JPH06273869A - Production of silver halide emulsion and photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably produce such a silver halide emulsion that >50% of the projected area of the whole silver halide particles is composed of planer silver halide particles having <0.6mum average particle diameter and >3 aspect ratio, and to provide a silver halide photographic sensitive material containing this emulsion. CONSTITUTION:Silver halide particles are produced in the process of forming nuclei, Ostwald ageing and growing particles. In this process, >=50wt.% of the dispersion medium for formation of nuclei is an aq. soln. of low mol.wt. gelatine having <=70000 mol.wt., or the dispersion medium for formation of nuclei contains polyalkylene oxide block copolymers. Further, the formation of nuclei is performed to obtain >=4.5mol% average silver iodide content.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a tabular silver halide emulsion and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art Recent technological trends of silver halide color photographic light-sensitive materials include the pursuit of higher sensitivity represented by ISO 1600 photographic light-sensitive materials and the small format such as 110 size system and disk size system. Satisfactory graininess and sharpness even with photosensitive materials used for shooting with specialized cameras, and photosensitive materials used for shooting with film with lenses such as "Sharing Run Hi" and "Sharing Run Panoramic" It is a pursuit of a light-sensitive material having color reproducibility and color reproducibility, and a higher standard is required for each performance.

In order to meet the above demands, tabular grains intended to improve sensitivity including improvement in color sensitizing efficiency by a sensitizing dye, improve sensitivity / granularity relationship, sharpness, and covering power. The technique used is US Pat. No. 4,434,22.
No. 6, No. 4,414, 310, No. 4,433, 048
Issue No. 4,414,306 Issue 4,459,353
JP-A-58-113927, 59-11935.
No. 0 and the like.

Further, a technique of using tabular grains having a relatively small size (diameter of silver halide grains is 0.6 μm or less) is
U.S. Pat. Nos. 4,439,520 and 4,435,49
9, No. 4,748,106, JP-A-62-9975.
No. 1, JP-A-4-324440 and JP-A-4-3304.
No. 29, etc. The small-sized tabular grains are not only effective for improving the sharpness based on the optical characteristics of the above-mentioned tabular grains, but in the presence of the prepared small-sized tabular grains, the tabular grains are further grown. To prepare,
It is also useful as a seed emulsion of a so-called seed crystal method. The properties required for a tabular seed emulsion include the following items. High flatness rate. The particles should have good monodispersity. Have a high aspect ratio. Stable grain shape and post-growth performance.

For the preparation of tabular silver halide grains of small size, only one step addition of the aqueous solution of silver nitrate and the mixed aqueous solution of potassium bromide and potassium iodide described in JP-A No. 62-18555 is used. There is a method of forming particles. According to this method, the yield of silver halide emulsion obtained is low with respect to the capacity of the reaction vessel, and there is a problem in terms of efficiency when actual production is assumed. The particles produced are polydisperse.

The second preparation method is disclosed in JP-A-62-9.
A method based on a method for preparing tabular grains having a relatively large grain size as described in Japanese Patent No. 9751, in which tabular nucleation by addition and ripening of an aqueous silver nitrate solution and an aqueous alkali metal halide solution, and subsequent nuclei Consists of the process of growing. According to this method, relatively monodisperse particles can be prepared by devising each condition. However, to apply this method to the preparation of tabular silver halide grains of small size, either finely divided tabular nuclei are prepared or used for growth as disclosed in JP-A-4-330429. It is necessary to reduce the amount of silver used. If atomization of the flat plate nuclei of the former is possible, monodispersion of the nuclei can be realized by subsequent aging, which is a more preferable method for obtaining monodisperse particles. Is extremely difficult to achieve.

To adjust the size of the flat plate nucleus, Japanese Patent Laid-Open No.
As described in JP-A-3-92942, various supersaturation factors (nucleation temperature, gelatin concentration, I ^- content in the aqueous alkali halide solution to be added, salt concentration, etc.) may be changed. By increasing the twinning probability, the number of plate nuclei (parallel double twins) remaining after aging increases,
Therefore, the size of the flat plate nucleus is reduced. However, if the supersaturation factor is extremely increased to reduce the size, the frequency of formation of multiple twins other than parallel double twins increases, and aging following nucleation selectively causes only parallel double twins. There are areas that can no longer be left. Therefore, as mentioned above, atomization of the flat plate nuclei is an extremely difficult technical problem.

On the other hand, as a hydrophilic protective colloid used when preparing a tabular core, JP-A-1-158426 discloses a technique of using low molecular weight gelatin, and European Patent No. 51.
No. 4,742 discloses a technique for using a polyalkylene oxide block copolymer, and it is shown that each is effective in preparing tabular silver halide grains having improved monodispersity. However, neither patent mentions atomization of plate nuclei.

[0009]

An object of the present invention is to provide a technique for atomizing tabular silver halide emulsion grains and stably producing them. Another object of the present invention is to provide a silver halide photographic light-sensitive material containing the emulsion.

[0010]

The object of the present invention is to obtain a silver halide grain having an average grain size of 0.6 μm through nucleation, Ostwald ripening and grain growth.
In the method for producing a silver halide emulsion in which tabular silver halide grains having an aspect ratio of 3 or more occupy 50% or more of the projected area of all silver halide grains, 50% by weight of the dispersion medium at the time of nucleation is The above is an aqueous solution of a low molecular weight gelatin having a molecular weight of 70,000 or less, and nucleation is performed so that the average silver iodide content is 4.5 mol% or more. The average grain size is 0.6 μm due to nucleation of silver halide grains, Ostwald ripening and grain growth.
In the method for producing a silver halide emulsion in which tabular silver halide grains having an aspect ratio of 3 or more account for 50% or more of the projected area of all silver halide grains, the dispersion medium at the time of nucleation is polyalkylene oxide. A method for producing a silver halide emulsion comprising a block copolymer and nucleating so that the average silver iodide content is 4.5 mol% or more, and the silver halide emulsion as described in the preceding paragraph. As a seed crystal, a method for producing a silver halide emulsion characterized by grain growth and adjustment, and a halogenation characterized by using a silver halide emulsion as described in the preceding paragraph as seed crystal and grain growth and adjustment Method for producing silver emulsion, silver halide photographic light-sensitive material characterized by having at least one silver halide emulsion layer containing the silver halide emulsion described in the preceding paragraph, and halogen described in the preceding paragraph A silver halide photographic light-sensitive material characterized by having at least one silver halide emulsion layer containing a silver halide emulsion on a support, and a silver halide emulsion layer containing the silver halide emulsion described in the preceding paragraph on a support. A silver halide photographic light-sensitive material having at least one layer, and a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion described in the preceding paragraph. Achieved by

The tabular silver halide emulsion of the present invention will be described in detail below. The process for preparing the tabular silver halide emulsion of the present invention comprises a grain forming process including nucleation, ripening and growth, followed by a desalting and washing process. This method
It is described in JP-A-51-39027 and 63-11928. Each step will be described below.

1) Nucleation In the present invention, nucleation is performed by using a low molecular weight gelatin aqueous solution as a dispersion medium, or a polyalkylene oxide block copolymer containing at least one hydrophilic unit and at least one hydrophobic unit in the dispersion. And nucleation is performed so that the average silver iodide content is 4.5 mol% or more. In this case, the low molecular weight gelatin has an average molecular weight of 70,000 or less, preferably 500 to 60,000, more preferably 1000.
~ 40,000. When the average molecular weight exceeds 70,000, the effect of the present invention becomes small. When the average molecular weight is less than 500, there are difficulties in producing gelatin. It is preferable that 50% by weight or more, and preferably 70% by weight or more of the dispersion medium is low molecular weight gelatin. Alkali-treated gelatin is usually used as the type of gelatin, but other acid-treated gelatin,
Modified gelatin such as phthalated gelatin can also be used. The concentration of the dispersion medium (for example, the concentration of gelatin in the aqueous gelatin solution) may be 0.05 to 5% by weight, but a low concentration range of 0.05 to 1.6% by weight is particularly effective.

The low molecular weight gelatin used in the present invention is
It can usually be made as follows. Usually used gelatin having an average molecular weight of 100,000 is dissolved in water, and a gelatin degrading enzyme is added to enzymatically decompose the gelatin molecule. For this method, see RJ Cox, Photographic Gelatin II,
Academic Press, London, 1976, P.233 ~ 251, P.335
The description of ~ 346 can be referred to. In this case, since the binding position at which the enzyme decomposes is determined, a low molecular weight gelatin having a relatively narrow molecular weight distribution can be obtained, which is preferable. In this case, the longer the enzymatic decomposition time, the lower the molecular weight. In addition, low pH (pH 1-3) or high pH (p
H10 to 12) A method of heating under an atmosphere and hydrolyzing can also be used. In this case, it is preferable to carry out an ion exchange treatment after the decomposition because the molecular weight can be lowered without mixing impurities (for example, enzymes). The average molecular weight of gelatin can be measured by gel filtration chromatography.

Next, the polyalkylene oxide block copolymer used in the present invention will be described. The copolymer is a nonionic surfactant containing at least one hydrophilic unit and at least one hydrophobic unit.
Regarding the copolymer, IR Schmolka, A Review of
Block Polymer Surfactants, J. Am. Oil Chem. Soc.,
54 (3), 1977, P110-118 and AS Davidsohn and
B. Milwidsky, Synthetic Detergents, John Wiley &
Sons, NY, 1987, P29-40 and European Patent No. 51
No. 4,742 can be referred to.

The first preferred structure of the copolymer used in the present invention is shown in the following general formula (I).

[0016]

[Chemical 1]

Here, O1 represents a terminal portion of a hydrophobic alkylene oxide block, and W1 represents a connecting portion composed of a hydrophilic alkylene oxide block. W1 part is 4 to 9
It accounts for 6% by weight. The molecular weight of the copolymer is 760 to 16,000. In the general formula (I), O1 is preferably the following repeating unit.

[0018]

[Chemical 2]

R ¹ is a hydrophobic group such as an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. In the general formula (I), W1 is preferably the following repeating unit.

[0020]

[Chemical 3]

Here, R ² is a hydrogen atom or a hydrophilic group in which the aliphatic hydrocarbon group of R ¹ is substituted with at least one hydroxyl group and / or a polar group such as a carboxy group.

In the general formula (I), the following compound A is particularly preferable.

[0023]

[Chemical 4]

Where x and x'are 6 to 120 and y is 2 to 300, respectively.

The second preferred structure of the copolymer used in the present invention is represented by the following general formula (II).

[0026]

[Chemical 5]

Here, W2 represents a hydrophilic alkylene oxide block terminal portion, and O2 represents a connecting portion composed of a hydrophobic alkylene oxide block. O2 part is 4 to 9
It accounts for 6 weight percent. The molecular weight of the copolymer is 1,
000 to 30,000. In the general formula (II), O2 is preferably the following repeating unit.

[0028]

[Chemical 6]

Here, R ¹ is a hydrophobic group such as an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. In the general formula (II), W2 is preferably the following repeating unit.

[0030]

[Chemical 7]

Here, R ² is a hydrogen atom or a hydrophilic group in which the aliphatic hydrocarbon group of R ¹ is substituted with at least one hydroxyl group and / or a polar group such as a carboxy group.

In the general formula (II), the following compounds are particularly preferable structures.

[0033]

[Chemical 8]

Where x is 13 to 490 and y
And y'are 1 to 320, respectively.

The third preferred structure of the copolymer used in the present invention is shown in the following general formula (III).

[0036]

[Chemical 9]

Here, W3 represents a hydrophilic alkylene oxide block terminal portion, and O3 represents a hydrophobic alkylene oxide block portion. L is a linking part of amine or diamine, and z is 1 or 2. The O3 part comprises 4 to 96 weight percent. The molecular weight of the copolymer is 1,100 to 60,000.

In the general formula (III), preferable structures include the following structures.

[0039]

[Chemical 10]

Here, W3 represents a hydrophilic alkylene oxide block end portion, and O3 represents a hydrophobic alkylene oxide block portion. R ³ , R ⁴ and R ⁵ are each a linking group composed of an aliphatic hydrocarbon having 1 to 10 carbon atoms, and a, b and c are each 0 or 1.

In the general formula (III), the following structures are also mentioned as preferable structures.

[0042]

[Chemical 11]

Here, W3 represents a hydrophilic alkylene oxide block end portion, and O3 represents a hydrophobic alkylene oxide block portion. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a linking group composed of an aliphatic hydrocarbon having 1 to 10 carbon atoms, and d, e, f and g are each 0 or 1.

In the general formula (III), O3 is preferably the following repeating unit.

[0045]

[Chemical 12]

Here, R ¹ is a hydrophobic group such as an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. General formula
In (III), W3 is preferably the following repeating unit.

[0047]

[Chemical 13]

R ² is a hydrogen atom or a hydrophilic group in which the aliphatic hydrocarbon group of R ¹ is substituted with at least one hydroxyl group and / or a polar group such as a carboxy group.

The fourth preferred structure of the copolymer used in the present invention is represented by the following general formula (IV).

[0050]

[Chemical 14]

Here, O4 represents a hydrophobic alkylene oxide block terminal portion, and W4 represents a hydrophilic alkylene oxide block portion. L is a linking part of amine or diamine, and z is 1 or 2. Part W4 comprises 4 to 96 weight percent. The molecular weight of the copolymer is 1,100 to 50,000.

In the general formula (IV), preferred structures include the following structures.

[0053]

[Chemical 15]

Here, O4 represents a hydrophobic alkylene oxide block terminal portion, and W4 represents a hydrophilic alkylene oxide block portion. R ³ , R ⁴ and R ⁵ are each a linking group composed of an aliphatic hydrocarbon having 1 to 10 carbon atoms, and a, b and c are each 0 or 1.

In the general formula (IV), the following structures are also mentioned as preferable structures.

[0056]

[Chemical 16]

Here, O4 represents a hydrophobic alkylene oxide block terminal portion, and W4 represents a hydrophilic alkylene oxide block portion. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a linking group composed of an aliphatic hydrocarbon having 1 to 10 carbon atoms, and d, e, f and g are each 0 or 1.

In the general formula (IV), O4 is preferably the following repeating unit.

[0059]

[Chemical 17]

Here, R ¹ is a hydrophobic group such as an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. In the general formula (IV), W4 is preferably the following repeating unit.

[0061]

[Chemical 18]

Here, R ² is a hydrogen atom or a hydrophilic group in which the aliphatic hydrocarbon group of R ¹ is substituted with at least one hydroxyl group and / or a polar group such as a carboxy group.

In the present invention, the above-mentioned copolymer is contained in the dispersion medium at the time of nucleation. The copolymer is used in an added amount of 0.1% by weight or more, preferably 1% by weight or more based on the amount of silver used for nucleation. Although the effect of the present invention can be obtained in a wide range of addition amount, in the compound represented by the general formula (I), 100% by weight relative to the amount of silver used for nucleation, the general formula (II) (III)
With the compounds represented by (IV) and 50% by weight, the effects of the present invention will not be more remarkable at the respective addition amounts, but in the compound represented by the general formula (I), silver used for nucleation is formed. An addition amount of 200% by weight or more, and 100% by weight or more of the compounds represented by the general formulas (II), (III) and (IV) can be used.

The dispersion medium to which the copolymer is added is
It is advantageous to use gelatin, but other hydrophilic colloids can also be used. Hydrophilic colloids include proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate, starch. Various kinds of synthetic hydrophilic polymeric substances such as derivatives, homopolymers or copolymers, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl. Pyrazole can be used.

The frequency with which twin planes are formed during nucleation depends on various supersaturation factors. Regarding this, JP-A-6
No. 3-92942. Usually, when these supersaturation factors are increased, the particles produced are
a) regular particles of octahedron → b) particles having a single twin plane → c) particles having two parallel twin planes (target) →
d) Particles having non-parallel twin planes and e) Particles having three or more twin planes, but the abundance ratio of the particles of c) is the effect of the present invention in the finally obtained grains. These various supersaturation factors are adjusted to be within the range.

Other preferable conditions for nucleation are as follows. Of the silver salt aqueous solution and the alkali halide aqueous solution added at the time of nucleation, it is preferable to use an aqueous solution in which the silver salt aqueous solution side or both aqueous solutions contain the dispersion medium in an amount of 0.05 to 2.0% by weight. As the dispersion medium in this case, ordinary photographic gelatin can be used, but the above-mentioned low molecular weight gelatin is more preferable. The temperature is 5 to 60 ° C, preferably 15 to 50 ° C. The addition rate of silver nitrate is preferably 0.5 g / min to 30 g / min per 1 liter of reaction aqueous solution. The composition of alkali halide solution added, Br ^- for I ^-
The content is not less than 4.5 mol% and not more than the solid solution limit, preferably,
It is in the range of 4.5 mol% or more and 10 mol% or less.

The irrelevant salt concentration in the reaction solution is 0 to 1 mol /
L is preferred. The pH of the reaction solution may be 2 to 10. The concentration of the silver halide solvent in the reaction solution is preferably ^{0 to} 3.0 × 10 ^-1 mol / liter.

2) Aging In the nucleation described in 1), fine tabular grain nuclei are formed, but at the same time, a large number of other fine grains (especially octahedral grains and single twin grains) are formed. Before entering the growth process described below, it is necessary to eliminate the grains other than the tabular grain nuclei to obtain nuclei having a shape which should be tabular grains and good monodispersity. As a method of making this possible, a method of performing Ostwald ripening after nucleation is known. As the aging method, the following method is also effective in addition to the matters described in JP-A-63-151618. After nucleation, an aqueous gelatin solution is added to adjust pBr and gelatin concentration. In this case, the preferable pBr is 1.3 to 2.0, and the gelatin concentration is 1
10 to 10% by weight. The gelatin used in this case has an average molecular weight of 1 commonly used in the photographic industry.
Gelatin of 0,000 to 300,000 is preferable. Next, when the temperature is raised and the first ripening is carried out, tabular grains grow and non-tabular grains disappear. Next, an AgNO ₃ aqueous solution is added to add p
After adjusting Br to 1.8 to 3.5, a silver halide solvent is added to perform second ripening. In this case, the preferred silver halide solvent concentration is 0 to 3 × 10 ^-1 mol / liter, more preferably 10 ^-4 to 2 × 10 ^-1 mol / liter. By aging in this manner, only tabular grains of approximately 100% are obtained.

3) Growth In the present invention, it is preferable that a grain growth step is performed after Ostwald ripening. In the present invention, it is preferable to keep pBr 1.4 to 3.5 during the crystal growth period following the ripening process. Further, the addition rate of silver ions and halogen ions during the crystal growth period is set to 20 to 100% of the crystal critical growth rate,
It is preferable to set the addition rate so that the crystal growth rate is preferably 30 to 100%. That is, as the growth atmosphere during the crystal growth period, when the pAg is low and the degree of supersaturation is higher, the tabular grains become more monodispersed as they grow,
preferable. In this case, the description of JP-A-63-151618 can be referred to for the method of adding silver ions and halogen ions along with the crystal growth. A silver halide solvent can be used to promote the growth during the crystal growth period. In that case, the concentration of the silver halide solvent is preferably 0 to 0.3 mol / liter, and
˜0.1 mol / liter is more preferred.

A silver halide solvent is useful for promoting the ripening of silver halide grains. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. It is therefore clear that introduction of an aqueous halide solution into the reactor can accelerate aging. Also, other ripening agents can be used.
The total amount of these ripening agents can be added to the dispersion medium in the reactor before adding the silver salt and the halide salt, and one or more halide salts, silver salts or peptizers can be added. It is also possible to add the agent and introduce it into the reactor. The ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than the halogen ions, ammonia, amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264,
Nos. 2,448,534 and 3,320,069. U.S. Pat. No. 3,271,157
Nos. 3,574,628 and 3,737,3
Well-known thioether ripening agents as described in No. 13 can also be used. Alternatively, JP-A-53-82408
It is also possible to use a thione compound as disclosed in No. 53-144319.

The tabular silver halide grains of the present invention may be any of silver iodobromide, silver iodochlorobromide and silver iodochloride.

The tabular silver halide grains of the present invention may have at least two layered structures having substantially different halogen compositions, or may have a uniform composition. In an emulsion having a layered structure with different halogen compositions, even an emulsion containing a high iodine layer in the core part and a low iodine layer in the outermost layer,
The emulsion may include a low iodine layer in the core part and a high iodine layer in the outermost layer. The particle size distribution may be narrow or wide, but monodispersion is more preferable.

The tabular silver halide emulsion of the present invention has an aspect ratio (ratio of circle equivalent diameter of silver halide grains / grain thickness) of 3.0 or more, preferably 3.0 or more and 15.0 or less,
Particularly preferred is an emulsion in which grains having a grain size of 3.0 or more and 10.0 or less are present in 50% or more of the projected area of all silver halide grains in the emulsion, preferably 70% or more, particularly preferably 85% or more. It is an emulsion. The average equivalent circle diameter of the tabular silver halide grains of the present invention is preferably 0.6 μm or less, and particularly preferably 0.2 μm or more and 0.6 μm or less. The average grain thickness of the tabular silver halide grains of the present invention is preferably 0.2 μm or less, particularly preferably 0.15 μm or less.

In the present invention, the tabular silver halide grains are preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but is preferably in the range of 2 to 10, and more preferably in the range of 3 to 8.
The pAg at the time of washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 10. As a method of washing with water, noodle washing method, dialysis method using semipermeable membrane, centrifugation method, coagulation sedimentation method,
It can be selected from the ion exchange methods and used. In the case of the coagulation sedimentation method, for example, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, and a method using a gelatin derivative can be selected.

The tabular silver halide emulsion thus prepared is subsequently chemically sensitized or used as a seed crystal for further growth.

Next, the steps including growth when the tabular silver halide emulsion of the present invention is used as a seed crystal will be described. The step including the growth of seed crystal particles includes a step of further growing the particles in the presence of the above-mentioned seed crystal particles, a step of washing with demineralized water, a chemical sensitization and the like. The amount of seed crystals used at this time is arbitrary, but is 1 with respect to the molar amount of silver salt supplied for growth.
It is preferable to use seed crystals in an amount corresponding to a silver molar amount of / 10 or less, more preferably 1/20 or less, particularly preferably 1
/ 25 or less. Although any time can be selected from the time when the seed crystal is prepared until the time when it is used for growth, it is preferably used for growth after being refrigerated for one day or more.

The growth in the presence of the seed crystal can be performed in the same manner as the growth in the seed crystal preparation described above. Further, washing and dispersion after growth can be performed in the same manner.

The tabular silver halide grains after growth may be any of silver iodobromide, silver iodochlorobromide and silver iodochloride.

The tabular silver halide grain after growth may have at least two layered structures having substantially different halogen compositions, or may have a uniform composition. In an emulsion having a layered structure with different halogen compositions, even an emulsion containing a high iodine layer in the core part and a low iodine layer in the outermost layer,
The emulsion may include a low iodine layer in the core part and a high iodine layer in the outermost layer. The particle size distribution may be narrow or wide, but monodispersion is more preferable.

The tabular silver halide emulsion after growth has an aspect ratio (ratio of equivalent circle diameter of silver halide grains / grain thickness) of 3.0 or more, preferably 3.0 or more and 15.0 or less,
Particularly preferred is an emulsion in which grains having a grain size of 3.0 or more and 10.0 or less are present in 50% or more of the projected area of all silver halide grains in the emulsion, preferably 70% or more, particularly preferably 85% or more. It is an emulsion. The average equivalent circle diameter of the tabular silver halide grains after growth is preferably 0.6 μm or more, and particularly preferably 1.0 μm or more. The average grain thickness of the tabular silver halide grains of the present invention is 0.3.
It is preferably not more than μm, particularly preferably not more than 0.2 μm.

The tabular silver halide emulsion of the present invention and the tabular silver halide emulsion obtained by growing the emulsion as a seed crystal can be subjected to chemical sensitization represented by sulfur sensitization and total sensitization. The location of chemical sensitization differs depending on the composition, structure, and shape of the emulsion grains and the intended use of the emulsion. In some cases, the chemically sensitized nuclei are embedded in the grain, at a shallow position from the grain surface, or in some cases the chemically sensitized nuclei are formed on the surface. The effect of the present invention is effective in any case, but particularly preferable is the case where a chemical sensitizing nucleus is formed near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is performed by TH James.
Author, The Photographic Process, 4th Edition, published by Macmillan, 1977, (TH James, The Theory of th
e Photographic Process, 4th ed, Macmillan, 1977) 6
It can be carried out using activated gelatin as described on pages 7-76, and also Research Disclosure 12
0, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. No. 2,64.
2,361, 3,297,446, 3,77
No. 2,031, No. 3,857,711, No. 3,90
1,714, 4,266,018 and 3,9
04,415 and British Patent No. 1,315,755.
, PAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be carried out using gold, platinum, palladium, iridium or a combination of plural sensitizers.

As the gold sensitizer used in the present invention, a gold complex salt (see, for example, US Pat. No. 2,399,083) can be preferably used. Of these,
Particularly preferred are potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazole methochloride. The content of the gold sensitizer in the silver halide grain phase is preferably 10 ⁻⁹ to 10 ⁻³ mol, and particularly preferably 10 ⁻⁸ to 10 ⁻⁴ mol per mol of silver halide.

Examples of the sulfur sensitizer used in the present invention include thiosulfates, thioureas, thiazoles, rhodanines, and other compounds (specific examples; US Pat. No. 1,574,741).
No. 944, No. 2,410,689, No. 2,27
No. 8,947, No. 2,728,668, No. 3,6
56,955, 4,030,928, 4,
No. 067,740), and among these, thiosulfates, thioureas and rhodanins are particularly preferable. The amount of the sulfur sensitizer can be selected as an optimum amount depending on the conditions such as grain size, temperature of chemical sensitization, pAg and pH. It is used in an amount of 10 ⁻⁷ to 10 ⁻³ mol, preferably 5 × 10 ⁻⁷ to 10 ⁻⁴ mol, and more preferably 5 × 10 ⁻⁷ to 10 ⁻⁵ mol, per mol of silver halide.

The chemical sensitization temperature can be appropriately selected within the range of 30 ° C. to 90 ° C., pAg of 5 to 10 and pH of 4 or more. In the present invention, a sensitizing method using a metal such as iridium, platinum, rhodium or palladium (for example, US Pat. Nos. 2,448,0660 and 2,566,245,
No. 2,566,263), a selenium sensitization method using a selenium compound, and a tellurium sensitization method using a tellurium compound can be used together.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
4, No. 3,544,757, JP-A-58-1265.
No. 26, and Duffin, "Photoemulsion Chemistry," 138
~ Page 143.

The silver halide emulsion used in the present invention is
It may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes,
It includes complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, that is, For example, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus as a nucleus having a ketomethylene structure,
Thiohydantoin nucleus, 2-thiooxazolidine-2,4
-5- to 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,
No. 229, No. 3,397,060, No. 3,522,0
No. 52, No. 3,527, 641, No. 3, 617, 29
No. 3, No. 3,628,964, No. 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,703,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1,507, 803, Japanese Patent Publication No. 43-493
6, No. 53-12375, JP-A No. 52-11061.
No. 8 and No. 52-109925. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

The dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly after the completion of chemical sensitization and before application, US Pat. No. 3,628,
It is also possible to perform spectral sensitization at the same time as chemical sensitization by adding it at the same time as the chemical sensitizer, as described in JP-A No. 969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in No. 8 or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, as described in US Pat.
It can be at any time during the formation of the silver halide grains, including the method taught in No. 183,756. The addition amount is 4 × 10 ⁻⁶ to 8 × 10 per mol of silver halide.
It can be used at ^-3 mol.

Gelatin is advantageously used as the protective colloid used in the preparation of the silver halide emulsion of the present invention and the binder of the other hydrophilic colloid layers, but other hydrophilic colloids may also be used. it can.

Examples of the hydrophilic colloid include proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein; cellulose derivatives,
For example, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; sugar derivatives, for example, sodium alginate, starch derivatives; various synthetic hydrophilic polymeric substances such as single or copolymers, for example polyvinyl alcohol, polyvinyl alcohol partial acetal, poly -N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole can be used.

Examples of the gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japa.
n, No. 16, P30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

The light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compound and the like, a color mixing inhibitor as commonly used May be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are preferably a high-sensitivity emulsion layer or a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two layer construction can be used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, for example, JP-A-57-112751, JP-A-62-200350, JP-A-62-206541.
No. 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. Specific examples of the arrangement of these photosensitive layers include, for example, a low-sensitivity blue photosensitive layer (BL) / a high-sensitivity blue photosensitive layer (BH) / a high-sensitivity green photosensitive layer (GH ) / Low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH /
BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL /
The order of RH is mentioned. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, from the side farthest from the support, the blue photosensitive layer / GL /
It can also be arranged in the order of RL / GH / RH. In addition, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, there may be mentioned an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order. In addition, in the above-mentioned three-layer structure, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,744
No. 4,707,436, JP-A-62-160448, 63-89850
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide grains other than the tabular grains used in the present invention will be described below. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643.
(December 1978), pp. 22-23, "I. Emulsion pr (Emulsion pr
eparation and types) ”and ibid. No. 18716 (November 1979)
Mon., pp. 648, ibid. 307105 (Nov. 1989), 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chimie et Physique Photographiq.
ue, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VL Zelikman et al., Making and Coating.
It can be prepared using the method described in Photographic Emulsion, Focal Press, 1964) and the like. Also, U.S. Patent Nos. 3,574,628 and 3,655,394 and British Patent No.
The monodisperse emulsions described in 1,413,748 are also preferred.

The silver halide grains used in the present invention may have a uniform crystal structure, may have different halogen compositions inside and outside, may have a layered structure, and may be epitaxial. Silver halides having different compositions may be bonded by bonding, or may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The silver halide emulsion which can be used in the present invention may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside. However, it must be a negative emulsion. Among the internal latent image types, JP-A-63-264740
The core / shell type internal latent image type emulsions described in JP-A No. 1994-242242 may be used. The method for preparing this core / shell type internal latent image type emulsion is
It is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used in the present invention is
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The additive used in such a process is R.I.
D. It is described in No.17643, No.18716 and No.307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, as described above, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the light-sensitive silver halide emulsion are contained in the same layer. It can be used as a mixture. U.S. Pat.No. 4,082,553, the surface of which is covered with silver halide grains, U.S. Pat.No. 4,626,498, the silver halide grains having the inside of the grains described in JP-A-59-214852, and colloidal silver. Can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface thereof means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
626,498 and JP-A-59-214852. The silver halide forming the inner nucleus of the fogged core / shell type silver halide grain may have the same halogen composition as the outer silver halide or a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.
75 μm, particularly preferably 0.05 to 0.6 μm. The particle shape is not particularly limited, and may be regular particles,
Although it may be a polydisperse emulsion, its grain size distribution is monodisperse (at least 80% of the weight or number of silver halide grains is used).
% Having a particle size within ± 30% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average diameter of circles corresponding to the projected area) of preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. in this case,
The surface of the silver halide grain need not be chemically sensitized nor spectrally sensitized. However, before adding this to the coating solution, triazole-based,
It is preferable to add a known stabilizer such as an azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention is 6.0 g / m ²
The following is preferable, and 4.5 g / m ² or less is the most preferable.

Known photographic additives that can be used in the present invention are also described in the above three R.S. D. , And the relevant locations are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866, 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Color sensitizer ~ page 649 right column 4. Whitening agent page 24 647 page right column 868 page 5. Antifoggant, page 24 ~ 25 page 649 right column 868 ~ 870 stabilizer 6 light absorber, 25 Page 26 Page 649 Right column Page 873 Filter dye, Page 650 Left column UV absorber 7. Stain inhibitor Page 25 Right column Page 650 Left column Page 872 Right column 8. Dye image stabilizer Page 25 Page 650 Left column Page 872 9. Hardener page 26 page 651 left column 874 to 875 page 10. Binder page 26 page 651 left column 873 to 874 page 11. Plasticizer and lubricant page 27 650 page right column 876 page 12. Coating aid , Page 26-27 page 650 right column 875-876 surface active agent 13. static page 27 page 650 right column 876-877 page anti-static agent 14. mat agent page 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 may be added to a light-sensitive material. preferable. In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-283
It is preferable to include the mercapto compound described in No. 551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. Dyes or European Patent No. 317,308A, US Pat. No. 4,420,555, and JP-A 1-259358 dispersed in the light-sensitive material of the present invention by the method described in International Publication WO88 / 04794 and Japanese Patent Publication No. 1-502912. It is preferable to include the dyes described in No.

Various color couplers can be used in the present invention, specific examples of which are described in the above-mentioned R.K. D. No.17643,
VII-C to G, and the patents described in No. 307105 and VII-C to G. Examples of the yellow coupler include, for example, U.S. Patent Nos. 3,933,501 and 4,022,620.
No. 4, No. 4,326,024, No. 4,401,752, No. 4,248,96
No. 1, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1
1,476,760, U.S. Pat.Nos. 3,973,968 and 4,314,023
Nos. 4,511,649 and EP 249,473A are preferred. The magenta coupler is preferably a 5-pyrazolone-based or pyrazoloazole-based compound, for example, U.S. Pat.Nos. 4,310,619, 4,351,897, European Patent 73,636, U.S. Pat.3,061,432, and 3,725,0.
No. 67, R.I. D. No. 24220 (June 1984), JP-A-60-335
No. 52, R.I. D. No. 24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat.Nos. 4,500,630 and 4,540,65.
The compounds described in No. 4, No. 4,556,630 and International Publication No. WO88 / 04795 are particularly preferable. Examples of the cyan coupler include phenol-based and naphthol-based couplers, for example, U.S. Pat.Nos. 4,052,212, 4,146,396, and 4,
228,233, 4,296,200, 2,369,929, and
No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308, No. 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453A, U.S. Patent No. 3,446,62.
No. 2, No. 4,333,999, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427,767, No. 4,690,889, No. 4,254,
Compounds described in JP-A Nos. 212 and 4,296,199 and JP-A-61-42658 are preferable. Further, JP-A-64-553 and 64-554
Nos. 64-555 and 64-556, and the imidazole-type couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are described in, for example, US Pat. Nos. 3,451,820 and 4,080,211.
No. 4,367,282, 4,409,320, 4,576,91
No. 0, British Patent 2,102,137 and European Patent 341,188A. Examples of couplers in which the color forming dye has appropriate diffusibility include U.S. Pat.No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication) 3,2
The compounds described in 34,533 are preferred.

Colored couplers for correcting unwanted absorption of color forming dyes are described in R.A. D. No.17643 Item VII-G, N
o.307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929, 4,138,258.
The compounds described in U.S. Pat. No. 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.

In the present invention, compounds which release a photographically useful residue upon coupling can also be preferably used. DIR couplers that release development inhibitors are described in R.S. D. No.17643, VII-F and No.307105, VII-F
Patents described in paragraphs, JP-A-57-151944 and 57-154234
Nos. 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. For example, R. D. No.11449, No.242
41, the bleaching accelerator releasing coupler described in JP-A-61-201247 is effective in shortening the processing time having a bleaching ability, and in particular, a light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,1.
Compounds described in JP-A-88, JP-A-59-157638 and JP-A-59-170840 are preferable. In addition, JP-A-60-107029 and JP-A-60-252340
No. 1, JP-A-1-44940, by the redox reaction with the oxidant of the developing agent described in 1-45687, for example, a foggant,
A compound that releases a development accelerator, a silver halide solvent, etc. is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,130,427.
Competitive couplers as described in U.S. Pat. No. 4,283,47.
No. 2, No. 4,338,393, No. 4,310,618 multi-equivalent couplers, for example, JP-A-60-185950, JP-A-62-24
No. 252, a DIR redox compound releasing coupler,
DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers releasing a dye that undergoes color restoration after separation described in European Patents 173,302A and 313,308A, for example, U.S. Pat. No. 4,555,477. A ligand-releasing coupler according to
Examples thereof include leuco dye releasing couplers described in JP-A-63-75747, and fluorescent dye releasing couplers described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. As an example,
Examples include an oil-in-water dispersion method and a latex dispersion method. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate), benzoic acid esters (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate)
, Amides (eg, N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis ( 2-
Ethylhexyl) sebacate, dioctyl azelate,
Glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene) Is mentioned. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide. The steps of the latex dispersion method, effects and specific examples of the latex for impregnation are described in U.S. Patent No. 4,199,363 and West German patent application (OL
S) No. 2,541,274 and No. 2,541,230.

In the color light-sensitive material of the present invention, for example,
Phenethyl alcohol and JP-A-63-257747 and 62-2722
48, and 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2
It is preferable to add various preservatives or antifungal agents such as -phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The light-sensitive material of the present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports which can be used in the light-sensitive material of the present invention are described in, for example, R. D. No.17643, page 28, No.1
8716, page 647, right column to page 648, left column, and No. 307105, item 8
It is described on page 79.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C, relative humidity 55
% Mean film thickness measured under humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A.Gree
n) Photographic Science and
Engineering (Photogr. Sci. & Eng.), 19 volumes, 2
No., pages 124 to 129
Can be measured by using. That is, T _1/2 is 90% of the maximum swollen film thickness reached when the photosensitive material is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1/2 of the saturated film thickness of the photosensitive material. It is defined as the time to reach. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. Also, the swelling rate is 150-4
00% is preferable. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
This back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. . The swelling ratio of this back layer is 150
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention can be prepared by the method described in R. D. No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-N, N-diethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino- Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl
-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer is a pH buffering agent such as an alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include a development inhibitor or an antifoggant such as
In addition, the color developing solution may contain various hydrazines such as hydroxylamine, diethylhydroxylamine, sulfite, N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, and catecholsulfonic acid, if necessary. Preservatives, organic solvents such as ethylene glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, such as 1-phenyl-3-pyrazolidone. Auxiliary developing agent, viscosity imparting agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and those Containing the salt of.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. These known black-and-white developing agents can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the light-sensitive material 1
It is 3 liters or less per square meter, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. Aperture ratio = [Area of contact between treatment liquid and air (cm ² )] ÷ [Volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. . As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. To further speed up the process, a bleach-fixing process may be performed after the bleaching process. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Examples thereof include polycarboxylic acids or complex salts such as citric acid, tartaric acid and malic acid. Among them, ethylenediaminetetraacetic acid iron (III) complex salts, and aminopolycarboxylic acid iron (III) complex salts including 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts
Is usually 4.0 to 8, but lower pH can be used for speeding up the treatment.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators include, for example, U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812, and 2,059,988.
No. 53-32736, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53-95631, 53-104
No. 232, No. 53-124424, No. 53-141623, No. 53-28426
No., R. D. Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978);
-140129 thiazolidine derivatives; JP-B-45-8506
No. 52-20832, 53-32735, U.S. Pat.
Thiourea derivatives described in 6,561; West German Patent No. 1,127,715
And iodide salts described in JP-A-58-16235; West German Patent No. 96
Polyoxyethylene compounds described in 6,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
Other JP-A-49-40943, 49-59644, 53-94927
No. 54-35727, No. 55-26506, No. 58-163940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858
The compounds described in No. 1, West German Patent No. 1,290,812 and JP-A No. 53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.
In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2 to 5
Specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Of these, the use of thiosulfates is common, with ammonium thiosulfate being the most widely used. It is also preferable to use a combination of thiosulfate and thiocyanate, a thioether compound, or a compound such as thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole. It is preferable to add 0.1 to 10 mol / liter.

The total time of the desilvering step in the development processing is preferably short as long as no desilvering failure occurs. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
℃. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.
In the desilvering process, it is preferable that the stirring is as strong as possible. As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
It is preferable to have the photosensitive material conveying means described in No. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid.
Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step is the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), for example, a replenishing method such as countercurrent or forward flow, It can be set in a wide range according to various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society.
of Motion Picture and Television Engineers 64th
Volume, P.248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above document, the amount of washing water can be significantly reduced, but, for example, due to an increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. There is a problem such as doing. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, edited by Sanitary Technology, "Microbial sterilization, sterilization, and antifungal technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (19
It is also possible to use the fungicide described in 1986).

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543 and 58-14
All the known methods described in No. 834 and No. 60-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and as an example, treatment with a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. Can be mentioned. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds,
Hexamethylenetetramine or aldehyde sulfite adduct can be mentioned. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water.

The silver halide photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Pat.
Indoaniline compounds described in No. 597, No. 3,342,599
No., R. D. No. 14850 and Schiff base type compounds described in No. 15159, aldol compounds described in No. 13924, metal salt complexes described in US Pat. No. 3,719,492, JP-A-53-13
The urethane compound described in No. 5628 can be mentioned. The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3, if necessary, for the purpose of promoting color development.
-Pyrazolidones may be incorporated. Typical compounds are described in, for example, JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide photographic light-sensitive material of the present invention is described in, for example, US Pat. No. 4,500,626 and JP-A-60-133449.
No. 59-218443, No. 61-238056, European Patent No. 210,66
It can also be applied to the photothermographic material described in No. 0A2.

The silver halide photographic light-sensitive material of the present invention, when applied to the lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784, etc., is more effective and more effective. Is.

[0132]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 Deionized alkali-treated gelatin (average molecular weight 100,000)
An aqueous solution prepared by dissolving 4 g and 2.8 g of potassium bromide in 1 liter of distilled water was stirred (600 rpm) at 30 ° C.,
A 1 M aqueous solution of silver nitrate and a 1 M aqueous solution of potassium bromide were added thereto at a flow rate of 100 cc / min for 40 seconds, then pAg was increased to 8.5 and 20 g of inactive gelatin (average molecular weight 100,000) was added, and the mixture was heated to 65 ° C. 50 g of ammonium nitrate and 1M aqueous solution of sodium hydroxide 10
0 cc was added and the mixture was aged for 30 minutes to form a plate nucleus. Subsequently, after adding 8 g of glacial acetic acid, 100% of a 1M aqueous solution of silver nitrate
A tabular silver bromide emulsion was grown by adding cc and a 1M aqueous solution of potassium bromide in equimolar amounts at an addition rate near the critical growth rate and shelling. At this time, the silver potential was maintained at ± 0 mV with respect to the saturated calomel electrode. A total of 135 g of silver nitrate was used for growth. The resulting emulsion was desalted by a usual flocculation method, and then gelatin was added to adjust the pH to 6.0 and pAg to 8.5, and the emulsion was refrigerated. In the obtained emulsion Em-1, grains having an aspect ratio of 3 or more are 8 times the projected area of all silver halide grains in the emulsion.
9% of the emulsion has an average grain size of 0.6 μm,
The equivalent spherical diameter was 0.52 μm, and the coefficient of variation was 27%.

In the method for producing Em-1, a 1M aqueous solution of potassium bromide at the time of nucleation was mixed with potassium bromide and potassium iodide so that the silver iodide content shown in Table 1 was obtained (1
M) to form grains to form emulsions Em-2 to Em-5.
Got

In the process for preparing the emulsions Em-1 to Em-5,
Emulsion Em was prepared by substituting enzyme-processed low-molecular-weight gelatin (average molecular weight 20,000) for grain formation only, and forming the grains.
-6 to Em-10 were obtained. The emulsions prepared as described above are summarized in Table 1.

[0135]

[Table 1]

From Table 1, in the case of gelatin having a normal molecular weight, the tabularization rate decreases as the silver iodide content of the nucleus is increased, whereas in low molecular weight gelatin, the tabularization rate hardly decreases. It is understood that tabular grains can be atomized by increasing the silver iodide content of the nucleus.

Example 2 In the method for producing the emulsion Em-1 of Example 1, the amount of gelatin at the time of nucleation was changed to the amounts shown in Table 2 to prepare emulsions Em-11 to Em-11.
Em-13 was obtained. In addition, in the method for producing the emulsion Em-12,
Emulsion Em-14 was obtained by forming grains by replacing the aqueous potassium bromide solution at the time of nucleation with a mixed aqueous solution of potassium bromide and potassium iodide so that the silver iodide content of the nuclei was 2.2 mol%.

In the process for producing the emulsion Em-6 of Example 1,
The amount of gelatin at the time of nucleation was changed to the amount shown in Table 2, and the aqueous potassium bromide solution at the time of nucleation was changed to potassium bromide so that the silver iodide content of the nuclei became the amount shown in Table 2. The emulsion was replaced with a mixed aqueous solution of potassium iodide to form grains Em-
15 to Em-23 were obtained. The emulsions prepared as described above are summarized in Table 2.

[0139]

[Table 2]

From Table 2, it can be seen that when silver iodide is not contained in the core, there is a limit to the atomization even if the amount of gelatin is changed, regardless of the molecular weight of gelatin used. On the other hand, in the case of low molecular weight gelatin, it is found that remarkable fine graining is possible by setting the silver iodide content of the nucleus to be 4.5 mol% or more.

Example 3 Emulsions Em-24 to Em-28 were prepared by substituting gelatin having an average molecular weight as shown in Table 3 for gelatin only at the time of nucleation in the method for producing emulsion Em-8 of Example 1. Got The results are summarized in Table 3.

[0142]

[Table 3]

From Table 3, the effect of improving the flattening rate by the low molecular weight gelatin is remarkable, and particularly the average molecular weight of 5,000.
It is recognized that the effect is large in the range of up to 40,000.

Example 4 Emulsions Em-29 to Em-34 were prepared by changing the stirring during nucleation from 600 rpm to the values shown in Table 4 in the method for producing the emulsions Em-3 and Em-8 of Example 1. Obtained. The results are summarized in Table 4.

[0145]

[Table 4]

From Table 4, it can be seen that the use of low molecular weight gelatin makes it possible to make the stirring rotation speed dependency during nucleation extremely small. This property is expected to contribute significantly to manufacturing stability. Actually Em-3 and E
When both m-8 were prepared by multiplying the preparation scale by 490 times, the flattening rate was lowered in Em-3 (35%).
However, with Em-8, an emulsion having almost the same tabularization rate (96%) could be obtained. (Here, the preparation apparatus used in Example 1 was used with a magnification of 490 times, and thus 7.88 times in the length dimension. Further, the stirring rotational speed during nucleation was 800 rpm. It was.)

Example 5 In the method for producing the emulsion Em-1 of Example 1, the product name PLURO was used as the polyalkylene oxide block copolymer.
0.3 g of NIC (registered trademark) -31R ₁ (x = x ′ = 25, y = 7 in the above-mentioned compound A) was added at the time of nucleation to form grains to obtain an emulsion Em-35.
Emulsions Em-36 to Em-39 were obtained by making the same changes as to the production methods of the emulsions Em-2 to Em-5. In addition, in the method for producing the emulsion Em-38, the amount of the above-mentioned copolymer added was changed as shown in Table 5 to obtain the emulsion Em-.
40 and Em-41 were obtained. The results are summarized in Table 5.

[0148]

[Table 5]

It is seen from Table 5 that the nucleation in the presence of the polyalkylene oxide block copolymer does not reduce the tabularization rate even if the silver iodide content during nucleation exceeds 4.5 mol%. It was also found that atomization is possible.

Example 6 Emulsions Em-2 to Em-4, E prepared in Examples 1 and 5
The emulsions of m-8 and Em-37 were sensitized with gold and sulfur. The temperature of each emulsion was raised to 60 ° C., and the sensitizing dye described below was added.
B1, B2 and B3 are respectively 2.2 × 10 ⁻³ , 3.
4 × 10 ⁻⁴ , 2.2 × 10 ⁻³ mol / mol Ag, sodium thiosulfate 8.3 × 10 ⁻⁵ mol / mol Ag, chloroauric acid 7.8 × 10 ⁻⁵ mol / mol Ag and thiocyanic acid Potassium 4.1 × 10 ⁻⁴ mol / mol Ag was sequentially added for optimum chemical sensitization, and finally antifoggant-C was added 8.
9 × 10 ⁻⁴ mol / mol Ag was added. Here, “optimally performing chemical sensitization” means performing chemical sensitization that maximizes the sensitivity when exposed for 1/100 seconds after chemical sensitization.

A coating sample was prepared by sequentially providing each layer of the following formulation on the triacetyl cellulose support from the support side. Samples 601 to 605 were prepared by using the emulsion having the emulsion layer chemically sensitized as described above.

(1) Emulsion layer-Emulsion-various emulsions (silver 2.4 x 10 ^-2 mol / m ² ) -Coupler D (1.2 x 10 ^-3 mol / m ² ) -trickle Zirrophosphate (1.10 g / m ² ), gelatin (2.30 g / m ² ) (2) Protective layer, 2,4-dichloro-6-hydroxy-S-triazine sodium salt (0.08 g / m ² ). -Gelatine (1.80 g / m ² ) These samples 601 to 605 were run at 40 ° C and 70% relative humidity.
After being left for 14 hours under the conditions described above, it was exposed for 1/100 seconds through a gelatin filter SC50 manufactured by Fuji Photo Film Co., Ltd. and a continuous wedge, and the following color development processing was performed.

The density of the treated sample was measured with a green filter.

Step Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleach fixing 3 minutes 00 seconds 40 ° C Water washing (1) 20 seconds 35 ° C Water washing (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Drying 50 seconds 65 ° C

Next, the composition of each processing solution used will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) After 5.0 ml Bleaching accelerator shown in Chemical formula 22 above 0.01 mol Water was added to 1.0 liter pH 6.0

(Washing liquid) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg /.
The solution was treated to a volume of 1 liter or less, and then 20 mg / liter of sodium isocyanurate dichloride and 1.5 g / liter of sodium sulfate were added to this solution to obtain a water washing solution. The pH of this liquid is in the range of 6.5 to 7.5.

(Stabilizing Solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 liter pH 5.0 ~ 8.0

The sensitivity of each sample was represented by the relative value of the reciprocal of the exposure dose expressed in lux · sec which gives a density of fog + 0.2. Regarding the sensitivity, the sensitivity of sample 601 is 100
Was evaluated by the relative sensitivity. Also, the gradation is fogging +
A value obtained by subtracting (fog + 0.2) from the optical density obtained when an exposure amount that is 10 times the exposure amount that gives an optical density of 0.2 is compared, and when the gradation of sample 601 is 100 It evaluated by the relative value. The results are summarized in Table 6.

[0160]

[Table 6]

From Table 6, it is understood that the tabular silver halide emulsion atomized by the method of the present invention has high sensitivity and high gradation.

[0162]

[Chemical 19]

[0163]

[Chemical 20]

[0164]

[Chemical 21]

[0165]

[Chemical formula 22]

Example 7 20 g of deionized gelatin (average molecular weight: 100,000), 1350 ml of an aqueous solution containing 0.08 silver mole of emulsion Em-2, which was stored as a seed crystal emulsion and then stored in the refrigerator for 1 day, was kept at 75 ° C. The pH was adjusted to 5.5. Next, an aqueous solution of silver nitrate (AgN
O ₃ (115 g) and an aqueous halogen solution (containing 2.0 mol% of KI with respect to KBr) were accelerated by a double jet and added over 32 minutes to grow particles at an addition rate close to critical growth. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode. Here 8.
After adding an aqueous solution containing 0 g of potassium iodide, an aqueous solution of silver nitrate (AgNO ₃ 53 g) and an aqueous solution of potassium bromide (K
Br37g) was added by double jet. The resulting emulsion was desalted by a usual flocculation method, added with gelatin, and then adjusted to pH 5.5 and pAg 8.8. The obtained emulsion Em-701 was an emulsion in which grains having an aspect ratio of 4.0 or more were present in 81% of the projected area of all silver halide grains in the emulsion, and the equivalent spherical diameter was 1.04 μm and the variation coefficient was 31%. It was a tabular grain.

The temperature of this emulsion Em-701 was raised to 60 ° C.,
Sensitizing Dyes-B1, B2 and B3 listed above at 3.0 x 1
0 ⁻⁴ , 1.2 × 10 ⁻⁵ and 3.5 × 10 ⁻⁴ mol / mol Ag, sodium thiosulfate 8.0 × 10 ⁻⁶ mol / mol A
g, chloroauric acid 1.8 × 10 ⁻⁵ mol / mol Ag, potassium thiocyanate 1.2 × 10 ⁻³ mol / mol Ag and N,
N-dimethylselenourea (5 × 10 ^-6 mol / mol Ag) was sequentially added for optimal chemical sensitization, and at the end, antifoggant-C (3.2 × 10 ^-4 mol / mol Ag) was added.
Here, “optimum chemical sensitization” means 1 after chemical sensitization.
/ 100 means chemical sensitization that maximizes sensitivity when exposed for 100 seconds.

In the process for preparing the emulsion Em-701, the seed crystal emulsion Em-2 was replaced with the emulsions Em-3, Em-4, Em-8 and Em-37, and the emulsions Em-702 to Em-702 were respectively prepared.
m-705 was prepared. Chemical sensitization is Em-7
The chemical sensitization was optimally performed according to the method of No. 01. The results are summarized in Table 7.

[0169]

[Table 7]

Then, using each emulsion in Table 7, a sample was prepared in the same manner as in Example 6, and the sensitivity and gradation were evaluated. Here, the sensitivity and the gradation are shown as relative values when the sensitivity and the gradation of the sample 701 are set to 100, respectively.
The results are shown in Table 8.

[0171]

[Table 8]

Table 8 shows that the emulsion obtained by using the tabular silver halide emulsion of the present invention as a seed crystal has high sensitivity and high gradation.

Example 8 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 801 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 801) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0175]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion of Sample 601 of Example 6 Silver 0.52 ExS-1 2.2 × 10 ^-3 ExS-2 3.4 × 10 ^-4 ExS-3 2.2 × 10 ^-3 ExC -1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.77 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion of Sample 701 of Example 7 Silver 1.45 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 3.5 × 10 ^-4 ExC -1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.6 × 10 ^-4 ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Thirteenth layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

14th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt.

[0189]

[Table 9]

In Table 9, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope.

[0191]

[Chemical formula 23]

[0192]

[Chemical formula 24]

[0193]

[Chemical 25]

[0194]

[Chemical formula 26]

[0195]

[Chemical 27]

[0196]

[Chemical 28]

[0197]

[Chemical 29]

[0198]

[Chemical 30]

[0199]

[Chemical 31]

[0200]

[Chemical 32]

[0201]

[Chemical 33]

[0202]

[Chemical 34]

[0203]

[Chemical 35]

[0204]

[Chemical 36]

[0205]

[Chemical 37]

The emulsion used in the third layer of Sample 801 was prepared as follows.
Samples 802-805 were prepared in place of the emulsions used in samples 602-605 of Example 6. The emulsion used for the fifth layer of Sample 801 was prepared as Sample 702-7 of Example 7.
Samples 806-80 in place of the emulsion used in
9 was created.

The color photographic light-sensitive materials 801-as described above
809 was exposed through a continuous wedge for 1/100 second, and then the following method was used using an automatic processor (until the cumulative replenishment amount of the bleaching solution became 3 times the mother liquor tank capacity).
Processed.

Treatment Method Process Treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 25 ml 10 liters Bleach 45 seconds 38 ℃ 5 ml 4 liters Bleach fixing (1) 45 seconds 38 ℃ ― 4 L bleach-fixing (2) 45 seconds 38 ℃ 30 ml 4 liters Water wash (1) 20 seconds 38 ℃ ― 2 liters Water wash (2) 20 seconds 38 ℃ 30 ml 2 liter stability 20 seconds 38 ℃ 20 ml 2 liter dry Dry 1 min 55 ℃ * Replenishment amount is 35 mm width per 1 m length

Each of the steps of bleach-fixing and washing with water was a countercurrent system from (2) to (1), and the overflow solution of the bleaching solution was all introduced into bleach-fixing (2). still,
In the above processing, the amount of the bleach-fixing solution brought into the washing step was 2 ml per 1 m length of the light-sensitive material having a width of 35 mm.

The composition of the treatment liquid used for each treatment is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 Potassium iodide 1.2 mg-Hydroxylamine sulfate 2.0 3.6 4- [N- Ethyl-N-β-hydroxyethylamino] -2-methyl-aniline sulphate 4.7 6.2 Add water 1.0 liter 1.0 liter pH 10.00 10.15

(Bleaching solution) Mother liquor (g) Replenishing solution (g) 1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 144.0 206.0 1,3-diaminopropanetetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4

(Bleach-fixing solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 25.0 Ammonium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320.0 ml Ammonia water (27%) 6.0 ml 15.0 ml Add water 1.0 liter 1.0 liter pH 6.8 8.0

(Washing Water) Common to mother liquor and replenisher tap water was prepared using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IRA-). Four
(00) and water are passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter of sodium isocyanurate dichloride and 150 mg / liter of sodium sulfate are added to this solution. Was added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 [C ₁₀ H ₂₁ —O— (CH ₂ CH ₂ O) ₁₀ —H] Ethylene glycol 1.0 Water 1.0 liter pH 5.0-7.0

After the treatment, the same evaluation as in Example 6 was carried out and the same effect was confirmed.

[0216]

As described above in detail, in the tabular silver halide emulsion preparation method according to the present invention, it is possible to atomize while maintaining a high tabularization rate, and the stability in the manufacturing process is greatly improved. The present invention has a remarkable effect in providing a high-sensitivity silver halide photographic light-sensitive material.

Claims (8)

[Claims] 1. A tabular silver halide grain having an average grain size of 0.6 μm or less and an aspect ratio of 3 or more is a whole silver halide by undergoing nucleation, Ostwald ripening and grain growth of silver halide grains. 50 of the projected area of the particle
%, 50% by weight or more of the dispersion medium at the time of forming the nuclei has a molecular weight of 7%.
A method for producing a silver halide emulsion, characterized in that it is an aqueous solution of gelatin having a molecular weight of 10,000 or less and nuclei are formed so that the average silver iodide content is 4.5 mol% or more. 2. A tabular silver halide grain having an average grain size of 0.6 μm or less and an aspect ratio of 3 or more is a total silver halide by undergoing nucleation, Ostwald ripening and grain growth of silver halide grains. 50 of the projected area of the particle
In the method for producing a silver halide emulsion occupying at least 1%, the dispersion medium at the time of nucleation contains a polyalkylene oxide block copolymer, and the average silver iodide content is 4.
A method for producing a silver halide emulsion, which comprises forming nuclei so that the content of the silver halide is 5 mol% or more. 3. A method for producing a silver halide emulsion, which comprises using the silver halide emulsion according to claim 1 as a seed crystal to grow grains for preparation. 4. A method for producing a silver halide emulsion, which comprises using the silver halide emulsion according to claim 2 as a seed crystal and growing the grains to prepare a seed crystal. 5. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 1 on a support. 6. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 2 on a support. 7. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 3 on a support. 8. A silver halide photographic light-sensitive material, comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 4 on a support.