidone and l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)cridine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.01 mol/12 to 1.2 mol/12
Preferably, it is used in an amount of .

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/Q or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably up to 2.5 mol/a.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 1O to 12.

The alkaline agents used for setting pl() include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethyl holemamide, methyl cellosolve, hexylene glycol, nitinol, methanol = 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, and antifoaming agents as necessary. , water softener, JP-A-56
It may also contain the amino compound described in No.-106244.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2゜193
．． No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 may also be used.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 60 g of gelatin was dissolved in water, and 2.0 g of each of the dyes shown in Table 1 was added thereto. Further, 40 raQ of a 1% aqueous solution of l-decyl-2-(3-inpentyl)succinate-2-sulfonic acid sodium salt as a spreading agent and 45 ml of a 4% aqueous solution of glyoxal as a hardening agent were added to give a total amount of 1 g. This gelatin-containing aqueous solution was applied to a polyethylene terephthalate film support with a gelatin content of 3.
A silver chlorobromide emulsion was prepared by the following method.

(Preparation of coating solution for emulsion layer) Solution A Water
980mI2 Sodium Chloride 2
．． 0 g gelatin 20 g 0.1% aqueous solution of hexachloroiridate potassium salt 2.8 ml a 0.001% aqueous solution of hexabromorodic acid potassium salt 2.5 yen a solution B Water
380mg sodium chloride
38g potassium bromide 42g
soluble aC water
380mg silver nitrate
To 170 g of the above solution kept at 40°C, while maintaining pI (3) and pAg (7.7), the above solutions B and C were simultaneously added functionally over a period of 80 minutes, and stirring was continued for an additional 5 minutes. After that, adjust the pH to 5.0 with an aqueous sodium carbonate solution.
6, after normal desalination and water washing process, 500tQ
of water and 30 g of gelatin are added and dispersed at 50° C. for 30 minutes.

As a result, an emulsion containing 62 mol % of silver chloride, 38 mol % of silver bromide, and 0.26 μl cubic grains with an average grain size of 0.26 μl was obtained. After gold sensitization and sulfur sensitization of this emulsion, /10 silver genide 1
4-hydroxy-6-methyl-1,3,3a per mole,
7-chitrazaindene 1.591-7 engineering=ru-5-
Add 0.2g of mercaptotetrazole and divide, Table 1
50 ml of a 0.1% methanol solution of the sensitizing dye shown in Figure 1 per mole of silver halide, 50 ml of a 10% methanol solution of hydroquinone as an antifoggant, 19 ml of a 20% saponin aqueous solution as a spreading agent, and styrene as a thickener. - 5% aqueous solution of maleic acid copolymer
Added 30g of high molecular weight polymer latex of 0ugly a1 ethyl acrylate, and added l-hydroxy-3,5 as a hardening agent.
-Dichlorotriazine sodium salt 1% aqueous solution 20II
Add Q and formalin 4% aqueous solution 10+12 and stir.
It was coated on the opposite side of the film from the gelatin coated side. Furthermore, an aqueous solution containing gelatin and 1-decyl-2-(3-inpentyl)succinate-2-sulfonic acid sodium salt was applied thereon as a protective layer.

The film thus produced was subjected to the following treatment.

Developer formulation Pure water (ion exchange water) Approximately 800L 14 Potassium sulfite 60g Ethylenediaminetetraacetic acid disodium salt Potassium dihydroxide
IO, 5g 5-methylbenzotriazole 300mg diethylene glycol
25g1-phenyl-4,4-dimethyl-3-pyrazolidinone 300mg1
-Phenyl-5-mercaptotetrazole 60Il1g Potassium bromide 3.5g Hydroquinone 20g Potassium carbonate
Add 15g of pure water (ion-exchanged water) to make a final volume of 1,000a12.

The p)I of the developer was approximately 1068.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid Acid (90% v/v aqueous solution) 13.5mc (composition) Pure water (ion exchange water) 17m 12 vinegar
Acid (50% v/v aqueous solution) 4.7 g aluminum sulfate (AQ, 20. aqueous solution with a converted content of 8.1% w/w) 2
6.5g When used, the above compositions were dissolved in 500mQ of water in the order of composition A1 and finished to 14 before use. The pH of this fixer is approximately 4.
．． It was 3.

The following '25 adventure\\ 2. ,;1 Comparative Dye Comparative Dye The above-mentioned treatments were carried out and the photographic properties were evaluated. However, the evaluation of stability over time was performed using the following method. That is, bisection t
-After controlling the humidity at 23°C and relative humidity of 48%, it was sealed in a moisture-proof material laminated with polyvinyl acetate (thickness: 100μ111) and heated in a constant temperature chamber at 55°C and relative humidity of 50% for 72 hours.
Heat treated for hours. After exposing the same-day and aged samples to a xenon flash for 10-' seconds through an optical wedge and a Koda 7 Klatten filter No. 88A, a Sakura Automatic Processor GR-14 (manufactured by Konica Corporation) was used as an automatic developer, and a developer was used. Development processing was performed using the developer and fixer described above, and evaluation was made. In addition, unexposed samples were also processed in the same manner for evaluation of residual color. The processing conditions are: development at 38°C for 20 seconds, and fixing at about 38°C.
8°C for 20 seconds, washing at room temperature for 20 seconds, drying at about 40°C
It was °C.

The results are shown in Table 1. However, the photographic sensitivity is expressed as a relative sensitivity when sample 1 is taken as 100. In addition, for samples processed without exposure, the residual color was visually evaluated and evaluated on a five-point scale, with "5" being colorless and rlJ being a strong blue residual color. Residual color below "3" is at a level that cannot withstand general use.

As shown in Table 1, it can be seen that the samples of the present invention have good sensitivity and residual color, and exhibit little deterioration in performance over time.

Example 2 Below, a silver chlorobromide emulsion (silver bromide 35 mol %, chloride I! 65 mol %, average grain 110.27 μm layer cubic grains) was obtained in the same manner as in Example 1.

Add 10 mL of 1% citric acid aqueous solution and 10 mff of 5% sodium chloride aqueous solution, pi(5,5,pAg'7
g = To the prepared emulsion, add 10 aff of 0.1% sodium thiosulfate aqueous solution and 7 r of 0.2% chloroauric acid aqueous solution.
Add aQ and mature at 57°C to reach maximum sensitivity.

The above emulsion was divided, and 0.1% methanol solutions of the sensitizing dyes of the present invention and comparison shown in Table 2 were added at 50 μm per mole of silver halide to each of the emulsions as an antifoggant. 0 of 5-mercaptotetrazole
．． 25 mL of 5% solution 4-hydroxy-6 as stabilizer
-Methyl 1.3,3a,? -1% solution of tetrazaindene 180■Q1 and 10% aqueous solution of gelatin 300■Q
was added to stop the ripening. Add 1 to these as a coating aid.
15 ffl12. As a thickener, 50 m<1 of a 4% aqueous solution of styrene-maleic acid copolymer and 30 g of butyl acrylate polymer latex were used.
20ml of 20% aqueous solution of hydroquinone as a stabilizer
2. Add and stir 20% of a 10% aqueous solution of potassium bromide, and add 50 mg of a 1:0.25 mol reaction product of tetrakis (vinylsulfonylmethyl)methane and taurine potassium salt per 1 g of gelatin as a hardening agent. The emulsified dispersion shown in Table 2 was added in an amount of optical brightener of 15 mg/m'', and the pH was adjusted to 5.6 with citric acid to prepare a coating solution for an emulsion layer.

(Preparation of coating solution for antihalation layer) 40 g of gelatin
The amount of the dye listed in Table 2 applied to the aqueous solution of 200+ag/m
Furthermore, the following emulsified dispersion was added as a fluorescent brightener amount to 15 mg/+11'', and 4% of methylene-maleic acid copolymer was added as a thickener.
A coating solution for an antihalation layer was prepared by adding 15ml of an aqueous solution.

(@Preparation of coating solution for membrane layer) In an aqueous gelatin solution, 30 mg/+o'' of 2-zulphosuccinic acid bis (2-ethylhexyl) ester sodium salt was added as a coating aid, and polymethyl methacrylate with an average particle size of 4 μl was added as a matting agent. 40mg/m'', 30mg/m2 of the following compound (S) as a fluorine-containing surfactant,
A protective layer coating solution was prepared by adding 10 mg of formalin per Ig of gelatin as a hardening agent.

Fluorine-containing surfactant (S) CH*C00C1(*(CFz)aH ■ Na03S C1(COOCHt(CFz)sH (Sample Preparation and Evaluation) Coating liquid and emulsion for Halesin prevention layer thus prepared The layer coating solution and the protective layer coating solution have a hydrophilic colloid backing layer and an undercoat layer, and contain 15% titanium dioxide.
Three layers were simultaneously coated on a polyethylene coated paper having a thickness of 110 μm and containing 5% by weight. The coated silver amount of the obtained sample was 1.
The coating amount of gelatin was 1.4 g/ta'' for the antihalation layer, 1.4 g/12 for the emulsion layer, and 0.9 g/+a' for the protective layer.

Each of the obtained samples was divided into two parts, one half was left as is, and the other half was placed in a polyethylene bag and then wrapped in a paper bag to check its stability over time.
Heat treatment was performed in a 0% constant temperature oven for 72 hours.

The residual color was evaluated in the same manner as in Example 1.

The results obtained are shown in Table 2. Note that the sensitivity is the reciprocal of the exposure amount required to give a density of 1.0, and is a relative value with sample 1 set as 100.

As is clear from the results in Table 2, the samples belonging to the present invention had good sensitivity and residual color, and showed little deterioration in performance over time.

(Preparation of emulsified dispersion of oil-soluble optical brightener) Dissolve 5.0 g of the following oil-soluble optical brightener (F) in a mixed solution of 100 m12 of talesyl phenyl phosphate and 100 mQ ethyl acetate, and add the entire amount of this solution to tripropylnaphthalene. 12% gelatin aqueous solution containing 3g of sulfonic acid sodium salt 1500
After mixing with o+0 and emulsifying and dispersing it by ultrasonic dispersion, the butyl acrylate polymer latex is mixed with lO as a solid content.
In addition, an emulsified dispersion of an oil-soluble optical brightener was prepared.

Fluorescent brightener (F) [Effects of the invention] As explained in detail in the above examples, according to the present invention,
It was possible to provide a red-sensitized silver halide photographic material with high sensitivity, little residual color, and extremely little deterioration in performance during storage.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer contains at least one additive selected from the following general formula [I]. 1. A silver halide photographic material comprising at least one hydrophilic colloid layer that is spectrally sensitized with a sensitive dye and contains at least one dye represented by the following general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R_1 and R_2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X_1 represents an anion. n_1 and n_2 represent 1 or 2. m represents 1 or 0, and when it is an inner salt, m=0. ] General formula [I
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Q represents an aliphatic group or an aromatic group, R represents a hydrogen atom, an aliphatic group, or an aromatic group, M represents a cation, L represents a methine group, n is 0, 1 or 2,
p is 1 or 2. ]