JP3248035B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent moisture resistance and high sensitivity.

[0002]

2. Description of the Related Art Conventionally, when various water-insoluble additives are added to a silver halide photographic emulsion, it is common practice to dissolve the additives in an organic solvent such as methanol or ethanol and then add the solution. Photographic spectral sensitizing dyes were no exception.

In general, the production of silver halide emulsions is often carried out at a high temperature. Therefore, when a large amount of an organic solvent is used, environmental problems such as harm to workers have been caused.

Therefore, a method of mechanically dispersing a photographic dye in an aqueous medium without using an organic solvent is disclosed in, for example, JP-A-3-288842. However, this method has a problem in that the silver halide photographic light-sensitive material is not excellent in storability when stored raw, and the sensitivity is reduced particularly when stored under high humidity.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in moisture resistance during raw storage of the light-sensitive material and has high sensitivity.

[0006]

The objects of the present invention have been attained by the following present invention.

[0007] substantially water-insoluble photographic spectral sensitizing dye was spectrally sensitized used in the solid state without the <br/> organic solvent <br/>, the silver iodide content is base particles surface With a surface ratio of 3 mol% or less
Consists of coated silver halide grains, (100)
A silver halide emulsion layer containing a silver halide emulsion occupying 50% or more of the total surface area of the silver halide grains was coated on a support.
A silver halide color photographic light-sensitive material,

Hereinafter, the present invention will be described in detail.

The substantially water-insoluble photographic spectral sensitizing dye used in the present invention is a water-soluble spectral sensitizing dye having a solubility of 1 × 10 ^{-4 at} 27 ° C. in an aqueous system free of an organic solvent and / or a surfactant.
~ 4 × 10 ^-2 mol / l, preferably 2 × 10 ^-4 to 4 ×
A spectral sensitizing dye having a concentration of 10 ^-2 mol / l is added to an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 μm or less.

In the present invention, the organic solvent is a solvent containing a carbon atom and liquid at room temperature. Conventionally, a water-miscible organic solvent has been used particularly as a solvent for the sensitizing dye. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, and 2-ethoxyethanol.

In the present invention, these organic solvents are not substantially contained. The surfactant includes an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant.

Conventionally, these surfactants have been used as dispersants for sensitizing dyes, but in the present invention, these surfactants are not substantially contained.

In the present invention, the aqueous system substantially free of an organic solvent and / or a surfactant is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably ion exchange. Refers to water.

[0014] solubility in water of the spectral sensitizing dye in the present invention is a 2 × 10 ^-4 ~4 × 10 ^-2 mol / liter, more preferably 1 × 10 ^-3 ~4 × 10 ^-2 mol / Liters. That is, if the solubility is lower than this region, the dispersion particle size is very large, and becomes non-uniform, or the sedimentation of the dispersion occurs after the dispersion is completed, or when the dispersion is added to the silver halide emulsion, It was found that the adsorption process of the dye on silver halide was hindered.

On the other hand, if the solubility is higher than this range, the viscosity of the dispersion is unnecessarily increased, and air bubbles are involved, which hinders the dispersion. If the solubility is higher, the dispersion becomes impossible. Has been clarified from the study of the present inventors.

The spectral sensitizing dye in the present invention is a dye which causes electron transfer to silver halide when photoexcited when adsorbed on silver halide and does not include an organic dye.

The spectral sensitizing dye of the present invention may be any dye as long as its solubility in water is in the range of 2 × 10 ^-4 to 4 × 10 ^-2 mol / l, and is preferably a cyanine dye.
More preferably the hydrophilic group (e.g., -SO ₃ H, -COOH, etc.)
Is a cyanine dye having

Specific examples and solubility in water are shown below, but the present invention is not limited to these.

[0019]

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[0020]

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[0021]

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In the present invention, various dispersers are effectively used for mechanically pulverizing and dispersing the spectral sensitizing dye in an aqueous solvent. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. In the present invention, a high-speed stirrer is preferable.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on a vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having an anchor blade is more preferable.

As a specific working example, after water is poured into a temperature-adjustable tank, a certain amount of powder of the spectral sensitizing dye is put into the tank, and a high-speed stirrer controls the temperature for a certain period of time. Stir, grind and disperse. The pH and temperature at which the spectral sensitizing dye is mechanically dispersed are not particularly limited. However, at low temperatures, the desired particle size is not reached even after long-time dispersion, and re-aggregation or decomposition occurs at high temperatures. And the problem that desired photographic performance cannot be obtained, and that when the temperature is increased, the viscosity of the solution system decreases, so that the efficiency of pulverization and dispersion of solids is greatly reduced. Therefore, the dispersion temperature is 15 ~
More preferably, it is 50 ° C. In addition, the stirring rotation speed at the time of dispersion requires a long time to obtain the desired particle size at a low rotation speed, and at a high rotation speed, bubbles are entrained and the dispersion efficiency is reduced. Is more preferable.

The fact that the solid fine particles of the spectral sensitizing dye dispersed by the method of the present invention are 1 μm or less means that the particle size is 1 μm or less in terms of volume equivalent diameter of a sphere, and is measured by a general method. it can.

The term "dispersion" as used herein means a suspension of a spectral sensitizing dye, preferably a dispersion in which the weight ratio of the spectral sensitizing dye in the suspension is 0.2% to 5.0%. Used.

The dispersion of the spectral sensitizing dye prepared according to the present invention may be added directly to a silver halide emulsion,
It may be appropriately diluted and added, but water is used as the diluent at this time.

In the silver halide emulsion according to the present invention, the (100) plane accounts for 50% or more , preferably 70% or more , of the total surface area of all silver halide grains.

The area ratio of the (100) plane can be determined by a known X-ray diffraction method or dye adsorption method.

The silver iodide content on the surface of the silver halide grains of the present invention can be determined by an XPS method (X-ray Photoelectron Spectrosco
py). JP-A-63-44751 has a detailed description of a general measuring method for photographic silver halide grains.

The general X described in JP-A-63-44751 is disclosed.
When the surface silver iodide content is measured by the PS method, the escape depth of the photoelectron serving as a measurement probe from the sample (escape depth)
Is about 40Å to 50Å (about 14 to 20 atomic layers).

The silver iodide content of the silver halide grains of the present invention is 3 mol% or less, preferably 2 mol% or less, as detected by the XPS method. It is more preferably at most 1 mol%.

The XPS method will be described as follows.

Prior to the XPS method, the emulsion is preprocessed as follows. First, a pronase solution was added to the emulsion, and
Stir for hours to effect gelatin degradation. Next, the emulsion particles are precipitated by centrifugation, and the supernatant is removed. Then, an aqueous solution of pronase is added, and the gelatin is decomposed again under the above conditions. After centrifuging the sample again and removing the supernatant, distilled water was added to re-disperse the emulsion particles in distilled water,
Centrifuge and remove the supernatant. After repeating this washing operation three times, the emulsion grains are redispersed in ethanol. This is thinly applied on mirror-polished silicon wear to obtain a measurement sample.

For the measurement by the XPS method, for example, an ESCA / SAM560 type manufactured by PHI is used as an apparatus, and the excitation X-ray is applied to Mg-K
The test is performed under the conditions of α-ray, X-ray source voltage 15 kV, X-ray source current 40 mA, and pass energy 50 eV.

In order to determine the surface halide composition, Ag3d,
The relative sensitivity coefficients of Br3d and I3d3 / 2 are 5.10, 0.81,
By using 4.592, the composition ratio is given in units of atomic percent.

In addition, regarding the halogen composition and structure of the silver halide grains of the present invention, in addition to the above-described XPS method and the like, X-ray diffraction, XMA method (X-ray Micro Analysi
s), it can be confirmed by combining X-ray fluorescence analysis.

For example, the XMA method will be described as follows. The silver halide particles were dispersed in an electron microscope observation grit loaded with an energy dispersive X-specialized analyzer in an electron microscope, and the magnification was set so that one particle could enter the CRT visual field by cooling with liquid nitrogen. Integrate the intensity of ILα radiation. The silver iodide content can be determined using a calibration curve prepared in advance for the enhancement of ILα / AgLα.

In the same manner as the method described in the abstract of Inoue et al., Published in the Abstracts of the Photographic Society of Japan, pp. 46-48, silver halide grains were dispersed and solidified in methacrylic resin, and ultrathin sections were obtained with a microtome. As described above, the halogen composition and structure in the grains can be confirmed by the above-described point analysis by the XMA method.

The X-ray diffraction method known as a method for examining the structure of a silver halide crystal is as follows.

Various characteristic X-rays can be used as the X-ray source. Among them, CuKα radiation targeting Cu is the most widely used one.

For example, silver iodobromide has a rock salt structure and CuKα
Since the signal intensity observed at 2θ 71 to 74 degrees is relatively strong and at a high angle, the (420) diffraction line is optimal for examining the crystal structure with good resolution.

In measuring the X-ray diffraction of a photographic emulsion,
It is necessary to remove the gelatin, mix a standard sample such as silicon, and measure by a powder method. Regarding the measurement method, it is possible to refer to Basic Analysis Chemistry Course 24 “X-ray analysis” (Kyoritsu Shuppan). The silver halide emulsion used in the light-sensitive material according to the present invention is preferably a monodisperse silver halide emulsion.
The silver halide contained within a grain size range of ± 20% around dm is 70% or more of the total silver halide weight, preferably 80% or more, more preferably 90% or more.

The average particle diameter dm herein, the product ni × di ³ of frequency ni and di ³ particles having a particle size di is defined as the particle size di of the time that maximizes (three significant figures, the least significant digit Is rounded off to the nearest 4).

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

The particle size can be determined by, for example, dispersing the particles so as not to overlap on a flat sample stage, photographing them with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the particle diameter on the print or the projection time. Can be obtained by actually measuring the area.
(The number of particles to be measured shall be 1000 or more indiscriminately.)

Particularly preferred monodisperse emulsions of the present invention are those having a distribution width of not more than 20% defined by (standard deviation of particle size / average particle size) × 100 = width of distribution (%),
It is more preferably at most 15%.

Here, the method for measuring the particle size is in accordance with the above-mentioned measuring method, and the average particle size is an arithmetic mean.

Average grain size = Σdini / Σn ₁ The average grain size of the silver halide emulsion according to the present invention is 0.05
~ 10.0μm, more preferably 0.1 ~
It is 5.0 μm, particularly preferably 0.1 to 3.0 μm.

The average silver iodide content of the silver halide emulsion according to the present invention is preferably from 0 to 6 mol%, particularly preferably from 0 to 4 mol%.

Monodisperse normal crystal emulsions are disclosed, for example, in
-177535, 60-138538, 59-52238, 60-14333
It can be produced by referring to the method disclosed in No. 1 or the like.

Monodisperse twin emulsions are described, for example, in JP-A-61-1.
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in No. 4636.

The surface phase of the silver halide grains referred to in the present invention is a constituent phase located on the outermost side in the silver halide composition structure of the grains. In the present invention, the surface phase does not need to cover the entire surface of the parent particle on which the surface phase is formed, and the present invention is applicable as long as at least a part of the surface of the parent particle is covered with the surface phase. Although the effects of the present invention can be exerted, it is preferable that 50% or more of the surface of the base particles is coated with the surface phase.
Further, it is preferably at least 60%, particularly preferably at least 70%.

The internal phase adjacent to the surface phase may or may not be the low iodide phase. That is, another silver iodide content phase (intermediate phase) may exist between the internal phase adjacent to the surface phase and the low iodine phase. In that case, the volume of the intermediate phase is preferably 70 mol% or less, more preferably 3 to 60 mol% of the whole particles.

In each of the above-mentioned embodiments, the silver halide grains of the present invention have a surface phase of the grains and a high iodide phase and / or a low iodide phase each having a part or all of a fine size. It is formed by a method of supplying silver halide grains (hereinafter sometimes referred to as a fine grain supply method). Here, a preferred embodiment is a case where part or all of the surface layer and the low iodine phase are formed by a fine particle supply method.

More preferably, the surface layer and each of the low iodide phase and the high iodide phase, and particularly preferably a part or all of all phases constituting the grains are formed by a fine particle supply method. This is the case. Further, in each of the above embodiments, it is preferable that 40% or more of the respective phases formed by the fine particle supply method be formed by the fine particle supply method, more preferably 60% or more, and further preferably 80% or more. Most preferred is when all of the phases are formed by a particulate feed method.

As methods for forming silver halide grains by supplying fine silver halide grains, there are a method of supplying only silver halide fine particles,
And a method involving supply of an aqueous solution of a halogen salt or a silver salt as described in JP-A-2-67537. In order to further enhance the uniformity of silver halide grains, a method of supplying only silver halide fine grains is particularly preferable.

In the method for forming the surface phase of silver halide grains of the present invention, there is no particular limitation except that part or all of the surface phase is formed using fine silver halide grains. For example, fine silver halide grains having a desired silver iodide content can be used so that the silver iodide content is higher than the internal phase adjacent to the surface phase. Alternatively, silver iodide fine grains may be used alone or as a mixture with silver halide fine grains having another silver halide composition so as to obtain a desired silver iodide content. The surface phase may be formed subsequent to the formation of the silver halide grains serving as the matrix forming the surface phase, or after the preparation of the matrix grains (for example, after desalting / washing or before, during, or after chemical sensitization). Later).
In order to form a surface phase having a high silver iodide content only at a specific site on the surface of the base grains, a crystal habit control agent can be used.

The formation of the surface phase may be performed once or may be performed several times.

The silver halide grains of the present invention may have any silver halide composition except that they contain silver iodide. For example, each of the above embodiments is composed of an arbitrary composition such as silver iodobromide, silver chloroiodide, silver chloroiodobromide, and a mixture thereof, but silver iodobromide is particularly preferably used.

The silver halide emulsion according to the present invention is prepared by adding silver ions (generally a water-soluble silver salt solution) and halogen ions (generally a water-soluble halide solution) to a solution containing a protective colloid. It can be prepared by forming silver particles. In this case, various techniques known to those skilled in the art can be used as a forming means. For example, JP-A-61-6643, JP-A-62-157024, JP-A-62-18556,
63-92942, 63-151618, 63-163451, 63-220
Nos. 238 and 63-311244 can be referred to.

For example, a so-called controlled double jet method for maintaining a constant pAg in a liquid phase in which silver halide is formed, which is one type of the double jet method, the double jet method, and the double jet method, and a soluble halogen salt having a different composition. Can also be used independently. Further, a pure mixing method can be used, and a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. In the emulsion of the present invention, a silver halide solvent can be used if necessary. Frequently used solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. Nos. 3,271,157, 3,790,387 and 3,574,628 can be referred to.

The mixing method is not particularly limited, but a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used.

The silver halide emulsion of the present invention can be washed with water by a known flocculation method, preferably at the end of mixing and immediately before the flocculation step.
The pAg is preferably 8 or more, more preferably 9
That is all.

The silver halide grains according to the present invention contain at least iodine. In this case, the method of adding iodide ions during grain growth is not particularly limited, and the silver halide grains may be added as an ionic solution such as potassium iodide. Is also good. or,
The grains may be added as grains having a lower solubility product than the growing silver halide grains, for example, silver iodide fine grains. In addition, they may be added as silver iodobromide fine particles. When added as silver iodobromide fine grains, it is preferable that silver ions and halogen ions are not added as an aqueous solution but added as silver halide fine grains having a desired halogen composition.

As long as the effects of the present invention are not impaired, the silver halide grains of the present invention are allowed to coexist with a water-soluble salt of a polyvalent metal compound or a complex salt thereof in the course of the formation or physical ripening of the silver halide grains. And examples thereof include cadmium, iridium, lead, rhodium, iron and the like. One or more polyvalent metal compounds can coexist.

In the present invention, other silver halide emulsions other than the present invention are not particularly limited, and for example, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[Item] [Page of D308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal habit Normal crystal 993 IA twin crystal 993 IA Epitaxial 993 I- Item A Halogen composition Uniform 993 IB Item Not uniform 993 IB Item Halogen conversion 994 IC Halogen substitution 994 IC Metal-containing 994 ID Monodispersion 995 IF Solvent addition 995 Section IF Latent image formation position Surface 995 IG Inside 995 IG Section Applicable photosensitive material negative 995 IH Positive (including internal fog particles) 995 IH Section Emulsion is mixed and used 995 I- Section J Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additives used in such processes are Research Disclosure
No.17643, No.18716 and No.308119 (hereinafter referred to as RD17
643, RD18716 and RD308119).
The places to be described are shown below.

[Items] [RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E-J 23 ~ 24 648 ~ 9 Supersensitizer 996 IV-AE, J section 23 ~ 24 648 ~ 9 Antifoggant 998 VI 24 ~ 25 649 Stabilizer 998 VI 24 ~ 25 649 Known photographs usable in the present invention Additives are also described in Research Disclosure, supra. The places to be described are shown below.

[Item] [RD308119 page] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- Item C, XIIIC 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1011 XXB Section Various couplers can be used in the present invention. Specific examples are described in the above-mentioned Research Disclosure. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues 1001 VII-F Emission coupler Alkali-soluble coupler 1001 VII-E Additive used in the present invention Can be added by a dispersion method described in RD308119XIV or the like.

In the present invention, the aforementioned RD17643, page 28, RD
The supports described in pages 18716 647-8 and RD308119 XIX can be used.

The light-sensitive material of the present invention is prepared by using the above-mentioned RD308119VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided.

As a support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like can be used.

The present invention can be applied to various silver halide color photographic light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films, and color reversal papers. However, it is preferably used for a silver halide color reversal photographic material for photography.

[0077]

The present invention will be described below with reference to examples.

Example 1 <Preparation of Spectral Sensitizing Dye Solid Dispersion SD-1> Illustrative spectral sensitizing dyes (S-5), (S-8) and (S-9) were converted into 333 each.
After weighing mg and adding 50 ml of water preliminarily adjusted to 27 ° C., the mixture was stirred with a high-speed stirrer (dissolver) at 3500 rpm for 30 to 120 minutes to obtain a sensitizing dye solid dispersion having an average particle size of 0.38 μm. (SD-1) was obtained.

<Preparation of methanol solution SD-2 of spectral sensitizing dye> Exemplary spectral sensitizing dyes (S-5), (S-8) and (S-
9) was weighed in an amount of 200 mg, and 100 ml of methanol previously adjusted to 27 ° C. was added thereto to dissolve at 27 ° C. to obtain a methanol solution (SD-2) of the spectral sensitizing dye.

<Preparation of Comparative Sample 1> On a cellulose triacetate film support having an undercoating process, layers having the following compositions were sequentially applied from the support side to prepare a comparative sample 1 of a multilayer color photographic light-sensitive material.

The coating amount of each component is shown in g / m ² . However,
The amount of silver halide is represented by a coating amount in terms of silver.

First layer (antihalation layer) Black colloidal silver 0.24 UV absorber U-1 0.14 UV absorber U-2 0.072 High boiling solvent O-1 0.31 High boiling solvent O-2 0.098 Poly-N-vinylpyrrolidone 0.15 Gelatin 2.02 Second layer (intermediate layer-1) Gelatin 0.50 Third layer (intermediate layer-2) Fine grain silver iodobromide emulsion with fogged surface (silver iodide 1.0 mol%, 0.06 μm) 0.05 Gelatin 0.50 Fourth layer (Low sensitivity red-sensitive silver halide emulsion layer) Em-8 0.6 coupler C-1 0.52 spectrally sensitized by 228 mg / mol Ag of sensitizing dyes (S-7, S-10, S-1, S-4) High boiling solvent O-2 0.6 Gelatin 1.3 Fifth layer (high-sensitivity red-sensitive silver halide emulsion layer) Spectroscopy with sensitizing dye (S-7, S-10, S-1, S-4) 83.7 mg / mol Ag Em-2 sensitized
0.7 coupler C-1 0.78 high boiling solvent O-2 1.2 gelatin 1.8 6th layer (intermediate layer-3) 2,5-di-t-octylhydroquinone 0.1 high boiling solvent O-1 0.2 gelatin 0.9 7th layer (intermediate layer) -4) Fine grain silver iodobromide emulsion whose surface is fogged (silver iodide 1.0 mol%, 0.06 μm) 0.05 2,5-di-t-octylhydroquinone 0.1 High boiling point solvent O-3 0.25 Gelatin 0.9 8th layer ( Low sensitivity green-sensitive silver halide emulsion layer) Em-7 0.55 coupler M-1 0.15 coupler M-2 0.04 spectrally sensitized with sensitizing dye (SD-2) 487 mg / mol Ag High boiling solvent O-3 0.25 gelatin 1.4 Ninth layer (high-sensitivity green-sensitive silver halide emulsion layer) Em-2 0.8 coupler M-1 0.56 coupler M-2 0.12 spectrally sensitized with 178 mg / mol Ag of sensitizing dye (SD-2) High boiling solvent O-3 1.0 Gelatin 1.5 10th layer (intermediate layer) Same as 6th layer 11th layer ( Yellow filter layer) Yellow colloidal silver 0.15 Gelatin 0.9 2,5-di-t-octylhydroquinone 0.1 High boiling solvent O-1 0.2 12th layer (Low sensitivity blue-sensitive silver halide emulsion layer) Sensitizing dye (S-2, S-6) Em-8 0.3 Em-2 0.3 coupler spectrally sensitized with 168 mg / mol Ag Y-1 1.4 High boiling point solvent O-3 0.6 Gelatin 1.3 Layer 13 (highly sensitive blue-sensitive silver halide emulsion layer) Sensitizing dyes (S-5) (S-2, S-6) Average grain size 0.90 µm containing 2.5 mol% of silver iodide spectrally sensitized with 78.4 mg / mol Ag, (100) face ratio 100% Silver iodobromide emulsion having an outermost surface iodine of 0.5 mol% 0.75 coupler Y-1 3.5 high boiling point solvent O-3 1.4 gelatin 2.1 14th layer: first protective layer UV absorber U-1 0.3 UV absorber U-2 0.4 2,5-Di-t-octylhydroquinone 0.1 High boiling solvent O-3 0.6 Gelatin 1.2 15th layer: 2nd protective layer Average Non-photosensitive fine grain silver halide emulsion composed of silver iodobromide containing 0.08 µm in diameter and 1 mol% of silver iodide 0.3 Polymethyl methacrylate grains (1.5 µm in diameter) 0.06 Surfactant SA-1 0.004 Gelatin 0.7 Each layer In addition to the above composition, gelatin hardener H-1,
H-2, a surfactant, and a preservative DI-1 were added.

In the above, the silver halide emulsion was subjected to chemical ripening using appropriate amounts of sodium thiosulfate, chloroauric acid and ammonium thiocyanate so as to exhibit optimum sensitivity. 4-hydroxy as a chemical ripening inhibitor
-6-Methyl-1,3,3a, 7-tetrazaindene was used, and the temperature was lowered at the same time as the addition. The details of the silver halide emulsions used are shown in Table 1 below.

[0084]

[Table 1]

The spectral sensitizing dye was added 30 minutes before the addition of sodium thiosulfate for spectral sensitization. The total film thickness after drying was 21 μm. The structural formula of the composition used for the sample is as follows.

[0086]

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[0087]

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[0088]

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Next, the silver halide emulsions and the spectral sensitizing dye solutions of the eighth and ninth layers of Sample 101 were changed as shown in Table 2,
Sample 112 was prepared from 102.

[0090]

[Table 2]

The sample prepared in this manner was subjected to a temperature of 40 ° C./80
After storing for 1 week under the condition of% RH, wedge exposure was performed simultaneously with the product stored at room temperature, and development processing was performed by the method described below.

Processing step Processing time Processing temperature First development 6 minutes 38 ° C Rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Rinse 4 minutes 38 ° C Stability 1 minute Room temperature Drying The composition of the processing solution used in the above process is as follows.

First developer sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Thiocyan Potassium acid 1.2g Potassium iodide (0.1% solution) 2cc. Water was added to make up to 1000cc. (PH 9.60) Reversal solution Nitrilotrimethylene phosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 cc. Water was added to make up to 1000 cc. (PH 5.75) Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 cc. Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 cc. (PH 11.70) Conditioner Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 cc. Glacial acetic acid 3 cc. (PH 6.15) Bleach solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 cc. (PH 5.56) Fixer ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to make up to 1000 cc. (PH 6.60) Stabilizing solution Formalin (37% by weight) 5 cc. KONIDAX (manufactured by Konica Corporation) 5 cc. (pH 7.00) The results obtained are shown in Table 3 below. However, the sensitivity in the table is represented by a sensitivity difference (ΔlogE) with the sensitivity of the green-sensitive layer of the sample 101 stored at room temperature being ± 0. As for the moisture resistance, the difference in sensitivity of the green sensitive layer between the room temperature storage product and the humidification storage product was indicated by (ΔlogE).

[0094]

[Table 3]

As apparent from Table 3, the sample of the present invention
It can be seen that the film has high sensitivity and excellent moisture resistance.

Example 2 <Preparation of Spectral Sensitizing Dye Solid Dispersion SD-3> (S-7) 455 mg, (S-10) 59 mg, (S-
1) 238 mg of (S-4) 227 mg of water previously adjusted to 27 ° C.
After adding 50ml, 3500 with high speed stirrer (dissolver)
By stirring at rpm for 30 to 120 minutes, a sensitizing dye solid dispersion (SD-3) having an average particle size of 0.38 μm was obtained.

<Preparation of Methanol Solution SD-4 of Spectral Sensitizing Dye> 302 mg of the exemplified spectral sensitizing dye (S-7) and (S-1)
100 ml of methanol was added to 39 mg of (0), 15 mg of (S-1) and 151 mg of (S-4) to obtain a methanol solution (SD-4) of the spectral sensitizing dye dissolved at 27 ° C.

(Preparation of Sample for Evaluation) Sample 101 of Example 1
Samples 201 to 2 in which only the silver halide emulsion and the spectral sensitizing dye solution used in the fourth and fifth layers were changed as shown in Table 4 below
No. 12 was prepared, and the sensitivity and the moisture resistance of the red-sensitive layer were measured.

[0099]

[Table 4]

[0100]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity and improved moisture resistance can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/10 G03C 1/035 G03C 1/06 502 G03C 7/00 530

Claims (1)

(57) [Claims] 1. A spectral sensitizing dye for photography which is substantially water-insoluble.
There spectral sensitization used in the solid state without the use of organic solvents
The, the base particle surface silver iodide content of 3 mol% or less in the table phase
Consisting of silver halide grains coated with
A silver halide emulsion layer containing a silver halide emulsion occupying 50% or more of the total surface area of all silver halide grains is coated on a support.
A silver halide color photographic material, comprising: