JPH041748A - Emulsified dispersion - Google Patents

Abstract

PURPOSE:To stably obtain a high UV absorbing effect by forming a specified mixture of plural UV absorbents. CONSTITUTION:A compd. shown by formula I and a compd. shown by formula II are mixed to obtain the mixture of plural UV absorbents. In the formulas, R1 is a halogen atom, substituted or non-substituted alkyl group, aryloxy group, etc., R2 is H atom, a substituted or non-substituted aryl group, etc., R3 is a substituted or non-substituted alkyl group or an aryloxy group, (n) is an integer of 0 to 4, (m) is an integer of 0 to 3, and R21-R24 are respectively hydrogen atom, a halogen atom, a substituted or non-substituted alkenyl group, a nitro group, a hydroxyl group, etc. A high UV absorbing effect is stably obtained in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an emulsified dispersion, and more particularly to an emulsified dispersion comprising a plurality of ultraviolet absorbers preferably used in photographic products. .

[Background of the invention] There are many known effects of ultraviolet light on photographic products.

For example, static light generated during coating and drying of photographic products and transport can cause undesirable exposure of photographic products, and color reproducibility can deteriorate due to differences in the intensity of ultraviolet light from various light sources during photography. It will be done.

In addition, in photographic products in which images are formed using pigments other than metallic silver, the color fading of the pigment image by ultraviolet rays is particularly large, so when displaying photographic products for ornamental purposes, the sunlight containing ultraviolet rays in the feldspar may significantly change the color of the pigment image. Discoloration occurs.

Furthermore, especially when polyethylene-coated paper is used as a support, the polyethylene is degraded by ultraviolet rays, resulting in cracking of the support.

In addition to these, various organic additives are introduced into photographic products, and the photodecomposition products produced by photodecomposition reactions are often colored, which can cause stains, especially in non-image areas. This is a phenomenon that is often seen. For example, it is known that the uncolored areas (white background) of color photographic paper do not yellow when irradiated with light (this is called photo stain).
Improvements are desired.

It is well known and widely used to incorporate ultraviolet absorbers into silver halide emulsion layers or non-light-sensitive photographic layers in photographic products in order to alleviate the above-mentioned effects of ultraviolet radiation.

Representative compounds of these ultraviolet absorbers are disclosed in, for example, U.S. Patent No. 2,685,512, U.S. Pat.
No. 2,739,888, No. 2,739,971, No. 2.747996, No. 2.784,087
No. 2.8N, 461, No. 3,112,338
No. 3.168.492, No. 3.206, 43
No. 1, No. 3.253.921, No. 3.692.5
No. 25, specifications of No. 3.754.919, Japanese Patent Publication No. 42-4786, No. 49-26139, No. 50-2
No. 5337, No. 55-12587, No. 55-3698
4, the specifications of International Publication No. 81-01473, and European Patent Publication No. 57.160.

Several methods have been proposed for dispersing such ultraviolet absorbers.

The first type is the so-called Fischer type dispersion, which is a method of dispersing finely divided particles.

Second, polymer latex particles are formed by gradually adding enough water to make the fillable polymer latex and the UV absorber insoluble in a solution of the UV absorber, etc. dissolved in a water-miscible organic solvent. There is a way to incorporate it. The miscible organic solvent and fillable polymer latex are described in detail in JP-A-51-59942 and JP-A-51-59943.

A third method is to dissolve an ultraviolet absorber or the like in a substantially water-insoluble high-boiling organic solvent or polymer and finely disperse it in a hydrophilic protective colloid to obtain an oil-in-water emulsion dispersion. .

This method is described, for example, in U.S. Patent No. 2.322027; ．． No. 901,170, No. 2,801,171
No. 2.870012 and No. 2,991.1
It is described in detail in each specification of No. 77. An example of applying this dispersion method particularly to ultraviolet absorbers is described in US Pat. No. 2,739,888.

Of these methods, the third method has been most widely used in recent years because it does not cause thickening of the coating solution in the coating solution preparation process, making it suitable for mass production, and because it has good absorption of ultraviolet absorbers. ing.

However, this method has the following practical problems. That is, as is well known, the stability of emulsified dispersions is low, which tends to cause coarsening of dispersed particles and precipitation of crystals, which tends to cause major troubles in the manufacturing process.

Although the use of ultraviolet absorbers is certainly effective in improving light resistance (and static mark resistance), it has been difficult to prevent dye images from fading under various light sources. Although it is possible to improve the light resistance of a dye image under changes in light sources to some extent by adding a large amount of an ultraviolet absorber to a photosensitive material, there is a limit to this as well.

Additionally, if too much UV absorber is added, micro or macro emulsified dispersion will precipitate, leading to a sudden loss of UV absorbing ability, resulting in poor light resistance and coating failure. .

On the other hand, there is a technique to use two or more kinds of ultraviolet absorbers in combination as a method of improving the precipitation property.
No. 496, No. 48-30493, No. 48-41572
No., JP-A-53-85425, JP-A-59-2153
It is described in each publication of No. 78.

Although this method is certainly effective in improving precipitation properties,
This is still unsatisfactory and has little effect on coarsening of dispersed particles over time.

Furthermore, the improvement in light resistance against various light sources was also insufficient.

As a result of various studies, the inventors of the present invention found that by combining specific ultraviolet rays and specific ultraviolet rays, it is possible to not only sufficiently prevent the precipitation and stability of the emulsified dispersion, but also improve the light resistance against various light sources. The inventors have discovered that both properties are improved, leading to the present invention.

Therefore, the first object of the present invention is to provide an emulsified and dispersed first tray that can stably provide a high ultraviolet absorption effect.

The second object is to provide an emulsified dispersion that, when applied to photographic products, can provide a high effect of improving light resistance against various light sources.

The above object of the present invention is to provide an emulsified dispersion containing oil droplets containing a plurality of ultraviolet absorbers, in which the plurality of ultraviolet absorbers are combined with at least one compound represented by the following general formula [I]. At least one of the compounds represented by []
This is achieved by an emulsified dispersion characterized in that it is a mixture of:

General Formula [I] [In the formula, R1 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. ! represents a substituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group.

R2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R3 represents a @-substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group.

n represents an integer of 0 to 4, and m represents an integer of 0 to 3. ] General formula [II] [wherein R2+, R22 and R23 are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxy group, Represents a substituted aryloxy group, substituted or unsubstituted alkenyl group, nitro group or hydroxyl group. ] In the compound represented by the general formula [I] according to the present invention, R1 is a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group), It represents a substituted or unsubstituted aryl group (eg, phenyl group), a substituted or unsubstituted alkoxy group (eg, methoxy group), or a substituted or unsubstituted aryloxy group (eg, phenoxy group).

R2 is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl group, t-butyl group, 2-ethyl-hexyl group, 5ec-dodecyl group, iso-tridecyl group, ci
s-9-octadecenyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group).

R3 is a substituted or unsubstituted alkyl group (e.g. t-amyl group, methyl group, etc.), a substituted or unsubstituted aryl group (e.g. phenyl group), a substituted or unsubstituted phenoxy group (e.g. methoxy group, 2-ethyl group) -hexyloxy group), substituted or unsubstituted 7-aryloxy group (for example, phenoxy group).

Among the compounds represented by the general formula [I], the following formula [I
A compound represented by -Al is preferred.

-Formula [l-Al tridecyl group, etc.), X' represents a hydrogen atom or a chlorine atom! j,] The most preferred is a compound represented by the following formula [I-C].

General formula [N] [wherein, X represents a hydrogen atom or a halogen atom, R2
- has the same meaning as R2 in formula [I]. ] General formula l-A
Among the compounds represented by l, more preferably the compound represented by the general formula [
I-8].

General formula [I-8] [In the formula, X'' represents a hydrogen atom or a chlorine atom, and R% and R5 each represent an alkyl group (e.g., ethyl group, butyl group, etc.)] A representative represented by general formula [I] [wherein,
R2'' is a branched alkyl group (for example, compound example!-6 ■-10 ■-11 ■-12 ■-13 ■-14 ■-15 ■-22 ■-16 ■-17 ■-18 ■-19 Next, The compound represented by the general formula [II] will be described.

General formula [I] (In the above general formula [II], R21, R22 and R
23 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkenyl group, Among the groups represented by R2+ and R22, which represent nido OJI or a hydroxyl group, hydrogen atoms, alkyl groups, alkoxy groups, and aryl groups are preferred, and hydrogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Among the groups represented by R23, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

At least one of R21 to R23 is preferably an alkyl group, and more preferably at least two are an alkyl group.

Next, specific examples of typical compounds represented by the general formula [nl] will be shown.V) Below, saliva I-6 ■-10 Emulsions consisting of compounds represented by the general formula [I] and the general formula [I[] The dispersion (hereinafter referred to as the emulsified dispersion of the present invention) can be suitably used in silver halide photographic materials. When such an emulsified dispersion of the present invention is applied to a silver halide photographic light-sensitive material, the emulsified dispersion of the present invention may be added to either a photosensitive layer or a non-photosensitive layer, but is preferably added to a non-photosensitive layer. added to the sexual layer. More preferably, it is added to the non-photosensitive layer that is farther from the support than the photosensitive layer that is furthest from the support. There is no limit to the amount of the compound represented by the general formula [I] and the compound represented by the general formula [Ir] added to the photographic light-sensitive material, but it is 005 to 15, respectively! II/
m' is preferable, more preferably 0.1 to 5 (1/1
'is.

Further, the addition ratio of the compound represented by the general formula [I] and the compound represented by the general formula [II] is preferably 1:99 to 99:1, more preferably 20:80 to 80:20.

Silver halide photographic materials containing the emulsified dispersion of the present invention include, for example, color negatives and positive CH.

Films and color photographic paper can be used, but the effects of the present invention are particularly effectively exhibited when color photographic paper intended for direct viewing is used.

This color photographic paper and other photosensitive materials may be monochromatic or multicolor. In the case of a multicolor silver halide photographic light-sensitive material, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually formed on a support in an appropriate number of layers. It has a structure in which layers are laminated in order, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

When the photographic material containing the emulsified dispersion of the present invention is a multicolor photographic material, the specific layer structure is as follows:
On the support, sequentially from the support side, a yellow dye image forming layer,
Particularly preferred is an arrangement of an interlayer, a magenta dye image-forming layer, an interlayer, a cyan dye image-forming layer, an interlayer, and a protective layer.

In the emulsion layer of the photographic light-sensitive material containing the emulsified dispersion of the present invention, a dye-forming coupler that forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer is used in the color development process. .

The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's light sensitive spectrum, with a yellow dye-forming coupler for the blue light sensitive emulsion layer. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, photosensitive materials may be produced using different combinations from the above.

Any dye-forming coupler used in the photographic light-sensitive material containing the emulsified dispersion of the present invention preferably has in its molecule a group called a ballast group having 8 or more carbon atoms that renders the coupler non-diffusive.

As the yellow dye-forming coupler, acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include British Patent 1.0
No. 77, 874, Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 4
No. 7-1031, No. 47-26133, No. 4B-94
No. 432, No. 50-87650, No. 51-3631
No. 52-115219, No. 54-99433, No. 54-133329, No. 56-30127, U.S. Patent No. 2,875,057, No. 3.253.924
No. 3,265,506, No. 3,408.194, No. 3.551.155, No. 3551.156, No. 3.664.841, No. 3. , No. 725.072, No. 3, 730.722@, No. 3,891,445,
No. 3,900,483, No. 3.929.484,
No. 3,933,500, No. 3,973,968, No. 3.990.896, No. 4,021,259, No. 4
, No. 022.620, No. 4,029,508, No. 022.620, No. 4,029,508, No.
4.057.432, 4.106,942, 4.057.432, 4.106,942,
4.133.958, 4.269.936, 4,286,053, 4.304.845, 4
, No. 314,023, No. 4,338,327, No. 4,
No. 356,258, No. 4386155, No. 4,401
, No. 752, etc.

Although pyrazolone couplers can be used as the magenta coupler, pyrazolotriazole couplers are preferably used.

Specific examples of magenta couplers that can be used include, for example, Japanese Patent Application No. 6
No. 3-166895, U.S. Patent No. 3.725.065,
JP 59-99437, JP 5B-42045, JP 59-162548, JP 59-171956, JP 60-33552, JP 60-43659, JP 60-
It is described in No. 172982 and No. 60-190779.

As the cyan dye-forming coupler, a phenol-based or naphthol-based cyan dye-forming coupler is used.

These cyan dye image-forming couplers are described in U.S. Pat.
No. 06,410, No. 2,356.475, No. 2.36
No. 2598, No. 2.367, No. 531, No. 2.369.
No. 929, No. 2.423730, No. 2,474,2
No. 93, No. 2,476.008, No. 2, 498.4
No. 66, No. 2,545,687, No. 2.728.
No. 660, No. 2.772.162, No. 2,895,8
No. 26, No. 2.976146, No. 3,002,836
No. 3.419.390, No. 3.446622,
3.476, 563, 3,737,316, 3,758.308, 3.839.044,
British Patent No. 478,991, British Patent No. 945,542, British Patent No. 478,991, British Patent No. 945,542,
No. 1,084,480, No. 1337233, No. 1
, No. 388,024, No. 1.543.040, JP-A-47-37425, No. 50-10135, No. 50
-25228, 50-112038, 50-
No. 117422, No. 50-130441, No. 51-
No. 6551, No. 51-37647, No. 51-5282
No. 8, No. 51-108841, No. 53-109630
No. 1: No. 54-48237, No. 54-66129, No. 54-131931, No. 55-32071, No. 5
No. 9-146050, No. 59-31953, No. 60
-117249 etc.

The dye-forming couplers mentioned above typically contain I x 10-3 per mole of silver halide in each silver halide emulsion layer.
mole to 1 mole, preferably 1X10-2 mole-8X10
The compound represented by the general formula [I] and the compound represented by the general formula [II] of the present invention can be used in a range of 1 to 10 molar amount. An emulsified dispersion can be obtained using a dispersion method, a latex dispersion method, etc.

Usually, the useful compounds of the present invention, including the compounds represented by the general formula [I] and the general formula [ff], have a boiling point of about 150"
It is dissolved in a high boiling point organic solvent of C or above in combination with a low boiling point and/or water soluble organic solvent as necessary, and then stirred using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. , using dispersion means such as homogenizers, colloid mills, flow jet mixers, ultrasonic devices, etc.
After being emulsified and dispersed, it is added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The high boiling point organic solvent used in emulsifying and dispersing the compounds represented by the general formula [E] and the general formula [I] of the present invention is preferably a compound having a dielectric constant of 5.5 or less, for example, a dielectric constant of 5.5 or less. These include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, hydrocarbon compounds, etc. More preferably, the dielectric constant is 5.0 or less.
It is a high boiling point organic solvent with a vapor pressure of 9 or more and a vapor pressure of 0.5 mmHg or less at 100°C. Among these, phthalate esters and phosphoric esters are more preferred. Most preferred are dialkyl phthalates having an alkyl group having 9 or more carbon atoms. Furthermore, the high boiling point solvent may be a mixture of two or more types.

Note that the dielectric constant indicates the dielectric constant at 30°C.

Preferred high boiling point organic solvents include the following compounds.

(1) Di-2-ethylhexyl phthalate (2) Dioctyl phthalate (3) Di-mi-nonyl phthalate (4) Di-mi-decyl phthalate (5) Didodecyl phthalate (6) Treaty-nonyl phosphate (7) Treaty-decyl Phosphate (8) tri-1-dodecyl phosphate (9) di-2-
Ethylhexyl adipate (10) Di-2-ethylhexyl azelate (11) Di-2-ethylhexyl sebacate (12) Octyl decyl phthalate (13) Oleyl benzoate (14) Benzyl benzoate The emulsified dispersion of the present invention As the binder (or protective colloid) used in photographic materials containing gelatin, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material containing the emulsified dispersion of the present invention can be prepared by using, alone or in combination, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened. It is desirable to add a hardening agent in a sufficient amount to harden the photosensitive material to the extent that it is not necessary to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

A photographic light-sensitive material containing the emulsified dispersion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material during development or are bleached.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto. In order to investigate the storage stability of emulsified dispersions containing the respective ultraviolet absorbers and the effect of improving light resistance in coating films, emulsified dispersions were prepared using the combinations shown in Table 1.

＋″〕〕〕 each D -V-1 V-2 An emulsified dispersion was created by the following procedure.

(a) 10 g of an ultraviolet absorber having the composition shown in Table 1, 10 g of a high boiling point organic solvent, and 20 C1 of ethyl acetate are mixed and heated to about 60° C. to dissolve.

(b) Photographic gelatin 15g, pure water 200*fl @v
'Mix at IA and allow to swell for 20 minutes. Next, about 60℃
After heating and dissolving the mixture, 201 g of a 5% aqueous solution of Alkanol B (manufactured by DuPont) was added and stirred uniformly.

(C) The solutions obtained in (a) and (b) were mixed and dispersed for 20 minutes using an ultrasonic disperser to obtain an emulsified dispersion. This was finished with pure water for 300 d.

In the above method, the composition of the ultraviolet absorber was varied as shown in Table 1 to obtain a total of 10 emulsified dispersions.

Next, a storage stability test for each emulsified dispersion was conducted.

(Storage stability test of emulsified dispersion) Containers each containing samples 1 to 1o of the obtained emulsified dispersion were stoppered and kept at 40°C for 48 hours. The degree of precipitation was investigated. The results obtained are shown in Table 2.

In addition, the degree of crystal precipitation is as follows:
The weight of the precipitate was determined by suction filtration, washing, and drying using 0 dT (7:1%) No. 5A (7) 1 paper (manufactured by Toyo A!! Paper Co., Ltd.).

Further, each of the emulsified dispersions prepared as described above was used in the fourth layer and the sixth JI of a photographic light-sensitive material to prepare a multilayer silver halide photographic light-sensitive material in order to examine light resistance.

Each layer having the structure shown in Table 2 is coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide and a blue tinting agent on the other side on the first layer side. Silver halide color photographic material sample 1 was prepared. The coating solution was prepared as follows.

Preparation of third layer coating solution] Magenta coupler (M-A>35p, stain inhibitor (HQ-1) 1.h and high boiling point organic solvent <DNP) 30
(Add 601 g of ethyl acetate to 1 liter and dissolve, and add this solution to 1
A magenta coupler dispersion was prepared by emulsifying and dispersing the mixture in 200 vQ of a 0% gelatin aqueous solution using an ultrasonic homogenizer.

This dispersion was mixed with a green-sensitive silver halide emulsion (containing silver 279) prepared under the following conditions to prepare a third layer coating solution.

Coating solutions for other layers were also prepared in the same manner as the third layer coating solution.

Further, samples similar to Sample 1 were prepared except that the ultraviolet absorbers in the fourth and sixth layers were changed to the combinations shown in Table 3. The following hardeners H-1 and H-2 were used.

death! C(CH2S02CH=CH2).

[Y4 production method of blue-sensitive silver halide emulsion] The following (liquid A) was added to 1000 d of a 2% gelatin aqueous solution moistened at 40'C.
and (liquid B) l) A<1 = 6.5, pH = 3.0
Add the following (solution C) and (solution D) simultaneously over 30 minutes while controlling
They were simultaneously added over a period of 180 minutes under controlled conditions.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Liquid A) Na C13,42g K B r O,03
! Add 11H20 200d
(Liquid B) AQN03 Add 10g H2O 200-(Liquid C) Na Cff1 102.7
gKBr 1.0p
Add H20 600. Q(D
Liquid) A! l NOa 300
After addition of pH 20 and Teoom6, desalination was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium FA acid, and then mixed with an aqueous gelatin solution to obtain an average particle size of 085 μm.
1 coefficient of variation (σ/Y) = 0.07, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-1 was obtained.

The following compound was used for the above emulsion EMP-1 at 50°C.
A blue-sensitive silver halide emulsion (
EmA) was obtained.

Sodium thiosulfate 0.8 mg 1 mol AgX gold chloride 1tti 0.5 mg 1 mol A (I
X stabilizer 53-5 6X10-4-E/l, /-E
/L, /'u X sensitizing dye D= 1 5xlO-4
mol/-El Ag In the same way as in 1, the average particle size was 0.43 μm1 the coefficient of variation (σ/te)
= 0.08, and a monodispersed cubic emulsion EMP-2 with a silver chloride content of 99.5 mol % was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
A green-sensitive silver halide emulsion (Eu+
B) was obtained.

Sodium thiosulfate 1.5mM mol 80 Chloroauric acid 1.0mg 1 mol, IX stabilizer 5
B-56x10-4 mol 1 mol A (JX sensitizing dye D-
2 Stabilizer 5B-5 Sensitizing dye D-3 6 x 10→mol 1 mol Ai+ 0 x 105 mol 1 mol At3 4.0 x 10-4 mol 1 mol Agx [Method for preparing red-sensitive silver halide emulsion] ( A liquid) and (B
The average particle size was 0.5 in the same manner as EMP-1 except for changing the addition time of liquid) and the addition time of (liquid C) and (liquid D).
A monodisperse cubic emulsion EMP-3 having a diameter of 0 μm, a coefficient of variation (σ/γ) = 0.08, and a silver chloride content of 99.5 mol % was obtained.

EMP-3 was chemically ripened for 90 minutes at 60°C using the following compound to produce a red-sensitive silver halide emulsion (Em C).
I got it.

Sodium thiosulfate 1, 8mQ 1 mol ApX chloroauric acid 2. omg,'Mole A(IX
Table-2 (1) B-5 C-1 Table-2 (2) T-2 T-3 T-4 BP OP NP IDP vP INP Table-2 (3) CH, CH.

(Dibutyl phthalate) (Dioctyl 7 talate) (Dinonyl 7 talate) (Diisodecyl 7 talate) (Polyvinylpyrrolidone) (Triisononyl 7 male 7 2-t) Below margin -2 == HQ-1 AI-2 V-1 ) (B -1 V-2 less than 1" C, H, (t) These samples were subjected to green light wedge exposure using a sensitometer (manufactured by Konica Corp., model KS-7). After that, processing was performed according to the following processing steps.

[Processing process] Temperature Time color development
35.0+0.3℃ 45 seconds bleach fixing
35.0±0.5℃ Stabilized for 45 seconds 3
Dry for 90 seconds at 0-34℃ 6
0-80℃ 60 seconds [Color developer] Pure water
800d triethanolamine
10 ON, N-diethylhuman Oxylamine 5g
Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite o3g 1-Hydroxyethylidene-1,1 diphosphonic acid 1.09 Ethylenediaminetetraacetic acid 1. Og disodium catechol-3,5-disulfonate m 1. OQN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate F
A4.50 Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative> 1.0 g potassium carbonate
Add 27G water and bring the total amount to 11
and adjust the pH to 10.10.

[Bleach-fix solution] Bleach-fix solution 12 contains: 60 Q ethylenediaminetetraacetic acid ferric ammonium dihydrate 3 g ammonium thiosulfate (70% aqueous solution) ioo ammonium sulfite (40% aqueous solution) 27.5 d. Adjust pH=5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid] Stabilizing liquid 1! Medium, 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol i,o gl-hydroxyethylidene-1,1-diphosphone H2,Og ethylenediaminetetraacetic acid @ 1.0 (]ammonium hydroxide (20% aqueous solution > 3.0!1 Contains 3.0 g of ammonium sulfite and 1.5 g of optical brightener (4,4'-diaminostilbene diphosphonic acid derivative). With sulfuric acid or potassium hydroxide I) H=7 Adjust to .0.

The processing was carried out after the sample was subjected to a 100f running process using an automatic developing machine with a multi-stage countercurrent stabilization system.

After the treatment, a light fastness test was conducted on the magenta colored image of each sample obtained as follows.

[Light resistance test] Each sample was exposed to sunlight for 30 days using an outdoor underglass @ an outdoor stand, and the green light reflection density before and after fading was measured. The degree of fading due to light (1 color rate) was determined as follows.

Fading rate = D0 - D x 100 [)0 = Concentration before photofading D = Degree after photofading In the same manner, each sample was tested for 60 days under daylight color fluorescent lamps (20,000J7UX). The results are shown in Table 3. .

As is clear from Table 3 below, the samples of the present invention not only have good dispersion stability but also good light resistance under each light source.

Example 2 Yellow coupler, magenta coupler, cyan coupler of Sample 1 of Example 1 and dye image stabilizer 5T in the third layer
-3,5T-4 was changed to the following compound. In addition, samples similar to those in Example 1 were prepared, except that the ultraviolet absorbers in the fourth and sixth layers were changed as shown in Table 4, and the same evaluations as in Example 1 were performed.

The results are shown in Table 4.'1j0 - Lower margin, White-1 Yellow coupler Table 4 Magenta coupler No. 3/lil dye image stabilizer This sample 19 had a DNP of 0.0 (J/v2).

As is clear from Table 4, the samples of the present invention not only had good dispersion stability, but also images with good light resistance were obtained with any light source.

Example 3 Paper support laminated on both sides with polyethylene (thickness 14
A color photographic material was prepared in which the following layers 1 to 9 were coated on the front side (5 μm), and the 10th layer was coated on the back side.

The first layer coating side of the polyethylene contains titanium white as a white pigment.

The emulsion used was an emulsion prepared in the same manner as emulsion EM-1.

(Photosensitive layer composition) The coating material (■) shown below is indicated by its components and Ig/dm'.

Silver halides are expressed in terms of silver.

Note that 5A-1 and 8A-2 were used as coating aids, and HA-1 and HA-2 were used as hardeners.

Preparation of Emulsion EM-1 While controlling an aqueous solution containing ossein gelatin at 40°C, an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr:Na Cj! in molar ratio) were mixed together.
=95: An aqueous solution containing 5) was simultaneously added using a controlled double jet method to obtain a cubic silver bromide emulsion with an average grain size of 0.45 μI.

At that time, the pH and pA (+) were controlled so that a cubic grain shape was obtained.The obtained cubic emulsion of 0.45 μm was further mixed with an aqueous solution containing ammonia and silver nitrate, and potassium bromide and sodium chloride (KBr in molar ratio). :Na
C1=40:60) and an aqueous solution containing the same were simultaneously added using a controlled double jet method to obtain an average particle size of 0.6.
A shell was formed to a thickness of μm. At that time, pH and 1) ACI were controlled so as to obtain a cubic particle shape. After washing with water to remove water-soluble salts, gelatin was added to obtain emulsion EM-1. (The width of the distribution was 8%.) The grain sizes of the core and shell of the silver halide emulsion grains used are as follows.

No. 111<Red Sensitivity 1) 0.18 μm cubic silver chlorobromide emulsion spectrally sensitized with red-sensitive sensitizing dyes (RD-1 and RD-2) 0.6 Red-sensitive sensitizing dyes (RD-1 and RD-2) -2) 0.9 μm cubic silver chlorobromide emulsion 0.9 spectrally sensitized with red-sensitizing dyes (RD-1 and RD-2) 0.55 μm cubic silver chlorobromide emulsion 1 spectrally sensitized with red-sensitizing dyes (RD-1 and RD-2) .5 Gelatin 13.8 Cyan coupler (CG-1) 2.1 Cyan coupler (CC-2) 2.1 Image stabilizer (AO-2
) 2.2 Solvent (So-1)
3.3 Stabilizer (ST-1,8T-2,5T
-3) Second layer (middle layer) Gelatin 7.5 Stain inhibitor (AS-1) 0.55 Solvent (So-
2) 0.72 third layer (green sensitive layer) 018μ spectrally sensitized with green-sensitive sensitizing dye (GD-1)
m-cubic silver chlorobromide emulsion 06 green-sensitive sensitizing dye (GD
0.30 μm cubic silver chlorobromide emulsion spectrally sensitized with -1> 0.9 0.55 μm cubic silver chlorobromide emulsion spectrally sensitized with green-sensitizing dye (GD-1) 15 Gelatin 13. O magenta coupler (MC-1) 2.4 Image stabilizer <AO-
1) 2.4 Image stabilizer (AO-2>
1.2 Solvent (So-3)
3.1 Stain inhibitor (As-2)
0.15 Stabilizer (ST-1, 5T-2, 5T-3) 4th layer (intermediate layer) Same as 2nd layer.

5th layer (yellow filter layer) Gelatin 4.2 Yellow colloidal silver 1.0 Ultraviolet absorber (U
V-1 > 0.5 UV absorber (UV-2
) 1.4 Stain inhibitor (AS-1)
0.4 solvent (So-2)
0.8 6th layer (color mixing prevention layer) Gelatin 40 Stain inhibitor (AS-1) 0.27 Solvent (So-2
) 0.36 7th layer (blue-sensitive layer) 0,31 spectrally sensitized with blue-sensitive sensitizing dye (BD-1)
μm tetradecahedral silver chlorobromide emulsion 1.2 blue-sensitive sensitizing dye (
0.55 μm cubic silver chlorobromide emulsion spectrally sensitized with BD-1) 1.8 0.75 μm cubic silver chlorobromide emulsion spectrally sensitized with blue-sensitizing dye (BD-1) 3
．． 0 Gelatin 13,5 Yellow coupler (YC-1>8.4 Image stabilizer (AO-3) 2.5 Solvent (So-1)
5.2 Stabilizer (ST-1,5T
-3,5T-4) 8th layer (ultraviolet absorbing layer) Gelatin 5.4 ultraviolet absorber (UV-1) 1.0 ultraviolet absorber (
UV-2>2.8 solvent (So-3)
1.2 9th layer (retention iJ layer) gelatin 12.3 10th layer gelatin 40.0 Separately, in place of UV-1°UV-2 in the 5th and 8th layers, compound I of the present invention -3 and U-9 as 511th and 8th
A sample of the present invention was prepared in the same manner as the color photographic material described above except that it was used as a layer.

RD-2 BD-1 IV-1 V-2 A-1 A-2 o-i C2Hs T-1 T-3 A-1 A-2 o-2 o-3 S-1 S-2 C! T-2 CH.

H3 A○-2 MC-1 O-3 C-1 c-i 1'\": The internal latent image type direct positive silver halide color photographic light-sensitive material prepared as above was wedged. exposed through.

These two exposed samples were processed in the following processing steps.

Treatment process (treatment temperature and treatment time) (1) Immersion (color development solution) 37℃ (2) Fog exposure 12 seconds 1 Lux 12 seconds 37℃ 1 minute 35 seconds 35℃ 45 seconds 25-30℃ 1 minute 30 seconds 75 ~80℃ 45 seconds (3) Color development (4) Bleach-fixing (5) Stabilization treatment (6) Drying Processing solution composition [Color developer] Benzyl alcohol CB2 (804) 3 Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride 511Q O,015Q d 2.5 g o,69 0.2 g Potassium carbonate 25.008T
-4o,ig Hydroxylamine sulfur ms 5.0(] Sodium diethylenetriaminepentaacetate g Developing agent N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate f4
1.5x10-2M optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1
．． 0 (] Potassium hydroxide 2.
0g diethylene glycol 15mQ Add water to make total amount 1! and adjust to pi-110,15.

[Bleach-fix solution] Ferric ammonium diethylenetriaminepentaacetate 90 (1 diethylenetriaminepentaacetic acid 39 Ammonium thiosulfate (70% solution) 180d Ammonium sulfite (40% solution) 27.5% 3-
Mercapto-1,2,4-triazole o, 15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 111.

"Stabilizing liquid" Ortho phenylphenol 0.3 g Potassium sulfite (50% solution'a) 12 vjl' Ethylene glycol 10 Ql-hydroxyethylidene-1,1-diphosphonic acid 2.59 Bismuth chloride 0.2 (1 zinc sulfate) Heptahydrate 0.7g Ammonium hydroxide (28% aqueous solution) 2.01;1 Polyvinylpyrrolidone (K-17) O,:J optical brightener (4
, 4'-diaminostilbendisulfonic acid derivative)
2 (1) Add water to bring the total volume to 1 l, and adjust to 7.5 p) with ammonium hydroxide or sulfuric acid.

The two samples treated in this way were evaluated in the same manner as in Example 1, and it was found that the sample of the present invention using the specific combination of ultraviolet absorbers of the present invention was UV-resistant.
Compared to the samples using UV-1 and UV-2, no coating failure occurred and images with good light resistance were obtained.

Claims (1)

[Scope of Claims] In an emulsified dispersion containing oil droplets containing a plurality of ultraviolet absorbers, the plurality of ultraviolet absorbers have the following general formula [I]
At least one compound represented by the following general formula [II]
An emulsified dispersion characterized in that it is a mixture consisting of at least one compound represented by: General Formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an unsubstituted aryloxy group. R_2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R_3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. n represents an integer from 0 to 4, and m represents an integer from 0 to 3. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, R_2_1, R_2_2, and R_2_3 are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or represents an unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkenyl group, a nitro group, or a hydroxyl group. ]