JPH0980657A - Manufacture of silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing flat particles such that most of the particles obtained have a low percentage of twin particles, and that their principal planes, most of which have two twin planes, consist of (111) faces. SOLUTION: In a method for manufacturing an emulsion made from high silver chloride flat particles consisting of at least 50mol% or more chloride for all halogens in silver halide particles and having a principal plane consisting mainly of a (111) face, a high silver bromide emulsion made from at least 50mol% or more bromide for all the halogens in the silver halide particles and having two parallel twin planes is prepared in the absence of a crystal phase controlling agent and this silver halide emulsion is used as a seed crystal emulsion; next, the seed crystal emulsion is grown in the presence of the crystal phase controlling agent to obtain flat silver halide emulsion particles whose principal plane consists mainly of a (111) face and which consist of flat particles for 50% or more of projected area.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a silver halide emulsion for photography. In particular, the present invention relates to a method for producing high silver chloride tabular grains having a chloride content of at least 50 mol% and a main surface mainly of a (111) plane.

[0002]

2. Description of the Related Art Generally, silver halide grains having a high silver chloride content (hereinafter referred to as "high silver chloride grains") are likely to be cubic or tabular grains having (100) faces as main surfaces. Basics of photographic engineering, p1 of silver salt photography (published by Corona Publishing Co., Ltd.)
As shown in FIG. 65, the tabular grains whose main surface is the (111) plane always have two parallel twin planes regardless of the halogen composition. It is easy to form cubic or tabular grains having no twin planes, the tabular grains having a high silver chloride grain with two parallel twin planes and a main surface consisting of (111) planes. It was very difficult to prepare. However, as a method for simultaneously performing twin plane formation and (111) plane formation, in the presence of a crystal habit control agent (also called a crystal habit control agent or a growth modifier),
For example, the following patents are known as a technique for forming tabular grains whose main surface is mainly (111) plane by forming grains.

1. U.S. Pat. No. 4,399,215. Regarding tabular grains of high silver chloride having a silver chloride content of 50 mol% or more, bromide and iodide were not contained therein, pAg was kept in the range of 6.5 to 10 and pH was kept in the range of 8 to 10. A method of forming particles in the presence of ammonia. 2. U.S. Pat. No. 4,400,463. A method for forming particles in the presence of a peptizer having an aminoazaindene and a thioether group. 3. JP-A-62-218959. A method of forming particles in the presence of a thiourea compound. 4. JP-A-62-163046. At least 0.5 mo
under a concentration of chloride ion and a methionine content of 30
A method of forming particles using gelatin having a concentration of less than μmol / g. 5. A method of forming grains in the presence of a sensitizing dye described in JP-A-64-70741. 6. A method of forming particles in the presence of a compound described in JP-A-1-155332. 7. A method of forming particles in the presence of a compound described in JP-A-2-32. 8. JP-A-6-11787, methionine content of 30μ
Method for forming particles in a dispersion medium containing chlorine ion and 4,6-di (hydroamino) -5-aminopyrimidine exceeding 0.5 mol concentration at least at pH 4.5 using high methionine gelatin exceeding mol / g . 9. A method for forming particles in the presence of a compound described in US Pat. No. 4,804,621. Etc. are known.

However, all of these patents realize the (111) plane formation and the twin plane formation by the presence of the crystal habit controlling agent from the stage of nucleation and with the aid of the controlling agent. 8. JP-A-6-11787 discloses an example in which a crystal habit controlling agent is added after nucleation, but in the text, the interaction between silver and a crystal habit controlling agent such as adenine during nucleation (formation of silver salt). In order to avoid the twinning, it is described that twinning is performed by adding a crystal habit controlling agent (growth modifier), and the chloride ion concentration at the time of nucleation and other conditions greatly differ from those of the present invention. The way of thinking about formation is completely different.
Further, the tabular grains prepared by the methods of the above-mentioned Patents 1 to 9 are more polydisperse than the well-known tabular grains of silver bromide and silver iodobromide, and have only one twin plane. So-called single twin grains, multiple twin grains having two or more non-parallel twin planes, and normal grains not having twin planes are mixed, and two parallel twin planes are present. The main plane with has (1
The proportion of tabular grains as the (11) plane is small, and it is very difficult to prepare these grains by the conventional method in which the crystal habit controlling agent is introduced at the time of nucleation.

[0005]

The object of the present invention is to obtain a high-concentration crystal having a main surface of (111) plane, which has very few non-parallel twin grains, and which is very monodisperse. It is to provide a method for producing tabular grains of silver chloride.

[0006]

The object of the present invention is to use all of the silver halide grains in a method for producing a silver halide emulsion comprising high silver chloride tabular grains whose main surface is a (111) plane. High-silver bromide grains having two parallel twin planes composed of 50 mol% or more of bromide with respect to the amount of silver were prepared in the absence of a crystal habit-controlling agent, and this seed crystal emulsion was treated with the crystal habit-controlling agent. 50% or more of the projected area of all silver halide grains characterized by being grown in the presence of
This is achieved by a method for producing a silver halide emulsion comprising tabular grains having a chloride content of 50 mol% or more based on the total amount of silver in the silver halide grains.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION That is, in the present invention, at least 50 mol% or more of bromide is used in the production of high silver chloride tabular grains composed of at least 50 mol% or more of chloride and having a major surface mainly of (111) faces. It was made possible by the method for producing tabular silver halide emulsion grains having a major surface mainly of (111) by growing a high-silver bromide tabular grain emulsion of as a seed crystal emulsion and growing it in the presence of a crystal habit controlling agent. .

The components of the present invention will be described in detail below. (High silver bromide seed crystal emulsion having two parallel twin planes) In the present invention, seed crystals are prepared without using a crystal habit controlling agent. The shape after the seed crystal is grown is mainly (1
The seed crystal is preferably a tabular grain in order to form a tabular grain having a 11) plane. The reason is that if the seed crystals are spherical or octahedral, it may be possible that only the aspect ratio of the tabular grains after growth is very low, depending on the grain size. This is because the tolerance of the aspect ratio of tabular grains that can be selected according to As a specific method for producing a seed crystal of high silver bromide tabular grains, the methods described in JP-A-1-158426 and JP-A-2-838 can be referred to. The bromide content of the seed crystal high silver bromide tabular grains is 50 mol% or more, preferably 75% or more, more preferably 90 mol% or more. It is also possible to allow a small amount of iodide to be present at the time of seed crystal formation, and 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, non-parallel twin grains or parallel twin crystals. It is possible to exist under the condition that the ratio of twin grains having three or more planes is not increased so much.

(Protective Colloid) In the present invention, gelatin is effective as a protective colloid used for seed crystal nucleation. Examples of gelatin include alkali-treated gelatin, acid-treated gelatin, and gelatin derivatives such as acetylated gelatin and phthalated gelatin. Among these, alkali-processed gelatin made from bovine bone is effective. The molecular weight of gelatin used for nucleation is preferably low molecular weight gelatin as described in JP-A-1-158426 and JP-A-2-838, but in the production method of the present invention, when the chloride content is increased, it is not parallel. Twinned particles tend to be formed, and as the chloride content increases, 30,000 or more, preferably 50.
It may be better to use gelatin having a high molecular weight of 000 or more. Other protective colloids include agar, starch, dextran, natural products such as silk fibroin, and synthetic protective colloids such as acrylamide, amino group, vinyl alcohol, acrylic acid, hydroxyquinoline, vinylpyrrolidone, styrene, vinylimidazole, azaindene, A homopolymer or copolymer having a functional group such as a thioether or pyridine group can be used. These can be variously selected and used in a region where the grain size at the time of nucleation is not extremely increased and a large number of non-parallel twin grains do not exist. The protective colloid during nucleation is usually preferably placed in the reactor as an aqueous solution in which the protective colloid has been previously dissolved before adding the silver salt solution. There is also a method of adding it by dissolving it in a silver salt solution or a halogen solution or a method of adding it in a solution or a solid state at the time of adding the silver salt solution or the halogen solution, which can be selected or combined depending on the purpose. .

After nucleation, ripening is carried out to eliminate normal grains having no twin planes or single twin grains having one twin plane as much as possible, and grains having two parallel twin faces. (Often tabular grains in the present invention) are grown as needed, but it is very effective to add an additional protective colloid during this period. The additional protective colloid can be selected and used from the above-mentioned protective colloids, but when added in the ripening step, gelatin having a molecular weight of 50,000 or more is preferably used. Further, natural products other than gelatin having a protective colloid property equivalent to or higher than that of gelatin having a molecular weight of 50,000 or a synthetic protective colloid can be used even if it has a low molecular weight.

The seed nucleation temperature may be in the range of 15 to 60 ° C., preferably 20 to 50 ° C., more preferably 20 to 45 ° C. 35 ° C. for growing the two grains having parallel twin planes (hereinafter sometimes referred to as double twin grains) remaining after aging.
It is preferred to grow in the range of ~ 95 ° C, preferably 40 ° C to 90 ° C, and more preferably 40 ° C to 85 ° C.

The pH at the time of preparing the seed crystal may be such that the silver halide grains are not fogged by themselves.
It is preferably carried out in the range of 1 to 10, more preferably p
The range of H3 to 9 is preferable.

The seed crystals used in the present invention are mainly (111)
The ratio of the diameter of the main surface, which is a plane, to the thickness of the tabular grains when converted to a circle (hereinafter referred to as the aspect ratio) exceeds 1 and is 100,
It is preferably 1 or more and 50 or less, more preferably 2 or more and 20 or less. The diameter of the tabular grains may be about 0.1 μm or more and 20 μm or less, but when used as a seed crystal, the range of about 0.1 μm or more and 5 μm or less is preferable. A suitable thickness is about 1 μm or less, but when used as a seed crystal, the thickness is 0.01 μm
It is preferably prepared in the range of 0.5 μm. However, the thickness referred to here is represented by the distance between two parallel principal planes constituting the tabular grain. In the present invention, the seed crystal tabular grains may be 50% or more of the projected area, preferably 60%.
The above is more preferable, and 70% or more is more preferable. The size distribution of the tabular grains of the seed crystal of the invention may be polydisperse or monodisperse. Generally, those having a coefficient of variation of about 60% to those having a good monodispersity of about 20% can be used according to the purpose.

After the seed crystals have been prepared, the emulsion can be desalted and washed with water by a conventional flocculation method, a natural precipitation method, a centrifugal separation method, an ultrafiltration method, an isoelectric point coagulation method, or the like. is there. Desalting is generally performed after seed crystal formation, but in the present invention, desalting may be carried out at any next stage depending on the purpose, for example, after aging and before growth, and washing may be carried out. You don't have to. Further, after forming the high silver bromide flat plate, the high silver chloride flat plate may be grown in the same reaction vessel as it is without desalting.

In the present invention, after the seed crystal is prepared, the seed crystal is grown to have a chloride content of 50 mol% with respect to the finally used silver.
Tabular grains are prepared as described above. At this time, as the Cl content increases, the particle surface becomes the (100) plane (1
11) Use a crystal habit controlling agent to maintain the surface. As the crystal habit controlling agent, those generally used for forming high silver chloride tabular grains can be used, and as typical compounds, there are patents shown in the above paragraphs (0003) 1 to 9.

In addition to these, the crystal habit controlling agents described in the following patents are also effective. (The compounds cited in these specifications or publications are effective crystal habit controlling agents in the present invention by citing the patents cited below.) US Pat. No. 4,399,215 and US Pat. No. 441430.
6, US Pat. No. 4,400,473, US Pat. No. 471.
3323, JP-A-62-163046, JP-A-59
-162540, U.S. Pat. No. 4,942,120, U.S. Pat. No. 5,061,617, U.S. Pat. No. 5,185,239.
No. 5,178,997, US Pat. No. 5,178.
998, US Pat. No. 5,176,992, US Pat. No. 5
183732, US Pat. No. 4,804,621, Japanese Patent Publication No. 55-42737, EP0532801A1, EP.
0481333A1, JP-A-62-218959,
JP-A-63-213836, JP-A-63-21893
No. 8, JP-A-63-293536, JP-A-3-116.
113, JP-A-2-32, and JP-A-3-212639.
JP-A-4-283742, JP-A-4-33563
No. 2, JP-A-3-137632, JP-A-3-2526.
49, JP-A-3-127045, JP-A-63-20.
43, JP-A-62-2999961, JP-A-63-4
1845, JP-A-3-288143, JP-A4-1
61947, JP-A-64-70741, JP-A-64
-79744, JP-A-1-155332, JP-A-1
No. 159646, Japanese Patent Application Laid-Open No. 1-250943, Japanese Patent Application Laid-Open No. 2-43535, Japanese Patent Application Laid-Open No. 4-6546, US Pat. No. 4,783,398, Japanese Patent Application Laid-Open No. 63-25643, EP0.
No. 534325A, Japanese Patent Publication No. 5-12696, US Pat. No. 5,176,991, US Pat. No. 4,804,621, JP-A-6-11787, US Pat. No. 5,250,408,
JP-A-1-102453, etc.

Specifically, the compounds represented by the general formula (I) described on page 3 of JP-A-1-155332 and the compounds described on pages 3 to 4 can be used. The following compounds may be mentioned as examples.

[0018]

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Further, the compounds represented by the general formulas (I) and (II) described on pages 3 to 4 of JP-A-2-32 and the compounds described on pages 4 to 6 are used. You can The following compounds may be mentioned as examples.

[0020]

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The applicant is Fuji Photo Film Co., Ltd., and the reference number 875 filed on Dec. 19, 1994.
The title of the invention, which is 00758, is described on pages 8 to 9 of the compound represented by formula (I) described on pages 6 to 8 of the specification of "Method for producing silver halide emulsion for photography". Compounds can be used. The following compounds may be mentioned as examples.

[0022]

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The crystal habit controlling agent may be added in a final required amount just before or at the same time as the growth is started, or may be added in a silver or halogen solution to be added during the growth, or a silver salt solution or a halogen. Various addition methods can be selected according to the purpose, such as a method of adding little by little or at a stretch during growth without mixing with the solution, or a method of adding a portion immediately before or at the start of growth and adding the rest during growth can do.

In order to grow the tabular grains of the seed crystal to a desired size, a silver salt solution (eg silver nitrate aqueous solution) and a halide solution (eg sodium chloride aqueous solution) may be added to the reaction solution. It is also possible to use a method of adding while accelerating or optionally decelerating the addition amount and the addition concentration. Regarding these methods, for example, British Patent No. 1335925 and US Patent No. 3672900.
No. 3,650,757, No. 4,242,445, JP-A Nos. 55-142329, 55-158124,
Reference can be made to the descriptions of No. 58-113927, No. 58-113928, No. 58-111934, No. 58-111936 and the like. It is also possible to grow fine grains by Ostwald ripening by adding a fine grain silver halide emulsion having a size smaller than that of the grains after ripening. The halide composition of the halide solution or fine grain silver halide emulsion to be added may be such that the chloride content of the finally obtained tabular silver halide emulsion grains is 50 mol% or more with respect to silver, and it is added at the time of growth. The halogen composition of halogen can be added while being arbitrarily changed within this condition.

The temperature during seed crystal growth is in the range of 25 ° C to 95 ° C, preferably 40 ° C to 90 ° C, and more preferably 40 ° C.
It is preferable to grow in the range of ℃ to 85 ℃. The pH during seed crystal growth may be such that the silver halide grains are not fogged by themselves, but is preferably in the range of pH 1 to 10, more preferably pH 3 to 9.

A silver halide solvent may be used at the time of seed crystal formation, nucleation and seed crystal growth. A typical silver halide solvent is thiocyanate (US Pat.
No. 22264, No. 2448534, No. 33200
69), thioether compounds (US Pat. No. 3271)
No. 157, No. 3574628, No. 3704130.
No. 4,297,439, No. 4,276,347, etc.), thione compounds and thiourea compounds (JP-A-53-53).
144319, 53-82408, 55-77.
737), amine compounds (JP-A-54-10071).
No. 7, etc.) and the like, and these can be selected and used variously according to the purpose. Ammonia can also be used within a range that does not cause fogging due to pH increase. Further, among these silver halide solvents, there are some which function as a crystal habit controlling agent which gives a (111) plane.

After the seed crystal growth, the emulsion can be desalted and washed with water by a conventional flocculation method, a natural precipitation method, a centrifugal separation method, an ultrafiltration method, an isoelectric focusing method or the like. is there. Desalting is generally performed after seed crystal growth, but in the present invention, desalting and washing with water may be performed at any time depending on the purpose, for example, before seed crystal growth.

The high silver chloride tabular grains obtained by the method of the present invention have a ratio of the diameter to the thickness of the tabular grains (hereinafter referred to as aspect ratio) of 1 when the main surface, which is mainly the (111) plane, is converted into a circle. It is preferably more than 1 and 50 or less, more preferably more than 1 and 50 or less, and further preferably 2 or more and 50 or less. A tabular grain having a diameter of 0.1 or more and 20 μm or so may be photographically suitable, but not limited to this range, various sizes can be prepared according to the purpose.
A thickness of 1 μm or less is suitable for photography, but
Various thicknesses can be selected and prepared according to the purpose. However, as a photographic light-sensitive material, it is generally 0.01 to 1 μm.
It is preferably in the range of m, 0.01 to 0.7 μm
It is even more preferable that it is within the range. However, the thickness referred to here is represented by the distance between two parallel principal planes constituting tabular grains. In the present invention, tabular grains have a projected area of 5
It may be 0% or more, preferably 60% or more, more preferably 70% or more. The size distribution of the tabular grains of the present invention may be polydisperse or monodisperse. Generally, those having a coefficient of variation of about 60% to those having a good monodispersity of about 20% can be used according to the purpose.

The high silver chloride tabular grain of the present invention may have a chloride content of 50% or more, preferably 65% or more, more preferably 85% or more. The chloride content of 50% or more means that the content of chloride is 50% or more with respect to the total silver halide after growth, and the halogen composition during the growth and the growth is optional depending on the purpose regardless of the above ratio. Can be changed to

Chemical Sensitization In the present invention, various kinds of chemical sensitizers usually used can be used. The chemical sensitizers used for chemical sensitization include chalcogen sensitization. Examples of chalcogen sensitizers include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and known ones such as those mentioned below can be mentioned. As the sulfur sensitizer, an unstable sulfur compound is used, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), allylisourea Well-known sulfur compounds such as thiocyanate, cystine, p-toluenethiosulfonate, rhodanines and mercaptos may be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. Appropriate amounts include pH, temperature, compatibility with other sensitizers, size of silver halide grains, etc. Although it varies depending on various conditions, as a guide, it is preferable to use it in the range of 10 ^-9 to 10 ^-1 mol per mol of silver halide.

In the selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) are used. ), Selenoketones, selenoamides, aliphatic isoselenocyanates (for example, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters, selenophosates, diethyl selenides, diethyl selenides and other selenides. Can be used. The amount of addition varies depending on various conditions as in the case of the sulfur sensitizer, but it is preferably used in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide.

In the present invention, in addition to the above chalcogen sensitization, sensitization with a noble metal can also be performed. First, in gold sensitization, the valence of gold may be +1 or +3,
Various gold compounds are used. Representative examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodooleate, tetraauric acid, ammonium aurothiocyanate, pyridyl trichlorogold,
Gold sulfide, gold selenide, gold telluride and the like. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is preferable to use it in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide. The gold sensitizer may be added at the same time as sulfur sensitization, selenium sensitization, or tellurium sensitization, during, before, after, or after the sulfur or selenium / tellurium sensitization step. It is also possible to use. The pAg and pH of the emulsion to be subjected to sulfur sensitization, selenium sensitization, tellurium sensitization or gold sensitization in the present invention are not particularly limited, but the pAg is preferably 5 to 11, and the pH is preferably 3 to 10. . In the present invention, noble metals other than gold can be used as the chemical sensitizer. As a noble metal other than gold, for example, a metal salt such as platinum, palladium, iridium and rhodium or a sensitizer based on a complex salt thereof can be used.

In the present invention, reduction sensitization can be further carried out. As the reduction sensitizer used in the present invention, ascorbic acid, stannous salts, amines and polyamines,
Hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention,
One of these known compounds can be selected and used,
Two or more compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid and aminoiminomethanesulfinic acid are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-9 to 10 ^-2 mol per mol of silver halide. In addition to the method of adding the above-described reduction sensitizer, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, a method of growing in a high pH atmosphere of pH 8 to 11 called high pH ripening, Alternatively, a method of aging, a method of passing hydrogen gas, or a method of reduction sensitization by hydrogen generated during electrolysis can be selected. Further, two or more methods can be used in combination. Although this reduction sensitization can be used alone,
It can also be used in combination with the above chalcogen sensitization or precious metal sensitization.

The emulsions of the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, 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 those generally used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like: a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; benzindo A renin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or the complex merocyanine dye includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanin nucleus as a nucleus having a ketomethylene structure. , 5 to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.

The dye may be added to the emulsion at any stage of emulsion preparation. Most commonly, the chemical sensitization is performed after the completion of the sensitization but before the coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, it is added simultaneously with the chemical sensitizer, Japanese Patent Application Laid-Open Publication No.
It can also be carried out prior to the chemical sensitization as described in JP-A-8-113928. Further, it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, it is possible to add these said compounds separately, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. Can be added later and can be at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. The color photographic light-sensitive material is particularly used for color paper, color photographic film, color reversal film, and the black-and-white photographic light-sensitive material includes X-ray film, general photographic film, printing light-sensitive film and the like. it can. Particularly, it can be preferably used for color paper.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 1
76 volumes, item 17643 (RD-17643), 187 volumes, item 18716 (RD-18716) and 307 volumes, item 307105, etc. can be referred to.

RD-17643 and RD-18716
The places where the various additives are described are listed below. ──────────────────────────────────── Additive type RD17643 RD18716 ───────── ──────────────────────────── 1 Chemical sensitizer page 23 648 Right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer 23〜 Page 24 648 Right column ~ Supersensitizer 649 Right column 4 Whitening agent Page 24 5 Fog inhibitor 24-25 Page 649 Right column ~ and Stabilizer 6 Light absorber, F 25-26 Page 649 Right column ~ Silter dye page 650 left column infrared absorber 7 stain inhibitor page 25 right column page 650 left to right column 8 dye image stabilizer page 25 9 hardening agent page 26 651 left column 10 binder 26 page ibid 11 plasticizer, Lubricants Page 27 Page 650 Right column 12 Coating aids, Interfaces 26-27 Same as above Activator 13 Static inhibitor Page 27 Same as above ────────────────────────────────────

Of the above-mentioned additives, antifoggants and stabilizers are azoles (for example, benzothiazolium salts,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles,
Aminotriazoles, etc.); Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and its derivatives), mercapto) Pyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), pentaazaindenes and the like}; benzenethiosulfones; benzenesulfinic acid; benzenesulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule, or a polymerized one. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion.
Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be included. Further, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. For example, as a magenta coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, a pyrazolotetrazole coupler,
There are cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), etc.,
Cyan couplers include naphthol couplers and phenol couplers. As cyan couplers, US Pat. Nos. 3772002, 2772162, and 375
No. 8308, No. 4126396, No. 4334011
Nos. 4327173, 3446622 and 43
No. 33999, No. 4451559, No. 4427767
Phenol couplers having an ethyl group at the meta position of the phenol nucleus, phenol couplers substituted with 2,5-diacylamino, phenols having a phenylureido group at the 2-position and an acylamino group at the 5-position Based couplers and couplers in which sulfonamide, amide, etc. are substituted at the 5-position of naphthol are preferred because of their excellent image fastness. The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be added to two or more different layers, as a matter of course.

As the anti-fading agent, hydroquinone, 6
-Hydroxychromans, 5-hydroxycoumarins,
Spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds are silylated and alkylated. The ether or ester derivative is a typical example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Photographic processing of a light-sensitive material using the present invention includes
Any of the known methods can be used, and a known treatment solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black and white photographic process) and a color photographic process including a developing process for forming a dye image can be applied. Black-and-white developers include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-
3-pyrazolidone), aminophenols (for example, N-
Known developing agents such as methyl-p-aminophenol) can be used alone or in combination. The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known general aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N). -Ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline). In addition, L. F. A.
226, published by Focal Press (1966), "Photographic Processing Chemistry" by Meson.
~ 229, U.S. Pat. Nos. 2,193,015 and 25,923.
Those described in each specification of No. 64 and JP-A No. 48-64993 may be used.

The developing solution may be a development buffer such as a pH buffering agent such as an alkali metal sulfite, a carbonate, a borate and a phosphate, a bromide, an iodide or an organic antifoggant. An anti-fogging agent or the like can be included. Also, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers Competitors, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity improvers, U.S. Pat.
It may contain a polycarboxylic acid-based chelating agent described in JP 0837323 A, an antioxidant described in West German Patent Publication (OLS) 2622250, and the like.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. Examples of bleaching agents include iron (III) and cobalt (III)
Compounds of polyvalent metals such as chromium (IV), copper (II), peracids, quinones, and nitroso compounds are used. For example,
Organic complexes of phenylicyanide, dichromate, iron (III) or cobalt (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid) Complex salts of organic acids such as tartaric acid and malic acid), persulfates, permanganates and nitrosophenols. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) acetate and ammonium ethylenediaminetetraacetate (III) acetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution. Bleaching or bleach-fixing solutions are disclosed in US Pat.
Nos. 520 and 3241966, Japanese Patent Publication No. 45-
In addition to the bleaching accelerators described in JP-A-8506 and JP-B-45-8836 and the thiol compounds described in JP-A-53-65732, various additives can be added. After bleaching or bleach-fixing, washing treatment may be performed, or only stabilizing bath treatment may be performed.

[0045]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Example 1 (Preparation of seed crystal) 890 cc of water, low molecular weight gelatin (molecular weight of about 15,000) and 0.25 g of potassium bromide were placed in a reaction vessel and dissolved at 40 ° C with stirring. Then the solution at 30 ℃
After stabilization, the solution A and solution B shown below were simultaneously added at a flow rate of 57.6 cc / min for 15 seconds. After 45 seconds, the temperature was raised to 75 ° C over 17 minutes. In addition, 1
Solution C was added at 5 minutes. One minute after the temperature reached 75 ° C., solution D was added for 10 minutes at a constant flow rate of 5.24 cc / min. 10 minutes after the addition was completed, this time, the liquid E was first added at 0.96 cc / mi.
It was added over 52 minutes and 36 seconds while performing primary acceleration so that the final n was 16.11 cc / min. At this time, the silver potential was controlled by the CDJ method so that the liquid F was used so as to be +30 mV with respect to the calomel electrode. After the addition was completed, the temperature was lowered to 35 ° C., washing with water was carried out by a usual flocculation method, and then water, gelatin, a preservative and sodium chloride were added to give an emulsion having a pH of 6.5 and a pAg of 8.6 at 40 ° C. . FIG. 1 shows an electron microscope replica photograph of emulsion grains. Average D
-Circle is about 0.87μm and average thickness is about 0.12μm
, Silver bromide tabular grains having an average aspect ratio of 7.25 were obtained. This emulsion is referred to as seed crystal A. (Preparation of high-silver chloride tabular grains whose main plane is (111)) 72 g of seed crystal A (corresponding to 0.053 mol of silver bromide), 24.2 g of deionized inert gelatin, and water 1 in a reaction vessel.
521 cc was added and dissolved at 40 ° C. with stirring to adjust the pH to 5.0. Next, after the temperature was raised to 75 ° C. and became stable, 150 cc of a 0.02 mol / liter solution of the crystal habit controlling agent shown in “Chemical formula 4” was added, and 1 minute after that, solution A-2 was initially added. The addition was carried out for 92 minutes and 6 seconds while the primary acceleration was performed so as to finally reach about 15.1 cc / min at 1 cc / min. At the same time as the addition of the solution A-2 was started, the solution B-2 was used to adjust the CDJ to +125 mV with respect to the calomel electrode.
The silver potential was controlled by a method to prepare silver bromochloride tabular grains having a Br content of about 7.5 mol% and a main plane consisting of (111) planes.
FIG. 2 shows an electron microscope replica photograph of emulsion grains. The tabular grains had an average D-circle of about 1.375 µm, an average thickness of about 0.56 µm, and an average aspect ratio of about 2.5.

(Composition of solution A) Silver nitrate 1.728 g Water is added to a total amount of 14.4 cc (Composition of solution B) Potassium bromide 1.2096 g Water is added to a total amount of 14.4 cc

(Composition of solution C) Deionized gelatin 30 g Water 300 cc (Composition of solution D) Silver nitrate 6.288 g Water was added to give a total amount of 52.4 cc

(Composition of solution E) 112.225 g of silver nitrate Water is added to give a total amount of 700 cc (Composition of solution F) 210 g of potassium bromide Water is added to give a total amount of 1200 cc

[0049]

Embedded image

(Composition of liquid A-2) 111.15 g of silver nitrate: total amount of water 741 cc (composition of liquid B-2): sodium chloride 63 g: total amount of water 1200 cc

Example 2 (Preparation of fine grain emulsion for growth) 1564 cc of water was added to a reaction vessel.
Deionized inert bone gelatin (molecular weight about 100,000) 6
Add 2g and 0.4g of sodium chloride and stir 40
After the gelatin was dissolved at ℃, the temperature was lowered to 35 ℃ and the temperature became stable. Then, the following liquids A-3 and B-3 were 45cc / mi each.
It was added at a constant rate of n for 20 minutes. 35 ° C after the addition is complete
As it is, sedimentation and desalting of the emulsion are carried out by an ordinary flocculation method, and then gelatin and water are added to disperse the pH.
It was adjusted to 6.3 and pAg 6.4. Thus, a silver chloride cubic fine grain emulsion for growth having a side length of about 0.13 μm was prepared. This emulsion is designated as Emulsion A. (Preparation of high silver chloride tabular grains whose main plane is (111) plane) 72 g of seed crystal A of Example 1 (0.053 silver bromide) was placed in a reaction vessel.
Mol equivalent), deionized inert bone gelatin (molecular weight about 100,000) 24.2 g, and 1521 cc of water were added and dissolved at 40 ° C. to adjust pH to 5.0, and silver potential to 40 mV against calomel electrode. Adjusted with sodium chloride. Next, after the temperature was raised to 75 ° C and became stable, 3 cc of a 2N solution of potassium thiocyanate was added, and 1 minute later, emulsion A was added.
Solution A-4 containing A was added over about 34 minutes while performing primary acceleration so that the flow rate of the solution A was 2.7 cc / min at the beginning and finally a flow rate of about 41 cc / min. Simultaneously with the start of addition of Solution A-4, Solution B-4 was added over a period of about 34 minutes while performing primary acceleration so that initially it was 3.8 cc / min and finally about 16.7 cc / min. Also during this addition, C-
The four liquids were controlled by the CDJ method so that the silver potential was +40 mV with respect to the calomel electrode. Average D-circle about 1.6μ
m, average thickness about 0.32 μm, average aspect ratio about 5
Tabular grains having a Br content of about 7.5 mol% and having a principal plane of (111) planes could be prepared.

(Composition of liquid A-3) 270 g of silver nitrate Water is added to give a total amount of 900 cc (Composition of liquid B-3) 93.375 g of sodium chloride Water is added to give a total amount of 900 cc

(Composition of Solution A-4) Nitric acid (0.1N) 11.8 cc Emulsion A 671 g (corresponding to 0.653 mol) Water 146 cc Total amount 741.5 cc (Composition of solution B-4) Potassium thiocyanate 19 cc Water Total amount added 348cc (Composition of C-4 solution) Sodium chloride 124.5cc Total amount added 1200cc

Example 3 1280 cc of water, 1.12 g of low molecular weight bone gelatin (molecular weight of about 15,000) and 0.48 g of potassium bromide were placed in a reaction vessel, dissolved at 40 ° C. with stirring, and then lowered to 30 ° C. to stabilize. After that, Solution A-5 and Solution B-5 shown below were simultaneously added at 48 cc / min for 15 seconds. End of addition 1
After 8 minutes, 8 cc of an aqueous solution containing 0.8 g of potassium bromide was added, and after 1 minute, the temperature was raised to 75 ° C over 15 minutes,
When the temperature reached 5 ° C, the C-5 solution was added as a solution. 75 ℃
After aging for 14 minutes, 250 cc of 0.02 mol / liter solution of the compound of "Chemical formula 4" was added. After 1 minute at the same temperature, the D-5 solution was mixed with 1.6 cc / mi at the beginning of the D-5 solution.
The addition was performed for 22 minutes while the primary acceleration was performed so that the flow rate was finally about 46 cc / min at n 2. Also D-
During the addition of solution 5, the silver potential was adjusted to +125 mV using solution E-5.
Was controlled by the CDJ method. Thus, silver bromochloride tabular grains having a Br content of about 2.49 mol% were prepared. The average D-circle of tabular grains is about 2.71 μm and the thickness is about 0.71.
It was 084 μm, and the average aspect ratio was about 32.3.
FIG. 3 shows an electron microscope replica photograph of tabular grains.

(Composition of liquid A-5) 2.4 g of silver nitrate and 12 cc of water added (composition of liquid B-5) 1.679 g of potassium bromide total of 12 cc (composition of liquid C-5) ) Deionized gelatin (molecular weight 100,000) 28.5g Water 227cc (composition of D-5 solution) Silver nitrate 167.392g Water is added Total 523.1cc (composition of E-5 solution) Sodium chloride 180g Water is added Total amount 1200cc

Example 4 Examples show that the high silver chloride tabular grains of the present invention are excellent in photographic properties. The emulsion prepared in Example 1 was designated as emulsion 1. Next, referring to Example 1 of JP-A-2-32, cubes and octahedra having the same halogen composition as Emulsion 1 were prepared in the same volume. However, when the octahedron was prepared, 200 cc of a 0.02 mol / liter solution of the compound of "Chemical formula 4" was used instead of the crystal habit controlling agent described in the examples. These emulsions are designated as emulsions 2 and 3. Next, these emulsions were desalted by a usual flocculation method and washed with water, and then gelatin and water were added to obtain emulsions having a pH of 6.3 and a pAg of 7.3. Also, differences in the amount and ratio of silver and gelatin in grain formation were corrected at this point. Next, these emulsions were optimally subjected to gold-sulfur sensitization with hypo and chloroauric acid at 75 ° C., and 4-hydroxy-6-methyl-1,4 was added as a coupler and a stabilizer described later.
3,3a, 7-Tetrazaindene, sodium dodecylbenzene sulfonate as a coating aid, tricresyl phosphate as a hardener, and gelatin were added, and 2,4-dichloro-hydroxy-1 was added to the triacetyl cellulose support. , 3,5-triazine sodium salt and a protective layer containing gelatin were applied by a simultaneous extrusion method to prepare samples 1, 2,
3 was obtained.

[0057]

Embedded image

After exposing these samples through an optical device, they were treated with the following developing solutions. Designated by Fuji Photo Film Co., Ltd. CN-16 treatment (developer for color negative) Designated by Fuji Photo Film Co., Ltd. CP-20 treatment (developer for color paper) Designated by Eastman Kodak Co., Ltd. D-76 treatment (for black and white negative) Developer) The photographic performance obtained by measuring the density of the processed sample (measured with a green filter in the case of color development) is shown in Table 1. However, the relative sensitivity is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fogging value + 0.2, and C
In the N-16 treatment, the 3'15 "sample 1 was CP-2
In the case of 0 treatment, the sample of 3'30 "was treated as sample 1 and in the case of D-76 treatment, sample 1 of 7'was set as 100. As is clear from Table 1, the tabular grain emulsions of the present invention are cubic and octahedral. The development was faster, the sensitivity was high, and the fog was very low as compared with the above, and the advantage of the present invention was proved in the photographic property.

[0059]

[Table 1]

[Brief description of drawings]

1 is an electron microscope replica photograph showing the crystal structure of seed crystal A of Example 1. FIG. The black spheres in the figure are latexes having an average size of about 0.5 μm, which were included for size comparison.

FIG. 2 is an electron microscope replica photograph showing the crystal structure of silver bromochloride tabular grains of Example 1. The black spheres in the figure have an average size of about 0.5 μm for size comparison.
Is latex.

FIG. 3 is an electron microscope replica photograph showing the crystal structure of the silver bromochloride tabular grain of Example 3. The black spheres in the figure have an average size of about 0.5 μm for size comparison.
Is latex.

[Procedure amendment]

[Submission date] November 21, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

After exposing these samples through an optical device, they were treated with the following developing solutions. Designated by Fuji Photo Film Co., Ltd. CN-16 treatment (developer for color negative) Designated by Fuji Photo Film Co., Ltd. CP-20 treatment (developer for color paper) Designated by Eastman Kodak Co., Ltd. D-76 treatment (for black and white negative) Developer) The photographic performance obtained by measuring the density of the processed sample (measured with a green filter in the case of color development) is shown in Table 1. However, the relative sensitivity is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fogging value + 0.2, and C
In the N-16 treatment, the 3'15 "sample 1 was CP-2
In the case of 0 treatment, the sample of 3'30 "was treated as sample 1 and in the case of D-76 treatment, sample 1 of 7'was set as 100. As is clear from Table 1, the tabular grain emulsions of the present invention are cubic and octahedral. The advantages of the present invention were proved in terms of photographic properties because the development was faster and the sensitivity was very low and the fog was very low .. Example 5 Emulsion 1 obtained in Example 1 was used in the example of JP-A-6-258788. Using the same as the fifth layer of the light-sensitive material of Sample 6 (Sample No. 101) of Example 3, good performance was obtained by the same process as in Example 6. Example 6 Emulsion 1 obtained in Example 1 was obtained. Screen B was used as an emulsion of the photosensitive material-X of Example 1 of JP-A-6-273860.
In combination with the above, the same processing was performed as in the example, and good performance was obtained. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 15, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

After exposing these samples through an optical device, they were treated with the following developing solutions. Designated by Fuji Photo Film Co., Ltd. CN-16 treatment (developer for color negative) Designated by Fuji Photo Film Co., Ltd. CP-20 treatment (developer for color paper) Designated by Eastman Kodak Co., Ltd. D-76 treatment (for black and white negative) Developer) The photographic performance obtained by measuring the density of the processed sample (measured with a green filter in the case of color development) is shown in Table 1. However, the relative sensitivity is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fogging value + 0.2, and C
In the N-16 treatment, the 3'15 "sample 1 was CP-2
In the case of 0 treatment, the sample of 3'30 "was treated as sample 1 and in the case of D-76 treatment, sample 1 of 7'was set as 100. As is clear from Table 1, the tabular grain emulsions of the present invention are cubic and octahedral. The advantages of the present invention were proved in terms of photographic properties because the development was faster and the sensitivity was very low and the fog was very low .. Example 5 Emulsion 1 obtained in Example 1 was used in the example of JP-A-6-258788. Using the same as the fifth layer of the light-sensitive material of Sample 6 (Sample No. 101) of Example 3, good performance was obtained by the same process as in Example 6. Example 6 Emulsion 1 obtained in Example 1 was obtained. Screen B was used as an emulsion of the photosensitive material-X of Example 1 of JP-A-6-273866.
In combination with the above, the same processing was performed as in the example, and good performance was obtained.

Claims (3)

[Claims] 1. A method for producing a silver halide emulsion comprising tabular grains of high silver chloride having a (111) plane as a main surface, wherein the content of silver halide grains is 50 mol% or more based on the total amount of silver used. A high silver bromide grain having two parallel twin planes made of bromide, prepared in the absence of a crystal habit-controlling agent, and the seed crystal emulsion is grown in the presence of the crystal habit-controlling agent. , 50 of the projected area of all silver halide grains
% Of the tabular grains whose main plane is the (111) plane and whose chloride content is 50 mol% or more based on the total silver amount of the silver halide grains. 2. The seed crystal emulsion grains have an average aspect ratio of 1.
2. The method for producing a silver halide emulsion according to claim 1, wherein the major surface of the silver halide emulsion is a tabular grain mainly composed of (111) planes. 3. The method for producing a silver halide emulsion according to claim 1, wherein grain growth is performed by adding a separately prepared fine grain emulsion.