JPH0789201B2 - Silver halide emulsion, method for producing the same, and silver halide light-sensitive material using the silver halide emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide emulsion, a method for producing the same, and a silver halide light-sensitive material using this emulsion. In particular, the present invention relates to a silver halide emulsion mainly composed of twinned grains, which is improved in high sensitivity, low illuminance reciprocity law failure characteristics and fog characteristics over time, a method for producing the same, and a silver halide light-sensitive material using the silver halide.

[Conventional technology]

In recent years, color negative films have become more sensitive and have a smaller format, and the demand for higher image quality of silver halide photographic materials has become more and more severe. In response to these demands, many studies have been conducted centering on the improvement of silver halide emulsions. In particular, studies have been conducted using monodisperse emulsions with respect to control techniques such as size / size distribution of silver halide grains, halogen composition structure inside grains, and crystal shape.

Further, attempts have been made to control the growth of silver halide emulsions composed of monodisperse twin grains, which are said to be particularly difficult to control. Regarding such technology, Japanese Patent Publication No. Sho 58-36762 and Japanese Patent Laid-Open No. 52-153
No. 428, No. 54-118823, etc.

The silver halide emulsions obtained by these techniques have high sensitivity and excellent graininess, but on the other hand, they have a problem that they have low sensitivity in long exposure with low illuminance and have a remarkable fog change due to heat. It was rare.

Further, in JP-A-60-147727, the content of the average iodine content of two layers having any adjacent homogeneous iodine distribution of silver halide grains having a multilayer structure and an aspect ratio of 5 or less is described. When the difference is 10 mol% or more, the average iodide content of the outermost layer is 40 mol% or less, and the above silver halide grains are chemically sensitized, the pressure such as stress fog can be reduced. A silver halide photographic light-sensitive material having improved properties is disclosed. However, this photosensitive material also has problems in sensitivity, low-illuminance reciprocity law failure characteristics, and fogging change due to heat.

[Object of the Invention]

It is a first object of the present invention to provide a silver halide emulsion mainly composed of twin crystals, which has improved low illuminance reciprocity law failure characteristics, a method for producing the same, and a silver halide light-sensitive material using silver halide. .

It is a second object of the present invention to provide a silver halide emulsion mainly composed of twins, which has a less fogging change with time, a method for producing the same and a silver halide light-sensitive material using silver halide.

[Structure and Action of Invention]

The above-mentioned object is to grow multi-twin grains and / or spherical particles obtained from multi-twin as seed grains, and
Silver halide grains having an average aspect ratio of less than 5: 1, containing 0.01-10 mol% of the total silver halide silver iodide halogen-substituted by iodide at any time during the formation of the mol%. And a silver halide emulsion characterized by containing

In addition, multi-twin grains and / or spherical particles obtained from the multi-twin grains are grown as seed grains, and the total grain content is 5 to 95 mol%.
0.01% of total silver halide at any time during the formation of
It is achieved by a method for producing a silver halide emulsion, which is characterized in that halogen substitution is carried out with 10 to 10 mol% of iodide.

In addition, multi-twin grains and / or spherical particles obtained from the multi-twin grains are grown as seed grains, and the total grain content is 5 to 95 mol%.
0.01% of total silver halide at any time during the formation of
A silver halide light-sensitive material, comprising a silver halide emulsion containing silver halide grains having an average aspect ratio of less than 5: 1, containing silver iodide halogen-substituted by 10 to 10 mol% of iodide. Is achieved by

Examples of the iodide to be added include potassium iodide, its aqueous solution, silver iodide, silver iodide emulsion and the like. In this case, if the addition position of iodide is less than 5 mol% of the final silver halide, the effect of the present invention is hard to appear, and if it exceeds 95 mol%, the sensitivity is lowered and both are not preferable.

The multiple twin particles according to the present invention have, for example, a pBr of −0.7 to 2.0.
It can be obtained by adding a water-soluble silver salt solution, or a water-soluble silver salt solution and a water-soluble halogen compound solution to a water-soluble protective colloid solution, for example, a gelatin solution, which is stirred under the condition of.

It is preferable that the multi-twin grains are subjected to the growth step as a dispersion system, that is, an emulsion, which is dispersed in a water-soluble colloidal dispersion medium.
The emulsion containing seed grains used in the growing step is hereinafter referred to as seed emulsion.

The seed emulsion containing multiple twin crystal grains according to the present invention (hereinafter referred to as multiple twin crystal seed emulsion) preferably has a ratio of double double twins of 30% by weight or more based on all seed grains contained in the emulsion.
It is more preferably 50% by weight or more.

The morphology of multiple twins is described in "Basic silver salt photography in photographic engineering" P.163.
~ 166 (Corona) is described in detail and can be distinguished by an electron microscope.

The seed emulsion containing spherical grains according to the present invention (hereinafter referred to as spherical seed emulsion) is obtained by ripening the emulsion containing multiple twin grains obtained by the above method in the presence of a silver halide emulsion. . Particularly preferable conditions are a temperature of 35 to
It is obtained by aging for 30 seconds to 5 minutes at 45 ° C. with 0.4 to 1.0 mol / liter of ammonia and 0.03 to 0.5 mol / liter of potassium bromide. In the present invention, a monodisperse silver halide emulsion is obtained by using a spherical seed emulsion rather than a multiple twin seed emulsion or a seed emulsion containing multiple twin grains and spherical grains obtained from multiple twins. From the point of, it is preferable.

The seed emulsion according to the present invention may be formed by mixing silver ions and halogen ions, and may be transferred to the next step in the same container, or may be prepared in another container in advance.

The seed grains contained in the seed emulsion preferably consist essentially of the seed grains of the present invention. The proportion of seed particles other than the seed particles of the present invention is preferably about 20% by weight at most.

The halogen composition of the seed emulsion comprising multi-twin grains and / or spherical seed grains according to the present invention is preferably silver iodobromide containing silver iodide in the range of 30 mol% or less, 10
It is more preferably at most mol%, particularly preferably at most 5 mol%.

The growth of the seed particles according to the present invention is preferably carried out under the condition that pBr is 0.7 to 4.0. Outside of this range, the monodispersibility may decrease, and it may be difficult to obtain the desired emulsion. A more preferable pBr range is 1.0 to 3.0.

In the present invention, in order to grow seed grains, it is preferable to mix a water-soluble silver salt solution and a water-soluble halide solution in the seed emulsion.

In the present invention, the water-soluble silver salt solution or the water-soluble silver salt solution and the water-soluble halogen compound solution in the step of growing seed particles is preferably performed at a rate of 30 to 100% of the crystal growth critical rate.

The critical speed of crystal is defined as the upper limit at which new nuclei are not substantially generated during the process of crystal growth, but it means that the weight of newly generated crystal nuclei is 20% of the total weight of silver halide. Hereinafter, it is more preferably 10% or less.

In the present invention, the step of growing seed grains is preferably a step of growing silver halide grains having an average grain size which is at least twice the average grain size of the seed grains.

In the seed grain growth step of the present invention, various silver halide solvents can be present for the purpose of promoting the crystal growth rate.

The silver halide solvent used in the present invention is described in (a) U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-1019 and 54-158917. Organic thioethers, (b) JP-A-54-82408
No. 55-77737, No. 55-29829 and No. 58-30571
Thiourea derivatives described in JP-A Nos. 1 and 12- (c)
JP-A-53-144319, AgX solvent having a thiocarbonyl group sandwiched between oxygen or sulfur atom and nitrogen atom, (d) imidazoles described in JP-A-54-100717, (e) ) Sulfite, (f) thiocyanate,
(G) Ammonia, (h) Hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228, (i) Mercaptotetrazoles described in JP-A-57-202531, (j) Characteristics Examples thereof include benzimidazoles described in JP-A-58-54333.

Next, specific examples of these silver halide solvents (a) to (j) will be given. The solvent used in the present invention is not limited to these exemplified compounds.

(E) K ₂ SO ₃ (f) NH ₄ SCN, KSCN (g) NH ₄ OH In the present invention, the pH of the atmosphere for grain growth in the step of growing seed grains is preferably in the range of 2.0 to 13.0. The range of 3.0 to 12.0 is more preferable.

In the present invention, the temperature of the emulsion in the step of growing seed grains can be carried out in the range of 30 ° C to 80 ° C.
More preferably, it is carried out at 35 ° C to 65 ° C.

In the present invention, as the water-soluble silver salt and the water-soluble halogen compound used for the production of seed particles and the growth of seed particles,
As the water-soluble silver salt, for example, silver nitrate can be used, and as the water-soluble halide, potassium bromide, sodium bromide, ammonium bromide, potassium iodide and the like can be used.

The silver halide emulsion obtained in the present invention may have a localized (unevenly distributed) composition distribution of silver iodide inside the grain or may be uniform. Examples of the localization of silver iodide include a core made of silver iodobromide having a high silver iodide content and a core having a shell made of silver iodobromide having a low silver iodide content or pure silver iodobromide. The shell type is preferred.

The core / shell type emulsion is a double jet method in which a water-soluble silver salt solution and a water-soluble halide solution are added to a gelatin solution containing multiple twin grains and / or spherical particles thus obtained, while controlling pAg and pH. It can be obtained by changing the composition of the water-soluble halide solution of the core part and the shell part in the method of adding by.

The core / shell type silver halide grain preferably used in the present invention has a grain structure composed of two or more layers having different silver iodide contents.
The silver iodide content in the outermost surface layer (shell portion) of the above layers is preferably lower than the silver iodide content in the inner layer (core portion). The silver iodide content of the core portion may be 5 to 40 mol%, and more preferably 6
-30 mol%, more preferably 7-20 mol%. The silver iodide content of the shell portion is preferably less than 5 mol%, more preferably 0.0 to 4.0 mol%.

In the case of a core / shell type emulsion, the difference in content between the core portion having a high silver iodide content and the shell portion having a low content of silver halide grains may have a sharp boundary, and the boundary is not always required. It may be a continuous change that is not obvious. As a method of continuously changing the halogen composition of the boundary between the core and the shell, a method of gradually changing the composition of the added halide in the double jet method can be used. Further, the silver iodide composition in the core portion and the shell portion may be unevenly distributed.

Further, the proportion of the shell portion of the core / shell type silver halide grain is preferably 10 to 80%, more preferably 15 to 70%.
%, Particularly preferably 20 to 60%.

The distribution state of silver iodide in silver halide grains can be detected by various physical measurement methods, for example, at a low temperature as described in the proceedings of the 56th Annual Meeting of the Photographic Society of Japan. It can also be investigated by measuring the luminescence of.

The silver halide emulsion of the present invention may be polydisperse or monodisperse. It is preferably monodisperse. Here, a monodisperse silver halide emulsion is one in which the weight of silver halide grains contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. Say Preferably 70
% Or more, particularly preferably 80% or more.

Here, the average particle diameter r, the frequency of the particles having a particle size r _i n _i
And r _i ³ are defined as particles r _i when the product n _i × r _i ³ is the maximum (three significant digits, rounding off the least significant digit).

The term "particle size" used herein means the diameter of spherical silver halide grains, and the diameter of grains having a shape other than spherical when the projected image is converted into a circular image having the same area.

The particle diameter can be obtained, for example, by enlarging the particles from 10,000 times to 50,000 times by an electron microscope and measuring the diameter of the particles on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) The silver halide grains contained in the silver halide emulsion of the present invention have an average aspect ratio of less than 5: 1. If the average aspect ratio is 5: 1 or more, the effect of the present invention will not be exerted because the monodisperse formation becomes insufficient. The average aspect ratio is preferably in the range of 1: 1 to 5: 1, 1.5: 1 to 4: 1
Is more preferable.

The aspect ratio here is (particle diameter): (thickness)
Is the ratio of The diameter of the silver halide grain means the diameter of the area equal to the projected area of the grain.

The average aspect ratio is an average value of the aspect ratios of the entire photosensitive particles.

The silver halide grains used in the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), and a rhodium salt (including a complex salt in the process of forming and / or growing the grain. ) And an iron salt (complex containing), a metal ion can be added using at least one selected from the group consisting of () and an iron salt (containing complex salt), and these metal elements can be contained inside the particle and / or on the surface of the particle. By placing it in the above, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. When removing the salts, Research Disclos
ure) 17643.

The silver halide emulsion of the present invention can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be prepared according to, for example, British Patent No. 618,06.
1, No. 1,315,755, No. 1,396,696, Japanese Patent Publication No.44-15748
U.S. Pat.Nos. 1,574,944, 1,623,499, 1,673,
No. 522, No. 2,278,947, No. 2,399,083, No. 2,410,689
No., No. 2,419,974, No. 2,448,060, No. 2,487,850,
2,518,698, 2,521,926, 2,642,361, 2,6
94,637, 2,728,668, 2,739,060, 2,743,18
No. 2, No. 2,743,183, No. 2,983,609, No. 2,983,610,
3,021,215, 3,026,203, 3,297,446, 3,2
No. 97,447, No. 3,361,564, No. 3,411,914, No. 3,554,75
No. 7, No. 3,565,631, No. 3,565,633, No. 3,591,385,
No. 3,656,955, No. 3,761,267, No. 3,772,031, No. 3,8
57,711, 3,891,446, 3,901,714, 3,904,41
No. 5, No. 3,930,867, No. 3,984,249, No. 4,054,457,
No. 4,067,740, Research Disclosure (Resea
rch Disclosure) 12008, 13452, 13654, TJ James, The Theory of the
Photographic Process "(THJames.The Theo
It is preferable to sensitize using a chemical sensitizer or a sensitizing method described in 4th Ed. Macmillan 1977, pp67-76.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benz Examples include imidazole nucleus and quinoline nucleus. These nuclei may be substituted on carbon atoms.

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

Examples of useful sensitizing dyes used in a blue-sensitive silver halide emulsion layer include West German Patent 929,080 and U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, No. 52-24844 and the like. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, and 2,
Representative examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 739,149, 2,945,763 and British Patent 505,979. Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
234, 2,270,378, 2,424,710, 2,454,629
Nos. 2,776,280 and the like, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical ones. Furthermore, U.S. Pat.Nos. 2,213,995, 2,493,748, 2,519,001, and cyanine dyes as described in West German Patent 929,080 and the like,
A merocyanine dye or a complex cyanine dye can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive halogen emulsion.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Typical examples are Japanese Examined Japanese Patent Publication No. 43-4932, No. 43-4933, No. 43-4936, No. 4
4-32753, 45-25831, 45-26474, 46-11627
No. 46, No. 46-18107, No. 47-8741, No. 47-11114, No. 47-
No. 25379, No. 47-37443, No. 48-28293, No. 48-38406
No. 48, No. 48-38407, No. 48-38408, No. 48-41203, No. 48
-41204, 49-6207, 50-40662, 53-12375
No. 54-34535, No. 55-1569, JP-A No. 50-33220,
50-33828, 50-38526, 51-107127, 51-11
No. 5820, No. 51-135528, No. 51-151527, No. 52-23931
No. 52-51932, No. 52-104916, No. 52-104917, No. 52-104917
52-109925, 52-110618, 54-80118, 56-257
No. 28, No. 57-1483, No. 58-10753, No. 58-91445, No. 58-
153926, 59-114533, 59-116645, 59-11664
7, U.S. Pat.Nos. 2,688,545, 2,977,229, 3,39
No. 7,060, No. 3,506,443, No. 3,578,447, No. 3,672,898
No., No. 3,679,428, No. 3,769,301, No. 3,814,609,
No. 3,837,862, etc.

Examples of dyes that are used together with sensitizing dyes and have no spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization include, for example, aromatic organic acid formaldehyde condensate ( For example, U.S. Pat.
7,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic ring groups (for example, US Pat. Nos. 2,933,390 and 3,635,721).
Those listed in the issue). U.S. Patent 3,615,613,
The combinations described in No. 3,615,641, No. 3,617,295, No. 3,635,721, etc. are particularly useful.

Antifoggants and stabilizers that can be used in the practice of the present invention include U.S. Patent Nos. 2,713,541 and 2,742.
Pentazaindenes described in 3,180 and 2,743,181, U.S. Pat.Nos. 2,716,062, 2,444,607, and 2,444,
No. 605, No. 2,756,147, No. 2,835,581, No. 2,852,375
Issue, Research Disclos
ure) 14851, tetrazaindenes described in US Pat. No. 2,772,164, and azaindenes such as polymerized azaindenes described in JP-A-57-211142; U.S. Pat. No. 2,131,038, same
3,342,596, thiazolium salts described in 3,954,478, pyrylium salts described in US Pat. No. 3,148,067, and quaternary onium salts such as phosphonium salts described in Japanese Patent Publication No. 50-40665; US Pat. No. 2,403,927 , The same 3,2
66,897, 3,708,303, JP-A-55-135835, 59-7
Mercaptotetrazoles described in 1047, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat.No. 2,824,001, mercaptobenzthiazoles described in U.S. Pat.No. 3,397,987, mercaptobenzimidazoles ,
Mercapto-substituted heterocyclic compounds such as mercapto oxadiazoles described in US Pat. No. 2,843,491 and mercapto thiadiazoles described in US Pat. No. 3,364,028; described in US Pat. No. 3,236,652, Japanese Patent Publication No. 43-10256 Catechols, resorcins described in JP-B-56-44413, and polyhydroxybenzenes such as gallic acid esters described in JP-B-43-4133; tetrazoles described in West German Patent 1,189,380 The triazoles described in U.S. Pat.No. 3,157,509, the benztriazoles described in U.S. Pat.No. 2,704,721, the urazoles described in U.S. Pat.No. 3,287,135, the pyrazoles described in U.S. Pat.No. 3,106,467, Such as indazoles described in US Pat. No. 2,271,229, and polymerized benztriazoles described in JP-A-59-90844 Azoles and U.S. Pat.No. 3,161,51
Pyrimidines described in US Pat. No. 5,751,297, 3-pyrazolidones described in US Pat. No. 2,751,297, and US Pat.
Heterocyclic compounds described in 1,213, such as polymerized pyrrolidone, that is, polyvinylpyrrolidones; JP-A-54-130
929, 59-137945, 140445, British Patent 1,356,
142, U.S. Pat. Nos. 3,575,699, and 3,649,267, and various other inhibitor precursors; U.S. Pat. No. 3,047,
Sulfinic acid and sulfonic acid derivatives described in 393; US Patent Nos. 2,556,263, 2,839,405 and 2,488,
Inorganic salts described in Nos. 709 and 2,728,663 are available.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
Hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

When gelatin is used as the binder of the silver halide emulsion of the present invention, the jelly strength of gelatin is not limited, but the jelly strength is preferably 250 g or more (value measured by the buggy method).

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide light-sensitive material of the present invention for the purpose of enhancing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. it can.

In the color development processing, the silver halide emulsion layer of the present invention forms a dye by undergoing a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.). Dye forming couplers can be used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ions even if they are 4 equivalents. Either of two equivalence may be used. The dye-forming coupler includes a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener fog agent, an antifoggant, a chemical sensitizer, by coupling with an oxidized product of a developing agent. Spectral sensitizers, and compounds that release photographically useful fragments such as desensitizers can be included. DIR which improves the sharpness of images and the graininess of images by releasing a development inhibitor with colored couplers which have the effect of color correction on these dye-forming couplers.
A coupler may be used in combination. At this time, it is preferable that the DIR coupler is of the same type as the dye formed from the coupler and the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not conspicuous, a different type is used. It may form a dye. Instead of the DIR coupler or in combination with the DIR coupler, a DIR compound which releases a development inhibitor at the same time as a colorless compound is formed by a coupling reaction with an oxidized product of a developing agent may be used.

The DIR couplers and DIR compounds that can be used include those in which the inhibitor is directly bonded to the coupling position and those in which the inhibitor is bonded to the coupling position via the divalent group and which are separated by the coupling reaction. Intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like so that the inhibitor is released (referred to as timing DIR coupler and timing DIR compound) are included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A coupling reaction is carried out with the oxidation product of the aromatic primary amine developer,
A colorless coupler that does not form a dye can also be used in combination with the dye-forming coupler.

In the practice of the present invention, dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, and ultraviolet absorbers that do not need to be adsorbed on the surface of silver halide crystals constituting a silver halide emulsion. Among the fluorescent whitening agents, various methods such as solid dispersion method, latex dispersion method, oil-in-water type emulsion dispersion method can be used for the hydrophobic compound, which is the chemical structure of the hydrophobic compound such as coupler. It can be appropriately selected according to the above. The oil-in-water emulsion dispersion method can be applied by various methods of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point and / or an aqueous solution in a high boiling point organic solvent having a boiling point of about 150 degrees or higher. With a water-soluble organic solvent, and using a surfactant in a fresh aqueous binder such as a gelatin aqueous solution, using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and an ultrasonic device. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

The ratio of high boiling organic solvent to low boiling organic solvent is 1: 0.1 to 1: 5
It is preferably 0, more preferably 1: 1 to 1:20.

In the practice of the present invention, dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, UV absorbers, fluorescent brighteners and the like have acid groups such as carboxylic acids and sulfonic acids. In some cases, it can be introduced into the hydrophilic colloid as an alkaline aqueous solution.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic surfactants can be used.

Between the emulsion layers (same color-sensitive layers and / or different color-sensitive layers) of the silver halide light-sensitive material of the present invention, the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or sharpness. An antifoggant can be used to prevent the deterioration of the toner and the conspicuous graininess.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer which prevents deterioration of a dye image can be used in the silver halide light-sensitive material of the present invention.

The protective layer of the silver halide light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is a UV ray for preventing fogging due to discharge caused by charging of the light-sensitive material due to friction or the like and for preventing deterioration of an image by UV light. It may contain an absorbent.

A formalin scavenger can be used in the light-sensitive material of the present invention in order to prevent deterioration of the macender dye-forming coupler and the like due to formalin during storage of the silver halide light-sensitive material of the present invention.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide light-sensitive material of the present invention, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. A compound that can be preferably used as a bleaching accelerator is Research Disclosure.
closure) 17463 Nos. XXI B to D compounds, and the development retarder is 17643 No. XXI Item E compounds. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The photographic emulsion layer of the silver halide light-sensitive material of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine compound for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may contain a quaternary ammonium compound, a urethane derivative, a urea derivative, an imidazole derivative and the like.

The support used in the silver halide light-sensitive material of the present invention includes a flexible reflective support such as paper or synthetic paper laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer). Cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
Films made of semi-synthetic or synthetic polymers such as polyamide, and flexible supports provided with a reflective layer on these films,
Includes glass, metal and pottery.

In preparing the silver halide light-sensitive material of the present invention, the silver halide emulsion layer and other protective colloid layers are used as Research Disclosure 17463.
It can be applied by the method described in A of No. XV of the issue and dried by the method described in B of the same.

The silver halide light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X-ray, γ-ray Any known light source such as light emitted from a fluorescent substance excited by α-rays or the like can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, exposure of 100 nanoseconds to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible.

The exposure may be performed continuously or intermittently.

Any method can be used for the development processing of the silver halide light-sensitive material of the present invention. This developing process may be either a process for forming a silver image (black and white developing process) or a developing process for forming a color image depending on the purpose. If an image is formed by the reversal method, a black and white negative development step is first performed, and then white exposure is performed, or a solution containing a fog agent is used for color development processing. [Alternatively, silver dye bleaching may be used in which a dye is contained in the light-sensitive material, a black-and-white development processing step is performed after exposure to form a silver image, and this is used as a bleaching catalyst to bleach the dye. The black and white development processing includes a development processing step, a fixing processing step,
A water washing process step is performed. When the stop processing step is performed after the development processing step or the stabilization processing step is performed after the fixing processing step, the water washing processing step may be omitted. Further, the developing agent or its precursor may be incorporated in the light-sensitive material, and the developing treatment step may be carried out only with the alkaline solution. A development process using a lith developer as a developer may be performed.

As a color developing process, a color developing process, a bleaching process, a fixing process, a washing process if necessary, and /
Alternatively, a stabilizing treatment step is carried out, but instead of the treatment step using the bleaching solution and the treatment step using the fixing solution, the bleach-fixing treatment step can be carried out using one bleach-fixing solution. It is also possible to carry out a monobath processing step using a 1-solution development bleach-fix solution capable of bleaching and fixing in 1 solution.

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these treatments, instead of the color development processing step, a color developing agent or its precursor may be contained in the material and the development processing may be performed by an activator solution, or an activator processing step may be performed instead of the monobath processing. It may be performed at the same time as the beta treatment and the bleaching and fixing treatments. A typical process is shown among these processes. (These steps are the final step, a washing step,
Any of a stabilization treatment process, a water washing treatment process, and a stabilization treatment process is performed. ) -Color development processing step-bleaching processing step-fixing processing step-Color development processing step-bleaching step-Pre-hardening processing step-neutralization processing step-color development processing step-
Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplementary color development process-Stopping process-Bleaching process- Fixing treatment step-Mono bath treatment step-Activator treatment step-bleach-fixing treatment step-Activator treatment step-bleaching treatment step-fixing treatment step [Examples of the invention] Next, the present invention will be specifically described with reference to examples. As will be explained, the present invention is not limited thereto.

Example 1 The following six types of solutions were prepared to prepare monodisperse spherical seed emulsions.

Solution A ₁ stirred at 40 ° C by the double jet method
B ₁ and C ₁ were added. Addition speed at the start of addition is 35 m / min
The volume was gradually changed to 80 ml per minute at the end of the addition. The pBr during the addition was kept at 1.1. The time required to complete the addition was 33 minutes.

After completion of the addition, desalted water was washed by a conventional method.

The emulsion consisted mostly of polydisperse grains that were multi-twin.

Next, while maintaining the temperature at 40 ° C., the solution D ₁ and the solution and E ₁ were added to this emulsion and ripened for 1 minute. At this time, the ammonia concentration was 0.89 mol / l and pBr was 0.5. Immediately thereafter, the solution F ₁ was added to be neutralized, and desalted and washed with a conventional method again. The silver halide grains contained in this emulsion had a mean grain size of 0.32 μm and were monodisperse spherical grains.

This emulsion is called Em-1.

Next, a core / shell type monodisperse emulsion was produced using the seed emulsion Em-1 and the following four kinds of solutions.

The amount of the seed emulsion corresponds to 8 mol% of the final silver halide.

That is, the solution B ₂ -1 and C ₂ were added to the solution A ₂ stirred at 40 ° C by the double jet method so that the silver iodide content was 1
The silver iodobromide emulsion is 0.0 mol% is grown, the addition of the solution B ₂ -1 has interrupted added on completion. At this time, 51% of the final silver halide was formed. After the preparation of pBr, the solutions B ₂ -2 and C ₂ were subsequently added by the double jet method to grow silver iodobromide having a silver iodide content of 1.0 mol%.

The pH and pBr during addition were controlled as shown in Table 1 by adding KBr solution and acetic acid solution.

Similarly, the speed of the added liquid is also shown.

After the addition is complete, adjust the pH to 6.00 with acetic acid,
Desalted water washing was performed by a conventional method. The emulsion thus obtained is called Em-2. Observation of the silver halide grains of Em-2 with an electron microscope revealed that the average aspect ratio was 4: 1, the average grain size was 0.70 μm, and the halogenation within the grain size range of ± 20% centered on the average grain size r. It was a monodisperse emulsion having a silver weight of 69% of the whole and containing twin grains of 86%.

Next, the manufacturing process of Em-3 to Em-5 will be described. In this step, before growing silver iodobromide containing 10.0 mol% of silver iodide, an amount of potassium iodide aqueous solution shown in Table 2 was added to Solution A ₂ and aged for 10 minutes. Produced Em-3 to Em-5 by the same operation as Em-2. Em-
Em-6 was prepared by adding the silver iodide emulsion in the amounts shown in Table 2 in place of the potassium iodide aqueous solution used in the production of 3 to Em-5 and ripening for 10 minutes.

Also, in the process of producing Em-2, the amount of potassium iodide aqueous solution shown in Table 2 was added at the end of the growth of silver iodobromide containing 10.0 mol% of silver iodide, and ripening was carried out for 10 minutes. Em-7 to Em-10 were prepared by the same operation as in 2.

The emulsion samples Em-2 to Em-10 prepared as described above were divided so that the silver halide content was equivalent to 0.35 mol, and chemical sensitization was performed using ammonium thiocyanate, sodium thiosulfate and chloroauric acid. And anhydro-5,5'-dichloro-9-ethyl-3, as a green-sensitive sensitizing dye.
3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide; anhydro-5,5'-diphenyl-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine; Anhydro-9-ethyl-3,3'-di- (3-sulfopropyl) -5,6,5 ', 6'- 20 mg each of dibenzooxacarbocyanine hydroxide was added, and further 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 5-phenyl-1-mercaptotetrazole were added. Next, a dispersion (M-1) having the following composition
1200 ml, saponin and 1,2-bisvinylsulfonylethane were added and coated on a cellulose triacetate base support so that the amount of silver was 15 mg / dm ^2, and dried to obtain a sample having a stable coating film. This sample is sample No. 1 to 9 in Table-2.
And

Dispersion (M-1) 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-tert-amylphenoxyacetamide) -benzamide] -5 as magenta coupler -Pyrazolone was used in an amount of 8 × 10 ^-2 mol per mol of silver halide, and 2- (1-phenyl-5-tetrazolylthio) -4-octadecylsuccinimide-1-indanone was used as 1 mol of silver halide as a DIR compound. 0.28 mol was used. This was mixed with tricresyl phosphate as a high boiling organic solvent in an amount 1 times the weight of the coupler, and ethyl acetate was added to these mixtures and heated to 60 ° C. to completely dissolve them. This solution was mixed with 50 ml of a 10% aqueous solution of Alkanol B (registered trademark, an alkylnaphthalene sulfonate manufactured by DuPont) and 700 ml of an aqueous solution of 10% gelatin and dispersed using a colloid mill.

These samples and comparative samples were exposed to green color for 8 seconds and 1/100 seconds with a KS-1 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) based on the JIS method, and then the following color development processing was performed. It was And fog, sensitivity of 8 second exposure and 1 /
The sensitivity of 100 second exposure was determined. The results are shown in Table-2.

[Color developer composition]

[Bleaching liquid composition] [Fixer composition] [Stabilized composition] Separately, samples No. 1 to No. 9 were forcibly deteriorated at 65 ° C. and 10% RH for 3 days, and then the above-described color development processing was carried out to measure the change in fog with time (heat fog stability). The measurement results at this time are also shown in Table 2.

From the results in Table-2, the photographic materials using the silver halide emulsion of the present invention (Samples No.3, No.4, No.5, No.7, No.8 in Table-2) were exposed at the time of long exposure. In addition to the remarkable improvement effect on the sensitivity decrease, it is recognized that the fluctuation of fog in the forced deterioration test is also significantly improved.

Example 2 Seed grains containing multiple twins having a silver iodide content of 6.5 mol% were prepared according to the method described in JP-A-55-142329 using the following three types of solutions.

Add solution B ₃ at 35 cc / min to stirred solution A ₃ at 40 ° C and
Solution C ₃ was added at 65 min −1 with a 0 second delay, each for 20 min. After the addition was completed, desalted water was washed by a conventional method. This emulsion is called Em-11.

This emulsion contains multiple twinned grains, single twinned grains and octahedral grains, and the ratio of the multiple twinned grains is about 30% and the average grain size is 0.27.
The variation coefficient of the particle size distribution was 32%.

Next, using the seed emulsion Em-11 and the following three kinds of solutions, a monodisperse emulsion having a silver iodide content of 4.2 mol% was prepared.

The amount of seed emulsion corresponds to 7.1 mol% of the final silver halide.

Solution D ₃ stirred at 40 ° C was added to solution E ₃ by the double jet method.
And solution F ₃ were added to grow a silver iodobromide emulsion having a silver iodide content of 4.2 mol%, and the addition was stopped when the addition of solution E ₃ and solution F ₃ was completed. The pH and pBr during addition were controlled as shown in Table 3 by adding a KBr solution and an acetic acid solution.

In addition, the addition rate of the addition solution is also shown in the table, but pB
The determination of r and the addition rate was carried out with reference to the conventional method disclosed in JP-A-55-142329.

After the addition is complete, adjust the pH to 6.00 with acetic acid,
Desalted water washing was performed by a conventional method. The resulting emulsion is called Em-12. Observation of the silver halide grains of Em-12 with an electron microscope revealed that the average aspect ratio was 3: 1, the average grain size was 0.77 μm, and the halide grains contained within the grain size range of ± 20% centered on the average grain size r. The silver weight is 64%, and twin particles are
A monodisperse emulsion containing 38% was obtained.

Next, in the manufacturing process of Em-12, the amount of potassium iodide aqueous solution shown in Table 4 was added to Solution D ₃ prior to the growth of 4.2 mol% of silver iodobromide, and the mixture was aged for 5 minutes. Em-13 to Em-16 were created by the same operation.

Further, except that the potassium iodide aqueous solution of Em-13 to Em-16 was replaced with the silver iodide emulsion in the amount shown in Table 4 and ripening was performed for 10 minutes, the procedure of Em-12 to Em-17 to Created Em-18.

Further, in the production process of Em-12, when 80 mol% of silver halide was formed with respect to the final amount of silver halide, the amount of potassium iodide aqueous solution shown in Table 3 was added and ripening was carried out for 10 minutes. Other than that, Em-19 was created by the same operation as Em-12.

Using the emulsions of Em-12 to Em-19 thus obtained, these emulsions were respectively coated on a support by the same method as in Example 1 to prepare Samples No. 10 to No. 17 of Table 4. It was prepared and sensitometric evaluation was carried out by the same method as in Example 1. The measurement results are shown in Table-4.

As can be seen from the measurement results in Table 4, the photographic material of the present invention shows a remarkable improvement effect in the sensitivity decrease at the time of long-time exposure, and also a remarkable improvement in the change of fog in the forced deterioration test.

[Effects of the Invention] As described above, according to the present invention, a silver halide emulsion having high sensitivity, low illuminance reciprocity law failure characteristics and improved fog characteristics over time can be produced. The silver halide photographic materials obtained by using the emulsion all have the above-mentioned excellent performance.

Front page continued (72) Inventor Hideaki Haraga No. 1 Sakura-cho, Hino City, Tokyo Inside Konishi Roku Photo Industrial Co., Ltd. (56) Reference JP-A-55-142329 (JP, A) JP-A-58-211143 (JP) , A) JP 59-111144 (JP, A) JP 60-147727 (JP, A) JP 57-154232 (JP, A)

Claims (3)

[Claims] 1. Multi-twin grains and / or spherical particles obtained from multi-twin grains are grown as seed grains to obtain 5 to 95% of all grains.
Silver halide grains having an average aspect ratio of less than 5: 1, containing 0.01-10 mol% of the total silver halide silver iodide halogen-substituted by iodide at any time during the formation of the mol%. A silver halide emulsion containing: 2. Multi-twin grains and / or spherical particles obtained from multi-twin grains are grown as seed grains to obtain 5 to 95% of all grains.
A method for producing a silver halide emulsion, which comprises substituting halogen with iodide in an amount of 0.01 to 10 mol% of total silver halide at any time during the formation of mol%. 3. Multi-twin grains and / or spherical particles obtained from multi-twin grains are grown as seed grains to obtain 5 to 95% of all grains.
Silver halide grains having an average aspect ratio of less than 5: 1, containing 0.01-10 mol% of the total silver halide silver iodide halogen-substituted by iodide at any time during the formation of the mol%. A silver halide light-sensitive material comprising a silver halide emulsion containing