JPH05297496A - Photographic additive and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the spectrally sensitizing dye substantially isoluble in water and dispersed in fine particles rapidly and stably without using any organic solvent or any wetting agent and superior in adsorption stability and stable coatability when added to silver halide grains, and to obtain the silver halide photographic sensitive material using this sensitizing dye. CONSTITUTION:The spectrally sensitizing dye having a solubility of 1X10<-4> to 4X10<-2>mol/l, preferably, 2X10<-4> to 4X10<-2>mol/l in water in the substantial absence of any organic solvent or any surfactant at 27 deg.C is dispersed in an amount more than the solubility mechanically into fine solid particles of sized to <=1mum, and added to the silver halide photographic sensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion of a spectral sensitizing dye in which solid fine particles are dispersed, and a silver halide photographic light-sensitive material containing such a sensitizing dye dispersion.

[0002]

BACKGROUND OF THE INVENTION Conventionally, when various water-insoluble photographic additives are introduced into a silver halide emulsion, the photographic additives are dissolved in an organic solvent such as methanol and the solution is added to the silver halide emulsion. The method was generally widespread. However, such a method has a problem that aggregates are formed in the silver halide emulsion by the organic solvent and a coating failure such as a lump or a streak occurs when the silver halide emulsion is coated. In addition, work and environmental problems have occurred due to the use of organic solvents.

Instead of such a conventional method, an additive is dispersed and prepared as an aqueous system in the presence of a wetting agent and a dispersant without using an organic solvent, and an aqueous dispersion of the obtained additive is prepared. Attempts have been made to add it to a silver halide emulsion.

That is, JP-A-52-110012 discloses an aqueous dispersion obtained by pulverizing a sensitizer in an aqueous phase in the presence of a dispersant (surfactant) which gives a constant surface tension. There is described a method in which water is removed from the emulsion and dried, and then added to the silver halide emulsion as it is or dispersed in water or an aqueous gelatin solution and then added to the silver halide emulsion.

Further, in JP-A-53-102733, a homogeneous mixture (paste mixture) comprising a fine grain additive for photography, a dispersant such as sorbitol and a protective colloid such as gelatin.
Is prepared, and it is made into noodles and dried with warm air to give granules. The resulting particles are added to a photographic aqueous colloid coating composition.

Further, in US Pat. No. 4,0060,25, a spectral sensitizer is mixed with water to form a slurry, and the temperature is raised to 40 to 50 ° C. in the presence of a surfactant to homogenize or mill to spectrally sensitize. A method in which a sensitizer is uniformly dispersed in water and the resulting dispersion is added to a silver halide emulsion is described.

However, all of these addition methods are methods of adding a photographic additive such as a spectral sensitizer in an aqueous system without using an organic solvent, but have the following practical problems. .. That is, since the aqueous dispersion is pulverized by freeze-drying or the like, the time required for adsorption of additives such as a spectral sensitizer to the silver halide grains becomes long, so that the desired photographic sensitivity cannot be obtained within a short time. Further, when such a silver halide emulsion is coated, coating failure due to precipitates or the like is likely to occur. Further, since a wetting agent or a dispersant is used to disperse the additives, the emulsion existing in the silver halide emulsion is destroyed, and the coating failure is increased due to the rapid coating of the silver halide emulsion. And the film formation of the produced silver halide photographic light-sensitive material deteriorates, which is a problem in product quality.

[0008]

SUMMARY OF THE INVENTION With respect to the above problems, the object of the present invention is to provide a rapid and stable method for dispersing a substantially water-insoluble spectral sensitizing dye without using an organic solvent, a wetting agent or a dispersant. And a silver halide photographic light-sensitive material, which are excellent in adsorption stability to silver halide emulsion particles, coating stability, raw storage stability and the like when dispersed in a silver halide emulsion and further added to a silver halide emulsion. Especially.

[0009]

The above object of the present invention is to achieve a solubility of 1 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant, preferably Is a spectral sensitizing dye characterized by adding a spectral sensitizing dye of 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter in an amount exceeding the solubility and mechanically dispersing it in solid fine particles of 1 μm or less. Dispersion method, dispersion, silver halide emulsion containing the dispersion of the spectral sensitizing dye, and silver halide photographic light-sensitive material containing the silver halide emulsion.

The present invention will be specifically described below.

A technique for mechanically dispersing an organic dye in an aqueous medium is known from JP-A-3-288842. However, this method is for making the organic dye resistant to diffusion in the photographic light-sensitive material, and is merely a dispersion addition method. On the other hand, the present invention has been made in order to uniformly and effectively adsorb the photographic spectral sensitizing dye to the silver halide grain surface, and the above-mentioned technique merely for adding the sensitizing dye is not effective. Is different from

In the present invention, the organic solvent means a solvent containing carbon atoms which is liquid at room temperature. Conventionally, a water-miscible organic solvent has been used as a solvent for sensitizing dyes. For example, alcohols, ketones, nitriles, alkoxy alcohols, etc. 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. Further, the surfactant includes an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine 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, an aqueous system substantially free of an organic solvent and / or a surfactant is water containing impurities at a level that does not adversely affect the silver halide photographic emulsion, and more preferably ion exchange. Refers to water.

The 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 / It is a liter. That is, if the solubility is lower than this region, the dispersed particle size becomes very large and non-uniform, so that the dispersion may precipitate after the completion of dispersion, or when the dispersion is added to a silver halide emulsion, It was found that it interferes with the adsorption process of dyes to silver halide.

Further, if the solubility is higher than this range, the viscosity of the dispersion increases more than necessary, air bubbles are entrained and the dispersion is hindered, and dispersion becomes impossible at higher solubility. However, it has become clear from the research conducted by the present inventors.

The solubility of the spectral sensitizing dye in water was measured by the following method.

Into a 50 ml Erlenmeyer flask, 30 ml of ion-exchanged water was added, and a dye which was not completely dissolved by visual observation was added to it.
The mixture was kept at 27 ° C and stirred for 10 minutes with a magnetic stirrer. The suspension was filtered with ToYo Co., Ltd. paper filter No.2.
The filtrate was filtered with Tosoh Corp. disposable filter,
Properly dilute the filtrate and spectrophotometer U-341 manufactured by Hitachi Ltd.
The absorbance was measured at 0. Thus, the solubility (mol / liter) was obtained from the Lambert-Beer law D = εlc (D: absorbance, ε: spectral absorption coefficient, l: cell length for absorbance measurement, c: concentration (mol / liter).

The spectral sensitizing dye in the present invention means a compound which causes electron transfer to the silver halide when it is photoexcited when it is adsorbed on the silver halide and does not include an organic dye. The spectral sensitizing dye of the present invention may be any one having a solubility in water in the range of 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter, preferably a cyanine dye.
More preferably a hydrophilic group (eg, —SO ₃ H, —COOH, etc.)
It is a cyanine dye with.

Specific examples and solubilities in water are shown below, but the present invention is not limited thereto.

[0022]

[Chemical 1]

[0023]

[Chemical 2]

In the present invention, various dispersers are effectively used for mechanically grinding 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. A high speed agitator is preferred in the present invention.

As a high speed stirring type dispersing machine, for example, FIG.
As shown in (a), there is a tank 1, a dissolver blade 2 and a vertical shaft 3. The dissolver 2 is shown in FIG.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on the vertical shaft or a multi-axis dissolver having a plurality of vertical shafts. Further, 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 putting water in a tank whose temperature can be adjusted, a certain amount of powder of the spectral sensitizing dye is put, and the mixture is stirred with a high-speed stirrer for a certain time under temperature control, Crush and disperse. When mechanically dispersing the spectral sensitizing dye, p
The H and temperature are not particularly limited, but at low temperature, the desired particle size cannot be reached even after long-time dispersion, and at high temperature, reaggregation or decomposition occurs, and desired photographic performance cannot be obtained. There are problems such as a problem and an increase in temperature lowers the viscosity of the solution system, which greatly reduces the efficiency of pulverizing and dispersing solids. Therefore, the dispersion temperature is more preferably 15 to 50 ° C. Furthermore, the stirring rotation speed during dispersion requires a long time to obtain the desired particle size at low rotation speeds, and at high rotation speeds entrains bubbles and reduces dispersion efficiency, so dispersion is performed at 1000 to 6000 rpm. More preferably.

The fact that the solid fine particles of the spectral sensitizing dye dispersed by the method of the present invention is 1 μm or less means that the particle size according to the volume average diameter of spheres is 1 μm or less, which is measured by a general method. it can.

The dispersion used in the present invention means a suspension of a spectral sensitizing dye, preferably a spectral sensitizing dye having a weight ratio of 0.2% to 5.0%. Used.

The dispersion of the spectral sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion, or
Water may be used as the diluting solution at this time, although it may be appropriately diluted before addition.

In the present invention, the silver halide emulsion is used after being physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are
Disclosure No.17643, No.18716 and No.308119
(Respectively abbreviated to RD17643, RD18716 and RD308119 below). The table below shows the locations.

[Item] [Page of RD308119] Iodine composition 993 I-A item Manufacturing method 993 I-A item and 994 E item Crystal habit (normal crystal) 993 I-A item (twin crystal) 993 I-A item Epitaxial 993 I-A item Halogen composition (uniform) 993 I-B item (not uniform) 993 I-B item Halogen conversion 994 I-C item Halogen substitution 994 I-C item Metal-containing 994 I-D item Monodisperse 995 I-F item Solvent addition 995 I-F item Latent image formation position (surface) 995 I-G item (internal) 995 I-G item Negative photosensitive material 995 I-H item Positive (including internal fog particles) 995 I -H Item Mixing and Using Emulsion 995 I-J Desalting 995 II-A In the present invention, the silver halide emulsion used is one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 17643, No. 18716 and No. 308119 (respectively RD
17643, RD18716 and RD308119).

The table below shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A, B, C, D, H, I, J 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 Known photographs usable in the present invention Additives are also described in Research Disclosure above.

The locations related to the table below are shown.

[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 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 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 and coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developers (included in photosensitive materials) 1011 XXB Item Also, to prevent deterioration of photographic performance due to formaldehyde gas. , U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in No.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643 and VII-C to G. ..

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, and 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739
No., British Patent Nos. 1,425,020, No. 1,476,760, U.S. Patent Nos. 3,973,968, No. 4,314,023, No. 4,511,649,
Those described in European Patent No. 279,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,636 are preferred.
No. 3,061,432, No. 3,725,067, No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
No. 2, Research Disclosure No. 24230 (6 June 1984)
Mon) JP 60-43659, 61-72238, 60-35730,
55-118034, 60-185951, U.S. Pat.No. 4,500,630
No. 4,540,654, 4,556,630, International Publication WO88
Those described in / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat. No. 4,052,
No. 212, No. 4,146,396, No. 4,228,233, No. 4,
No. 296,200, No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent No. 121,365A
No. 249,453A, U.S. Patent No. 3,446,622, No. 4,3
33,999, 4,775,616, 4,451,559, 4,
No. 427,767, No. 4,690,889, No. 4,254,212, No. 4
Those described in 4,296,199 and JP-A-61-242658 are preferable.

Research Disclosure No. 1 is a colored coupler for correcting unnecessary absorption of a coloring dye.
7643, Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258,
Those described in British Patent No. 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is preferable to use a coupler having a precursor group as a leaving group.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,57.
No. 0, European Patent No. 96,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820, 4,080,211 and US Pat.
4,367,282, 4,409,320, 4,576,910, and British Patent 2,102,173.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is RD described above.
17643, Patents described in Section VII-F, JP-A-57-151944
Nos. 57-154234, 60-184248, 63-37346, US Pat. Nos. 4,248,962, and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,140 can be used.
No. 2,131,188, JP-A-59-157638, 59-17084.
Those described in No. 0 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,33.
Multi-equivalent couplers described in JP-A-8,393 and JP-A-4,310,618, and DIR described in JP-A-60-185950 and JP-A-62-24252.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox releasing redox compound, European Patent No.
No. 173,302A, a coupler that releases a dye that undergoes color restoration after release, RD No. 11449, 24241, a bleaching accelerator releasing coupler described in JP-A No. 61-201247, U.S. Pat.
Ligand releasing coupler described in JP-A-63-75747, a coupler releasing a leuco dye described in JP-A-63-75747, US Pat.
Examples thereof include couplers that release the fluorescent dye described in JP 774,181.

Further, various couplers can be used in the present invention. Specific examples thereof are described in RD below. The relevant parts are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-G item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 VII-F item VIIF item BAR coupler 1002 VII-F item Other useful residues Release coupler 1001 VII-F item The additive used in the present invention is the dispersion described in RD308119XIV. It can be added by a method or the like.

In the present invention, the above-mentioned RD17643 page 28, R
The supports described in D18716647 pages 8-8 and RD308119 XIX can be used.

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

The light-sensitive material of the present invention is the above-mentioned RD308119VII-
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section K can be adopted.

Suitable supports usable in the present invention are described in, for example, RD. No. 17643, page 28 and No. 18716, page 647, right column to page 648, left column.

As a concrete support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like can be used. The thickness of the support is usually 50 to 200 μm.

The present invention can be applied to various color 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. ..

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 24 μm or less, more preferably 20 μm or less, still more preferably 18 μm or less. The film swelling speed T1 / 2 is preferably 30 seconds or less, more preferably 20 seconds or less. Film thickness is 25 ° C relative humidity
Mean film thickness measured under 55% humidity control (2 days), film swelling T
1/2 can be measured according to a method known in the art. For example, A. Green (A.Gree
n) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), Vol. 19, No. 2,
It can be measured by using a swellometer (swelling meter) of the type described on pages 124 to 129, and T1 / 2 is 30 in a color developer.
90% of the maximum swollen film thickness reached when treated at 3 ℃ for 15 minutes
Is the saturated film thickness, and is defined as the time until the film thickness of T1 / 2 is reached.

The film swelling speed T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the above-described conditions according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No.17643, pages 28-29, and No. 18716, 615, left column to right column, the development can be carried out by a usual method.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it be housed in a cartridge. The most common cartridges are
It is a 135 format patrone. In addition, the cartridges proposed in the following patents can also be used (Shokai 58-673).
29, JP-A-58-181035, JP-A-58-182634, Shoukai-58-1
95236, U.S. Pat.No. 4,221,479, Japanese Patent Application No. 63-57785,
63-183344, 63-325638, Japanese Patent Application No. 1-21862, 1
-25362, 1-30246, 1-20222, 1-21863,
1-37181, 1-33108, 1-85198, 1-172595
No. 1-172594, No. 1-172593, U.S. Patent No. 4,846,41
No. 8, No. 4,848,693, No. 4,832,275).

Further, the present invention can be applied to Japanese Patent Application No. 4-16934, "Small Photographic Roll Film Patrone and Film Camera". To obtain a dye image using the light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure.

The light-sensitive material of the present invention is the above-mentioned RD17643, 28-29.
Development can be carried out by a usual method described in pp. RD18716, pp. 647 and XII of RD308119.

[0060]

EXAMPLES The effects of the present invention will be illustrated below with reference to examples.

Example 1 As the high speed stirring type disperser used in the present invention, the one shown in FIG. 1 was used.

The following sensitizing dyes were used for comparison.

[0063]

[Chemical 3]

(Sample 1) The spectral sensitizing dye (D-5) 1.
0 g was added to 200 g of methanol and dissolved at 27 ° C. to obtain a methanol solution of the spectral sensitizing dye.

(Sample 2) The spectral sensitizing dye (D-5) 1
Methanol 4.9g and water 485.1 that 0.0g was adjusted to 27 ℃
Immediately after adding to the mixed solution of g, a high speed stirrer (dissolver) shown in FIG. 1 was stirred at 3.500 rpm for 30 to 120 minutes to obtain a dispersion in which the spectral sensitizing dye was dispersed. ..

(Sample 3) The spectral sensitizing dye (D-5) 1
Immediately after adding 0.0 g to 490 g of a 0.1% aqueous solution of triisopropylnaphthalenesulfonic acid whose temperature had been adjusted to 27 ° C, immediately
At 3.500 rpm with the high-speed stirrer (dissolver) shown in
A dispersion liquid in which the spectral sensitizing dye was dispersed was obtained by stirring for 30 to 120 minutes.

(Sample 4) The spectral sensitizing dye (D-11) 1
Immediately after adding 0.0g to 490g in water that was adjusted to 27 ℃,
3.500 rpm with the high speed stirrer (dissolver) shown in Fig. 1.
A dispersion liquid in which the spectral sensitizing dye was dispersed was obtained by stirring for 30 to 120 minutes.

(Sample 5) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-12) dispersion liquid was obtained.

(Sample 6) The spectral sensitizing dye (D-13) 1
When 0.0g was added to 490g of water that had been adjusted to 27 ℃,
(D-13) was completely dissolved, and (D-13) could not be dispersed only with water.

(Sample 7) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-9) dispersion liquid was obtained.

(Sample 8) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-10) dispersion liquid was obtained.

(Sample 9) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-5) dispersion liquid was obtained.

(Sample 10) By the same formulation as in (Sample 1), the spectral sensitizing dye (D
A methanol solution of -3) was obtained.

(Sample 11) By the same formulation as in (Sample 1), the spectral sensitizing dye (D
A methanol solution of -4) was obtained.

(Sample 12) By the same formulation as in (Sample 1), the spectral sensitizing dye (D
A methanol solution of -9) was obtained.

(Sample 13) By the same formulation as in (Sample 1), the spectral sensitizing dye (D
A methanol solution of -8) was obtained.

(Sample 14) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-3) dispersion liquid was obtained.

(Sample 15) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
-4) dispersion liquid was obtained.

(Sample 16) By the same formulation as in (Sample 4), the spectral sensitizing dye (D
A dispersion of (8) was obtained.

The average particle size of the spectral sensitizing dye in the dispersions obtained in Samples 2 to 9 was measured immediately after the preparation of the sample in the state of primary particles. Further, when the dispersions obtained in Samples 2 to 9 were allowed to stand at 27 ° C. for 1 week and the dispersion state was visually evaluated,
It became like Table 1.

[0081]

[Table 1]

From the results shown in Table 1, it is clear that the samples of the present invention have excellent dispersion stability. Example 2 Emulsions 1 to 4 were prepared by the following method.

(Emulsion 1) Sample 1 was prepared from a silver halide emulsion in which Em-4 used in the example of Japanese Patent Application No. 3-168850 was optimally chemically sensitized with sodium thiosulfate and chloroauric acid. 1.0 × 10 ⁻⁴ mol of the adjusted methanol solution of the spectral sensitizing dye was added to 1 mol of silver halide, and the mixture was stirred at 55 ° C. for 30 minutes.

(Emulsion 2) (Sample 2) was used in place of (Sample 1) in (Emulsion 1).

(Emulsion 3) (Sample 3) was used in place of (Sample 1) in (Emulsion 1).

(Emulsion 4) In (Emulsion 1), (Sample 1) was replaced with (Sample 9).

After collecting an appropriate amount of each of these emulsions 1 to 4 and centrifuging, the supernatant was collected and the concentration of the spectral sensitizing dye (D-5) was measured with a spectrophotometer. By taking the reciprocal of 10 as a simple index of the adsorption force, the standard value is 100
The result is as follows.

[0088] From this result, it is clear that the emulsion using the sample prepared by the method of the present invention has excellent adsorption of the sensitizing dye.

In the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 3 One side (surface) of triacetyl cellulose film support
Was subjected to an undercoating treatment, and then the support was sandwiched between the layers, and a layer having the following composition and a support were sequentially formed on the surface (back surface) opposite to the surface subjected to the undercoating treatment.

Back side first layer Alumina sol AS-100 (aluminum oxide) 100 mg / m ² (manufactured by Nissan Chemical Industries, Ltd.) Diacetyl cellulose 200 mg / m ² Back side second layer diacetyl cellulose 100 mg / m ² Stearic acid 10 mg / m ² Silica fine particles (average particle size 0.2 μm) 50 mg / m ^{2 On} the surface of a triacetyl cellulose film support that has been subjected to undercoating, each layer having the composition shown below is sequentially formed from the support side to obtain a multilayer color photographic light-sensitive material-101. Created.

First layer: antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent ( Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) High boiling point solvent (Oil-1) 0.5 g Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Iodour Silver halide emulsion (average grain size 0.3 μm) 0.4 g (average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S- 1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / Silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR Compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.9 g (Average iodine content 7.5 mol%) Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point Solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) High boiling point solvent (Oil-1) 0.5 g Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 0.6 g (average iodine content 8.0 mol%) Silver iodobromide emulsion (average grain size 0.3 μm) 0.2 g (average iodine content 2.0 mol%) Sensitizing dye ( S- ⁴ ) 6.7 × 10 ^-4 (mode Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-- 1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size) 0.7 μm) 0.9 g (average iodine content 7.5 mol%) Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Agent (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low sensitivity blue-sensitive emulsion layer ( BH) Silver iodobromide emulsion (average grain size 0.3 μm) 0.25 g (average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4 μm) 0.25 g (average iodine content 8.0 mol%) Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound ( D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 μm) 0.5 g (average) Iodine content 8.5 mol%) Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler ( Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV Absorber (UV-1) 0.07g Ultraviolet absorber (UV-2) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling solvent (Oil-1) 0.07g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer; Second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: Ethyl methacrylate: Copolymer of methacrylic acid = 3: 3: 4 (weight ratio) (average particle size 3 μm) 0.13 g gelatin 0.5 g The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content 2 mol%) as seed crystals.

The solution <G-1> was heated to 70 ° C., pH 7.8 and pH 7.
The seed emulsion corresponding to 0.34 mol was added while maintaining the ratio at 7.0 while stirring well.

<Formation of Internal High Iodity Phase-Core Phase> After that, while maintaining the flow rate ratio of <H-1> and <S-1> at 1: 1, the accelerated flow rate (the flow rate at the end is Initial flow rate of 3.6
Doubling) and added over 86 minutes.

<Formation of External Low Iodity Phase-Shell Phase> Next, <H-2> and <S while maintaining pH Ag10.1 and pH 6.0.
-2> was added at a flow rate accelerated at a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ocein gelatin 100.0 g 10% by weight solution of Compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml 5000.0 ml with water

[0100]

[Chemical 4]

<H-1> Oscein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% ammonia solution equivalent Finish with water 1030.5 ml <H-2 ＞ Ocein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finish with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% aqueous ammonia solution Equivalent with water 3776.8ml By the same method, average particle size of seed crystal , Temperature, pAg, pH,
The emulsions having different average grain sizes and silver iodide contents were prepared by changing the flow rate, addition time and halide composition.

In each case, the distribution was 20% in the following core / shell type monodisperse emulsion. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

[0103]

[Chemical 5]

[0104]

[Chemical 6]

[0105]

[Chemical 7]

[0106]

[Chemical 8]

[0107]

[Chemical 9]

[0108]

[Chemical 10]

[0109]

[Chemical 11]

[0110]

[Chemical 12]

[0111]

[Chemical 13]

Incidentally, the above-mentioned photosensitive material 101 further comprises the compound S
U-1, SU-2, viscosity modifier, hardener H-1, H-
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1 (9.
4 mg / m ² ).

[0113]

[Chemical 14]

(Sensitive Material A) Sixth of the color photographic sensitive material 101
In the layer, (Sample 10) was used as (S-4), and (S
(Sample 11) was used as -5). In the seventh layer, (Sample 12) was used as (S-6), (Sample 13) was used as (S-7), and (Sample 1) was used as (S-8).

(Sensitive Material B) Sixth of the color photographic sensitive material 101
In the layer, (Sample 14) was used as (S-4), and
(Sample 15) was used as -5). In the seventh layer, (Sample 7) was used as (S-6), (Sample 16) was used as (S-7), and (Sample 9) was used as (S-8).

The (light-sensitive material A) and (light-sensitive material B) produced as described above were exposed to white light through a step wedge for sensitometry and processed under the following conditions.

Treatment process Treatment process Treatment time Treatment temperature ℃ Replenishment amount Water Color development 3 minutes 15 seconds 38 ± 0.3 780ml Bleach 45 seconds 38 ± 2.0 150ml Fixation 1 minute 30 seconds 38 ± 2.0 830ml Stability 60 seconds 38 ± 5.0 830 ml Dry 1 min 55 ± 5.0- * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

Color developing replenisher liquid 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-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2.0 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter and adjust to pH 10.18 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was used. Adjust to pH 4.4.

Bleaching Replenisher Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.0 with aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher liquid water 800 ml ammonium thiocyanate 150 g ammonium thiosulfate 180 g sodium sulfite 20 g ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizer and stable replenisher water 900 ml

[0126]

[Chemical 15]

Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml Water was added to make 1 liter, and then ammonia water Alternatively, adjust the pH to 8.5 with 50% sulfuric acid.

Photosensitive Material-101 except that the backside first layer and the backside second layer were added to the following composition.
The effect of the present invention was also obtained in the light-sensitive material prepared in the same manner as in.

Backside first layer

[0130]

[Chemical 16]

Backside second layer Diacetyl cellulose 107.6 mg / m ² Aerosil 200 (particle size 0.2 μm silica fine particles) 10.8 mg / m ² (manufactured by Nippon Aerosil Co., Ltd.) Citric acid half ethyl ester 6.4 mg / m ² Created next (Sensitive material A) and (Sensitive material B)
The sample was left to stand in an atmosphere of 80% for 7 days for a raw storability test by forced deterioration.

The increase in fog (ΔFog) of the sample after forced deterioration with respect to the untested sample and the sensitivity of the untested sample were set to 100.
When the relative sensitivity (S) of the sample after forced deterioration was measured, the result was as follows.

[0133] From this result, it is clear that the photosensitive material using the sample prepared by the method of the present invention has excellent raw storability.

[0134]

According to the production method of the present invention, an aqueous dispersion of a photographic additive can be produced rapidly and effectively. By using this dispersion, the time required for adsorption to silver halide grains is long. It takes no time, the desired sensitivity can be obtained within a certain time, and the raw storage stability of the silver halide color photographic light-sensitive material is improved. Further, it is possible to prevent the occurrence of coating failure due to precipitates and the like during the coating of silver halide photographic emulsions, and it has been considered to be essential in the past when dispersing a substantially water-insoluble photographic additive in an aqueous system. Since it can now be performed without using the wetting agent or dispersant, it is possible to prevent adverse effects such as emulsion destruction, adverse effects on high-speed coating, and poor adhesion. It was possible to improve the state of adsorption of the additives for use on the silver halide grains.

[Brief description of drawings]

FIG. 1A is a schematic view of a high-speed stirring type disperser. FIG. 1B is a perspective view of an impeller.

[Explanation of symbols]

 1 Tank 2 Dissolver 3 Vertical Axis 4 Liquid to be Dispersed 5 Impeller 6, 7 Blades

Claims (8)

[Claims] 1. The solubility at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant is 2 × 10 ⁻⁴ to.
A method for dispersing a spectral sensitizing dye, which comprises adding 4 × 10 ^-2 mol ^/ liter of a spectral sensitizing dye in an amount exceeding the solubility and mechanically dispersing it in solid fine particles of 1 μm or less. 2. The solubility at 27 ° C. is 1 × 10 ⁻³ to 4 × 10.
^The method for dispersing a spectral sensitizing dye according to claim 1, wherein the amount is ⁻² mol ^/ liter. 3. The solubility at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant is 2 × 10 ⁻⁴ to.
A dispersion of a spectral sensitizing dye, characterized in that a spectral sensitizing dye of 4 × 10 ^-2 mol ^/ liter is added in an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 μm or less. 4. The solubility at 27 ° C. is 1 × 10 ⁻³ to 4 × 10.
The dispersion of the spectral sensitizing dye according to claim 3, wherein the dispersion is ^-2 mol ^/ liter. 5. The solubility at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant is 2 × 10 ⁻⁴ to.
Halogen characterized by adding a spectral sensitizing dye prepared by a method of adding 4 × 10 ^-2 mol / liter of spectral sensitizing dye in an amount exceeding the solubility and mechanically dispersing it in solid fine particles of 1 μm or less. Silver halide photographic emulsion. 6. The solubility of the spectral sensitizing dye at 27 ° C. is 1.
The silver halide photographic emulsion according to claim 5, which has a concentration of x10 ^-3 to 4x10 ^-2 mol / liter. 7. The solubility at 27 ° C. in an aqueous system substantially free of an organic solvent and / or a surfactant is 2 × 10 ⁻⁴ to.
Halogenation to which a dispersion of a spectral sensitizing dye prepared by a method of mechanically dispersing into solid fine particles of 1 μm or less by adding a spectral sensitizing dye of 4 to × 10 ^-2 mol / liter in an amount exceeding the solubility is added. A silver halide photographic light-sensitive material containing a silver photographic emulsion. 8. The solubility of the spectral sensitizing dye at 27 ° C. is 1.
8. The silver halide photographic light-sensitive material according to claim 7, which has a content of × 10 ^-3 to 4 × 10 ^-2 mol / liter.