JP3273263B2 - Silver halide photographic emulsion - Google Patents

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 for a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic emulsion used for a silver halide photographic light-sensitive material having improved sensitivity and graininess. For emulsions.

[0002]

2. Description of the Related Art In recent years, the use of photographing equipment such as cameras has become increasingly widespread, and opportunities for photographing using silver halide photographic light-sensitive materials have been increasing. Accordingly, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials have been increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

However, as generally practiced, the sensitivity tends to decrease as the size of silver halide grains is reduced to improve image quality, and both high sensitivity and high image quality are required. Had limitations.

Techniques for improving the sensitivity / size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. One of such techniques is tabular silver halide grains. The technology used is JP-A-58-111935
No. 58-111936, No. 58-111937, No. 58-113927,
No. 59-99433. When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as octahedrons and hexahedrons, the surface area increases when the volume of the silver halide grains is the same, and therefore, the surface area increases. Sensitizing dye can be adsorbed, and there is an advantage that higher sensitivity can be achieved.

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

As described above, in addition to the technique for improving the sensitivity by improving the grain structure and shape, the doping of metal ions into the silver halide grains allows the generation of photoelectrons and holes in the silver halide grains. Techniques are known for improving motion and modifying its photographic properties.

As a technique for achieving high sensitivity by doping metal ions, Japanese Patent Application Laid-Open No. 2-20853 discloses a doping technique for a cyano complex of rhenium, ruthenium and osmium. Japanese Patent Application Laid-Open No. 1-121844 discloses a divalent Fe.
A technique is disclosed in which ions are doped into the minimum portion of the band gap in silver halide grains.

Japanese Patent Application Laid-Open No. 62-260137 discloses a technique in which silver halide grains are locally doped with a high concentration of polyvalent metal ions.

As described above, various techniques have been tried, but at present, sufficient effects have not yet been achieved for increasing the sensitivity and image quality of silver halide photographic materials.

[0011]

Accordingly, an object of the present invention is to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material having high sensitivity and excellent graininess.

[0012]

The object of the present invention has been found to be achieved by a silver halide photographic emulsion having the following constitution. That is, contains two or more kinds of polyvalent metal ions
In a silver halide photographic emulsion containing silver halide grains mainly composed of silver iodobromide, at least one of the metal ions has a different valence and is contained in a portion of 30% by volume from the surface of the silver halide grains. Of the metal ions
Maximum metal ion content Ri lowest valence der in said volume portion and of the metal ions contained at least 1
Species are metal ions of groups 2 to 6 and 14 and 15 of the periodic table
Oh silver halide photographic emulsion, wherein the Rukoto.

Hereinafter, the present invention will be described in more detail.

In the silver halide photographic emulsion of the present invention,
In order to contain a polyvalent metal ion in the silver halide photographic emulsion, a solution containing the metal ion is directly added to a silver halide emulsion preparation. Further, a metal compound may be added in advance to an aqueous solution containing halide ions, an aqueous solution containing silver ions, or a solution containing silver halide fine particles.
The addition of the solution containing the metal compound may be performed instantaneously, or may be performed continuously using an arbitrary function.

In the present invention, the timing of adding the polyvalent metal ion is arbitrary as long as it is between 0% and 100% of the amount of silver added during crystal growth of silver halide grains.

In the present invention, the amount of the polyvalent metal ion added per species is preferably from 10 ^-9 mol to 10 ^-1 mol, more preferably from 10 ^-7 mol to 10 ^-2 mol per mol of silver halide grains. Mol or less, most preferably 10 ^-6 mol or more and 10 ^-3 mol or less.

In the present invention, the timing of adding the polyvalent metal ion having the highest valence among the polyvalent metal ions to be added is as follows.
The amount of silver added for growing silver halide grains is preferably from 0% to 70%, more preferably from 0% to 40%.

The metal ions used in the present invention are Mg,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb,
Mo, Ru, Rh, Pd, Cd, In, Sn, Sb, B
a, La, Hf, Ta, W, Re, Os, Ir, Pt,
Au, Tl, Pb, etc. can be used Bi, small
At least one type of metal ion is selected from groups 2 to 6 and 14 to 15 of the periodic table.
It is characterized by being a group metal ion.

These can be added in the form of salts such as chlorides and bromides. For example, K ₄ Fe (CN) ₆ , CoCl ₂ , CuB
r, Zn (NO ₃ ) ₂ , YCl ₃ , K ₄ Ru (CN) ₆ , La (NO ₃ ) ₃ , TaCl _{5 and the} like. These polyvalent metal compounds are preferably added by dissolving in a suitable solvent such as water or ethanol.

^Examples of combinations of expensive and low-valent metal ions include W ⁶⁺ and La ³⁺ , Zr ⁴⁺ and Zn ²⁺ , and Sn ⁴⁺ and La ³⁺ .

The distribution of polyvalent metal ions in the silver halide grains in the present invention is determined by, for example, examining the concentration of polyvalent metal ions in a solution of the silver halide grains while etching the silver halide grains using a silver halide solvent. Can be obtained by

In the present invention, "a portion of 30% by volume from the surface of a silver halide grain" refers to a portion of the surface of the silver halide grain which is equally divided according to the distance from the center to each point on the surface. And the ratio is determined by the volume of the particle.
It refers to the area up to 30%.

The silver halide grains contained in the silver halide photographic emulsion of the present invention may be grains whose latent image is mainly formed on the surface or grains whose latent image is mainly formed inside the grain. Good.

The silver halide grains may have a regular crystal form such as cubic, octahedral or tetradecahedral,
It may have an irregular crystal form such as a sphere or a plate. In these particles, the ratio between the {100} plane and the {111} plane can be arbitrarily used. In addition, those having a complex form of these crystal forms may be used, and grains of various crystal forms may be mixed, but a twin silver halide grain having two opposing parallel twin planes is preferable. .

A twin is a silver halide crystal having one or more twin planes in one grain, and a classification of the twin is based on the report by Klein and Moiser in Photographic Corspondents. [Photographishe Korrespondenz]
It is described in detail in Volumes 99, 99, 100, and 57.

In the present invention, when tabular silver halide grains are used, the average value of the ratio of the diameter to the thickness of the tabular grains (also referred to as aspect ratio) is preferably less than 5, more preferably from 1.1 to 4.5. Less, particularly preferably 1.
2 or more and less than 4. This average value is obtained by averaging the ratio of the diameter to the thickness of all tabular grains.

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

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

As the monodispersed silver halide emulsion, those in which the weight of silver halide contained within a range of ± 20% of the center of the average particle diameter r is 60% or more of the total weight of silver halide grains. It is preferably 70% or more, more preferably 80% or more.

[0030] Here, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the minimum Digits are rounded off to the nearest 5).

Here, the particle diameter ri is a diameter when a projected image of silver halide grains is converted into a circular image having the same area.

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

Particularly preferred highly monodispersed emulsions of the present invention have a distribution width of 20 when the distribution width is defined by (particle size standard deviation / average particle size) × 100 = width of distribution (%). %
It is the following, more preferably 15% or less.

Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

In the present invention, silver halide includes
It is characterized by using silver iodobromide, and the silver iodide content is preferably not more than 15 mol%, more preferably, as an average silver iodide content in the whole silver halide grains. It is at most 12 mol%, particularly preferably at most 10 mol%.

The silver halide grains contained in the silver halide emulsion of the present invention may be so-called core-shell grains having a different halogen composition distribution within the grains, or grains having a uniform halogen composition distribution. You may.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are prepared by preliminarily presenting an aqueous solution containing a protective colloid and seed grains in a reaction vessel, and if necessary, silver ions, halide ions or silver halide fine grains. Is supplied to cause seed particles to grow. here,
Seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. Halogen composition of the seed particles, silver bromide, silver iodide, is any der Rukoto of iodo silver bromide preferred.

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 tetrahedron, or may have an irregular shape such as a sphere or a plate. It may have a different crystal form. In these particles, the ratio between the {100} plane and the {111} plane can be arbitrarily used. Also, those having a composite form of these crystal forms may be used,
Particles of various crystal forms may be mixed.
It is preferable to use the monodisperse spherical seed particles described in the specification of the '8178 application.

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

In the production of the silver halide photographic emulsion of the present invention, halide ions and silver ions may be mixed at the same time, or one of them may be mixed in the presence of the other. Further, the growth may be carried out by sequentially or simultaneously adding halide ions and silver ions while controlling the pH and pAg in the mixing vessel while taking into consideration the critical growth rate of the silver halide crystals. The silver halide composition of the grains may be changed by using a conversion method in any step of 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, thiourea and the like can be used.

The silver halide grains contained in the silver halide photographic emulsion of the present invention can be placed inside a grain and / or on the surface of the grain by placing it in a suitable reducing atmosphere during the grain formation and / or growth. Can be provided with a reduction sensitizing nucleus.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, use Research Disclosure (Re
search Disclosure (hereinafter abbreviated as RD) 17643 No. II.

In the silver halide photographic emulsion of the present invention,
In order to incorporate the metal compound of the present invention into the silver halide photographic emulsion, a method in which an additive is generally added to the silver halide photographic emulsion 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. Further, a dispersion method described in Japanese Patent Application No. 4-714 as a method of dispersing a spectral sensitizing dye can be used.
That is, the metal complex of the present invention can be added in an amount exceeding the solubility in an aqueous system substantially free of an organic solvent and / or a surfactant, and can be mechanically dispersed into fine particles of 1 μm or less and added.

In the production of the silver halide photographic emulsion according to the present invention, conditions other than those described above are described in JP-A-61-6643.
No. 61-14630, No. 61-112142, No. 62-
No. 157024, No. 62-18556, No. 63-92942,
JP 63-151618, JP 63-163451, JP 63-220238
Optimum conditions can be selected with reference to known methods disclosed in JP-A-63-11244 and JP-A-63-311244.

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

In constructing a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention, a silver halide photographic emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additive used in such a process is R
D Nos. 17643, 18716 and 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The places to be described are shown below.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer page 996 III-A page 23 648 Spectral sensitizer page 996 IV-A-A, B, C, D, H, I , J, p. 23-24 p. 648-9, supersensitizer p. 996 IV-AE, J, p. 23-24, p. 648-9, antifoggant p. 998 VI, p. 24-25, p. 649, stabilizer 998 VI, pages 24 to 25, page 649 Known photographic additives which can be used in forming a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention are also described in the above-mentioned Research Disclosure.
The relevant sections are described below.

[Item] [RD308119] [RD17643] [RD18716] Anti-turbidity agent, page 1002, section VII-I, page 25, page 650 Dye image stabilizer page 1001, section VII-J, page 25 Brightener 998, page 24, UV Page 1003 VIII-C, XIII-C section 25-26 Light absorber page 1003 VIII page 25-26 Light scattering agent page 1003 VIII Filter dye page 1003 VIII page 25-26 Binder page 1003 IX page 26 page 651 Static Inhibitor page 1006 XIII page 27 page 650 Hardener page 1004 X page 26 page 651 Plasticizer page 1006 XII page 650 page Lubricant page 1006 XII page 27 650 Activator / coating aid page 1005 XI pages 26-27 Page 650 Matting agent Page 1007 XVI Developer (contained in the light-sensitive material) Page 1011 Section XXB In constructing a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention, various couplers are used. RD17643 and RD308 below.
119. The relevant sections are described below.

[Items] [RD308119] [RD17643] Yellow coupler, page 1001, section VII-D, page 25, VII-C to G magenta coupler, page 1001, section VII-D, page 25, VII-C to G, cyan coupler page 1001, VII- Section D Page 25 VII-C to G Colored Coupler Page 1002 Section VII-G Section 25 VII-G DIR Coupler Page 1001 VII-F Section 25 VII-F BAR Coupler Page 1002 Section VII-F Other useful residues Group Releasing coupler, page 1001, section VII-F Alkali-soluble coupler, page 1001, section VII-E The additive used to construct a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is RD308119 100
It can be added by the dispersion method described in section XIV on page 7.

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

A color photographic light-sensitive material using the silver halide photographic emulsion of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119 VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention may have various layer constitutions such as a forward layer, a reverse layer and a unit constitution described in the aforementioned RD308119 VII-K. it can.

The silver halide photographic emulsion of the present invention can be used as a general or movie color negative film, a slide or television color reversal film, a color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by a color positive film and a color reversal paper.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pp. 28-29, RD18.
The development can be carried out by a usual method described on pages 716 to 615 and RD308119 XIX.

[0056]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 [Preparation of Comparative Emulsion Em-1] While maintaining the solution A at 40 ° C., the solution B and the solutions C ₁ and C ₂ were added by the double jet method at the addition rates shown in Table 1 with sufficient stirring. Was added. At this time, pH and pAg were controlled as shown in Table 1 using the solution D and the solution E. The resulting emulsion was washed and dispersed in a conventional manner,
It was set to -1.

As a result of observation with an electron microscope, the average particle size was 1.0 μm.
Octahedral particles.

[0059]

[Table 1]

[0060] 276mg in Comparative Preparation of Emulsion Em-2] C ₁ solution
Of WCl ₆ and 0.34 g of lanthanum nitrate were added to the C ₂ solution.
Emulsion Em-2 was obtained in the same manner as Em-1, except that 9 mg of WCl ₆ was added.

[0061] 276mg in Comparative Preparation of Emulsion Em-3] C ₁ solution
WCl ₆ were added, except for added WCl ₆ and 0.034g lanthanum nitrate 139mg to C ₂ solution, to give an emulsion Em-3 in the same manner as Em-1.

[0062] Comparative Preparation of Emulsion Em-4] 0.68 C ₂ solution
Emulsion Em-4 was obtained in the same manner as Em-1, except that g of lanthanum nitrate was added.

[0063] to [Emulsion Preparation of Em-5 of the present invention] C ₁ solution 2
76 mg of WCl ₆ was added, and 139 mg of WCl ₆ and 0.68 g were added to the C ₂ solution.
Emulsion Em-5 was obtained in the same manner as Em-1, except that lanthanum nitrate was added.

[0064] to [Emulsion Em-6 preparation of the present invention] C ₁ solution 2
And WCl ₆ of 76 mg, was added to the lanthanum nitrate of 0.68 g, except for adding lanthanum nitrate 0.34g to C ₂ solution, to give an emulsion Em-6 in the same manner as Em-1.

In the above emulsion preparation, WCl ₆
Used was dissolved in 100 ml of ethanol and left stirring for 1 hour in a light room.

Solution A Ossein gelatin 101.7 g Polyisopropylene-polyoxyethyleneoxy-succinate sodium salt (10% methanol) 30.0 ml Acetic acid (56%) 93.3 ml Ammonia (28%) 155.4 ml Silver bromide Emulsion (average particle size 0.240μ) Equivalent to 0.1465 mol 10593.0ml in pure water B liquid 1775.1g ammonia (28%) 1448.0ml 4975.5ml in pure water C ₁ liquid ossein gelatin 66.3g potassium bromide 811.9g potassium iodide 23.11 g 500.0 mL with pure water 3314.7ml C ₂ solution ossein gelatin 33.2g potassium bromide 406.8g potassium iodide 11.58g deionized water 1660.8Ml D liquid acetic acid (56%) 3000.0ml E solution potassium bromide 208.0g deionized water To the emulsions Em-1 to Em-6, 1.2 × 10 ^-6 mol of sodium thiosulfate was added per mol of silver halide at a temperature of 55 ° C. to perform optimal chemical sensitization.

Then, 1 g of the silver halide per mole was used.
4-Hydroxy-6-methyl-3.3.3a.7-tetrazaindene, 31 g of ossein gelatin, 0.28 g of sodium triisopropylnaphthalenesulfonate were added, and the amount of silver coated was reduced to 30 g / m ² . Samples 101 to 106 were obtained by coating on a triacetate cellulose support and drying.

Each of Samples 101 to 106 was exposed to blue light for 1/100 second, and the photographic sensitivity was evaluated. The sensitivity was obtained by taking the reciprocal of the exposure amount that gives a density of fog + 0.1 and obtaining a relative value when the sensitivity of the sample 101 was 100.

The developing conditions are as follows.

<Development Processing Conditions> Development (20 ° C.) 10 minutes Stop 2 minutes Fix 5 minutes Rinse 10 minutes Dry The processing liquid composition used in each processing step is as follows.

(Developer) Methol 2.5 g L-ascorbic acid 10 g Sodium metaborate (tetrahydrate) 35 g Potassium bromide 1 g Water was added 1 liter (stop solution) 56% by weight acetic acid aqueous solution 53.6 ml Water was added 1 Liters (fixing solution) Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1 liter, and adjust to pH 6.0 with acetic acid.

Table 2 shows the sensitivity of each sample.

[0073]

[Table 2]

As is evident from Table 2, the valence of the polyvalent metal ion having a plurality of polyvalent metal ions having different valences and being contained at a maximum of 30 vol. It can be seen that the emulsion of the present invention, which is characterized by the lowest, achieves high sensitivity.

[0075]

According to the present invention, it is possible to provide a silver halide photographic emulsion which provides a silver halide photographic material having high sensitivity and excellent graininess.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/035 G03C 1/08-1/09

Claims (1)

(57) [Claims] 1. It contains two or more kinds of polyvalent metal ions ,
In a silver halide photographic emulsion containing silver halide grains mainly composed of silver iodobromide, at least one of the metal ions has a different valence and is 30
Of the metal ions contained in the volume percent of the portion, at least one of said metal ion is a metal ion of the maximum content of Ri <br/> Ah at the lowest valence in the volume portion, and is contained
The silver halide photographic emulsion, wherein metal ions der Rukoto the Periodic Table 2-6 and Group 14 Group.