JPH06308645A - Silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a silver halide emulsion high in sensitivity and improved in high intensity reciprocity law failure by forming a phase high in silver chloride content and containing a multi-valent metal, too in the inside of silver halide grains. CONSTITUTION:The photosensitive silver halide grains has the phase high in silver chloride content in the inside of each grain and contains the multivalent metal in this phase and the surface phase of each grain contains silver iodide. The phase means a region different in the silver halide composition in the inside of each grain, and the phase high in silver chloride means the phase in which the silver chloride content is higher than that in the other regions, thus permitting the obtained silver halide emulsion to be high in sensitivity and also small in the high intensity reciprocity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and more particularly to a silver halide emulsion having high sensitivity and improved illuminance failure.

[0002]

2. Description of the Related Art In recent years, there have been increasing opportunities for general users to take pictures at night or indoors, or take pictures with a simple picture taking unit such as a film with a lens, and it is desired to take good pictures more easily. . In terms of the performance of silver halide emulsion grains, these can be improved by further increasing the sensitivity and improving reciprocity law failure (= illumination failure), and it can be said that there is still a high demand for these performances.

Various studies have been made so far for the purpose of increasing the sensitivity of silver halide emulsion grains, and one of them is a so-called core-shell emulsion grain in which the inside and outside of the silver halide grain have different halogen compositions. Are known. The technical contents are described in JP-A-59-99433 and JP-A-60-143.
No. 331 and Japanese Patent Laid-Open No. 61-245151.

Similarly, many studies have been made for the purpose of improving the reciprocity law failure of silver halide emulsion grains, and one of them is known to contain a polyvalent metal in the silver halide grains. ing. The technical contents are
2-20852, JP-A-2-20853, JP-A-2-20854, JP-A-2-20855, JP-A-3-118535 and JP-A-3-118536.

Further, as a configuration combining these techniques, Japanese Patent Laid-Open Nos. 1-121844, 2-156239 and 2-23
It is disclosed in No. 4151.

Usually, in order to contain a polyvalent metal in a silver halide grain, a polyvalent metal is added to a growing grain by the same manner as silver or halogen until the growth of the silver halide grain is completed ( For details, see below or the above patent)
It seems to be done in the pattern.

However, in the case of the core-shell grains as described above, most of the added polyvalent metal is not contained in the silver halide grains and is washed away with excess salt during the desalting step after grain formation or halogenated. Since the silver particles remain on the surface of the silver particles, a sufficient effect cannot be obtained, and the metal remaining on the surface of the particles adversely affects the photographic performance such as a decrease in sensitivity.

[0008] The above-mentioned JP-A No. 2-20852 discloses a complex of a polyvalent metal so that it can be easily incorporated into a silver halide grain and various ligands thereof are disclosed. However, the effect of the polyvalent metal could not be sufficiently obtained, and the adverse effect could not be prevented.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a means for obtaining a sufficient effect by incorporating most of the added polyvalent metal into the particles, that is, with high sensitivity and illumination failure. The object is to provide an improved silver halide emulsion.

[0010]

Therefore, as a result of earnest research, the inventors of the present invention are characterized by having a high silver chloride-containing phase inside a silver halide grain and containing a polyvalent metal in the phase. The objective was achieved with a silver halide emulsion.

It is a preferred embodiment that the surface phase of the silver halide grains contains silver iodide.

The present invention will be described in detail below.

The silver halide grain according to the present invention is not particularly limited as long as it has a high silver chloride phase inside the grain.

In the present invention, the inside of a particle means the whole or a part inside the region of several 10Å from the surface of the particle toward the center of the particle.

The term "phase" as used in the present invention means a region having a different halogen composition in a silver halide grain (each portion).
The high silver chloride phase means a phase in which the silver chloride content in that phase is higher than that of other silver halides. That is,
The halogen composition of the phase may contain silver bromide or silver iodide as long as silver chloride is contained in an amount exceeding 50 mol%. The silver chloride content of the high silver chloride phase is preferably higher, preferably 70 mol% or more, more preferably 8 mol% or more.
It is 5 mol% or more.

The volume ratio of the high silver chloride phase inside the grain is not particularly limited, but 5 mol% or more and 50 mol% or more of the silver halide amount per grain.
Less than mol% is preferred.

In the present invention, it is preferable to have a high silver chloride phase in a region closer to the center of the grain. However, the phase may not include the central part of the particles.

The halogen composition inside the silver halide grains according to the present invention can be confirmed by an X-ray diffraction method or by examining a section of the silver halide grains dispersed in the resin by an X-ray microanalysis method.

The X-ray microanalysis method will be described.

Silver halide grains are dispersed in a grid for electron microscope observation in which an energy dispersive X-ray analyzer is used in an electron microscope, and the magnification is set so that one grain is in the CRT field of view by cooling with liquid nitrogen, and the magnification is constant. Time AgLα and ILα ray intensities are integrated. The silver iodide content can be calculated using the ILα / AgLαK intensity ratio and a calibration curve prepared in advance.

The center of the particle is the center of the circumscribed circle.

The polyvalent metal that can be used in the present invention includes Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr and M.
n, V, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Os, Ir,
Pt, Cd, Hg, Tl, In, Sn, Pb, Bi and the like are mentioned, but not limited to these.

In the present invention, the polyvalent metal may be added as an inorganic salt or a complex, but it is preferably added as a complex.

The examples of the compounds used in the present invention are shown below.

[0025]

[Chemical 1]

[0026]

[Chemical 2]

[0027]

[Chemical 3]

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

In the silver halide photographic emulsion of the present invention,
In order to incorporate the metal complex of the present invention into the silver halide photographic emulsion, a method generally used in the art in which an additive is added to the silver halide photographic emulsion can be applied. For example, these compounds can be dissolved in a suitable organic solvent represented by alcohols or water in advance and added. Further, the dispersion method described in Japanese Patent Application No. 4-714 as a dispersion method of the spectral sensitizing dye can be used.

That is, in a water system in which substantially no organic solvent and / or surfactant is present, the metal complex of the present invention is added in an amount exceeding the solubility to mechanically disperse it into solid fine particles of 1 μm or less and then added. You can

In the present invention, the metal complex may be added at any time in the process for producing a silver halide photographic emulsion, and may be during the process for forming silver halide grains.
Further, it may be added at any time after the particle formation is substantially completed and before the coating step. It is preferably added by the end of the chemical ripening step.

In the silver halide photographic emulsion of the present invention,
To add a metal complex to the silver halide photographic emulsion, a solution containing the metal complex can be added directly to the silver halide photographic emulsion, and when it is added during the growth of silver halide grains, a halide can be added. The metal complex 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. Further, the solution containing the metal complex may be added instantaneously or continuously using an arbitrary function.

In the present invention, the content of the polyvalent metal in the high silver chloride phase is not particularly limited, but is preferably 5 × 10 ^-9 mol to 1 × 10 ^-3 mol per mol of silver halide formed. Is suitable, preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻³ mol, more preferably 5 × 10 ⁻⁸ mol to 5 × 10 ⁻⁴ mol.

In the present invention, GDMS is used as a method for quantifying the content of metal ions in silver halide emulsion grains.
A method (glow discharge mass spectrometry), an ICP method (high frequency inductively coupled plasma optical emission spectroscopy), an ICP-MS method (high frequency inductively coupled plasma mass spectrometry), an atomic absorption analysis method and the like can be used. In order to quantify the amount of metal ions in the silver halide grains, it is necessary to separate the metal ions contained in the binder such as gelatin of the emulsion and the metal ions physically adsorbed on the surface of the silver halide grains. is necessary. Therefore, it is necessary to carefully remove the gelatin by oxygen decomposition and wash the surface of the silver halide grains, and then quantify the metal ion content in the grains using each of the above-mentioned analytical methods.

The silver halide grains in the present invention may have a surface phase. The surface phase in the present invention refers to a phase that includes the grain surface and is outside the high silver chloride phase, and its halogen composition and volume ratio are not particularly limited, but the phase contains silver iodide. Is preferred. The silver iodide content of the surface phase may be appropriately changed depending on the use of silver halide grains, but is preferably less than 10 mol%.

The silver iodide content of the surface phase of the silver halide grains according to the present invention can be confirmed by X-ray electron photospectroscopy.

The X-ray photoelectron spectroscopy will be described.

Prior to measurement by X-ray photoelectron spectroscopy,
The emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and gelatin is decomposed by stirring at 40 ° C. for 1 hour.

Next, the emulsion particles are settled by centrifugation and the supernatant is removed. Then, an aqueous solution of pronase is added, and gelatin is decomposed again under the above conditions. After centrifuging this sample again to remove the supernatant, distilled water is added to redisperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. After repeating this washing operation three times, the emulsion particles are redispersed in ethanol. This is thinly applied on a mirror-polished silicon wafer to obtain a measurement sample.

For measurement by X-ray photoelectron spectroscopy, for example, an ESCA / SAM560 type manufactured by PHI is used as an apparatus, and X
Line to Mg ^- Kα line, X-ray source voltage 15KV, X-ray source current 40m
A, the pass energy is 50 eV.

Ag 3d, B for determining the surface halide composition
Detects r3d and I3d3 / 2 electrons.

Calculation of the composition ratio is as follows. The relative sensitivity coefficient method is used using the integrated intensity of each peak. Ag3d, Br3d, I3d
As 3/2 relative sensitivity coefficient, 5.10, 0.81, 4.59 respectively
By using 2, the composition ratio is given in atomic percent.

The crystal habit of the silver halide grains according to the present invention is not particularly limited. It can be appropriately selected depending on the application of the silver halide grain. In the case of a crystal having a (111) plane, silver halide grain formation is described in US Patent No. 4,400,463,
4,414,306, 4,399,215, 4,713,323, 4,8
04,621, 4,801,523, 4,942,120, 5,035,99
No. 2, No. 5,178,997, No. 5,178,998, No. 5,176,992,
5,176,991, and JP-A-62-299961, JP-A-1-7214.
2, JP-A-1-70741, JP-A-3-116133, JP-A-4-14
It is preferable to carry out in the presence of a compound described in the scope of claims of 1649.

When the silver halide emulsion used in the present invention contains grains having an average grain size / grain thickness of less than 2, the grain size distribution is preferably monodisperse.

The monodisperse silver halide emulsion means an emulsion in which the weight of silver halide contained in the grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. , Preferably 70% or more, more preferably 80% or more.

Here, the average particle size is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri becomes maximum (three significant digits and the minimum digit). Numbers are rounded to 4).

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a non-spherical grain whose projected image is converted into a circular image of the same area. Is.

The particle size can be obtained, for example, by taking an image of the particle with an electron microscope from 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (measurement particle). The number is indiscriminately 1000 or more.) The particularly preferred highly monodisperse emulsion of the present invention is (standard deviation / average grain size) × 100 = broadness of distribution defined by breadth (%) of distribution. Is less than 20%,
It is more preferably 15% or less.

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

The core / shell type silver halide emulsion according to the present invention is disclosed in JP-A-59-177535, JP-A-60-138538 and JP-A-59-5223.
8, 60-143331, 60-35726, 60-258536 and the like can be produced by known methods.

When a core / shell type silver halide emulsion is grown starting from seed grains as in the method described in JP-A-60-138538, it has a halogen composition region different from the core in the grain central portion. It is possible.

In such a case, the halogen composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide and silver chloride. Silver iodobromide or silver bromide having a silver content of 15 mol% or less is preferable.

The proportion of the seed grains in the total silver halide is preferably 50% or less, more preferably 10% or less by volume.

The core / shell type silver halide grain according to the present invention may be a regular crystal such as a cube, a tetradecahedron or an octahedron, may be composed of twins, or may be a mixture thereof. However, normal crystals are preferred.

In the tabular silver halide emulsion having an average grain size / grain thickness of 2 or more, the average grain size / grain thickness is more preferably 3 or more and 7 or less, and particularly preferably 3 or more and 5 or less. .

In the tabular silver halide emulsion having an average grain size / grain thickness of 2 or more, the average grain size / grain thickness is more preferably 3 or more and 7 or less, and particularly preferably 3 or more and 5 or less. .

The average grain size of all silver halide emulsions in the silver halide color light-sensitive material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm or less.

In the present invention, when the silver halide emulsion is twinned, an emulsion containing grains having two twin planes parallel to the principal plane is preferable, and its average aspect ratio is less than 5. Certain emulsions are preferred. In the case of such an emulsion, the shape of the main plane has a maximum adjacent side ratio of 1.0 to 2.0.
Is preferably used, and an octahedral emulsion is also preferably used.

As the hydrophilic colloid in the production of the silver halide emulsion of the present invention, general photographic gelatin is preferably used, and the tyrosine content of the gelatin is dry gelatin 1.
More preferably, the gelatin is 30 μmol or less per gram.

As the silver halide emulsion of the present invention, those prepared by a known method are also preferably used. For example, the grain growth condition may be any environment of so-called acidic method, ammonia method and neutral method, and the silver potential and temperature during the growth can be set to any values as required.
As a method for producing an emulsion mainly composed of twin crystals, it is preferable to form grains through a nucleation step and an Ostwald ripening step. In this case, the nucleation temperature is preferably 40 ° C. or lower, and pBr 1.0 to 2.5.

It is preferable to control the development so that the development is started at or near the apexes of all or part of the grains of the silver halide emulsion of the present invention, or at the ridges or near the ridges.
Particularly in the case of twinned grains, it is preferable that the development is controlled to start from the intersection of the twinned plane and the ridge.

In the method for producing a silver halide emulsion of the present invention, the average mixing time of the added liquid in the reaction vessel is preferably 10 seconds or less.

The silver halide emulsion of the present invention is desalted by a conventional method, but it is not preferable to use a so-called aggregating agent because the aggregating agent remains on the grain surface or in the vicinity thereof.

These cause a problem that, for example, after the grain formation as usual, it becomes an obstacle when the sensitizing dye or the chemical sensitizer is adsorbed on the grain.

When the silver halide emulsion of the present invention is tabular, the longest distance between two or more parallel twin planes of tabular grains is the same as in the claims of JP-A-63-163451. Grains having a ratio of (a) to grain thickness (b) of 5 or more are preferably 50% or more of all tabular grains.
The twin plane distance is 10Å ~ 100Å as in the claim of 3043
Is more desirable.

When the silver halide emulsion of the present invention contains grains having two or more kinds of halogen, it is disclosed in JP-A-2-67537.
An emulsion containing silver halide grains grown in the presence of silver halide grains having a solubility product smaller than that of the growing silver halide grains for at least one period of the grain growth process as in the claims. It is desirable to use silver iodide as the silver halide grain having a small solubility product.

The silver halide emulsion of the present invention is described in JP-A-1-18.
It is also preferable to grow grains by using fine silver halide grains in the same manner as the grains disclosed in Nos. 3417, 1-183644 and 1-183645. In particular, Japanese Patent Application No. 3-218608
There are two or more kinds of silver halide fine grains used for grain growth, as defined in the claims of Japanese Patent No.
It is preferable that the seed consists of only one kind of halogen element.

The silver halide emulsion of the present invention is described in JP-A-3-19.
It is preferable to add an oxidizing agent for silver during grain growth in the same manner as the grains disclosed in Nos. 6135 and 3-196138.
In particular, when it is produced by using seed particles as in the method of the claims of Japanese Patent Application No. 4-15845, it is preferably added before the growth of seed particles. Further, as the oxidizing agent, an inorganic acid such as a halogen element or nitric acid is preferable.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salts. Thiourea dioxide, polyamine ascorbic acid and the like; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride or ruthenium, palladium,
Water-soluble sensitizers such as platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or fog depending on the amount). It acts as an inhibitor, etc.) or separately and appropriately combined (for example, a gold sensitizer and a sulfur sensitizer are used together, a gold sensitizer and a selenium sensitizer are used together), and chemically sensitized. May be done.

The silver halide emulsion of the present invention is chemically ripened by adding a sulfur-containing compound and contains at least one kind of hydroxytetrazaindene and a mercapto group before, during or after the chemical ripening. You may include at least 1 sort (s) of a nitrogen heterocyclic compound.

In the silver halide emulsion of the present invention, an appropriate sensitizing dye is added in an amount of 5 × 10 ^{−5 to} 3 × 10 ^{5 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. ^-3 mol may be added to cause optical seduction. Various sensitizing dyes can be used, and 1 type or a combination of 2 or more types of sensitizing dyes can be used.

Examples of the sensitizing dye that can be advantageously used in the present invention include the followings.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion, for example, West German Patent 929,080, US Patents 2,231,658, 2,493,748, 2,503,776, and US Pat.
2,519,001, 2,912,329, 3,656,959, 3,67
2,897, 3,694,217, 4,025,349, 4,046,572
No., British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, 52-2
Those listed in No. 4844 and the like can be mentioned. In particular, the dye disclosed in Japanese Patent Application No. 3-343348 is preferably used.

Examples of the sensitizing dye used in the green-sensitive silver halide emulsion include, for example, US Pat.
72,908, 2,7 З9,149, 2,945,763, British special poem 5
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in No. 05,979.

Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, US Patent Nos. 2,269,234 and 2,2.
70,378, 2,442,710, 2,454,629, 2,776,28
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in No. 0 and the like. Furthermore, U.S. Patent 2,2l3,995
, 2,493,748, 2,519,001, West German Patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-187 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone,
Also, these may be used in combination.

If desired, optical sensitization may be carried out in a desired wavelength range by a spectral sensitization method using a single dye or a combination of cyanine or merocyanine dyes.

A typical example of a particularly preferable spectral sensitization method is, for example, Japanese Patent Publication No. Sho-Kai-Sho on combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine
43-4936, 43-22884, 45-18433, 47-37443
No. 48-28293, No. 49-6209, No. 53-12375, JP-A No. 52-23931, No. 52-51932, No. 54-80118, and No. 58-153.
Methods described in No. 926, No. 59-116646, No. 59-116647 and the like can be mentioned.

The combination of carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine is described in, for example, Japanese Patent Publication Nos. 45-25831 and 47.
-11114, 47-25379, 48-38406, 48-38407
No. 54-34535, No. 55-l569, JP-A-50-33220,
50-38526, 51-l07127, 51-1l5820, 51-1
35528, 52-104916, 52-1049l7 and the like.

Further, the combination of benzoxazolocarbocyanine (oxacarbocyanine) and other carbocyanine is described in, for example, JP-B-44-32753,
No. 46-11627, JP-A No. 57-1483, and those relating to merocyanine include, for example, Japanese Patent Publication Nos. 48-38408 and 48-41204.
No. 50-40662, JP-A-56-25728, 58-10753,
58-91445, 59-116645, 50-33828 and the like.

Regarding combinations of thiacarbocyanine with other carbocyanines, for example, Japanese Examined Patent Publication Nos. 43-4932, 43-4933, 45-26470, and 46-l8107.
No. 47-8741 and JP-A-59-114533, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye is advantageously used. be able to.

To add these sensitizing dyes, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or Japanese Patent Publication No.
It is used by dissolving it in a hydrophilic organic solvent such as fluorinated alcohol described in 50-40659.

The silver halide emulsion may be added at any time during the start of chemical ripening, during ripening, and at the end of ripening, and in some cases it may be added immediately before the emulsion coating.

The combination of sensitizing dyes which is particularly preferable in the present invention is the combination disclosed in Japanese Patent Application No. 3-109171.
That is, a combination of at least one of the asymmetric cyanine dyes and a symmetric cyanine dye having each of the heterocyclic nuclei constituting the dye is preferable.

The silver halide 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 emulsion of the present invention, the silver halide emulsion is
Those that have been physically aged, chemically aged and spectrally sensitized are used. Additives used in such processes are
Disclosure No.17643, No.18716 and No.308
119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 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 constituted by using an 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 Matting agents 1007 XVI Developer (contained in light-sensitive material) 1011 XXB Item Color photographic light-sensitive material using the silver halide emulsion of the present invention Various couplers can be used in the construction of, and specific examples thereof 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 emulsion of the present invention Additives used to construct color photographic light-sensitive materials are RD308119 page 1007 XIV
It can be added by the dispersion method described in the section.

When a color photographic light-sensitive material is constructed using the silver halide emulsion of the present invention, the above-mentioned RD17643, page 28, RD
The supports described in 18716, pages 647-8 and RD308119, page XVII, section XVII can be used.

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

The color photographic light-sensitive material using the silver halide 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 emulsion of the present invention comprises various color photographic light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Can be preferably applied to.

The color photographic light-sensitive material using the silver halide emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716 615.
Development can be carried out by a usual method described in page and RD308119, XIX.

[0102]

EXAMPLES Specific examples of the present invention are shown below, but the present invention is not limited thereto.

[Preparation of Comparative Emulsion EM-1] A seed emulsion of Comparative Emulsion EM-1 was prepared by using 6 kinds of solutions as follows.

While the solution (SA solution) kept at 60 ° C. and pH 1.92 was sufficiently stirred, (SB solution) and (SC solution) were added over 28 minutes. After the addition of (SB solution) and (SC solution) was completed, 13.4 ml of K ₄ [Fe (CN) ₆ ] 0.5% aqueous solution was added, followed by (SD solution) and (SE solution) over 105 minutes. Was added. During this period, pAg was kept at 7.54 using (SF solution).

Finally, a seed emulsion having an average grain size of 0.27 μm was obtained. Subsequently, desalting treatment was performed according to a conventional method.

(SA liquid) Potassium bromide 0.37 g Gelatin 1.00 g Water added 230 ml (SB liquid) Potassium bromide 1.30 g Gelatin 0.55 g Water added 53 ml (SC liquid) Silver nitrate 1.85 g Nitric acid (conc.) 0.11 ml Water added 54.3 ml (SD liquid) Potassium bromide 19.8 g Gelatin 0.83 g Water added 66.7 ml (SE liquid) Silver nitrate 28.15 g Nitric acid (conc.) 0.23 ml Water added 70.4 ml (SF liquid) Odor Comparative emulsion EM-1 was prepared using the seed emulsion thus prepared.

(CB solution) and (CC solution) were added over 45 minutes while sufficiently stirring (CA solution) kept at 40 ° C. and pH 9.00. During this period, pAg was kept at 8.59 using (CF solution).

Finally, a comparative emulsion EM having an average grain size of 0.85 μm
-1 was obtained. Subsequently, desalting treatment is performed according to a conventional method, and pH is 5.
8, pAg8.54 was prepared.

(CA liquid) Gelatin 5.5 g Water 1000 ml Seed emulsion
1/3 amount (CB liquid) Potassium bromide 167.8g Gelatin 13.4g Water added 600ml (CC liquid) Silver nitrate 300g Ammonia equivalent Water added 809.4ml (CF liquid) Potassium bromide 42.2g Water added 101
ml [Preparation of Comparative Emulsion EM-2] Comparative emulsion EM-2 was prepared using 5 kinds of solutions as follows.

1000% 2% gelatin aqueous solution kept at 40 ° C
The following (Solution A) and (Solution B) were simultaneously added into 30 ml over 30 minutes while controlling pAg = 6.5 and pH 3.0. Further below (liquid C)
And (D solution) were added for 85 minutes while controlling pAg = 7.3 and pH = 5.5, and then (E solution) and (D solution) were added to pAg = 8.6 and pH =
It was added for 24 minutes while controlling at 9.0.

[Preparation of Comparative Emulsion EM-3] Comparative Emulsion EM
-2 after the addition of (D liquid) and (E liquid) was completed, K ₄ [Fe
EM-3 was prepared in the same manner as EM-2 except that 13.4 ml of (CN) ₆ ] 0.5% aqueous solution was added.

[Preparation of Inventive Emulsion EM-4] Comparative Emulsion E
By the time the addition of M-2 (C liquid) is completed, K ₄ [Fe (CN) ₆ ]
EM-4 was prepared in the same manner as EM-2 except that 13.4 ml of 0.5% aqueous solution was added.

[Preparation of Emulsion EM-5 of the Present Invention] EM-5 was prepared in the same manner as EM-4 except that the solution (E solution) used for preparing the emulsion EM-4 of the present invention was changed to (F solution). did.

[Preparation of Emulsion EM-6 of the Present Invention] EM-6 was prepared in the same manner as EM-5 except that 164.7 mg of adenine was added to (B liquid) of the emulsion EM-5 of the present invention.

[Preparation of Emulsions EM-7 to EM-14 of the Present Invention]
EM-7 to EM-14 were prepared by changing the added polyvalent metal compound of the emulsion EM-5 of the present invention as shown in Table 1.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.33 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 48.75 g Potassium bromide 0.135 g Water was added to 300 ml (D) Silver nitrate 300g Water added 600ml (E) Potassium bromide 110.5g Water added 300ml (F) Potassium bromide 101.7g Potassium iodide 12.3g Water added 300ml (Silver Halide Photosensitive) Preparation of Material) The emulsions of EM-1 to EM-14 prepared as described above were optimally subjected to gold / sulfur sensitization, and these emulsions were used to produce the following on a triacetyl cellulose film support. Each layer having the composition shown below was sequentially formed from the support side to prepare a sample of a multilayer color photographic light-sensitive material.

The constitution of the multilayer color photographic light-sensitive material [Sample-1] is as follows.

The addition amount in the light-sensitive material is the number of grams per 1 m ² unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in mol per mol 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 Compound (SC-1) 0.15 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 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size) 0.27 μm, silver iodide content 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 point 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 m %) 0.62 Silver iodobromide emulsion (average grain size 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 point solvent (Oil-1) 0.30 Gelatin 0.93 5th layer; High-sensitivity red-sensitive layer [Em-1] 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 solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer Compound (SC-1) 0.09 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 Silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average particle diameter 0.27 [mu] m, 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 silver iodobromide emulsion (average grain size 0.59 .mu.m, a silver iodide content of 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 ninth layer: high sensitivity green-sensitive layer [Em-1] 1.27 sensitizing dye (SD-6) 1.4 × 10 -4 sensitizing dye (SD-7) 1.4 × 10 -4 Ma Coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta 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 size 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; Medium sensitivity blue Sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, Silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6 × 10 ^-4 Sensitizing dye (SD-9) 7.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) ) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer; High-sensitivity blue-sensitive layer [Em-1] 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 UV 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 16 layers; second 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 In addition to the above composition, coating aid Su-1, dispersion aid 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.

[0121]

[Chemical 12]

[0122]

[Chemical 13]

[0123]

[Chemical 14]

[0124]

[Chemical 15]

[0125]

[Chemical 16]

[0126]

[Chemical 17]

[0127]

[Chemical 18]

[0128]

[Chemical 19]

Samples 2 to 14 were prepared in the same manner as Sample 1 except that the emulsion EM-1 of Sample 1 was changed to EM-2 to 14.

The samples 1 to 14 produced as described above were evaluated.

[Evaluation of Sensitivity] Each sample was exposed to a white wedge for 1/100 second by a conventional method, subjected to the following development treatment, dried, and then transmitted with green light using a density measuring instrument manufactured by X-rite. The density was measured and a sensitometric curve (logarithm of exposure dose logEvs density D curve) was obtained.

The sensitivity of each sample was determined from the obtained sensitometric curve. The sensitivity is calculated from the logarithm of the exposure dose that gives the minimum density + 0.1, and the sensitivity of Sample 1 is 100
Is expressed as relative sensitivity.

[Evaluation of Reciprocity Failure (High Illuminance Failure)] High illuminance failure was evaluated in the same manner as the sensitivity evaluation except that the exposure time for each sample was changed to 1/10000 seconds. The result of high illuminance failure was also expressed as relative sensitivity when the sensitivity of Sample 1 when exposed to 1/100 second was 100.

The development processing steps are as follows.

[0135]

[Table 1]

In Table 1, the replenishment amount is 1 m ² of photographic light-sensitive material
It is the value per hit.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof were prepared as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g potassium hydroxide 1.0 g Water was added to make 1 liter, and the pH was adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water was added to make 1 liter, and pH was adjusted with ammonia water.
Adjusted to 6.0.

<Fixing Solution> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH 6.0 was adjusted using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and add potassium hydroxide or 20%
The pH was adjusted to 10.18 with sulfuric acid.

<Bleach replenisher> Water 700 ml 1/3 Diaminopropanetetraacetate Iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Ammonia water or glacial acetic acid adjusted to pH 4.0 After that, water was added to make 1 liter.

<Fixing replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Ammonium water or glacial acetic acid was used to adjust the pH to 6.5, and then water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

Table 2 shows the results of the above evaluations.

[0147]

[Table 2]

From the table, it is understood that Samples 4 to 14 of the present invention have higher sensitivity and less high illumination failure than Comparative Samples 1 to 3.

[0149]

According to the present invention, it is possible to provide a silver halide emulsion in which the added polyvalent metal is taken up by the silver halide grains, the sensitivity is high, and the high illuminance failure is small.

Claims (2)

[Claims] 1. A silver halide emulsion having a high silver chloride-containing phase inside a silver halide grain and containing silver halide grain containing a polyvalent metal in the phase. 2. The silver halide emulsion according to claim 1, wherein the surface phase of the silver halide grains contains silver iodide.