JPH09120124A - Emulsified dispersion and silver halide color photographic sensitive material containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsified dispersion of a UV absorbed excellent in aging stability and preventing the photodegradation of the UV absorber by a method not accompanied by defective coating by using a specified compd. and a specified high b.p. org solvent. SOLUTION: This emulsified dispersion consists of a compd. represented by formula I and a high b.p. org. solvent satisfying the condition of X>=85 in the equation X=24.7×log10 Y-11.7×Z+43.7 [where Y is the viscosity (in mPas unit) of the solvent at 25 deg.C, Y is preferably 100-600mPas and Z is the water content (wt.%) of the solvent]. The solvent is not phthalic ester or a compd. having an epoxy group. In the formula I, each of R<1> -R<6> is H, halogen, alkyl, etc., and R<5> and R<6> may bond to each other to form a 6-membered ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion dispersion and a silver halide color photographic light-sensitive material containing the same. More specifically, the light fastness of an ultraviolet absorber and hence the fastness of a dye image are improved and the dispersion is improved. The present invention relates to a silver halide color photographic light-sensitive material excellent in stability.

[0002]

2. Description of the Related Art In silver halide color light-sensitive materials,
It is desired that the dye image formed by the reaction of the oxidant of the aromatic primary amine developing agent and the coupler does not fade even when exposed to light for a long time. Therefore, in recent years, an ultraviolet absorber has been added to a light-sensitive material particularly for the purpose of improving the light fastness of a dye image, but the light fastness of an image dye formed from a yellow, magenta and cyan coupler is still insufficient. is not. As a means for improving this, a method of preventing alteration or disappearance of the ultraviolet absorber by dissolving the ultraviolet absorber in a high boiling point organic solvent selected from phthalic acid ester or phosphoric acid ester is disclosed in JP-A-58-58.
However, its effect is insufficient. Other means for improving the light fastness of image dyes include JP-B-48-31255 and JP-B-48-304.
No. 93 proposes to combine a benzophenone ultraviolet absorber and a benzotriazole ultraviolet absorber. However, its ability is insufficient due to the photolysis of the UV absorber itself. As another means, a method of impregnating a polymer latex with an ultraviolet absorber is disclosed in British Patent No. 2,016,017A. The disadvantage is that many polymer latices have to be used.

Further, a method using an ultraviolet absorbent polymer latex is disclosed in Japanese Patent Application Laid-Open No. 185677/1983, but it only slightly prevents yellow stain generated by light irradiation on a white background. On the other hand, by emulsifying and dispersing the ultraviolet absorber with a specific hydrophobic polymer,
A method for improving the light fastness of the ultraviolet absorber itself and the dye image is described in JP-A-63-264748. However, the following problems were found in putting the above method into practical use. That is, many polymers must be added to the ultraviolet absorber in order to sufficiently improve the light fastness of the ultraviolet absorber. Therefore, a long dissolution time is required, and the mixed solution has a high viscosity, so that it is difficult to emulsify and disperse, and coarse particles are liable to be generated, which causes defective coating. On the other hand, as a method of improving the dispersion stability of an emulsion over time, there is a technique in which two or more kinds of ultraviolet absorbers are used in combination to increase the solubility by lowering the melting point of the ultraviolet absorbers. -549
No. 6, No. 48-30493, No. 48-41572,
JP-A-53-85425, JP-A-59-215378
However, the effect is insufficient.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an ultraviolet absorber which is excellent in dispersion stability over time of an emulsion and which is free from problems such as coating failure and which prevents the ultraviolet absorber from being decomposed by light. An object of the present invention is to provide an emulsion dispersion, and a silver halide color light-sensitive material in which discoloration of a dye image is eliminated by using the emulsion dispersion.

[0005]

The present inventors have found that the above-mentioned problems can be achieved by the following emulsion dispersions (1) to (4) and a silver halide color photographic light-sensitive material (5). It was (1) An emulsified dispersion comprising at least one compound represented by the general formula (1) and at least one high boiling organic solvent satisfying the condition of X ≧ 85 in the formula (A) (provided that Excluding compounds with phthalate ester and epoxy groups as high boiling organic solvents. General formula (1)

[0006]

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(In the above general formula (1), R ¹ , R
² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group. Represents a group, a carbamoyl group or a sulfo group. R ⁵ and R ⁶ may combine with each other to form a 6-membered ring. Table viscosity and weight% in terms of) formula (A) X = 24.7 × Log 10 Y-11.7 × Z + 43.7 ( wherein Y and Z, mPas units in 25 ° C. of the high boiling organic solvent And (2) the high boiling point organic solvent has a viscosity of 10 at 25 ° C.
The emulsified dispersion according to item (1), which is 0 mPas or more and 6000 mPas or less, and (3) the emulsion according to item (1), wherein the high-boiling organic solvent is selected from the following. Dispersion, phosphoric acid ester represented by general formula (2), trimellitic acid ester represented by general formula (3), fatty acid ester represented by general formula (4), chlorination represented by general formula (5) Paraffin General formula (2)

[0008]

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(In the general formula (2), R ⁷ , R ⁸ and R
Each ⁹ independently represents an aliphatic group or an aryl group. In addition, a, b, and c each independently represent 0 or 1. ) General formula (3)

[0010]

[Chemical 6]

(In the general formula (3), R ¹⁰ , R ¹¹ and R
¹² independently represents an aliphatic group or an aryl group. ) General formula (4) R ¹³ COOR ¹⁴ (In the general formula (4), R ¹³ represents a hydrogen atom or an aliphatic group. R ¹⁴ represents an aliphatic group or an aryl group.) General formula (5) C _d H _{(2d-e + 2)} Cl _e (in the general formula (5), d and e represent positive integers, provided that e ≦ 2d + 2), (4) The high boiling point organic solvent is the general formula (3). ),
In the formula, R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group and a trimellitic acid ester having a total carbon number of 24 to 36, which is an emulsified dispersion according to the item (1). (5) at least one compound represented by the general formula (1) and the condition of X ≧ 85 in the formula (A) are satisfied, and the temperature is 25 ° C.
An emulsion dispersion comprising at least one high boiling organic solvent having an epoxy group having a viscosity of 100 mPas or more and 6000 mPas or less, (6) a photosensitive silver halide emulsion layer coated on a support, and At least one layer with the photosensitive hydrophilic colloid layer,
At least one of the compounds represented by the general formula (1) and a high-boiling-point organic solvent satisfying the condition of X ≧ 85 in the formula (A) (excluding compounds having a phthalate ester and an epoxy group). A silver halide color photographic light-sensitive material containing at least one kind, and (7) at least one layer of a light-sensitive silver halide emulsion layer coated on a support and a non-light-sensitive hydrophilic colloid layer To
At least one compound represented by the general formula (1) and the formula (A) satisfy the condition of X ≧ 85, and have a viscosity at 25 ° C. of 100 mPas or more and 6000 or more.
It is intended to provide a silver halide color photographic light-sensitive material containing at least one high boiling point organic solvent having an epoxy group and having a viscosity of mPas or less.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the above (1),
The layer containing the emulsion dispersion described in the items (2), (3), (4) and (5) is preferably a non-photosensitive hydrophilic colloid layer, more preferably the emulsion dispersion. This is the case when the layers contained are one or more light-sensitive silver halide emulsion layers and one or more non-light-sensitive hydrophilic colloid layers.
More preferably, the photosensitive and / or non-photosensitive hydrophilic colloid layer contains the emulsified dispersion dispersed as microdroplets. Further, an emulsified dispersion prepared by dissolving the compound represented by the general formula (1) in a known organic solvent and emulsifying and dispersing it in an aqueous solution, and the above high boiling point organic solvent according to the present invention in an aqueous solution. It may be added to the coating solution for the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer in a mixture with or separately from the emulsion dispersion prepared by emulsion dispersion. The specific constitution of the present invention will be described in more detail below. Some specific examples of the compound represented by formula (1) are shown in Tables 1 to 6, but the present invention is not limited thereto.

[0013]

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[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

The residual ratio of the compound represented by the general formula (1) (ultraviolet absorber) in the photostability by the forced test was multivariately analyzed by the viscosity of the high boiling point organic solvent and the specific water content, and shown in the examples. As described above, it showed good agreement with the value of X in the formula (A). When the value of X is 85 or more, the discoloration of the dye image is at a level where there is no practical problem. As the high boiling point organic solvent satisfying the condition that the value of X is 85 or more, any solvent may be used as long as it does not particularly affect the photographic performance, and a single substance or a mixture of a plurality of components such as isomers may be used. When the high boiling point organic solvent is a mixture, the structural formula is represented by the average composition. The high-boiling organic solvent used in the present invention more preferably has a value of X in the formula (A) of 9
It is 0 or more, more preferably 95 or more. The upper limit of X is not particularly limited, but is preferably 160 or less. The high-boiling organic solvent has a melting point of 100 ° C. or lower and a boiling point of 14
A compound having a temperature of 0 ° C. or higher is preferable, and it may be liquid or solid at room temperature. A more preferable high-boiling point organic solvent has a melting point of 80 ° C or lower and a boiling point of 160 ° C or higher (more preferably 170 ° C or higher). A more preferable high-boiling point organic solvent has a viscosity at 25 ° C. of 100 mPas or more and 6000 mPas or less. More preferably, the viscosity of the high boiling point organic solvent at 25 ° C. is 200 mP.
It is not less than as and not more than 4000 mPas. The specific water content of the high boiling point organic solvent is preferably 3% by weight or less, more preferably 1% by weight or less.

Here, the viscosity of the high boiling point organic solvent was measured at 25 ° C. and 55% RH using a B type viscometer (manufactured by Tokyo Keiki Co., Ltd.). When the high-boiling organic solvent was a solid at 25 ° C., the viscosity was measured while slowly cooling from 120 ° C., and the viscosity was extrapolated to 25 ° C. using the Andrade viscosity formula to obtain the viscosity.
Regarding the specific water content of the high-boiling point organic solvent, 50 ml of ion-exchanged water was added to 50 ml of the solvent, and the mixture was mixed for 15 minutes using an ultrasonic cell disruptor (Powersonic 50 type manufactured by Yamato Scientific Co., Ltd.) and left still for 12 hours or more. After that, the solvent was taken out and evaluated by the Karl Fischer method as a weight fraction of water per unit weight of the solvent. If the solvent and water are not separated by the above method, use a centrifuge (CR7B3 type manufactured by Hitachi Koki)
The solvent was taken out after processing for 30 minutes at a centrifugal acceleration of 000G. When the high-boiling organic solvent became a solid at room temperature, the high-boiling organic solvent was dissolved in the same volume of hexane, and the specific water content of hexane was used as a blank to measure the specific water content by the above method. The melting point of the high boiling point organic solvent in a solid state at room temperature is a value measured by using a melting point measuring device (510 melting point measuring device manufactured by Büch). Further, more preferably, the high boiling point organic solvent is selected from the following. Phosphoric acid ester represented by general formula (2) Trimellitic acid ester represented by general formula (3) Fatty acid ester represented by general formula (4) Chlorinated paraffin represented by general formula (5) When R ⁷ to R ¹⁴ in the general formulas (2) to (4) are an aliphatic group or a group containing an aliphatic group, the aliphatic group may be linear, branched or cyclic. It may also contain an unsaturated bond or an ether bond.
Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group,
There are hydroxyl group, acyloxy group and the like.

When R ⁷ to R ¹⁴ in the general formulas (2) to (4) are cycloaliphatic groups, that is, cycloalkyl groups or groups containing cycloalkyl groups, the cycloalkyl groups are 3 to 8 It may contain an unsaturated bond in the member ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, an alkyl group and an ether group, and examples of the cross-linking group include methylene, ethylene and isopropylidene. . Of these, trimellitic acid ester is most preferable as the high-boiling point organic solvent of the present invention, and the total carbon number of the alkyl part is 2
Those of 4 to 36 are preferable. Further, in the case of a compound having an epoxy group as the high-boiling organic solvent, as shown in the examples, if X ≧ 85 or more and the viscosity at 25 ° C. is 100 mPas or more and 6000 mPas or less in the formula (A), the emulsion ages The dispersion stability and the light fastness of the dye image were good. Typical examples of the high boiling point organic solvent of the present invention are shown below, but the invention is not limited thereto.

[0023]

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[0024]

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[0025]

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The amount of the high-boiling organic solvent used in the formula (A) satisfying the condition of X ≧ 85 is not particularly limited, but the amount of the high-boiling organic solvent is preferably represented by the general formula (1). The weight ratio to the compound is in the range of 0.1 to 10. The weight ratio is more preferably 0.1 to 2, and still more preferably 0.1 to 0.7. The high-boiling point organic solvent (for example, Solv-3, 4) of the present invention can be used not only as a dispersion medium for an ultraviolet absorber but also as a dispersion medium for a yellow coupler, a magenta coupler, a cyan coupler, and the like. When used as a dispersion medium for couplers, the effect of improving emulsion stability (particle size stability, precipitation resistance, etc.) and image fastness (stain prevention, color image fastness, etc.) can be obtained. .

One of the methods for preparing a dispersion containing a compound represented by the general formula (1) of the present invention and a high-boiling organic solvent satisfying the condition of X ≧ 85 of the formula (A) is as follows. After completely dissolving the compound represented by the formula (4) in a high-boiling organic solvent, the solution is dissolved in water, preferably in a hydrophilic colloid aqueous solution, more preferably in a gelatin aqueous solution, with the aid of a dispersant,
Disperse as fine droplets by ultrasonic waves, colloid mill, high speed stirrer, etc. Alternatively, a dispersion aid such as a surfactant and a compound represented by the general formula (1) are completely dissolved in a high-boiling organic solvent, and water or a hydrophilic colloid aqueous solution such as a gelatin aqueous solution is added to the solution, and the water is accompanied by phase inversion. Oil droplets may be dispersed. In the emulsified dispersion of the present invention, the weight ratio of the oil component to water is not particularly limited, but 2 to 1/1
00 is general, 2 to 1/50 is preferable, and 1 to 1/10 is more preferable. Conventionally known surfactants can be used for preparing the emulsion of the present invention. As the surfactant, anionic, cationic, betaine, nonionic surfactants and synthetic and natural surfactants can be used. Specifically, for example, JP-A-62-215
No. 272, pages 203 to 210, W-1
To the compound of W-99 and the compound represented by the following W-100 are used. Among them, W-7, W-47 and W-1
00 is preferable.

[0028]

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An auxiliary solvent may be used when preparing these dispersions. The auxiliary organic solvent may be removed from the prepared dispersion by a method such as distillation, washing with noodles, ultrafiltration or degassing under reduced pressure. The auxiliary organic solvent referred to here is an organic solvent useful at the time of emulsification and dispersion, and is a solvent that is finally removed from the light-sensitive material substantially by a drying step at the time of coating, a low boiling point organic solvent, or water. A solvent that has a certain degree of solubility with respect to and can be removed by washing with water. Auxiliary organic solvents include lower alcohol acetates such as ethyl acetate and butyl acetate, ethyl propionate,
Examples include primary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and cyclohexanone. Further, if necessary, an organic solvent which is completely miscible with water, such as methyl alcohol, ethyl alcohol, acetone or tetrahydrofuran, can be partially used in combination. These organic solvents can be used in combination of two or more kinds. The lipophilic fine particles of the ultraviolet absorbent thus obtained have an average particle size of 0.04 μm to 2
μm is preferable, but 0.04 μm to 0.4 μm is more preferable. More preferably 0.04 to 0.2
0 μm. The particle size of the lipophilic fine particles can be measured by, for example, a measuring device such as Nanosizer manufactured by Coulter, UK. The emulsified dispersion of the present invention is used in various applications as an ultraviolet absorbent composition that takes advantage of the properties of the compound represented by the general formula (I), and the applications are not limited, but preferred are It is used for a photographic light-sensitive material. Various photographic hydrophobic substances can be contained in the lipophilic fine particles of the emulsion dispersion of the present invention. Examples of hydrophobic substances for photography include color or non-color couplers, developers, developer precursors, development inhibitor precursors, development accelerators, gradation regulators such as hydroquinones, dyes, dye releasing agents, oxidation. Inhibitors, fluorescent whitening agents, anti-fading agents and the like. Further, these hydrophobic substances may be used in combination with each other. The emulsion dispersion of the ultraviolet absorber according to the present invention can be contained in the light-sensitive silver halide emulsion layer and / or the non-light-sensitive hydrophilic colloid layer according to a conventional method. The total coating amount of the ultraviolet absorber used in the present invention is 0.1 to 10.
0 g / m ² is preferable, and more preferably 0.1-5.0.
g / m ² .

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. Especially, for the purpose of rapid processing, iodide is used. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of substantially no silver of 90 mol% or more, further 95 mol% or more, and particularly 98 mol% or more. The term "substantially free of silver iodide" means 1 mol% or less, and it is preferably free of any. In the light-sensitive material according to the present invention, a hydrophilic colloid layer for the purpose of improving the sharpness of an image is provided with a dye capable of being decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76. However, an oxonol type dye) is added so that the optical reflection density of the light-sensitive material at 680 nm becomes 0.70 or more, or a dihydric or tetrahydric alcohol (eg trimethylol) is added to the water resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with ethane or the like.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, a combination with a pyrazoloazole coupler or a pyrrolotriazole coupler is preferable. That is, a compound that chemically bonds with an aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound and / or an aromatic amine-based remaining after color development processing. It is possible to use, in combination or alone, a compound that chemically bonds with an oxidized product of a color developing agent to form a chemically inactive and substantially colorless compound. It is also preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the oxidant with the coupler.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent. The support used in the light-sensitive material according to the present invention may be a white polyester support for display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. Further, it is preferable to set the transmission temperature of the support in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred. In addition, upon exposure, the band described in US Pat. No. 4,880,726
It is preferable to use a stop filter. This eliminates photobleaching and significantly improves color reproducibility. The exposed photosensitive material is preferably subjected to bleach-fixing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As the additive, those described in the following patent publications, particularly European Patent EP0,355,650A2 are preferably used.

[0033]

[Table 7]

[0034]

[Table 8]

[0035]

[Table 9]

[0036]

[Table 10]

[0037]

[Table 11]

Further, as a cyan coupler, JP-A-2-
No. 33144, a diphenylimidazole-based cyan coupler, European Patent EP 0,333,185A2, a 3-hydroxypyridine-based cyan coupler, and JP-A-64-32260, a cyclic active methylene-based cyan coupler. Coupler, European Patent EP 0,45
6,226A1 specification, pyrrolopyrazole-type cyan coupler, European Patent EP 0,484,909, pyrroloimidazole-type cyan coupler, European Patent E
P0,488,248 and EP0,491,1
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred. Examples of magenta couplers used in the present invention include WO 9
2/18901, WO92 / 18902 and WO
The aryl-thio-eliminating 5-pyrazolone-based magenta couplers described in No. 92/18903 are preferable in terms of image storability and little change in image quality due to processing. Further, a pyrazoloazole-based magenta coupler is used in the present invention. Among them, JP-A-61-6 is used in terms of hue, image stability, color developability and the like.
Pyrazolotriazole couplers in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-5245 and EP 571,959A, JP-A-61-65246. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-147254, and pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254 and EP 226. , 84
No. 6 described in No. 9A and No. 294,785A.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position. Especially European Patent No. 57
The 6-t-butyl-2-phenylene type pyrazolotriazole couplers described in No. 1,959A are preferred.

As the yellow coupler, known acylacetanilide type couplers are preferably used, and among them, a pivaloylacetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring,
European Patent EP 0,447,969A, JP-A-5-10
7701, JP-A-5-113642, etc., acylacetanilide type couplers in which the acyl group is a cycloalkanecarbonyl group substituted at the 1-position, European Patent EP 0,48
The malondianilide type couplers described in 2,552A, EP 0,524,540A and the like are preferably used. Further, a group that a pivaloyl acetanilide type yellow coupler, an acyl acetanilide type yellow coupler in which an acyl group is a 1-substituted cycloalkanecarbonyl group, or a malondianilide type yellow coupler is released by reacting with an oxidized product of a developing agent. In the case of
The leaving group may be any of the known groups described above, but the molecular weight of the leaving group is preferably 250 or less. For example, an N-benzyl-ethoxy-N-hydantoyl group,
Etc. can be used. More preferably, a leaving group having a molecular weight of 150 or less is used, and for example, a 4,4-dimethyl-N-hydantoyl group can be used.
As the method for processing the color light-sensitive material of the present invention, in addition to the method described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-207250. 973
The processing materials and processing methods described in No. 55, page 5, upper left column, line 17 to page 18, lower right column, line 20 are preferable.

[0040]

Next, the present invention will be described in more detail with reference to examples. Example 1 UV absorber UV-A (UV-24: UV-21: UV
-39: UV-36 = 50: 17: 17: 16 mixture (weight ratio) 50 g
Dissolved in 7.5 g, 333 g of a 15% gelatin aqueous solution and 30 ml of a 10% aqueous solution of the above-mentioned surfactant W-7 were added, and the average particle size of oil droplets in the emulsion was adjusted to 0.1 with a homogenizer (Nippon Seiki). The emulsion was emulsified to 12 μm. The average particle size of the oil droplets was measured by using Nanosizer manufactured by Coulter, England. Further, an aqueous gelatin solution was added to this emulsion, and the emulsion was coated on a polyethylene terephthalate transparent support so that the coating amount was as follows. (As a hardener, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used. ) Coating amount UV absorber (UV-A) 0.32 Solvent (Solv-2) 0.18 Gelatin 2.00 This coated material was designated as Sample 001.

Hereinafter, Sample 0 was prepared in the same manner as Sample 001 except that the type of high boiling point organic solvent was replaced as shown in Table 12.
02-005 and 009-012 were produced. Furthermore, an emulsion was prepared so that the weight (g / g) of the high-boiling-point organic solvent Solv-2 with respect to the weight of the ultraviolet absorber A was 0.7, 0.8, and 1.0, respectively, with respect to the sample 001. After that, coated samples 006, 007, and 008 were prepared.
The ultraviolet spectral absorption concentration in transmission of these samples was measured, and the concentration value of the absorption peak was read. For those having two peaks, the peak value on the long wavelength side near 350 nm was read. After that, these samples were exposed to a xenon fade meter at 200,000 lux for 21 days, and then ultraviolet spectral absorption measurement was performed again to read the concentration value at the same wavelength as the absorption peak before exposure. The ratio of the concentration after exposure to the concentration before exposure was taken to examine the residual rate of the ultraviolet absorber. Residual rate = (concentration after exposure / concentration before exposure) × 100
(%)

The viscosities and specific water contents of Samples 001 to 012 were measured according to the methods described in the text. From these measured values, X = 24.7 × log ₁₀ Y−11.7 × Z + 43.7 was calculated. Here, Y and Z are 25 of a high boiling point organic solvent.
Viscosity in mPas unit at ° C and specific water content in% by weight. The stability of the emulsion was maintained at 5 ° C for 30 days, and after dissolution at 40 ° C for 2 days,
300 L / m ² filtration was performed using a 0 μmφ filter, and the residue on the filter was observed. When there was no residue, the degree of stability was evaluated as 0, and an integer of up to 12 depending on the degree of residue was used to evaluate the degree of stability. The allowable range for the stability of the emulsion is 6 or less.

[0043]

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Table 12 shows the value of X of the high boiling point organic solvent used in Samples 001 to 012, the viscosity at 25 ° C. and 55% RH, the specific water content, and the weight of the high boiling point organic solvent with respect to the weight of the ultraviolet absorber (g. / G), the residual ratio of the ultraviolet absorber after exposure, and the stability of the emulsion. Samples 009 and 010 using a high-boiling-point organic solvent having an X value of less than 85 have a low residual ratio of the ultraviolet absorber and a sample 0 having a lower viscosity.
No. 10 had a low stability of the emulsion. Further, 011 using a phthalic acid ester as a high-boiling organic solvent and 012 using an epoxy compound having a viscosity of less than 100 mPas had low stability of the emulsion. On the other hand, the emulsion of the present invention showed high stability, and the ultraviolet absorber maintained a high residual rate even after exposure to the coating film.

[0045]

[Table 12]

Example 2 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing a surfactant W-7, and further coating various photographic constituent layers.
A multilayer color photographic paper (021) having the following layer structure was produced. The coating solution was prepared as follows. Preparation of fifth layer coating solution Cyan coupler (ExC) 25.0 g, UV absorber U
V-B (UV-21: UV-24: UV-36: UV-
39 = 2: 5: 2: 2) 21.0 g, color image stabilizer (Cp
d-1) 21.0 g, color image stabilizer (Cpd-6) 1.0
g, color image stabilizer (Cpd-8) 1.0 g, color image stabilizer (Cpd-9) 1.0 g, color image stabilizer (Cpd-10)
1.0 g was dissolved in 1.0 g of the solvent (Solv-16), 19.0 g of the solvent (Solv-6) and 50 ml of ethyl acetate, and this solution was added with 14 g of the surfactant (W-7) in 14%. An emulsified dispersion A was prepared by emulsifying and dispersing in 450 g of an aqueous gelatin solution. The particle size of the emulsified dispersion is Coulter submicron particle analyzer model N4
(Coulter Electronics Co., Ltd.) and the average was 0.20 μm. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a grain size of 0.41 μm (silver molar ratio). Coefficient of variation of grain size distribution is 0.09 each
And 0.11. 0.8 mol% silver bromide for each size emulsion,
(Partially contained on a part of the surface of the grain based on silver chloride)
Was prepared. In this emulsion, the red sensitizing dyes G and H shown below were 5.0 × 10 ^-6 mol for each large-sized emulsion C per mol of silver, and for each small-sized emulsion C: Each of them is added in an amount of 8.0 × 10 ^-6 mol. The chemical thermal sensitization of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion C were mixed and dissolved, and further Cpd-18 was added,
A fifth layer coating solution was prepared to have the composition shown below.
The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-11, Cpd
The total amount of -12, Cpd-13, and Cpd-14 was 15.0 mg / m ² , 6.0 mg / m ² , 5.0 mg, respectively.
/ M ² and 10.0 mg / m ² were added.
The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

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[0049] (per mol of silver halide to the large size emulsion, 1.4 × 10 ^-4 mol, respectively, also to the small size emulsion, and 1.7 × 10 ^-4 mol per mol, respectively. ) Green-sensitive emulsion layer

[0050]

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(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mole was added. ) Red-sensitive emulsion layer

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(1 mol of silver halide was added to the large-sized emulsion at 5.0 × 10 ^-5 mol, and to the small-sized emulsion at 8.0 × 10 ^-5 mol. ) Further, the following compounds were added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) is used.
-5-Methylcaptotetrazole was added in an amount of 3.3 x 10 ^-4 mol, 1.0 x 10 ^-3 mol and 5.9 x 10 ^-4 mol per mol of silver halide, respectively. In addition, the second layer,
0.2 mg / m 2 for each of the 4th, 6th and 7th layers
² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

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(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ; content 15% by weight) and bluish dye (ultra-blue)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion ( Cubic, 3: 7 mixture of large size emulsion A with an average grain size of 0.88 μm and small size emulsion A of 0.70 μm (silver molar ratio). The variation coefficient of grain size distribution is 0.08 and 0.10, respectively. For each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride) 0.27 Gelatin 1.40 Yellow coupler (ExY) 0.64 Color image stability Agent (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.09 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer ( Cpd-16) 0.01 Solvent (Solv-16) 0. 22

Second layer (color mixing preventing layer) Gelatin 1.44 Color mixing preventing agent (Cpd-4) 0.11 Solvent (Solv-16) 0.07 Solvent (Solv-17) 0.28 Color image stabilizer (Cpd) -7) 0.17 Solvent (Solv-22) 0.01 Third layer (green sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with average grain size 0.55 μm and small size 0.39 μm) 1: 3 mixture (silver molar ratio) with Emulsion B. Coefficients of variation of grain size distribution are 0.10 and 0.08, respectively. Emulsion of each size is based on 0.8 mol% of silver bromide and silver chloride as a base. 0.13 Gelatin 1.32 Magenta coupler (ExM) 0.14 UV absorber (UV-C) 0.13 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0.01 Color image stability Constant (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.09 Color image stabilizer (Cpd-8) 0.03 Color image stabilizer (Cpd-13) 0.002 Solvent (Solv- 19) 0.30 Solvent (Solv-20) 0.10 Solvent (Solv-23) 0.20 Note) Here, UV-C is a mixture of UV19: UV24: UV36: UV39 = 3: 4: 2: 2 ( Weight ratio).

Fourth layer (color mixing prevention layer) Gelatin 0.82 Color mixing inhibitor (Cpd-4) 0.08 Color image stabilizer (Cpd-7) 0.12 Solvent (Solv-16) 0.05 Solvent (Solv -17) 0.20 Solvent (Solv-22) 0.007 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with average grain size 0.50 μm and small size with 0.41 μm) 1: 4 mixture (silver molar ratio) with Emulsion C. Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively.Emulsion of each size is based on 0.8 mol% silver bromide and silver chloride. 0.20 Gelatin 0.91 Cyan coupler (ExC) 0.25 UV absorber (UV-D) 0.21 Color image stabilizer (Cpd-1) 0.21 Color image stabilizer (Cpd-6) 0.01 Color image stability Constant (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv- 16) 0.01 Solvent (Solv-C) 0.19

Note) Here, UV-D means a mixture (weight ratio) of UV-21: UV-24: UV-36: UV-39 = 2: 5: 2: 2. Sixth layer (UV absorber layer) Gelatin 0.75 UV absorber (UV-E) 0.33 Solvent (Solv-3) 0.18 Note) UV-E is UV-24: UV-20: It shows a mixture (weight ratio) of UV-18: UV-21: UV-36: UV-39 = 6: 3: 2: 2: 2: 2. Seventh layer (protective layer) Gelatin 1.00 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-15) 0.03

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[0065]

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[0066]

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[0067]

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With respect to the sample 021 prepared as described above, the high-boiling organic solvent was changed to the high-boiling organic solvent shown in Table 13 with respect to the total weight of the sixth layer (ultraviolet absorber layer) of the ultraviolet absorbent. Samples 022 to 032 were prepared in the same manner as the sample 021 except that they were replaced so as to have an equal weight ratio. Approximately 35% of the coated silver amount was developed using the sensitometer (FWH type manufactured by Fuji Film Co., Ltd., color temperature of light source: 3200 ° K) on each of Samples 021 to 032, and exposure was performed so as to give gray. . The above sample was subjected to continuous treatment of 200 m ² by using a paper treating machine and using a liquid having the following treating process and treating liquid composition. Treatment process Temperature Time Replenisher * Tank capacity Color development 35 ° C 45 seconds 161ml 10 liters Bleach fixing 35 ° C 45 seconds 218ml 10liters Rinse (1) 35 ° C 30 seconds-5 liters Rinse (2) 35 ° C 30 seconds -5 L Rinse (3) 35 ° C. 30 seconds 360 ml 5 L Dry 80 ° C. 60 seconds * Replenishment amount per 1 m ^{2 of the} light-sensitive material (rinse was a three-tank countercurrent system from (3) to (1))

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 2.5 g-Potassium bromide 0.01 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, Sumitomo Chemical Co., Ltd.) 1.0 g 2.5 g Sodium sulfite 0.1 g 0.2 g Disodium- N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g 8.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0g 7.1g Add water 1000ml 1000ml pH (25 ° C / potassium hydroxide and sulfur With acid) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate iron 5 g Ammonium bromide 40 g Sulfur (67%) ) 30 g Water added 1000 ml pH (25 ° C./acetic acid and ammonia water) 5.8 Rinse solution (tank solution and replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 For each sample thus obtained, 2 x 100,000 lux with a xenon fade meter
The light fastness was evaluated by performing a fading test for 0 days and determining the residual rate (%) of the yellow (Y), magenta (M), and cyan (C) dye images at the initial density of 2.00. Table 13 shows the results.

[0071]

[Table 13]

As is clear from the results shown in Table 13, the sample No. using the high boiling organic solvent in which the value of X is less than 85 is used.
In Nos. 029 and 030, the fading due to light of the dye image produced from the coupler was extremely large. In addition, sample No. 1 using phthalic acid ester as the high boiling point organic solvent. 031
And sample No. 1 using a compound having an epoxy group whose viscosity is less than 100 mPas. As described in Example 1, 032 has low emulsion stability. On the other hand, the multilayer color light-sensitive material prepared from the emulsion of the present invention is improved in fading due to light of the dye image produced from each coupler as compared with the comparative example, and each dye image remains in a well-balanced state even when exposed to light for a long time. It was Example 3 In contrast to Example 1, the ultraviolet absorber was UV-24: UV-
19: UV-21: UV-39: UV-36 = 42: 2
The weight ratio was changed to 0: 12: 14: 14 (weight ratio), and the type of the high boiling point organic solvent and the weight (g / g) of the high boiling point organic solvent with respect to the weight of the ultraviolet absorber were changed as shown in Table 14. Otherwise, Samples 041 to 052 were prepared in the same manner as Samples 001 to 012 and evaluated in the same manner as in Example 1. Further, each sample of 041 to 052 was applied in the same manner as in Example 2 except that the sixth layer (ultraviolet absorber layer) of the multilayer color light-sensitive material was replaced so that the coating amount of the ultraviolet absorber was equal. Then, the same evaluation as in Example 2 was performed. The results are shown in Table 14.

[0073]

[Table 14]

As is clear from the results in Table 14, the multi-layer color light-sensitive material prepared from the emulsion of the present invention has improved long-term fading due to light in the dye image produced from each coupler even if the ultraviolet absorber is different. Each dye image remained in good balance even when exposed to light for a long time, and the emulsion also had high stability.

Example 4 UV absorber UV-A (UV-24: UV-21: UV
50 g of a mixture (weight ratio) of −39: UV-39 = 50: 17: 17: 16) was dissolved in 27.5 g of ethyl acetate,
To this solution was added 333 g of a 15% gelatin aqueous solution and 30 ml of a 10% aqueous solution of the above-mentioned surfactant W-7, and the average particle size of oil droplets in the emulsion was 0.10 μm with a homogenizer.
Until emulsified. On the other hand, 27.5 g of the high boiling point organic solvent shown in Table 15, 120 g of 15% gelatin aqueous solution and 30 ml of 10% aqueous solution of surfactant W-7 were mixed to prepare an emulsion having an average particle diameter of 0.07 μm. It was prepared in.
An ultraviolet absorber emulsion and a high boiling point organic solvent emulsion 45
Coating was carried out in the same manner except that the ultraviolet absorber of the sixth layer (ultraviolet absorber layer) of the multilayer color light-sensitive material of Example 2 was replaced by using the emulsion mixed at 0 ° C. so that the coating amounts were equal. Then, the same evaluation as in Example 2 was performed. Table 15 shows the results.

[0076]

[Table 15]

As is clear from the results shown in Table 15, the multi-layer color light-sensitive material prepared by adding the high boiling point organic solvent of the present invention to the emulsion of the ultraviolet absorber has improved the discoloration of the dye image due to light.

[0078]

According to the emulsified dispersion of the present invention, the dispersion of the emulsified dispersion is excellent in stability over time, and it is possible to prevent the ultraviolet absorber from decomposing to light by a method which does not cause problems such as coating failure. It is possible to obtain an excellent silver halide color light-sensitive material which is improved so as not to cause discoloration.

Claims (7)

[Claims] 1. An emulsified dispersion comprising at least one compound represented by the general formula (1) and at least one high boiling point organic solvent satisfying the condition of X ≧ 85 in the formula (A) ( However, the phthalic acid ester and the compound having an epoxy group are excluded as the high boiling point organic solvent). General formula (1) (In the above general formula (1), R ¹ , R ² , R ³ , R
⁴ , R ⁵ and R ⁶ may be the same or different from each other,
Each represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, a carbamoyl group or a sulfo group. R ⁵ and R ⁶ may combine with each other to form a 6-membered ring. Table viscosity and weight% in terms of) formula (A) X = 24.7 × Log 10 Y-11.7 × Z + 43.7 ( wherein Y and Z, mPas units in 25 ° C. of the high boiling organic solvent The respective specified moisture contents are shown.) 2. The emulsified dispersion according to claim 1, wherein the viscosity of the high-boiling organic solvent at 25 ° C. is 100 mPas or more and 6000 mPas or less. 3. The emulsified dispersion according to claim 1, wherein the high boiling point organic solvent is selected from the following. Phosphoric acid ester represented by general formula (2) Trimellitic acid ester represented by general formula (3) Fatty acid ester represented by general formula (4) Chlorinated paraffin represented by general formula (5) General formula (2) [Chemical formula 2] (In the general formula (2), R ⁷ , R ⁸ and R ⁹ each independently represent an aliphatic group or an aryl group.
a, b, and c each independently represent 0 or 1. ) General formula (3) (In the general formula (3), R ¹⁰ , R ¹¹ and R ¹² each independently represent an aliphatic group or an aryl group.) General formula (4) R ¹³ COOR ¹⁴ (In the general formula (4), R ¹³ is hydrogen. Represents an atom or an aliphatic group, and R ¹⁴ represents an aliphatic group or an aryl group.) General formula (5) C _d H _{(2d-e + 2)} Cl _e (in the general formula (5), d and e are positive) Represents the integer, provided that e ≦ 2d + 2.) 4. The high-boiling organic solvent is represented by the general formula (3), wherein R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group, and the total number of carbon atoms is 24 to 36. The emulsified dispersion according to claim 1, which is a trimellitic acid ester. 5. At least one compound represented by the general formula (1) and the condition of X ≧ 85 in the formula (A) are satisfied, and the viscosity at 25 ° C. is 100 mPas or more and 6000 or more.
An emulsified dispersion comprising at least one high boiling organic solvent having an epoxy group of mPas or less. 6. A photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer coated on a support, and at least one layer of the compound represented by the general formula (1) in at least one layer. A silver halide color photograph containing at least one of high boiling point organic solvents satisfying the condition of X ≧ 85 in the formula (A) (excluding compounds having a phthalate ester and an epoxy group) Photosensitive material. 7. A photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer coated on a support, and at least one layer of the compound represented by the general formula (1) in at least one layer. In the above formula (A), the condition of X ≧ 85 is satisfied, and the viscosity at 25 ° C. is 100 mPas or more 60
A silver halide color photographic light-sensitive material containing at least one high-boiling point organic solvent having an epoxy group and having a viscosity of 00 mPas or less.