JPH06186661A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the silver halide emulsion capable of obtaining a silver halide photographic sensitive material superior in sensitivity to fog relationship and graininess and latent image endurance by incorporating an indium compound in the photographic emulsion containing photosensitive silver halide grains composed substantially of silver bromide and/or silver iodobromide. CONSTITUTION:The silver halide grains used for this photographic emulsion is composed substantially of silver bromide and/or iodobromide, and this emulsion contains the indium compound, and each of mono-, di-, or tri-valent indium compound may be used, but the trivalent compound is preferable because it is generally easily available and stable, and they are embodied by In(II) oxide, sulfide, nitride, hydroxide, sulfate, nitrate, oxalate, halogenocomplex, and indium acid salt, organoindium compounds, and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material, more specifically, a silver halide photographic emulsion used in a silver halide photographic light-sensitive material having improved sensitivity and graininess. Regarding

[0002]

2. Description of the Related Art The spread of photography equipment such as cameras has been increasing in recent years, and the opportunity for photography using silver halide photographic light-sensitive materials has been increasing. Along with this, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials are also increasing.

[0003] One of the dominant factors for high sensitivity and high image quality of silver halide photographic light-sensitive materials is silver halide grains, and silver halide grains aiming at higher sensitivity and higher image quality Particle development has traditionally been pursued in the industry.

However, as is generally done, the sensitivity tends to decrease as the grain size of silver halide grains is made smaller in order to improve the image quality, and both high sensitivity and high image quality are satisfied. There was a limit.

A technique for improving the sensitivity / size ratio per silver halide grain is being researched in order to further improve the sensitivity and the image quality. One of them is a tabular silver halide grain. The technology of using is Japanese Patent Laid-Open No. 58-111935
Issue 58-111936, Issue 58-111937, Issue 58-113927,
It is described in each of the publications such as 59-99433. Comparing these tabular silver halide grains with so-called normal crystal silver halide grains such as octahedron and hexahedron, tabular silver halide grains have a larger surface area when the silver halide grains have the same volume. Therefore, there is an advantage that a larger amount of sensitizing dye can be adsorbed on the surface of the silver halide grain and a higher sensitivity can be achieved.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular halide. Japanese Patent Laid-Open No. 63-163451 discloses a technique of using silver grains, and a technique of using tabular silver halide grains having a ratio of grain thickness to the longest distance between twin planes of 5 or more. The effects on sensitivity and graininess are shown.

In addition to the technique of improving the sensitivity by improving the grain structure and shape as described above, the photoelectrons and holes in the silver halide grains can be changed by doping the silver halide grains with metal ions. Techniques are known for improving movement and modifying its photographic properties.

As a technique for adding a metal ion to achieve high sensitivity, there is a technique for adding a polyvalent metal salt such as lead and cadmium in JP-A-61-160739 and JP-A-62-260137. It is disclosed. Further, Japanese Patent Application Laid-Open No. 1-121844 discloses a technique of doping an iron compound into a layer having a small band gap in a multilayer structure particle. Furthermore, JP-A 2-2085
No. 2, No. 2-20853, No. 2-20854, No. 2-222653, No. 2-2
Each publication such as 24545 discloses a technique of combining a polyvalent metal and a novel ligand.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material excellent in fog sensitivity relation and graininess. Another object of the present invention is to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material excellent in latent image storability.

[0010]

It has been found that the objects of the present invention can be achieved by a silver halide photographic emulsion having the following constitution. (1) A photosensitive silver halide photographic emulsion substantially containing photosensitive silver halide grains consisting of silver bromide and / or silver iodobromide, which contains at least one indium compound. A photosensitive silver halide photographic emulsion characterized by:

(2) The photosensitive silver halide photographic emulsion as described in the item (1), wherein the photosensitive silver halide grains are core / shell type silver halide grains.

The present invention will be described in more detail below.

The silver halide grains used in the present invention are
Substantially consisting of silver bromide and / or silver iodobromide. The term "substantially consisting of silver bromide and / or silver iodobromide" as used herein means that silver bromide other than silver iodobromide or silver iodobromide, for example, silver chloride is contained within a range not impairing the effects of the present invention. It means that it may be used. Specifically, in the case of silver chloride, the ratio is preferably 1 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion of the present invention may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and grains of various crystal forms may be mixed, but preferably twinned silver halide having two facing parallel {100} twin planes. Particles are used.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the average ratio of diameter to thickness of tabular grains (also referred to as aspect ratio) is preferably less than 5, more preferably 1.1 or more. Less than 4.5, particularly preferably
It is 1.2 or more and less than 4. This average value is obtained by averaging the ratio of diameter to thickness of all tabular grains.

The diameter of the silver halide grain is indicated by the circle equivalent diameter of the projected area of the silver halide grain (the diameter of the circle having the same projected area as the silver halide grain),
The thickness is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, and particularly preferably 0.3 to 3.0 μm.

The silver halide photographic emulsion according to the present invention may be any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution, but a monodisperse emulsion is preferred.

As the monodisperse silver halide emulsion, the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. A certain amount is preferable, more preferably 70% or more, further preferably 80% or more.

[0020] Here, the average particle diameter r, the particle size when the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is maximum
Define as ri (3 significant digits, round off the least significant digit).

The term "particle size" as used herein means a diameter of a projected image of a silver halide grain converted into a circular image having the same area.

The particle size can be obtained, for example, by enlarging the particle by an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (measurement particle). The number is indiscriminately 1,000 or more).

A particularly preferred highly monodisperse emulsion of the present invention is (standard deviation / average grain size) × 100 = 20% or less when the distribution width is defined by the distribution width (%). It is preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 0.1 mol% or more as the average silver iodide content in the entire silver halide grains.
It is preferably 15 mol% or less, more preferably 5
It is at least mol% and at most 12 mol%, particularly preferably at least 6 mol% and at most 10 mol%.

The silver halide composition structure of the silver halide grain according to the present invention is not particularly limited. Even if the silver halide composition is substantially uniform within the grain, the silver halide composition is continuous. It may be changed to a so-called core / shell structure. In order to efficiently achieve sensitization, core / shell type silver halide grains are used. In this case, it is preferable to have a high silver iodide containing phase having a silver iodide content of 8 mol% or more inside the grain. Further, it is preferable to have a high silver iodide-containing phase of 10 to 45 mol%, and it is particularly preferable to have a high silver iodide-containing phase of 20 to 40 mol% silver iodide content.

The outermost phase of the silver halide grain having a high silver iodide content phase in the present invention is formed of a low silver iodide content phase having a lower silver iodide content than the high silver iodide content phase. . The silver iodide content of the low silver iodide-containing phase forming the outermost phase is preferably 10 mol% or less, more preferably 6 mol% or less, and particularly preferably 0 to 4 mol%.

An intermediate phase having a different silver iodide content may be present between the outermost phase and the high silver iodide containing phase. The silver iodide content of the intermediate phase is preferably 10 to 22 mol%, particularly preferably
It is 12 to 20 mol%. The silver iodide contents of the outermost phase and the intermediate phase, and the silver iodide contents of the intermediate phase and the high silver iodide containing phase are preferably 6 mol% or more, particularly preferably 10 mol% or more. Good.

In the above embodiment, there are further silver halide phases in the central part of the internal high silver iodide containing phase, between the internal high silver iodide containing phase and the intermediate phase, and between the intermediate phase and the outermost phase. You may. Moreover, the volume of the outermost phase is preferably 4 to 70% of the whole particles,
10 to 50% is more preferable. The volume of the high silver iodide-containing phase is preferably 10 to 80% of the total grain, more preferably 20 to 50%. The volume of the intermediate phase is preferably 5 to 60%, and more preferably 20 to 55% of the whole particles.

These phases may be a single phase having a substantially uniform composition, or may be a group of phases having a composition that changes in a stepwise manner composed of a plurality of phases having a uniform composition. Alternatively, it may be a continuous phase whose composition continuously changes in any phase, or a combination thereof.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are prepared by preliminarily containing an aqueous solution containing a protective colloid and seed grains in a reaction vessel, and if necessary, silver ions, halogen ions or silver halide fine grains. It is preferable from the viewpoints of particle size distribution and productivity that the seed particles are obtained by crystal growth of the seed particles. Here, the seed particles can be prepared by a single jet method, a controlled double jet method or the like well known in the art.
When the seed grains are used in the present invention, the halogen composition thereof is substantially composed of silver bromide or silver iodobromide.

When seed particles are used in the present invention, the seed particles may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or an irregular shape such as a sphere or a plate. It may have a crystalline form. In these particles,
Any ratio of {100} plane to {111} plane can be used. Further, grains having various crystal forms may be mixed, and grains of various crystal forms may be mixed, but preferably twinned silver halide grains having two opposing parallel {111} twin planes. Is used.

As the means for forming the silver halide photographic emulsion according to the present invention, various methods well known in the art can be used. That is, the single jet method,
The double jet method, the triple jet method and the like can be used in any combination. Further, a method of controlling pAg and pH in a liquid phase in which silver halide is produced in accordance with the growth rate of silver halide can also be used.

The silver halide photographic emulsion of the present invention can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of the silver halide photographic emulsion of the present invention, the halide ion and the silver ion may be mixed at the same time, or while either one is present, the other may be mixed. Further, halide ions and silver ions may be grown sequentially or simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of the silver halide photographic emulsion of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salt is formed in the process of forming and / or growing the grain. ), Rhodium salt (including complex salt), iron salt (including complex salt), etc. can be added to allow these metal elements to be contained inside the particle and / or on the surface of the particle, and in an appropriate reducing atmosphere. By setting, the reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

The silver halide grain contained in the silver halide emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain. .

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained therein. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item 11.

The indium compound contained in the silver halide photographic emulsion of the present invention may be a monovalent compound,
Although it may be a divalent compound or a trivalent compound, a trivalent indium compound is generally preferred because it is easily available and stable.

Silver halide / oxide / sulfide / nitride /
In addition to hydroxides, various indium compounds such as sulfates, nitrates, oxalates, or halogeno complex salts, organic indium compounds, indium salts can be used.

Specific examples of the indium compound used in the present invention are shown below, but the present invention is not limited thereto.

InCl ₃ · nH ₂ O (NH ₄ ) ₃ · [InF ₆ ] InBr ₃ · nH ₂ OK ₃ InCl ₆ · 2H ₂ O InI ₃ · nH ₂ O (NH ₄ ) ₂ · [InCl ₅ (H ₂ O)] In ₂ O ₃ (CH ₃ ) ₄ NInCl ₄ In ₂ S ₃ [C ₅ H ₅ N ・ HCl] ₃ InCl ₄ InN (NH ₄ ) ₂ InBr ₅・ H ₂ O In (OH) ₃・ nH _{2 OK 3 InBr 6 · 2H 2 O} In 2 (SO 4) 3 · nH 2 O (CH 3) 4 NInBr 4 In (NO 3) 3 · 3H 2 O In In 2 (CrO 4) 3 · 6H 2 O present invention In order to incorporate the indium compound of the present invention into the silver halide photographic emulsion described in (1) above, a method of adding an additive to the silver halide photographic emulsion generally used in the art can be applied. For example, these compounds can be dissolved in a suitable organic solvent represented by alcohols or water in advance and added. Furthermore, Japanese patent application
It is possible to use the dispersion method described as the dispersion method of the spectral sensitizing dye in the application of No. 4-714. That is, it is possible to add the metal complex of the present invention in an amount exceeding the solubility and mechanically disperse it into solid fine particles of 1 μm or less in an aqueous system in which substantially no organic solvent and / or surfactant is present.

In the present invention, the indium compound may be added at any time during the production process of the silver halide photographic emulsion, but it is during the period from the grain formation process to the start of the chemical sensitization process. It is preferable that the growth of silver halide grains is completed, and it is particularly preferable.

In the silver halide photographic emulsion of the present invention,
To add an indium compound to the silver halide photographic emulsion, a solution containing the indium compound can be added directly to the silver halide photographic emulsion. The indium compound may be added in advance to an aqueous solution containing ions, an aqueous solution containing silver ions, or a solution containing fine silver halide grains. The solution containing the indium compound may be added instantaneously or continuously using an arbitrary function.

The amount of the indium compound added in the present invention is 1.0 × 10 ^-8 mol or more per mol of silver halide grains.
1.0 × 10 ^-1 mol or less is preferable, more preferably 1.0 × 10
^-7 mol or more and 1.0 x 10 ^-2 mol or less, most preferably 1.0 x 10
^-6 mol or more and 1.0 x 10 ^-3 mol or less.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142, No. 62-157024,
62-18556, 63-92942, 63-151618, 63-1634
The optimum conditions can be selected with reference to the known methods according to the respective publications such as No. 51, No. 63-220238 and No. 63-311244.

The silver halide photographic emulsion of the present invention can be preferably used in a silver halide color photographic light-sensitive material.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the silver halide photographic emulsion used is one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter referred to as RD17643, RD18716 and RD30, respectively).
Abbreviated as 8119). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Silver halide of the present invention Known photographic additives that can be used when a color photographic light-sensitive material is constructed using a photographic emulsion are also described in the above Research Disclosure.
Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25 to 26 Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Color photographic light-sensitive using the silver halide photographic emulsion of the present invention Various couplers can be used in constructing the material, specific examples of which are described in Research Disclosure below. The relevant locations are shown below.

[Item] [RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC to G item Magenta coupler 1001 VII-D item VIIC to G item Cyan coupler 1001 VII-D item VIIC to G item Colored coupler 1002 VII- Item G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Using the silver halide photographic emulsion of the present invention Additives used to construct color photographic light-sensitive materials are RD308119 1007
It can be added by the dispersion method described in page XIV.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the above-mentioned RD17643 28 is used.
The supports described in pp. RD18716 pp. 647-8 and RD308119 pp. 1009, section XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K. .

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by color positive films and color reversal papers.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in the above-mentioned pages RD1764328-29, RD18716 6.
The development can be carried out by a usual method described on page 15 and RD308119, XIX.

[0058]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Manufacturing method of Em-A) Average particle size (side length in cubic equivalent) 0.28 μm, silver iodide content 2 mol% (uniform composition), particle size distribution 18.9% Monodisperse silver iodobromide octahedron grains were prepared using the normal crystal grains of dispersible silver iodobromide (equivalent to 0.0775 mol of silver) and the following three types of solutions.

A1 liquid ossein gelatin 33.9 g Compound I ethanol solution (10%) * 10.0 cc. Ammonia aqueous solution (28%) 51.8 cc. Water 3383 cc. B1 liquid ossein gelatin 32.9 g Potassium bromide 402.8 g Potassium iodide 11.5 g Water 1471cc. C1 solution Silver nitrate 586.8g Aqueous ammonia solution (28%) 478.7cc. Water 1031cc. * Compound I ・ ・ ・ Polyisopropylene / polyethyleneoxy / disuccinate sodium salt (also used to prepare Em-M) The normal crystal seed of silver iodobromide was added to solution A1 and kept at 40 ° C.
While stirring, A1 and B1 liquids were acceleratedly added at the same flow rate over 150 minutes. At this time, the pH and pAg were controlled as shown in Table 1 using an acetic acid aqueous solution and a potassium bromide aqueous solution. After the addition was completed, desalting was performed according to the usual method, and ossein gelatin was added to
After adding g, the pH was adjusted to 6.0.EAg = 100 mV (40 ° C.) to obtain Em-A. As a result of observing Em-A with a scanning electron microscope, it was found that the particles were monodisperse octahedral particles having an average particle size of 1.0 μm (iodine content: 2 mol%).

[0061]

[Table 1]

(Manufacturing method of Em-B) In the method for preparing Em-A, the following solution was used as the B1 solution.
Em-B was prepared in the same manner as in -A. As a result of observing Em-B with a scanning electron microscope, it was found that the particles were monodisperse octahedral particles having an average particle size of 1.0 μm (iodine content rate: 4.4 mol%). However, in order to suppress the generation of small particles and to make the final shape uniform with an octahedron, the addition rate and pAg were adjusted slightly.

Liquid B1 of Em-B Ossein gelatin 32.9 g Potassium bromide 392.5 g Potassium iodide 25.9 g Water 1470 cc. (Preparation of Em-C and D) In the preparation method of Em-A, B
Em-C and Em are the same as Em-A except that B1-1 solution and B1-2 solution shown in Table 2 are used in place of the first solution.
-D was prepared.

As a result of observing Em-C and Em-D with a scanning electron microscope, monodisperse octahedron grains (iodine content, Em-C: 4.5 mol%, Em-
D: 6 mol%). However, Em-B
In order to suppress the generation of small particles and to make the final shape an octahedron, the addition rate and pAg were adjusted slightly as in the preparation of.

[0065]

[Table 2]

(Em-E, Em-F, Em-G, Em-
Manufacturing method of H) In the preparation of Em-A, Em-B, Em-C, and Em-D, 1.0 × 10 ⁻⁴ mol of lead nitrate was added to A1 liquid per mol of silver based on the total amount of silver. Others are Em
-A, Em-B, Em-C, Em-D in the same manner as E
m-E, Em-F, Em-G, Em-H were prepared.

(Em-I, Em-J, Em-K, Em-
In the preparation of Em-E, Em-F, Em-G, and Em-H, indium chloride (II
I-), Em-E, Em-F, Em-G, E
Em-I, Em-J, Em-K, E in the same manner as m-H
m-L was prepared.

As a result of observation using Em-E to Em-L scanning electron microscopes, it was confirmed that the particles were monodisperse octahedral particles having an average particle size of 1.0 μm.

(Preparation of emulsion-1) A part of Em-A was heated to 50 ° C.
And heat-dissolve it, and add sensitizing dye [A] 100 mg / mol silver halide and sensitizing dye [B] 90 mg / mol silver halide, 15
Adsorbed for a minute. Furthermore, sodium thiosulfate / pentahydrate 3.5
× 10 ^-6 mol / mol silver halide, chloroauric acid 1.0 × 10 ^-6 mol / mol silver halide, ammonium thiocyanate 4.0
× 10 ^-4 mol / mol Add silver halide and ripen for 120 minutes, then add 4-hydroxy-6-methyl- (1,3,3a, 7) -tetrazaindene as a stabilizer and let it cool and solidify. Emulsion-1
Got

[0070]

[Chemical 1]

The sensitizing dyes [A] and [B] are also used in the preparation of Emulsion-13.

(Preparation of Emulsion-2 to Emulsion-12) Emulsion-2 to Emulsion-12 were prepared in the same manner as Emulsion-1 except that Em-B to Em-L were used instead of Em-A.

Preparation of Single Emulsion Layer Coated Samples 101-112 Emulsions 1-3 obtained as described above were coated on a triacetyl cellulose film which had been subjected to an undercoating treatment with the following coating formulation as a support. Apply and dry, apply sample 101
~ 112 were made.

<Coating Prescription> In order from the support side, the first layer: green-sensitive silver halide emulsion layer Emulsion ... Silver coating amount 2.5 g / m ² magenta coupler (MI) 0.01 mol Colored magenta coupler (CM-I) ... 0.005 mol per mol of silver DIR compound (D-I) ... 0.0002 mol per mol of silver HBS-I (tricresyl phosphate: TCP) 0.22 g / m ² Second layer: Yellow filter layer Yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone and HI (2,4-dichloro-6-hydroxy-s-triazine sodium salt)

[0075]

[Chemical 2]

(Evaluation of Sensitometry) The coated samples 101 to 112 obtained as described above were subjected to wedge exposure using green light, and then processed in the following processing steps to obtain a characteristic curve to obtain a fog density and relative sensitivity. (The reciprocal of the exposure amount that gives a fog density + 0.1 is represented by a relative value), and RMS granularity (a fog density + 0.4 density dye image is scanned with a microdensitometer having a circular scanning aperture of 25 μm). The standard deviation of the fluctuation of the concentration value that occurs from time to time is represented by a relative value).

Treatment process (38 ° C.) Color development 2 minutes 50 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each treatment The composition of the treatment liquid used in the process is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 liter and adjust the pH to 10.0.

<Bleach> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and pH was adjusted with ammonia water.
Adjust to 6.0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 cc. Conidax (Konica Corporation) 7.5 cc. Add water to make 1 liter.

Table 3 shows the evaluation results of the coated samples 101 to 112.

[0083]

[Table 3]

As can be seen from the results shown in Table 3, the emulsion containing the indium compound according to the present invention is more effective as a means for achieving sensitization without increasing fog or grain deterioration. Was done. Further, it is more preferable to use core / shell type silver halide grains as the silver halide grains because the sensitizing effect of the indium compound can be obtained without deteriorating fog and graininess (particularly graininess). Recognize.

Example 2 (Manufacturing method of Em-M) Average particle size 0.3 μm, particle size distribution 16.8%
Prepare low-aspect-ratio silver iodobromide core / shell twin grains using the following solution, using the monodisperse spherical pure silver bromide twin grains (89% parallel twin twin number ratio) as a seed crystal. did.

A2 liquid ossein gelatin 262.5 g Compound I ethanol solution (10%) 1.5 cc. Ammonia aqueous solution (28%) 528.0 cc. Acetic acid aqueous solution (56%) 795.0 cc. Water 4450 cc. B2 liquid 4.0 wt% ose 3.5N potassium bromide aqueous solution containing ingelatin.

C2 liquid 3.5N ammoniacal silver nitrate aqueous solution.

(However, the pH was adjusted to 9. with ammonium nitrate.
Adjusted to 0. ) D2 liquid 3 wt% gelatin and silver iodide grains (average grain size 0.04 μm)
Fine grain emulsion E2 liquid consisting of 3 wt% gelatin, and silver iodobromide grains (silver iodide content 1 mol%, average grain size 0.04 μm) fine grain emulsion D2 and E2 liquid are prepared as follows. Is.

<D2> Contains 0.06 mol of potassium iodide 6.
To 5 liters of a 0% by weight ossein gelatin solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added over 10 minutes. The pH was maintained at 2.0 with nitric acid and the temperature was kept at 30 ° C during the formation of the particles. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

<E2> Contains 0.06 mol of potassium bromide 6.
To 5 liters of 0% by weight ossein gelatin solution, 200 cc. Of an aqueous solution containing 7.06 mol of silver nitrate, and 2 liters of an aqueous solution containing 6.99 mol of potassium bromide and 0.07 mol of potassium iodide were respectively applied for 10 minutes. Added. The pH was maintained at 2.0 with nitric acid and the temperature was kept at 30 ° C during the formation of the particles. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

Liquid A2 in the reaction vessel was heated to 70 ° C., pAg7.8,
While maintaining the pH at 7.2, a seed emulsion corresponding to 0.286 mol was added while stirring well. Then, the B2 solution, the C2 solution, and the D2 solution are shown in Table 4.
At the flow rate ratio necessary to form the silver halide composition shown in
Accelerated addition was carried out by the triple jet method in 140 minutes until the added silver amount ratio reached 78%. Subsequently, E2 corresponding to 28% of the amount of added silver was added in 10 minutes, and ripening was performed for 10 minutes.

The pH and pAg during grain growth were controlled to the values shown in Table 4 by adding an aqueous potassium bromide solution and an aqueous acetic acid solution to the reaction vessel. After the particles were formed, they were washed with water according to a conventional method, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C, respectively.

[0093]

[Table 4]

Observation of the obtained emulsion grains with a scanning electron microscope revealed that the average equivalent projected area equivalent circle diameter was 1.18 μm (sphere equivalent particle size 1.0 μm), the distribution was 8.6%, the average aspect ratio was 1.3, and the parallel aspect was It was confirmed that this was a low aspect monodisperse twin crystal emulsion in which the number ratio of the two grains having twin planes was 86%. This emulsion is designated as Em-M.

(Manufacturing method of Em-N) In the preparation of Em-M, based on the amount of silver after grain formation in the B2 solution, silver 1
Em-N was prepared in the same manner as Em-M except that lead nitrate was added in an amount of 1.0 x 10 ^-4 mol per mol.

(Production Method of Em-O) Em-O was prepared in the same manner as Em-N except that indium (III) nitrate was used instead of lead nitrate in the preparation of Em-N.

(Preparation of Em-P) In the preparation of Em-M, except that 1 × 10 ⁻⁴ mol of indium nitrate per mol of silver was added to the E2 solution based on the amount of silver after the grain formation was completed. Em-P was prepared in the same manner as Em-M.

(Manufacturing method of Em-Q) In the preparation of Em-M, in the halide solution at the time of preparing E2 solution, 1 × 10 ⁻⁴ mol of indium nitrate corresponding to 1 mol of silver based on the amount of silver after completion of grain formation was used. Em is the same as Em-M except that
-Q was prepared.

(Manufacturing method of Em-R) In the preparation of Em-M, 1 × 10 ^-4 mol of indium nitrate equivalent to 1 mol of silver was added after the completion of grain formation and before the desalting step, for 30 minutes. Em-R was prepared in the same manner as Em-M except that it was aged.

Observation of the obtained Em-N to Em-R with a scanning electron microscope revealed that they all had the same diameter and diameter as Em-M.
It was confirmed to be a low aspect ratio monodisperse twin crystal emulsion having a distribution, an aspect ratio, and a grain ratio having two parallel twin planes.

(Preparation of emulsion-13) A part of Em-M was heated to 50 ° C.
And heat-dissolve in sensitizing dye [A] 110 mg / mol silver halide, sensitizing dye [B] 100 mg / mol silver halide, 1
Adsorbed for 5 minutes. Furthermore, sodium thiosulfate / pentahydrate 3.5
× 10 ^-6 mol / mol silver halide, chloroauric acid 1.0 × 10 ^-6 mol / mol silver halide, ammonium thiocyanate 4.0
× 10 ^-4 mol / mol Add silver halide and ripen for 120 minutes, then add 4-hydroxy-6-methyl- (1,3,3a, 7) -tetrazaindene as a stabilizer and let it cool and solidify. Emulsion-13
Got

(Preparation of Emulsions-14 to 18) The same procedures as those for Emulsion-13 except that Em-N to R were used instead of Em-M were carried out.
Emulsions-14-18 were prepared.

(Preparation of Emulsion-19) Em-M was dissolved by heating at 60 ° C, and pAg was adjusted to 9.5 with a potassium bromide solution.
After adding 1.0 × 10 ⁻⁴ mol of indium nitrate per mol of silver and ripening for 20 minutes, the emulsion was readjusted at 40 ° C. under conditions of pH = 5.8 and pAg = 8.06. Thereafter, the same treatment as that for Emulsion-13 was carried out to prepare Emulsion-19.

(Preparation of Emulsion-20) Emulsion-20 was prepared in the same manner as Emulsion-19 except that indium nitrate was not added in the preparation of Emulsion-19.

(Preparation of Multilayer Coated Samples 201-208 / Evaluation of Sensitometry) In the following multilayer coated sample formulations, the above emulsions-13 to 20 were used as the silver iodobromide emulsion I of the high-sensitivity green-sensitive layer (9th layer). The multilayer coating samples 201 to 208 were prepared by using each of the above.

<Multilayer Coating Formulation> In the following multilayer coating formulation, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver halide.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point organic solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point organic solvent (Oil-2) 0.17 Gelatin 1.27 Third layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD -4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling solvent (Oil-1) 0.53 Gelatin 1.30 4th layer; Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.62 Silver iodobromide emulsion The average particle diameter of 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD─1) 2.3 × 10 ^-4 Sensitizing dye (SD─2) 1.2 × 10 ^-4 Sensitizing dye (SD─3) 1.6 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; High-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) ) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High Boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer High boiling point organic solvent (Oil-2) 0.11 Gelatin 0.80 7th layer; Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, iodine Contains silver oxide Rate 8.0 mol%) 0.61 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 sensitizing dye (SD-4) 7.4 × 10 ^-5 sensitizing dye (SD- ⁵ ) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 8th layer; Medium sensitivity green-sensitive layer Iodine Silver bromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler ( M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 No. 9 layers; high-sensitivity green-sensitive layer Silver iodobromide emulsion I 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Color Doma Coupler (CM-1) 0.012 High boiling point solvent (Oil-1) 0.27 High boiling point solvent (Oil-2) 0.012 Gelatin 1.00 10th layer; Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer; Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain) Diameter 0.38 μm, silver iodide content 3.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ^-4 yellow Coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer; middle-sensitive blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 µm, silver iodide) content of 8.0 mol%) 0.30 sensitizing dye (SD─8) 1.6 × 10 ^-4 sensitizing dye (S ─9) 7.2 × 10 ^-5 Yellow coupler (Y─1) 0.10 DIR compound (D─1) 0.010 High-boiling solvent (Oil─2) 0.046 Gelatin 0.47 14th layer: high sensitivity blue-sensitive layer Silver iodobromide emulsion ( Average grain size 1.00 μm, silver iodide content 10.0 mol%) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer; 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer; 2nd protective layer Alkali-soluble matting agent ( Average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 Besides, coating aids Su-1, dispersing aid composition Su-
2, viscosity modifier, hardener H-1, H-2, stabilizer ST-
1, antifoggant AF-1, two types of AF-2 having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, and preservative D1-1 were added. The amount of DI-1 added is 9.4 mg / m ²
Met.

The structures of the compounds used in the above samples are shown below.

[0109]

[Chemical 3]

[0110]

[Chemical 4]

[0111]

[Chemical 5]

[0112]

[Chemical 6]

[0113]

[Chemical 7]

[0114]

[Chemical 8]

[0115]

[Chemical 9]

[0116]

[Chemical 10]

Multilayer coating samples 201 to 208 prepared as described above
Was cut into strips. One part was subjected to wedge exposure with white light (exposure time 1/100 second) to evaluate fog and sensitivity. One part was subjected to wedge exposure (1/100 second) and then stored for 2 days under the conditions of a temperature of 55 ° C. and a relative humidity of 20%, and then developed to evaluate the storage stability of the latent image.

For the developing treatment, a treating solution having the same formulation as that used in Example 1 was used, and each treating time was as follows.

Treatment process (38 ° C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Settling 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry green Sensitivity Table 5 shows the results of evaluation of fog, sensitivity, RMS granularity, and latent image storability of the layer.

[0120]

[Table 5]

The sensitivity was defined as the reciprocal of the exposure amount required to give a fog density + 0.1, and the relative sensitivity was shown with the sensitivity of the sample 201 at the 1/100 second exposure being 100.

The fog density in the table is the difference between the fog density of the sample subjected to the ordinary processing step and the fog density of the sample subjected to the developing agent-free processing step.

The RMS granularity is a relative value with respect to the standard deviation of the density value produced when a dye image having a density of fog density +0.8 is scanned with a microdensitometer having a circular scanning aperture of 25 μm, with the value of Sample 201 being 100. Shown by value. The latent image storability was shown relative to the sensitivity after storage, with the sensitivity of the same day development of each sample being 100.

From the results shown in Table 5, it was found that the emulsion containing the indium compound of the present invention was highly effective in achieving high sensitivity without causing fog rise and grain deterioration even in the evaluation in the color negative multilayer coating sample system. It turns out to be an effective means. It is also found that the same sensitizing effect can be obtained by adding the indium compound of the present invention before starting the desalting step after grain formation or before starting the chemical ripening step, not during grain formation. .

Further, conventional iron salt (or lead salt is also the same).
It was found that the emulsion containing ## STR3 ## had a problem that an extreme increase in sensitivity was observed during storage after exposure, but the emulsion of the present invention was excellent in latent image storability.

[0126]

According to the silver halide photographic emulsion of the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity and excellent latent image storability without causing fog rise and graininess deterioration. You can

Claims (2)

[Claims] 1. A photosensitive silver halide photographic emulsion containing photosensitive silver halide grains consisting essentially of silver bromide and / or silver iodobromide, which comprises at least one indium compound. Characteristic photosensitive silver halide photographic emulsion. 2. The photosensitive silver halide photographic emulsion according to claim 1, wherein the photosensitive silver halide grains are core / shell type silver halide grains.