JP2821502B2 - Silver halide photographic material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material which can be rapidly processed, has high sensitivity, and has a high photographic performance with a change in temperature and humidity during exposure. The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a clear image with little change and no residual color contamination.

[Background of the Invention]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials are widely used today because of their high sensitivity, excellent gradation and excellent color reproducibility.

Improvements in equipment such as printers and automatic developing machines have made it possible to continuously develop and print a large amount of photographic light-sensitive materials, and have significantly increased the productivity in the laboratory. On the other hand,
The downsizing of the equipment and the extremely simple handling make it possible to print at department stores, photo shops and other stores. The number of such so-called minilabs has been further increased due to the development of silver halide photographic light-sensitive materials and development processing solutions capable of further reducing the development processing time.

One of the problems with minilabs is that the processing conditions are more variable than large equipment because of the small amount of processing solution used and the large fluctuations in the amount of photographic material processed. It is. Also, since it is installed in a small space at the storefront, it is easily affected by outside air and cooling and heating, and the temperature and humidity fluctuate greatly during the day. This caused a phenomenon that the print yield was reduced.

When a high chloride silver halide emulsion is used, development processing can be performed in a short time, and a photosensitive material suitable for minilab use can be obtained. There was a disadvantage that the fluctuation was large.

On the other hand, various compounds such as anti-irradiation dyes and anti-halation dyes are used in photosensitive materials for the purpose of obtaining clear images. These compounds have been sought to satisfy performances such as spectral absorption characteristics, decolorization during development, and dissolution. For example, JP-A-63-264745,
No. 63-244034, No. 63-34533, No. 62-273527, etc.
Disclosed are compounds having excellent properties and capable of reducing fluctuations in photographic performance with respect to fluctuations in humidity. However, it is still not enough in terms of the improvement in photographic performance fluctuations due to the above-mentioned humidity change during exposure, and even compounds which increase performance fluctuations in terms of photographic performance fluctuations due to temperature fluctuations during exposure. It is a certain situation.

Japanese Patent Application Laid-Open No. Sho 63-163 discloses a technique for reducing photographic performance fluctuation due to temperature fluctuation during exposure of a high chloride silver halide emulsion.
No. 188129 discloses a method of adding a water-soluble bromide in a coating solution preparation step. However, this method is still insufficient to improve performance fluctuations due to temperature fluctuations. In particular, although fluctuations in sensitivity are reduced, improvements in gradation fluctuations are insufficient.

[Object of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of suppressing fluctuations in photographic performance due to fluctuations in temperature and humidity during exposure and efficiently obtaining an image having excellent color reproducibility in a short time. Is to do.

[Configuration of the invention]

An object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion in the silver halide emulsion layer is at least 80 mol% or more. Which is spectrally sensitized with a sensitizing dye represented by the general formula [I] and a sensitizing dye represented by the general formula [II], and wherein at least one layer in the silver halide photographic material has the general formula This is achieved by a silver halide photographic light-sensitive material emulsion layer containing the dye represented by [III].

 Where R₁₁, R₁₂, R₁₃And R₁₄Is a hydrogen atom, a halo
Gen atom, alkyl group, alkoxy group, aryl group or
Represents a hydroxyl group, R_FifteenAnd R₁₆Represents an alkyl group
Represent. X₁₁ Represents an anion and l₁₁Represents 0 or 1.

 Where Y₁And Y_TwoRepresents a sulfur atom or a selenium atom, respectively.
At least one is a selenium atom. R_{twenty one}, R_{twenty two}, R
_{twenty three}And R_{twenty four}Represents a hydrogen atom, a halogen atom, an alkyl
Group, alkoxy group, aryl group or hydroxyl group
Then R_{twenty five}And R₂₆Each represents an alkyl group. X_{twenty one} Is shade
ON, l_{twenty one}Represents 0 or 1.

Wherein R ₃₁ and R ₃₂ are each -CN, -CFR ₃₅ R ₃₆ , -CO
R ₃₇ represents —COOR ₃₇ or —CONHR ₃₅ ; R ₃₅ and R ₃₆ each represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, and R ₃₇ represents an alkyl group or an aryl group. R
₃₃ and R ₃₄ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group, alicyclic group, aromatic group or heterocyclic group. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group.

 Hereinafter, the present invention will be described in more detail.

The silver halide grains of the present invention preferably have a silver chloride content of 80 mol% or more, a silver bromide content of 20 mol% or less, and a silver iodide content of 0.5% or less. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.6 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
The range is 1.2 μm. In addition, the said particle diameter can be measured by various methods generally used in the said technical field. Typical methods include Loveland's "Particle Size Analysis" (ASTM Symposium on Right Microscopy, 1955, pp. 94-122) or "Theory of Photographic Processing" (Mies and James, 3rd ed. Edition, Chapter 2 of Macmillan Publishing Company (1966)).

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

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

Here, ri represents the particle size of each particle, and ni represents its number. The particle size referred to here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle when the projected image is converted into a circular image of the peripheral area. Represent.

The silver halide grains used in the emulsion of the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Furthermore, Japanese Patent Application Laid-Open
PAg-Controlled- described in 54-48521 and the like
The double jet method can also be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation. The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and 4,225,666;
No. 55-26589, Japanese Patent Publication No. 55-42737, The Journal
Photographic Science (J.Photgr.Sc
i.), 21 , 39 (1973), etc., particles having shapes such as octahedral, tetrahedral, and dodecahedral can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains used in the emulsion of the present invention may be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt during the process of forming and / or growing the grains. Alternatively, a metal ion can be added using a complex salt to be contained inside the grains and / or on the grain surface, and by placing the grains in a suitable reducing atmosphere, reduction sensitization nuclei can be formed inside the grains and / or on the grain surface. Can be granted.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the emulsion may be kept contained. . The removal of the salts can be performed based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion of the present invention may be grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain. Preferably, the latent image is a particle mainly formed on the surface.

The emulsion of the present invention is chemically sensitized by a conventional method. That is,
Sulfur sensitization using compounds containing sulfur that can react with silver ions, active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, noble metal sensitization using gold or other noble metal compounds Etc. can be used alone or in combination.

In the sensitizing dye of the general formula [I] used in the present invention, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or a hydroxyl group. Specifically, examples of the halogen atom include a chlorine atom, and examples of the alkyl group include a methyl group and an ethyl group having 1 to 6 carbon atoms. Examples of the alkoxy group include, for example, a methoxy group and an ethoxy group having 1 to 6 carbon atoms. Preferably at least one is a chlorine atom, especially R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄
Of these, those containing two chlorine atoms are preferred.

R ₁₅ and R ₁₆ each represent an alkyl group, and this alkyl group includes those having a substituent. Preferably R ₁₅ , R ₁₆
Is an unsubstituted alkyl group, or an alkyl group substituted with a carboxyl group or a sulfo group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably the number of carbon atoms. 1 to
4 is a sulfoalkyl group or a carboxyalkyl group. R ₁₅ and R ₁₆ may be the same or different, but preferably one of them is an alkyl group having 1 to 4 carbon atoms substituted by a carboxyl group.

 X₁₁ Represents an anion. For example, but not limited to,
Halide ion (Br , I Etc.)
You.

When l ₁₁ is 0, an anion may not be contained, and R ₁₅ or R ₁₆ forms an inner salt.

The sensitizing dyes represented by the general formula (I) are individually known compounds, for example, British Patent No. 660,408, U.S. Pat.
No. 49,105 or JP-A-50-4127 or "The Cyanine Soybeans and Related Compounds" by Hemer (Interscience Publishers,
New York, 1969) (FMHamer, “The Cyanine Dye
s and Related Compounds "Interscience Publishers, Ne
w York 1969), pages 32 to 76, and can be easily synthesized.

Specific examples of the sensitizing dye represented by the general formula [I] used in the present invention are shown in the following table, but the compounds that can be used in the present invention are not limited thereto.

In the sensitizing dye of the general formula [II] used in the present invention, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or a hydroxyl group. Specifically, examples of the halogen atom include a chlorine atom, a bromine atom and a fluorine atom, and a chlorine atom is particularly preferable. As the alkyl group, one having 1 to 4 carbon atoms
Are preferable, and examples thereof include a methyl, ethyl, propyl, i-propyl, and butyl group, and a methyl group is particularly preferable. As the alkoxy group, a methoxy, ethoxy, propoxy group or the like having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable. As the aryl group, a substituted or unsubstituted phenyl group (eg, phenyl, p-tolyl group, etc.) is preferred, and a phenyl group is particularly preferred.

R ₂₅ and R ₂₆ each represent an alkyl group, and this alkyl group includes those having a substituent. Preferred substituents include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an alkylsulfonyl group, and the like. Specifically, a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, i-propyl, sec-butyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, There are substituted alkyl groups such as sulfobutyl, carboxymethyl, 2-carboxyethyl, 2-ethoxycarbonylethyl, 2-hydroxyethyl, and 2-methanesulfonamidoethyl, and sulfo or carboxy-substituted alkyl groups are preferred. The sulfo group and the carboxyl group may form an alkali metal salt (eg, sodium, potassium) or an ammonium salt (eg, pyridinium, triethylammonium).

 X_{twenty one} As the anion represented by
ON (Cl , Br , I ), P-toluenesulfonic acid
And the like, but halide ions are preferred.
l_{twenty one}Is 0, an anion may not be contained, and R_{twenty five}Or
R₂₆Forms an inner salt.

Specific examples of the sensitizing dye represented by the general formula [II] are shown in the following table, but the compounds that can be used in the present invention are not limited thereto.

The above compounds are generally known, and can be easily synthesized by the method described in the above-mentioned "The Dianin Soybean and Related Compounds".

The blue-sensitive sensitizing dyes (I) and (II) according to the present invention have a ratio of 30: 7
It is preferably used in a molar ratio of 0 to 98: 2, more preferably 40:60 to 97: 3.

The amount used is preferably 5 × 10 ^-5 to 2 × 10 ^-3 mol, more preferably 1 × 10 ^{-4 to} 7 × 10 ^-4 mol, per mol of silver halide in combination of [I] and [II]. Used in the range.

These sensitizing dyes may be added at any time from the formation of silver halide grains to coating, but it is particularly preferable to add the sensitizing dyes from the end of formation of silver halide grains to coating.

These sensitizing dyes may be dispersed in a water-miscible organic solvent without dissolution, and the dispersion may be added to a silver halide emulsion, or may be mixed with water or a water-miscible solution such as methanol, ethanol, acetone, and dimethylformamide. May be added to the silver halide emulsion by dissolving in a neutral organic solvent alone or in a mixture.

Next, the dye represented by formula (III) will be described.

When R ₃₁ and R ₃₂ represent -CFR ₃₅ R ₃₆ , each of R ₃₅ and R ₃₆ represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, and specifically, monofluoromethyl, difluoromethyl , Trifluoromethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2,3,3,4,4-octafluorobutyl and the like.

Alkylcarbonyl group R ₃₁ and R ₃₂ is represented by -COR _37, the aryl group, specifically acetyl, propionyl, benzoyl, and the respective group such as 4-methoxybenzoyl.

Specific examples of the alkoxycarbonyl group and the aryloxycarbonyl group in which R ₃₁ and R ₃₂ are represented by —COOR ₃₇ include ethoxycarbonyl, benzyloxycarbonyl, 4-sulfophenoxycarbonyl and the like.

Examples of the carbamoyl group in which R ₃₁ and R ₃₂ are represented by —CONHC ₃₅ include groups such as carbamoyl, 2-hydroxyethylcarbamoyl, and trifluoromethylcarbamoyl.

R ₃₃ and R ₃₄ each represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group, among which, as the aliphatic group, an alkyl group or an alkenyl group is an alicyclic group; Examples of the formula group include a cycloalkyl group. The aromatic group typically includes an aryl group such as a phenyl group and a naphthyl group. Further, as a heterocyclic group, for example,
A benzothiazolyl group or a benzooxazolyl group can be mentioned as a typical example.

The aliphatic group, alicyclic group, aromatic group and heterocyclic group represented by R ₃₃ and R ₃₄ include those further having a substituent.

L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represented methine group,
Also included are those substituted with an alkyl group or aryl group having 1 to 4 carbon atoms.

Representative specific examples of the dye of the present invention represented by the general formula [III] are shown in the table, but the present invention is not limited to these.

The compound represented by the general formula (III) may be added to any layer in the silver halide color photographic light-sensitive material according to the present invention, but has sensitivity to the same light as the light absorbed by the dye. It is preferably added to the layer or a layer located between the layer and the support.

The preferable addition amount is 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol / m ² , more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ mol / m ² .

In the present invention, a pivaloylacetanilide yellow coupler is preferably used.

The layer to which the yellow coupler is added may be any silver halide emulsion layer, but is preferably a blue-sensitive silver halide emulsion layer.
× 10 ^{-3 to} 5 × 10 ^-1 mol is preferable, and 1 × is more preferable.
It is 10 ^{-2 to} 5 × 10 ^-1 mol.

The following are typical examples of the yellow coupler that are preferably used, but the present invention is not limited thereto.

As the magenta coupler used in the present invention, pyrazoloazoles and 3-anilinopyrazolones are preferable.

The addition amount is not fixed depending on the compound, but is usually 1 × 10 ⁻³ to 2 mol, preferably 1 × 10 ⁻³ mol per mol of silver halide.
It is used in the range of ^-2 to 1 mol.

Hereinafter, typical examples of preferable magenta couplers will be shown, but the present invention is not limited thereto.

In the present invention, a 2-acylaminophenol-based and / or 2,5-diacylaminophenol-based cyan coupler is preferably used.

The addition amount is not fixed depending on the compound, but is usually 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻³ mol per mol of silver halide.
^-2 to 8 × 10 ^-2 mol.

In order to add each coupler preferably used in the present invention to a silver halide emulsion, an oil-in-water emulsion dispersion method in which the coupler is dissolved in a high boiling point organic solvent and dispersed therein can be applied.
The high-boiling organic solvent having a boiling point of about 150 ° C. or higher is dissolved in combination with a low-boiling point and / or a water-soluble organic solvent if necessary,
Using a surfactant in a hydrophilic binder such as an aqueous gelatin solution with a stirrer, a homogenizer, a colloid mill, a flow mixer, and a dispersing means such as an ultrasonic device,
After emulsification and dispersion, it may be added to the target hydrophilic colloid layer.

After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added.

Examples of high boiling organic solvents used for such purposes include dibutyl phthalate and di- (2-ethylhexyl).
Phthalates such as phthalate, dinonyl phthalate, dicyclohexyl phthalate, tricresyl phosphate, tri- (2-ethylhexyl) phosphate,
Phosphates such as di-phenyl-cresyl phosphate and trihexyl phosphate, diethyl lauramide,
Organic acid amides such as dibutyl lauramide, phenols such as dinonylphenol and p-dodecylphenol, hydrocarbons such as decalin and dodecylbenzene, 1,4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane, dinonyl adipate And the like. Among them, phthalic acid, phosphoric acid, and other organic acid esters are more preferably used. These high-boiling organic solvents may be used alone or in combination of two or more.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative negative and a positive film, and a color photographic paper. The effect is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention including the color photographic paper is usually a silver halide emulsion containing magenta, yellow, and cyan couplers as photographic couplers in order to perform color-reduced color reproduction. The layer and the non-photosensitive layer have a structure in which the number of layers and the order of layers are laminated on the support in an appropriate number, and the number of layers and the order of layers may be appropriately changed depending on the emphasis performance and the purpose of use.

The specific layer constitution of the silver halide photographic light-sensitive material of the present invention includes a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, an intermediate layer, and a cyan dye image forming layer on a support in order from the support side. , An intermediate layer and a protective layer are particularly preferred.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter, referred to as the silver halide emulsion of the present invention) includes silver bromide, silver iodobromide, silver iodochloride, and chloroodor. Any of those used for ordinary silver halide emulsions such as silver chloride and silver chloride can be used, preferably silver chlorobromide, and more preferably silver bromide content.
Silver chlorobromide of 20 mol% or less is preferable in terms of enabling rapid processing, and the effect of the present invention is also greatly useful.

Further, a dye known as a sensitizing dye in the photographic industry can be used to optically sensitize a desired wavelength region of green light and red light. Further, the silver halide emulsion of the present invention may contain a known antifoggant or stabilizer for the purpose of preventing fog and / or stabilizing photographic performance.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, gelatin is advantageously used. In addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives A hydrophilic colloid such as a single or copolymerized hydrophilic polymer material such as a copolymer can also be used.

The silver halide photographic light-sensitive material of the present invention, in addition to the above additives, if necessary, a hardener, a plasticizer, a polymer latex, a color antifoggant, an ultraviolet absorber, a mordant, a development accelerator, a development retarder, An optical brightener, a matting agent, a lubricant, an antistatic agent, a surfactant and the like can be appropriately contained.

The silver halide photographic light-sensitive material of the present invention comprises a silver halide emulsion layer and another hydrophilic colloid layer provided by a conventional method on a support generally used in the photographic industry.

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

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material of the present invention include aminophenol-based and p-phenylenediamine-based derivatives widely used in various color photographic processes. .

In addition to the above-mentioned primary aromatic amine-based color developing agent, a known developer component compound can be added to the color developing solution applied to the development processing of the silver halide photographic light-sensitive material of the present invention. .

Further, the silver halide photographic light-sensitive material of the present invention is preferably processed with a color developing solution containing no benzyl alcohol.

The silver halide photographic light-sensitive material of the present invention, after color development,
Bleaching and fixing are performed. The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 Each layer having the composition shown in Table 1 was coated on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer on the other side. A silver color photographic material was prepared. The coating solution was prepared as described below.

First layer coating solution Yellow coupler (YC-4) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.7
g, 0.67 g of an antistain agent (HQ-1) and 6.7 g of a high boiling point organic solvent (DNP) were dissolved by adding 60 ml of ethyl acetate, and this solution was dissolved in 200 ml of a 10% aqueous solution of gelatin containing 10 ml of 10% sodium alkylnaphthalenesulfonate. The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the conditions described below to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. In the second, fourth and seventh layers, the following H-1 and H-2 were used as hardeners, and the following S-1 and S-2 were used as coating aids.
-2 was used.

[Preparation of Blue-Sensitive Silver Halide Emulsion] The following (Solution A) and (Solution B) were simultaneously added to 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C. over 30 minutes while controlling pAg = 6.5 and pH = 3.0. And (D) and (D)
Liquid) was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water and 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm. Thus, a monodisperse cubic emulsion Em-1 having a coefficient of variation (S /) of 0.07 and a silver chloride content of 99.5 mol% was obtained.

Using the following compound for the above emulsion Em-1, at 50 ° C
After a chemical ripening for 80 minutes, a blue-sensitive silver halide emulsion (Em-1
B) got.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer SB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye (I-3) 4.7 × 10 ^-4 mol / mol AgX sensitizing dye (II-4) 0.3 × 10 ^-4 mol / mole AgX [Preparation Method of Green-Sensitive Silver Halide Emulsion] Addition time of (Solution A) and (Solution B) and (Solution C) and (D
Liquid), except that the addition time was changed.
A monodisperse cubic emulsion Em-2 having an average particle size of 0.43 μm, a coefficient of variation (S /) = 0.08, and a silver chloride content of 99.5 mol% was obtained.

Em-2 was chemically ripened at 55 ° C. for 110 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-2G).

Sodium thiosulfate 1.2 mg / mol AgX chloroauric acid 1.5 mg / mol AgX stabilizer SB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4.0 × 10 ^-4 mol / mol AgX [red-sensitive halogenation Preparation method of silver emulsion] (solution A) and (solution B) addition time and (solution C) and (D
Liquid), except that the addition time was changed.
A monodispersed cubic emulsion Em-3 having an average particle size of 0.50 μm, a coefficient of variation (S /) = 0.08, and a silver chloride content of 99.5 mol% was obtained.

Em-3 was chemically ripened at 60 ° C. for 90 minutes using the following compound to obtain a red-sensitive silver halide emulsion (Em-3R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer SB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 8.0 × 10 ^-5 mol / mol AgX [silver bromide content Method of preparing silver halide emulsion with high content] (solution C) was changed to the following (solution C), and the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) Em-4 (average particle diameter 0.84 μm) was carried out in the same manner as Em-1 except that the addition time was changed and the pAg at the time of addition of (C ′ solution) and (D solution) was changed to 7.8.
m, coefficient of variation (S /) = 0.09, monodisperse cubic emulsion having a silver chloride content of 75 mol%).

Next, Em-4 was chemically ripened in the same manner as Em-1 except for changing the ripening time to obtain a blue-sensitive emulsion Em-4B.

(C 'solution) 76.2 g of sodium chloride 54.1 g of potassium bromide 600 ml by adding water [Preparation of blue-sensitive emulsion using sensitizing dye alone] For Em-1 and Em-4, sensitizing dye (I -3) 5 × 10 ^-4
Mol-mol AgX, (II-4) Blue-sensitive emulsion Em-1 in the same manner as Em-1B except that 5 × 10 ^-4 mol / mol AgX was used.
B ', Em-1B ", Em-4B', Em-4B" were prepared.

Emulsifier Blue-sensitive sensitizing dye Em-1B 'Em-1 (I-3) 5 × 10 ^-4 mol / mol AgX Em-1B ″ Em-1 (II-4) 5 × 10 ^-4 mol / mol AgX Em-4B 'Em-4 (I-3) 5 × 10 ^-4 mol / mol AgX Em-4B ″ Em-4 (II-4) 5 × 10 ^-4 mol / mol AgX Samples shown in Table 2 were prepared from various combinations of silver halide emulsions, blue-sensitive sensitizing dyes and dyes.

This sample was exposed according to a conventional method, and then processed according to the following processing steps.

However, the temperature at the time of exposure was changed to 20, 55, 80% RH (25 ° C.). (Leave the sample in the atmosphere for 1 hour and then expose) [Processing process] Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60 ~ 80 ° C 60 seconds [Color developing solution] Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonate disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-
3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to adjust the total amount to 1, and the pH is adjusted to 10.10.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total amount 1 and add potassium carbonate or ice Adjust to pH = 5.7 with acetic acid.

[Stabilizing solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethynylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% Aqueous solution) 3.0 g Ammonium sulfite 3.0 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Add water to make the total amount 1 and adjust to pH = 5.0 with sulfuric acid or potassium hydroxide.

The dye image obtained by the above-mentioned development processing was converted to Konica Corporation.
The B concentration was measured with a PDA-65 densitometer manufactured, and the sensitivity and fog were determined. For each sample, the sensitivity at 25 ° C. and 55% RH was defined as 100, and the sensitivity at 20% and 80% RH was expressed as a relative value. Table 2 shows the results.

Combination of silver halide emulsion and dye according to the present invention (No. 1
09) shows that the desensitization that occurs under high humidity conditions is significantly reduced.

Further, it can be seen that the effects of the dyes are much larger than those predicted from the comparison between Nos. 107 and 110 and Nos. 108 and 111. Also, N
The effects of the dyes predicted from the comparison between o.110,111 and No.112 are significantly higher.

In addition, comparison with Sample No. 106 using an emulsion having a low silver chloride content shows that this improvement effect is an effect peculiar to an emulsion having a high silver chloride content.

A silver chlorobromide emulsion containing 82 mol% of silver chloride was em-
The effect of the present invention was also confirmed for a color paper prepared according to the preparation method described above and using it instead of Em-1.

Example 2 Using Sample Nos. 101 to 112 produced in Example 1, exposure was performed by changing the temperature at the time of exposure to 10 ° C., 25 ° C., and 35 ° C. (55% RH), and development processing was performed. (The sample was allowed to stand in the atmosphere for 1 hour at the time of exposure and then exposed.) The obtained dye image was measured for B density using a PDA-65 densitometer manufactured by Konica Corporation to determine the sensitivity.

The results are shown in Table-3. The sensitivity at 25 ° C and 55% RH is 100
The sensitivity at 10 ° C. and 35 ° C. was shown as a relative value.

Combination of silver halide emulsion and dye according to the present invention (No. 1
09) shows that sensitization occurring under high temperature conditions is significantly reduced.

Comparing Samples Nos. 107 to 109 and Nos. 110 to 112, Dye (III-9) has an effect of increasing sensitization, but this is sufficiently improved in the sample according to the present invention. .

The effect of the sensitizing dye predicted from the comparison between Samples Nos. 110 and 111 and No. 112 is remarkably large.

It can be seen that this effect is slightly reduced in the emulsion having a low silver chloride content.

A silver chlorobromide emulsion containing 82 mol% of silver chloride was em-
The effect of the present invention was also confirmed for a color paper prepared according to the preparation method described above and using it instead of Em-1.

Example 3 A blue-sensitive emulsion was prepared in the same manner as in Example 1 except that the blue-sensitive sensitizing dye was changed using Em-1, and a color paper was prepared using the emulsion. This was evaluated in the same manner as in Examples 1 and 2. However, all dyes used were III-9.

 The results are shown in Table-4.

As is evident from Table-4, the combination of the sensitizing dyes according to the present invention provides stable performance with a small change in sensitivity regardless of the temperature and humidity conditions at the time of exposure.

Regarding the structure of the sensitizing dye, the exemplified compound (I-
A compound in which a halogen atom is substituted on the benzothiazole nucleus as in 3) is more advantageous in the effect of the present invention than a compound in which a methoxy group or the like is substituted as exemplified compound (I-6). Can be used. Further, a compound in which two basic nuclei are a benzoselenazole nucleus, such as exemplified compound (II-4), has a benzoselenazole nucleus and a benzothiazole nucleus, as exemplified compound (II-1). Compared with compounds, the effects of the present invention are great and advantageous.

Further, as can be seen from Sample Nos. 216 to 220, the ratio of the compound of the general formula [I] to the compound of the general formula [II] was 30:70.
The effect of the present invention can be obtained over a wide range of up to 98: 2. Further
More effects can be obtained in the range of 40:60 to 97: 3.

The sensitizing dyes are represented by (I-1), (I-5), (I-12),
(II-7), (II-10), and (II-14) were combined and evaluated in the same manner.
The effect of the present invention that the sensitivity variation with respect to the humidity variation is small was obtained.

Example 4 Sample of Example 1 except that the dye was changed to various compounds
A color paper was prepared in the same manner as in No. 109, and
The same evaluation as in 2 was performed.

 The results are shown in Table-5.

As is evident from the table, the use of the dye of the present invention shows stable performance in combination with the silver halide emulsion of the present invention without being affected by temperature and humidity during exposure.

In addition, it can be seen that the compounds having a carbonyl group at the portion bonded to the mother nucleus as R ₃₁ and R ₃₂ in the general formula [III] have high performance stability.

Further, the blue-sensitive emulsion was changed to that used in Example 3,
Dyes (III-5), (III-7), (III-9), (III-
17) and (III-25), color paper was prepared and evaluated, and the effect of the present invention was confirmed.

Example 5 Samples Nos. 401 and 402 were prepared in the same manner as in the preparation of the blue-sensitive emulsion coating solutions of Samples Nos. 107 and 109 of Example 1 except that potassium bromide was added in an amount of 0.6 g per mol of silver halide. The same evaluation as in Example 2 was performed.

As a characteristic value, a gradation was obtained as a gradient of a characteristic curve between 0.5 and 1.5 in addition to the sensitivity.

 Table 6 shows the results.

The method of adding potassium bromide as described above,
It can be seen that there is an effect of improving the change in sensitivity due to temperature fluctuation during exposure, but it is insufficient, and there is almost no effect of improving gradation change.

However, in the process of preparing the silver halide photographic light-sensitive material according to the present invention, the addition of potassium bromide can slightly improve the effect.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-196033 (JP, A) JP-A-54-69429 (JP, A) JP-A-58-28738 (JP, A) 196039 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 1/16 G03C 1/035 G03C 1/83

Claims (1)

(57) [Claims] 1. A silver halide having at least one layer on a support
A silver halide photographic material having an emulsion layer;
When the silver halide emulsion in the silver halide emulsion layer is at least
80% by mole or more of silver chloride, represented by the general formula [I]
Sensitizing dye and a sensitizing dye represented by the general formula [II].
In the silver halide photographic light-sensitive material.
At least one layer contains a dye represented by the general formula [III]
A silver halide photographic material.(Where R₁₁, R₁₂, R₁₃And R₁₄Is a hydrogen atom, a halo
Gen atom, alkyl group, alkoxy group, aryl group or
Represents a hydroxyl group, R_FifteenAnd R₁₆Represents an alkyl group
Represent. X₁₁ Represents an anion and l₁₁Represents 0 or 1
You. ](Where Y₁And Y_TwoRepresents a sulfur atom or a selenium atom, respectively.
At least one is a selenium atom. R_{twenty one}, R_{twenty two}, R
_{twenty three}And R_{twenty four}Represents a hydrogen atom, a halogen atom, an alkyl
Group, alkoxy group, aryl group or hydroxyl group
Then R_{twenty five}And R₂₆Each represents an alkyl group. X_{twenty one} Is shade
ON, l_{twenty one}Represents 0 or 1. ](Where R₃₁And R₃₂Are -CN and -CFR respectively₃₅R₃₆, -CO
R₃₇, -COOR₃₇Or -CONHR₃₅And R₃₅And R₃₆Is each
Hydrogen, fluorine, substituted or unsubstituted alkyl
R₃₇Represents an alkyl group or an aryl group. R
₃₃And R₃₄Is a hydrogen atom, a substituted or unsubstituted
Represents an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group. L₁,
L_Two, L_Three, L_FourAnd L_FiveRepresents a methine group. ]