JPS6021372B2 - Aqueous dispersion for photographic coating solutions - Google Patents

Description

[Detailed description of the invention] The present invention relates to aqueous dispersions suitable for photographic coatings.

More specifically, it has good flexibility, dimensional stability, pressure resistance, etc. when applied as a coating film, and is particularly suitable for use as a photographic coating liquid and as part of a photographic element of a silver halide photographic light-sensitive material. without adversely affecting photographic properties.
The flexibility of coated photographic elements (coatings) can be improved, and the dimensional stability, pressure resistance, light resistance, etc. The present invention relates to an aqueous fraction solution for photographic coating solutions, in which the stability of these hydrophobic substances for photography is good and favorable photographic properties can be obtained when an absorbent or the like is added. It has been known to use aqueous dispersions containing various polymer particles as photographic coating solutions.

The term "photographic coating liquid" as used herein refers to a solution in which an aqueous dispersion is used alone for coating as part of a photographic element, or a solution in which an aqueous dispersion is mixed with a hydrophilic colloid solution such as gelatin and coated as part of a photographic element. A solution for adding a photographic hydrophobic substance to an aqueous dispersion, impregnating the polymer particles in the aqueous dispersion with the photographic hydrophobic substance, and coating it as part of a photographic element. It is a generic term. Examples of conventionally known aqueous dispersions include, for example, U.S. Pat. issue(
n-butyl acrylate, styrene, acrylamide,
(Aqueous dispersion containing polymer particles formed by monomer or copolymerization of monomers such as methacrylamide), No. 28 of the same
52 Maki No. 2 (Polymer particles obtained by grafting ptagene, isoprene, chlorophrene, styrene, acrylonitrile, vinyl acetate, vinylidene chloride, isoprobenyl acetate, acrylamide, n-butyl acrylate, etc. to gelatin or protein, etc.) (aqueous dispersion containing methyl methacrylate, n-butyl acrylate,
Aqueous dispersion containing particles of monomers or copolymers of glycidyl methacrylate, putadiene, styrene, vinyl acetate, acrylonitrile, vinyl chloride, etc.), Tsubaki Seki No. 51-59942 and No. 51-59 Group 3
(Aqueous dispersion containing polymer particles obtained from a monomer having 2 to 25% by weight of a carboxylic acid group, a carboxylate group, a sulfonic acid group, or a sulfonate group), etc. .

These aqueous dispersions contain photographic hydrophobic substances such as couplers, UV absorbers, antioxidants, dyes, hardeners, poppy
(optical brighteners, etc.) are impregnated into polymer particles in the aqueous dispersion and applied as part of a photographic element. Furthermore, US Pat. No. 2,376,005 (aqueous dispersion containing polymer particles such as vinyl acetate), US Pat.
No. 6 (aqueous dispersion containing polymer particles such as alkyl acrylate), Hakama Kosho 45-Gi 81 (containing polymer particles such as n-butyl acrylate, methyl acrylate, styrene, putadiene, vinyl acetate, acrylonitrile, vinyl chloride, etc.) (Aqueous dispersion containing polymer particles such as alkyl acrylate, acrylic acid, sulfoalkyl acrylate, etc.), Shigeru No. 46-101
Examples include those described in Publication No. y (Aqueous dispersion containing polymer particles such as glycidyl methacrylate, glycidyl acrylate, and alkyl acrylate). These aqueous dispersions are mixed with gelatin solutions and used for the purpose of improving the physical properties of gelatin films. However, when these aqueous dispersions are mixed with gelatin solutions,
When a photographic hydrophobic substance is added or in the presence of organic solvents or salts, the polymer particles in the aqueous dispersion may aggregate,
It has disadvantages such as sedimentation and non-uniformity of particle size.

Additionally, some aqueous dispersions stabilize the polymer particles with low-molecular-weight surfactants, but the diffusion of the core low-molecular-weight surfactants can adversely affect photographic performance.
In such cases, it is necessary to remove the surfactant by water dialysis, but this removal has the drawback of causing aggregation of the polymer particles. Therefore, the first object of the present invention is to provide excellent stability, especially when used as a photographic coating liquid, without affecting the photographic properties, and to provide good flexibility, dimensional stability, pressure resistance and An object of the present invention is to provide an aqueous dispersion that can exhibit light resistance.

A second object of the present invention is that when impregnated with a photographic hydrophobic substance, the stability of the photographic hydrophobic substance is good;
Another object of the present invention is to provide an aqueous dispersion that provides desirable photographic properties. A third object of the present invention is that when a UV absorber is contained as one of the photographic hydrophobic substances,
The objective is to provide an aqueous dispersion that has good dispersibility, has a high level of concentration in the ultraviolet region, has a low optical density in the visible region, and can exhibit sharp cutoff characteristics.

A fourth object of the present invention is to provide an aqueous dispersion that exhibits excellent dispersibility and has an excellent effect on graininess when it contains, for example, a DIR substance as one of the hydrophobic substances for photography. It is to be.

The above objects of the present invention are obtained by emulsion polymerizing a surfactant containing a compound represented by the following general formula [1], [D] and/or [m] as a main component, and a single base body having a vinyl group. This is achieved by an aqueous dispersion for photographic coating solutions. - Monshi formula [1] [In the formula, R is a substituted or substituted divalent organic group, M,
represents a hydrogen atom or a monovalent cation, and n is 30
~95 mol%, the peak represents 70-5 mol%.

[In the formula, R2 is a hydrogen atom or a lower alkyl group,
3, earth and M5 each represent a hydrogen atom or a monovalent cation, n3 is 30 to 95 mol%, and the mountain is 70 to 0
Mol% means 70 to 0 mol%.

However, the content of Yamajuha is 70 to 5 mol%. ] - Takeshiki [town]
[In the formula, R3 is a hydrogen atom or a lower alkyl group, pigeon, M
7, M and M9 each represent a hydrogen atom or a monovalent cation, n6 is 30 to 70 mol%, the ratio is 5 to 50
Mol%, ~ represents 70 to 5 mol%.

However, the ratio +& is 70 to 30 mol%. ] Next, to specifically explain the general formulas [1], m] and [m], R represents ethylene, trimethylene, tetramethylene, hexamethylene, brobenylene, 3,6-dioxaoctane-1,8- diyl, 2,2-dimethyltrimethylene,
Divalent residues of unsubstituted aliphatic hydrocarbons such as propylene, 1,4-cyclohexylene, or 1,2-dichloroethylene, 2-chlorotrimethylene, 2-bromotrimethylene, 1-thia/methylethylene, 1- 2 of aliphatic hydrocarbons substituted with halogen atoms, sia/groups, alkyloxy groups, aryloxy groups, etc., such as chloromethylethylene, 1-toxymethylethylene, and 1-phenoxyethylene.
valent residue, or 1,4-phenylene, 1,3-tolylene,
2-chloro-1,4-phenylene, 2-cyano 1,4
-phenylene, 2-methoxy-1,5-phenylene, unsubstituted or substituted with a halogen atom, a cyano group, an alkyloxy group, etc., or a divalent residue of an aromatic hydrocarbon, or 1,1'-(1, 4-phenylene) dimethyl, 2,2
-(2-chloro-1,4-phenylene)diethyl, 2,
Examples include divalent residues of aliphatic hydrocarbons bonded to aryl groups that are unsubstituted or substituted with halogen atoms, cyano groups, etc., such as 2-(2-cyano-1,4-phenylene)jetyl. M,,M2,M3, earth and pigeon represent hydrogen atoms or monovalent cations of alkali metals such as lithium, sodium, potassium, or ammonium cations.

Next, typical examples of the polymeric surfactant of the present invention will be exemplarily listed below, but the invention is not limited thereto.

Exemplary compound '1' (However, n,: = 50 mol%: 50 mol%, average molecular weight (MW) = about 10000) Exemplary compound [21 (However, n,: - = 30 mol%: 70 mol%, MW = approximately 6000) Exemplary compound '3' (However, n,:ri = 95 mol%: 5 mol%, MW = approximately 2
0000) Exemplary compound [41 (However, n,: mountain = 70 mol%: 30 mol%, MW = about 30000) Exemplary compound side - (However, n,: - = 75 mol%: 25 mol%, MW = about 20000) Exemplified Compound '6- (However, n,: ratio = 50 mol%: 50 mol%, MW = about 25000) Exemplified Compound '7} (However, n,: ratio = 30 mol%: 70 mol%, MW = about 21000) Exemplary compound Leg (however, n,: -i30 mol%: 70 mol%, MW = about 15000) Exemplary compound Side (however, n,: mountain = 50 mol%: 50 mol%, MW = about 2000 ) Exemplary compound '10 (However, n,: mountain: n3 = 80 mol%: 10 mol%: 1
0 mol%, MW = about 6000) Exemplary compound (11) (however, n,:&=95 mol%: 5 mol%, MW = about 3
000) Exemplary compound (12) (However, n,: mountain = 50 mol%: 50 mol%, MW = about 10000) Exemplary compound (13 (how, n,: mountain: n3 = immediate mol%: 45 mol%: (5 mol %, MW=about 15,000) A typical method for synthesizing the polymeric surfactant of the present invention is illustrated below.

Synthesis Example '11 [Synthesis Example of Exemplified Compound 01] Maleic anhydride, 1,6-hexanediol 118
1 hour of paratoluenesulfonic acid and 200 hours of benzene.
Put M in a Kolben, warm it to 120qo (external temperature), and heat it to 6
I worshiped time.

The water flowing out during the reaction was removed by 16 ml to complete the reaction. Next, after distilling off the benzene, 500% of ethanol was added to dissolve the reactant, and a 250M aqueous solution of 52% of acidic sodium sulfite was added dropwise to this solution over 3 minutes, and the internal temperature was 8.
It was incubated at 5°C for 6 hours. Next, ethanol and water were distilled off and the mixture was dried to obtain the desired product (230 mm). In addition, elemental analysis method, NM
The target product was confirmed using the old method and viscosity method. Synthesis Example (2) [Synthesis Example of Exemplary Compound Side] Polybutadiene 130 (Sumikaol #) with a molecular weight of 650
50...Made by Sumitomo Chemical) and 117.6 ml of maleic anhydride were placed in a Kolben 1000 [, and 180 q.
I worshiped the lights for 4 hours at C~19000.

To this reaction mixture, a solution of 150 g of taurine and 48 g of caustic soda dissolved in 500 g of water was added, and the mixture was heated at 6,000 ml for 8 hours.
It was entrained while passing nitrogen through it. The obtained solution was evaporated to dryness to obtain the desired product (370 mm). In addition, it was confirmed that it was the desired product by elemental analysis, NMR method, and viscosity method. Synthesis Example [3] [Synthesis Example of Exemplified Compound (12)] In a 500-ml autoclave, put 54 parts of butadiene, 98 parts of maleic anhydride, 200 parts of acetone, and 0.5 parts of asopisisobutyronitrile. I did Toazusa for 3 hours at 60oo.

After cooling, the analyzed solid was collected in a furnace to obtain a powder of 140 mm.
63 minutes of this powder was put in a 300-pound bottle, and an aqueous solution of 75 pounds of taurine and 20 pounds of soda dissolved in 200 pounds of water was added, and the mixture was heated at 60 qC for 5 hours while passing nitrogen through it. The obtained reaction solution was evaporated to dryness to obtain the target product 14.
I got 09. In addition, it was confirmed that it was the desired product by elemental analysis, NMR method, and viscosity method. Other polymeric surfactants of the present invention can be easily synthesized according to the above synthesis method.

The aqueous dispersion according to the present invention is produced by emulsion polymerization of a monomer having a vinyl group using the polymer surfactant of the present invention. The polymer that is the dispersoid of the aqueous dispersion obtained by emulsion polymerization of the present invention may have a composition that is substantially insoluble in water, and the composition may include hydrophobic monomers such as alkyl acrylate and alkyl methacrylate. It may be a monomer or a polymer of a hydrophobic monomer and a hydrophilic monomer such as acrylic acid, methacrylic acid, or N-pinylpyrrolidone.
Representative examples of monomers having vinyl groups are listed below.

'1' Acrylic acid esters (e.g. methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, dodecyl acrylate, etc.) '2}
Methacrylic acid esters (e.g. methyl methacrylate, butyl methacrylate, hexyl methacrylate, dodecyl methacrylate, etc.)'3} Acrylamides (
For example, N-butyl acrylamide, dimethyl acrylamide, etc.) '4' Methacrylamide (e.g. N-butyl methacrylamide, dimethyl methacrylamide, etc.) '5
1 Vinyl esters (e.g. vinyl acetate, vinyl butyrate, etc.) ■ Vinyl halides (e.g. vinyl chloride, etc.)
7- Vinyl halides (e.g. vinylidene chloride, etc.) '8] Vinyl ethers (e.g. vinyl methyl ether, etc.) '9} Styrenes (e.g. styrene, b-methylstyrene, p-hydroxystyrene, etc.) Others Ethylene, propylene, butylene, phtadiene, isobrene, acrylonitrile, methacrylonitrile, vinylpyrrolidone, methacrylic acid, acrylic acid, acrylamide, methacrylamide, 3-methacryloyloxyp.

Pan-1-sulfonic acid sodium salt, 3-acryloyloxypropane-1-sulfonic acid sodium salt, sodium 2-acrylamido-2-methylpropanesulfonate, and the like can be mentioned. The aqueous dispersion according to the present invention can be obtained by emulsion polymerization of a monomer having a vinyl group using the polymeric surfactant of the present invention as described above. The emulsion polymerization mentioned here means known emulsion polymerization, for example, adding the required amount of the polymer surfactant and polymerization initiator of the present invention to distilled water degassed with nitrogen gas, and if necessary, Add a surfactant, a molecular weight regulator, etc., add 10 to 6% by weight of monomer (including at least one type of hydrophobic monomer),
It can be synthesized by heating it for several hours.

Here, as the low-molecular surfactant, for example, anionic surfactants such as sodium alkylbenzenesulfonate, nonionic surfactants such as polyoxyalkylene derivatives, amphoteric surfactants such as sulfobetaine type, etc. can be used.

As the polymerization initiator, potassium persulfate, ammonium persulfate, etc. can be used, and as the molecular weight regulator, for example, a mercaptan compound, isopropanol, etc. can be used. The amount of the polymeric surfactant of the present invention used here is arbitrary, but is usually 0.5% to 99.5% by weight based on the monomer having a pinyl group, preferably 1% by weight. % to 9% by weight.

Further, as an example of another method for obtaining the aqueous dispersion according to the present invention, there is the following method.

That is, the polymeric surfactant of the present invention and the monomer having a pinyl group are dissolved in a suitable solvent, the necessary amount of polymerization initiator is added, and the mixture is heated to 40 to 90°C and left for several hours. Next, by vigorously mixing the obtained reaction liquid with an aqueous solvent, an aqueous dispersion according to the present invention can be obtained. The preferred particle size of the polymer particles contained in the aqueous dispersion according to the invention obtained by these methods is about 0.
The concentration of the polymer is arbitrary, but usually 5 to 6% by weight is desirable.

Moreover, the molecular weight of the polymer is 2,000 to 1,000,000, preferably 5,000 to 500,000. The aqueous dispersion according to the present invention thus obtained can be put to practical use as it is, or after being subjected to water dialysis treatment if necessary. Examples of manufacturing the aqueous dispersion according to the present invention are listed below.

[Production Example 1] Production Example 1 of an aqueous dispersion containing Exemplified Compound '11.
(with a dropping funnel) for 5 nights,
400ml of distilled water was added, nitrogen gas was introduced for 15 minutes, and the temperature was brought to 60°C.

Next, add 0.25 m of ammonium persulfate and 0.1 m of acidic sodium sulfite, and immediately add 95 m of ethyl acrylate.
The mixture was dropped for 0 minutes, and the reaction was continued for 2 hours after the drop. Next, the temperature was returned to room temperature and the reaction was completed. This aqueous dispersion contains a resin content of 2% by weight and has a particle size of approximately 0.5% by weight.
It was 07〃. The resin content was extracted and subjected to elemental analysis and NM.
As a result of analysis by R method, this aqueous dispersion contained 5% by weight of Exemplary Compound m and 95% by weight of ethyl acrylate units.
It was found that it contains a polymer containing. [Manufacturing example 2
] Example of manufacturing an aqueous dispersion containing Exemplified Compound '3' In the same manner as in Production Example 1, add Exemplified Compound [3} for 10 nights to 1 and 4 heads, add sodium dodecylbenzenesulfonic acid for 1 night, and distilled water for 450 nights. and passed nitrogen gas for 15 minutes to lower the temperature to 7.
and set it to 0.

Next, 0.5 hours of azobisisocyanocyanoacetic acid was added, and immediately 10 hours of styrene and 30 hours of n-butyl acrylate were added for 60 minutes.
It was added dropwise over a period of minutes. After dropping, the reaction was continued for 3 hours and cooled to room temperature to complete the reaction. The bound aqueous dispersion had a resin content of 1% by mass and a particle size of 0.1r. As a result of extracting the resin content and analyzing it by elemental analysis method and NMR method,
This aqueous dispersion contained a polymer containing 2% by weight of exemplary compound '3', 2% by weight of styrene units, and 6% by weight of n-butyl acrylate units. [Production Example 3] Production Example 1 of an Aqueous Dispersion Containing the Exemplified Compound Side 400 ml of distilled water was placed in a four-headed kolben, and nitrogen gas was passed through it for 18 minutes.

The temperature was flooded to 60°C, 0.2 parts of potassium persulfate and 0.1 parts of acidic sodium sulfite were added, and immediately 45 parts of sec-butyl acrylate was added from one dropping funnel, and the exemplified compound was added from another dropping funnel. (2) An aqueous solution containing 55 ml of water was simultaneously added dropwise over a period of 45 minutes. After dropping 1. I continued to pray for insect time. Next, the reaction was completed by cooling to room temperature. The aqueous dispersion obtained contained a resin content of 1% by weight and had a particle size of 0.
It was an aqueous dispersion containing polymer particles of female Buddha. As a result of extracting the resin component and analyzing it by elemental analysis and NMR, it was found that this aqueous dispersion contained the exemplified compound [9' in 1% by weight, se
It was an aqueous dispersion containing a polymer containing 90% by weight of c-butyl acrylate units. [Production Example 4] Production Example 1, Part 3 of aqueous dispersion containing Exemplified Compound 00
In a head colben (with a thermometer, reflux condenser, and a bezel), add the exemplified compound OQ for 20 minutes, sodium triisopropylnaphthalene sulfonate for 2 hours, distilled water for 390 hours, and isopropanol.
After adding nitrogen gas for 15 minutes, it was flooded to 700 ml.

Next, 1.0 ml of azobisisocyanocyanoacrylic acid, 30 ml of hydroxyethyl acrylate, and 50 ml of ethyl nacrylate were added at the same time, and the light period was continued for 3 hours. The reaction was completed by cooling to room temperature. The resulting aqueous dispersion had a resin concentration of 2% by weight and contained polymer particles with a particle size of 0.09 μm. As a result of analyzing the resin content by elemental analysis and NMR, it was found that this aqueous dispersion contained 2
% by weight of hydroxyethyl acrylate units, and 5% by weight of ethyl acrylate units. [Production Example 5] Production example of an aqueous dispersion containing the exemplified compound (12) In the same manner as in Production Example 1, 2.5 mL of the exemplified compound X12, 390 mL of distilled water, and 10 mL of isoprobal After turning on the water, nitrogen gas was introduced for 15 minutes.

Next, after flooding at 60°C, ammonium persulfate was added for 0.25 hours.
0.125 ml of acidic sodium sulfite was added, and immediately 20 ml of pinylpyrrolidone and 77.5 ml of n-butyl acrylate were added dropwise from the dropping funnel over 60 minutes. After the dropwise addition, the mixture was allowed to cool for 2 hours and then returned to room temperature to complete the reaction. The resulting aqueous dispersion contained 2% by weight of resin and had a particle size of 0.05 mm. As a result of analyzing the resin content by elemental analysis and NMR,
This aqueous dispersion contained a polymer containing 2.5% by weight of Exemplary Compound X12, 20% by weight of vinylpyrrolidone units, and 77.5% by weight of n-butyl acrylate. Other aqueous dispersions according to the present invention can be easily produced according to the above production example.

The aqueous dispersion according to the present invention is an excellent new aqueous dispersion in which the drawbacks of conventional aqueous dispersions have been improved.

That is, the polymers in the aqueous dispersion of the present invention can be used when mixed with hydrophilic colloids such as gelatin, when hydrophobic substances, especially photographic hydrophobic substances are added, and in the presence of organic solvents, acids, alkalis, and salts. It is extremely stable without agglomeration of particles, does not cause color staining due to interaction with color developing agent, and does not discolor the dye produced by reaction between coupler and color developing agent. Furthermore, in addition to having such excellent properties, when applied as a photographic coating liquid onto a support as part of a photographic element, it exhibits good dimensional stability and curling properties, as well as good tensile strength and flexibility. sex,
Pressure resistance, drying properties, etc. are greatly improved. In this specification, a part of a photographic element means a non-photosensitive layer and a photosensitive emulsion layer provided on a support.

The non-photosensitive layer means a layer other than the photosensitive layer that has a practical sensitivity, and in ordinary silver halide photographic materials, examples thereof include an intermediate layer, an antihalation layer, a filter layer, a protective layer, etc. In the diffusion transfer silver halide photographic light-sensitive material, examples include an image-receiving layer and a timing layer.

The aqueous dispersion of the present invention can be advantageously used in each of the above layers either alone or in combination with a hydrophilic colloid such as gelatin. Further, the aqueous dispersion of the present invention may be purified by water dialysis, or may be used as it is without being purified. For example, when using the aqueous dispersion of the present invention as an intermediate layer, the polymer particle concentration is preferably 5 to 6% by weight, and if coated on a photosensitive silver halide emulsion layer by a conventional method, good.

Alternatively, it can be mixed with a hydrophilic colloid such as gelatin in any proportion and applied. Preferably, the amount of polymer particles of the aqueous dispersion according to the invention is from 5 to 50 parts by weight per 10 parts by weight of hydrophilic colloid. At this time, if necessary, it is also possible to form an intermediate layer by adding silica or silver halide, which has extremely low practical sensitivity. Furthermore, the aqueous dispersion according to the present invention does not cause aggregation even when antistatic agents (for example, inorganic salts, organic salts, anionic polymers, nonionic polymers, amphoteric polymers, various surfactants, etc.) are added, Since the antistatic ability is not weakened, it can also be used as an antistatic layer.

Furthermore, the aqueous dispersion according to the present invention can also be applied to a photosensitive layer.

The mode of application to the photosensitive layer is to prepare a halogenated line in an aqueous dispersion according to the present invention (polymer particle concentration of 5 to 6% by weight), and to prepare a halogenated line in an aqueous dispersion according to the present invention and gelatin, etc. It is possible to prepare silver halide in a mixture of hydrophilic colloids, or to prepare silver halide in a hydrophilic colloid such as gelatin and then add the aqueous dispersion according to the present invention.

As the silver halide used at this time, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc. can be used. . Silver halide preparation methods include single jet method, double jet method,
Methods called jet method etc., forward mixing method, back mixing method,
Methods called simultaneous mixing methods, methods called acid methods, neutral methods, ammonia methods, etc., methods in which the addition rate is varied continuously or stepwise, methods that combine the above various mixing methods, and mixing methods. Methods such as interrupting and adding physical ripening and then continuing mixing can be applied, methods of performing physical beating aging while promoting specific physical aging factors, methods of providing a mixing tank and a physical aging tank separately, Good results can be obtained by any preparation method, such as a method for preparing an emulsion that is expected to have the Claideso effect, a method for preparing a compound emulsion, and the like.

Further, atoms such as iridium, rhodium, osmium, cobalt, bismuth, and cadmium may be contained in these silver halide crystal grains.

Further, it may be a surface latent image type or an internal latent image type. Additionally, silver halides prepared by a variety of different methods may be mixed. The halogenated radiation emulsion prepared using the aqueous dispersion according to the present invention can be sensitized with various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer, selenium sensitizer, reduction sensitizer, noble metal sensitizer, etc. can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. The halogenated emulsion using the aqueous dispersion according to the present invention can be preferably stabilized using, for example, pyrimidines, gallic acid esters, mercaptans, benztriazoles, benzimidazoles, and the like. In addition to gelatin, hydrophilic colloids used at this time include colloidal albumin, agar, gum arabic,
Examples include alginic acid, hydrolyzed cellulose acetate, cellulose derivatives such as carboxymethyl cellulose, and synthetic binders. The aqueous dispersion according to the present invention can be used alone or mixed with a hydrophilic colloid as a part of various photographic elements as described above, but in particular various photographic hydrophobic substances can be used in the aqueous dispersion according to the present invention. Significant effects are seen when impregnated or filled into polymeric particles and coated as part of a photographic element.

As mentioned above, various aqueous dispersions have been proposed as dispersion media for photographic hydrophobic substances, but none of them have been fully satisfactory; however, the aqueous dispersion according to the present invention Even when used as a dispersion medium, it does not have a momme point unlike the aqueous dispersion liquids used in its preparation.

This is because the aqueous dispersion according to the present invention not only has many excellent properties, but also does not impair the original performance of the hydrophobic substance for photography, and in some cases, has the polymer surface activity of the present invention. This is based on the fact that due to the synergistic effect of the use of the agent with the polymer particles of the aqueous dispersion according to the present invention, an effect exceeding the original performance of the hydrophobic substance for photography was observed.
In order to impregnate the polymer particles of the aqueous dispersion according to the present invention with a photographic hydrophobic substance, a solution of the photographic hydrophobic substance in a suitable organic solvent is added to the aqueous dispersion according to the present invention. Alternatively, the aqueous dispersion according to the present invention may be added to the solution of the photographic hydrophobic substance while adding the aqueous dispersion according to the present invention.

Another method is to simultaneously mix a solution of a photographic hydrophobic substance and an aqueous dispersion according to the present invention.
As yet another method, the photographic hydrophobic substance may be directly added to the aqueous fraction according to the present invention without being dissolved in an organic solvent. In this case, various surfactants may be used if necessary. Further, the aqueous dispersion according to the present invention can be mixed with a hydrophilic colloid such as gelatin to make it difficult to disperse.

In this case, the mixing weight ratio is arbitrary, but preferably 10 to 20 parts by weight, more preferably 20 to 10 parts by weight to 10 parts by weight of the hydrophilic colloid. Of course, it is also possible to combine the photographic hydrophobic substance in the aqueous dispersion according to the invention and then mix it with the hydrophilic colloid. As the organic solvent used to dissolve the photographic hydrophobic substance in the aqueous dispersion according to the present invention, for example, an organic solvent that is immiscible with water having a boiling point described in U.S. Pat. No. 23-027 can be used. I can give you something.

Particularly preferred are dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, triphenyl phosphate, tricresyl phthalate, N,N-diethyl dodecanamide, N,N-dibutyl dodecanamide, benzyl phthalate, monophenyl di-pt
-butylphenyl phosphate, dimethoxyethyl phthalate, and US Pat. No. 3,779,765,
Special Seki No. 49-90523, No. 51-27 Rudder No. 1, No. 5
Examples include high boiling point solvents that are immiscible with water, as described in Publication No. 1-27 Rudder No. 2 and Specification of Tokushiroka No. 50-2070.

Also, low boiling point or water-soluble organic solvents that can be used in conjunction with or in place of high boiling point solvents are described in U.S. Pat. No. 2,801,171.
The following can be cited: No. 2, No. 6 of the same No. 2 Base, Bird Watching Specifications, etc.

For example, organic solvents with a low boiling point that are aesthetically immovable in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and water-soluble organic solvents. Examples include acetone, methyl lysoptyl ketone, moethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxy Examples include ethanol, etc. Each of these solvents can be used alone or in combination of two or more.

The amount of photographic hydrophobic material to be impregnated into the polymer particles of the aqueous dispersion of the present invention is preferably about 0.1 to 2 hours per 1 night of the polymer particles of the aqueous dispersion of the present invention.

The aqueous dispersion according to the invention containing polymer particles impregnated with a photographic hydrophobic substance can be used as a photographic coating without removing the organic solvent; however, if necessary, the aqueous dispersion may be cooled. The organic solvent may be removed by washing with water in the form of noodles or by using an evaporator or the like to obtain a photographic coating solution.

If necessary, a suitable hardening agent may be added to the photographic coating liquid, such as aldehyde, azilysine, vinyl sulfone, ethyleneimine, isocyanate, dioxane derivative, oxystarch, etc., and additives preferred for the photographic coating liquid. can be added as necessary. The prepared photographic coating solution is coated on a known photographic support, and may be air-dried or heat-dried to remove the organic solvent or water.

Typical examples of the support include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene phthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc. Each of these supports is included as a C.

It is selected depending on the purpose of use of the silver germide photographic material. Photographic aqueous substances that can be impregnated into the polymer particles of the aqueous dispersion according to the invention include, for example, hydrophobic dye-forming couplers, hydrophobic poppies, photobrighteners, hydrophobic antistain agents, hydrophobic Hardener, hydrophobic sensitizing dye, hydrophobic lubricant, hydrophobic development inhibitor releasing substance, hydrophobic redox dye releasing agent (DRR substance), hydrophobic diffusive dye releasing coupler, hydrophobic ultraviolet absorber, electrostatic charge Examples include inhibitors.

Typical examples of hydrophobic dye-forming couplers are those belonging to phenol derivatives, naphthol derivatives, 5-pyrazolone derivatives and acylacetamide derivatives, but of course those having structures other than these may also be used. In addition, 2-equivalent couplers, such as colored couplers, which are colored themselves, those that produce a colorless compound through a coupling reaction, and those that liberate a compound with a special action through a coupling reaction, such as DIR couplers. All 4-equivalent couplers are included. Typical hydrophobic dye-forming couplers that can be used in the present invention are U.S. Patent No. 712, U.S. Patent No. 89805, U.S. Patent No. 232027, U.S. Patent No. 23573,
235 $82, 237 class 21, 24390 spot, 2455170, 2474293, 2 balls 0349, 2 mice 5 total 7, 2550661, 2 balls 9004, 2607 abbreviation, 2657134, 265 $29, 271 female 02, 27217
Spot number, No. 2772161, No. 2801170, No. 2
No. 865751, No. 2875057, No. 289 26
No. 289 Group No. 43, No. 29 Female No. 73, No. 29209
No. 61, No. 2927928, Private No. 30, No. 30
No. 62653, No. 3127269, No. 3148062
No. 3227551, No. 3227554, No. 32
No. 65506, No. 11476, No. 3 powder, No. 4, No. 071, No. 071, No. 081, No. 39, No. 39, No. 18129, No. 3 AI 414,
Doji No. 47, No. 8, No. 59552, No. 666,
Dou 3 Kou No. 1714, Dou 351 Pekin PI No., Dou 351 Group 29
No. 3551155, No. 3551156, No. 35
Waza PI No. 9, Waza 35 Ball No. 700, Waza 3 Spot No. 0721, Waza 3 Spot No. 23 Female, Waza 3 Waza No. 8971, Waza 3591 Shigeru No.,
No. 3615504, No. 3617291, No. 3676
No. 137, Belgian Patent No. 697112, Hakama Kosho No. 39-5 Pay No. 7, No. 39-275, No. 42-113
No. 03, Hakamako No. 49-2175, JP-A No. 47-261
It is described in No. 3, Hakama-Seki Shobi-5 Uroko-magu, Tokkan Sho 48-173147, etc. In order to impregnate the polymer particles of the aqueous dispersion according to the invention with these hydrophobic dye-forming couplers, the couplers are usually dissolved in an organic solvent and added to the aqueous dispersion according to the invention.

The amount of the coupler varies depending on the type of coupler used and the type of photosensitive material, but is usually 0.01 to 1 mol, preferably 0.05 to 0.6 mol, per mol of silver halide. As the organic solvent, any of the organic solvents mentioned above can be selected. This coupler is usually a 10-7% solution by weight,
The coupler is impregnated into the polymer particles by adding, preferably as a 30-6% by weight solution, into a 5-6% by weight aqueous dispersion according to the invention at room temperature. . Examples of this method include mixers, homogenizers, colloid mills, ultrasonic dispersers, etc., but it is also possible to use an ordinary magnetic stirrer. After impregnating the coupler, the organic solvent is removed and the emulsion is mixed with a separately prepared silver halide emulsion to prepare a color photographic emulsion. Coating aids such as surfactants such as saponin and other photographic additives can be added to the prepared color photographic emulsion as required. Hydrophobic optical brighteners are compounds that are soluble in organic solvents and emit purple to blue fluorescence when irradiated with ultraviolet light.
For example, coumarin, furan, stilbene, oxazole,
It has a basic structure such as imidazole or naphthalimide.

In order to impregnate these hydrophobic optical brighteners into the polymer particles of the aqueous dispersion according to the present invention, the optical brighteners are dissolved in an organic solvent in the same manner as the hydrophobic dye-forming couplers described above, and the optical brighteners according to the present invention are It can be added to an aqueous dispersion. The amount of optical brightener varies depending on the type of optical brightener used and the type of halogenated synthetic fiber photographic light-sensitive material to which it is applied, but usually the coating area is 1.
0.01 evening to 2.0 evening, preferably 0.02 evening to
It is 1.0 evening. As the organic solvent, any of the organic solvents mentioned above can be selected. The optical brightener is usually a 5-8% by weight solution, preferably a 20-6% by weight solution, and the solution is added to a 5-6% by weight aqueous dispersion according to the invention at room temperature. By adding the optical brightener to the polymer particles, the optical brightener is impregnated into the polymer particles. Azusa's means. This can be done in various ways in the same manner as described above. After impregnating with the optical brightener, the organic solvent is removed and mixed with a separately prepared silver halide emulsion, or mixed with a separately prepared hydrophilic colloid solution for an intermediate layer, etc., and if necessary, With the addition of photographic additives such as coating aids, it can be used as part of photographic elements such as color photographic papers and diffusion transfer photosensitive materials. Hydrophobic antifouling agent (Antista
As inAgent (antistain agent), hydroquinone compounds are generally used.

For example, US Pat. No. 2,336,327, US Pat. No. 2,360,290, US Pat.
No. 1197, No. 2704713, No. 272865y, No. 273230, No. 370045, British Patent No. 891158, Hakama Sekisho 50-156438
Alkyl-substituted hydroquinones described in US Pat. No. 2,735,765, bishydroquinones described in US Pat.
Typical examples include polymer-based materials described in the specification of the above patent. These may be added to the photosensitive material singly or in combination of two or more. In order to impregnate the polymer particles of the aqueous dispersion according to the present invention with these hydrophobic antifouling agents, the antifouling agents are usually dissolved in an organic solvent;
It may be added to the aqueous dispersion according to the present invention. The amount of anti-staining agent varies depending on the type of anti-staining agent used and the type of photosensitive material to which it is applied, but it is usually 0 per coated area.
．． 0.01 to 0.5 evening, preferably 0.05 to 0.3 evening. As the organic solvent, a suitable one can be selected from the above-mentioned organic solvents. These hydrophobic stain inhibitors are usually 10-8% by weight solutions, preferably 20-60% by weight.
The polymer particles are impregnated with the hydrophobic antifouling agent by adding the solution into a 5-6% by weight aqueous dispersion according to the invention at room temperature. The worship method can be performed in various ways as described above. After impregnating the polymer particles of the aqueous dispersion according to the present invention with a hydrophobic stain preventive agent, the organic solvent is removed and the mixture is mixed with a separately prepared color silver halide emulsion, a hydrophilic colloid solution for the intermediate layer, etc. ,．． It is used as part of photographic elements such as emulsion layers and intermediate layers of color light-sensitive materials by adding coating aids and the like as necessary, and exhibits an excellent stain prevention effect. Examples of hydrophobic ultraviolet absorbers include benztriazoles,
Triazines, benzophenone compounds or acrylonitrile compounds, Tinuvin from Ciba-Geigy,
Examples include Tinuvin 320, Tinuvin 320, Tinuvin 327, and Tinuvin 328.

These hydrophobic ultraviolet absorbers can be impregnated into the polymer particles of the aqueous dispersion according to the present invention in the same manner as in the case of hydrophobic dye-forming couplers. The amount of this hydrophobic ultraviolet absorber varies depending on the type of hydrophobic ultraviolet absorber used and the type of photosensitive material to which it is applied, but is usually 0.001 to 0.1 per coating area, preferably 0. .002 Evening~
It is 0.008 evening. As the organic solvent, a suitable one can be selected from the above-mentioned organic solvents. The hydrophobic UV absorber is usually a 10-9% by weight solution, preferably a 20-7% by weight solution, and the solution is added to a 5-6% by weight aqueous dispersion according to the invention at room temperature. By adding the UV absorber at the same time, the ultraviolet absorber is impregnated into the polymer particles. After impregnating this hydrophobic ultraviolet absorber, the organic solvent is removed, and the mixture is mixed with a separately prepared color silver halide emulsion and a hydrophilic colloid solution for the intermediate layer. It can be used as a photographic element, such as an interlayer. These are mainly used in color photographic papers, diffusion transfer photosensitive materials, etc., and exhibit excellent ultraviolet absorption effects. Representative examples of hydrophobic development inhibitor releasing substances (hereinafter referred to as DIR substances) include U.S. Pat. No. 3,632,345, U.S. Pat.
No. 136125, No. 50-15273, No. 51-67
Examples include those described in Publication No. 24 and the like.

These hydrophobic development inhibitor-releasing substances are impregnated into the polymer particles of the aqueous dispersion according to the present invention, mixed with a silver halide emulsion or a non-photosensitive liquid such as gelatin, and if necessary,
Photographic additives such as stabilizers, coating aids, etc. can be added and used in portions of photographic elements, such as halogenated emulsion layers, interlayers, etc. These products are especially suitable for use in emulsion layers, intermediate layers, etc. of color negative films, color photographic papers, color reversal films, color cine films, etc.
The effects of IR substances can be brought out. Hydrophobic lubricants are used on the surface of the film, the top layer of the emulsion layer, etc. for the purpose of reducing slippage and preventing scratches on the film. Useful hydrophobic lubricants that can be applied to the aqueous dispersion according to the present invention include higher fatty acid higher alcohol esters, higher fatty acids, higher alcohols, paraffins, higher alkyl phosphate esters, and silicone compounds. In particular, U.S. Pat.
The compounds described in the specifications of No. 82157, No. 3121060, No. 385064, Japanese Patent Application No. 1983-65657, etc. can be used alone or in combination of two or more. These hydrophobic lubricants can be impregnated into polymer particles in an aqueous dispersion according to the invention and used alone or mixed with a hydrophilic colloid solution as photographic elements, such as protective layers, packing layers, etc.

Examples of hydrophobic hardeners include epoxy compounds, vinyl sulfone compounds, ethyleneimine compounds, aldehyde compounds, isocyanate compounds, diacrylate compounds,
Examples include cyanuric acid compounds.

An aqueous dispersion containing polymer particles impregnated with these hydrophobic hardeners is mainly added to a hydrophilic colloid solution such as gelatin, and is used to form photographic elements such as emulsion layers and intermediate layers of color negative films, color photographic papers, etc. An excellent hardening effect can be obtained by using it as a part of a film. The hydrophobic sensitizing dye, which is normally used by being dissolved in a suitable solvent and added to the silver halide emulsion, is added to the silver halide emulsion by impregnating the polymer particles in the aqueous dispersion according to the present invention. By doing so, a desired tingling effect can be obtained.

As a hydrophobic DRR substance, Mochiseki Sho 49-126331
Examples include hydrophobic DRR substances described in Japanese Publications No. 49-126332 and No. 52-7727. These hydrophobic DRR substances can be impregnated into the polymer particles of the aqueous dispersion according to the invention in a manner similar to the method in which the couplers were impregnated. Aqueous dispersions containing polymer particles impregnated with hydrophobic DRR materials can be mixed with conventional silver halide emulsions or diffusion transfer silver halide emulsions for use as photographic elements. Examples of antistatic agents include, for example, Tokukan Sho 48-152223 and Sho 51
-16903 Publication, Special Publication No. 51-444, “
Antistatic agents are described in Hideo Ichimaru Shigeru (Saiwai Shobo), pages 164-165. These antistatic agents are impregnated into the polymer particles of the aqueous dispersion according to the invention in the same manner as the hydrophobic dye-forming couplers described above. An aqueous dispersion containing polymer particles impregnated with an antistatic agent can be used alone or mixed with a hydrophilic colloid solution etc. for photographic elements such as protective layers, packing layers, etc., and can be used for various photosensitive materials such as color negative films. , color photographic paper, color reversal film, color cine film, monochrome film, X-ray film, etc., and provides an excellent antistatic effect. Various developing agents can be applied to the silver halide photographic material containing the aqueous dispersion according to the present invention described above as part of the photographic element, and the silver halide photographic material is suitable for color use. There is no color contamination,
There is no discoloration of the produced pigment.

The above-mentioned developing agents include metol, hydroquinone, phenidone, atmar, glycine, 4-amino-N,N
-diethylaniline, 3-methyl-4-amino-N,N
-diethylaniline, 4-amino-N-ethyl-N-8
-Hydroxyethylaniline, 3-methyl-4-amino/
-N-ethyl-N-8-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-8-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-8-methoxyethylaniline, 3-
8-methanesulfonamidoethyl-4-amino-N,N
-Diethylaniline, 3-methoxy-4-amino-N-ethyl-N-3-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-8-methoxyethylaniline, 3-acetamido 4-amino-N,N -diethylaniline, 4-amino-N,N-dimethylaniline, N-ethyl-N-8-[B-(8-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-8- methoxyethoxy)
Examples include ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, and p-toluene sulfonate. Furthermore, JP-A-48-164932,
Publication No. 50-131526, Tokuiso Sho 50-17246
issue specifications and the Journal of the American Chemical Society by Pent et al.
theAmericanChemicalSratio
) Vol. 73, 3100-3125 (1951). Next, the present invention will be specifically illustrated with reference to Examples, but the embodiments of the present invention are not limited thereby, and good results can be expected with various embodiments. Example-1 Control sample [1] Into 200 qo of 2% by weight inert gelatin kept at 55°C, solutions (1) and (0) having the following composition were added to 60 qo while keeping it at 60 qo.
At the same time, it took 2 minutes to flow down.

After mixing, the temperature was maintained at 60 oo for 4 minutes, followed by completion of the rinsing process, and excess salt was removed by the decanting method.

This emulsion is chemically ripened using a gold sensitizer and a sulfur sensitizer,
After adding 250 m9 of 4-hydroxy-6-methyl-1,3,ne,7-tetrazaindene and 150 mg of spirobis(3,3-dimethyl-5,6-dihydroxyindane) and stirring thoroughly, the emulsion was added again. The mixture was heated and kept at 500 psi, and a sensitizing dye was added. It was then coated on a polyethylene terephthalate support at a ratio of 9/100 silver 50. Comparative sample [A] 2% by weight inert gelatin 20 of control sample [1]
Completely the same as control sample [1] except that instead of Z in Z, an aqueous dispersion containing 2% by weight of a polymer obtained by emulsion polymerization of ethyl acrylate using sodium dodecylbenzenesulfonate as an emulsifier was used. A comparative sample [A] was prepared.

Comparative sample [B] 2% by weight inert gelatin 20 of control sample [1]
Control sample [1] except that an aqueous dispersion 200' containing a 2% by weight polymer obtained by emulsion polymerization of n-butyl acrylate was used instead of '0' using sodium oleate as an emulsifier. Comparative sample [
B] was made.

Comparative sample [C] 2% by weight inert gelatin 2 of control sample [・1]
00' was replaced with an aqueous dispersion containing 2% by weight of a polymer obtained by emulsion polymerization of sec-butyl acrylate using the following compound (average molecular weight, approximately 20,000) as an emulsifier. A comparative sample [C] was made using exactly the same machine as sample [1].

Comparative sample [D] 2% by weight inert gelatin 20 of control sample [1]
An aqueous dispersion containing 2% by weight of a polymer obtained by emulsion polymerization of 8% by weight of ethyl acrylate and 2% by weight of styrene using the following compound (average molecular weight, approximately 50,000) as an emulsifier instead of 0. Control samples [1] were used except for using solution 200 [1].
] A comparative sample [D] was prepared in exactly the same manner.

Sample of the present invention [M. 1] 2% by weight inert gelatin 20 of control sample [1]
Aqueous dispersion 20 of the present invention synthesized in Production Example 1
The sample of the present invention [No. 1] was made.

Sample of the present invention [ship. 2] Sample of the present invention [M. The aqueous dispersion synthesized in Production Example 1 of 1) was replaced with the aqueous dispersion synthesized in Production Example 2 to prepare a sample of the present invention [Shame. 2] was made.

Sample of the present invention [Yuzu. 3] Sample of the present invention [ship. 1], the aqueous dispersion synthesized in Production Example 1 was replaced with the aqueous dispersion synthesized in Production Example 3, and the subject of the present invention [Ship. 3] was made.

When a part of the coating solution of each of the above samples was observed under bright light, aggregates were observed in comparative sample [B] and comparative sample [C], and when a part of each coated sample was observed under bright light,
Coating unevenness was observed in Comparative Sample [A], Comparative Sample [B], Comparative Sample [C], and Comparative Sample [D].

Furthermore, each sample was exposed to light through a wedge and subjected to the following treatments to observe the flexibility, sensitivity, and capri of the coating film.

[Processing process]

The following developer composition was used.

[Developer]

Furthermore, the flexibility (radius of curvature) of the coating is determined by the radius of curvature of the sample being 2
After being left for 3 days under conditions of 0oo and 20% relative humidity, it was measured and evaluated.

These results are shown in Table 1. In Table 1, the sensitivity is a relative sensitivity with the sensitivity of the control sample being 100.

As is clear from Table 1, the aqueous dispersion according to the present invention has no adverse effect on the sensitivity or fog of silver halide photographic materials, and the flexibility of the coating film is significantly improved. I understand that.

Example-2 The sample used in Example-1 was developed, fixed, washed with water, and dried in the same manner as in Example-1.

Next, to check the dimensional stability, each sample was heated to a dry bulb temperature of 2 to 0.
After adjusting the humidity by keeping it in an atmosphere with a relative humidity of 55% for 2 hours, using a humidity expansion/contraction tester (dimension measuring machine), the relative humidity was measured at 20% and 60% at a dry bulb temperature of 20:00. The dimensions were measured, and the hygroscopic expansion coefficient of each sample was determined according to the following formula. Hygroscopic expansion coefficient (1/%RH) - (Dimensions at 60%RH) - (Dimensions at 20%RH) -
(Dimensions at 60% RH) x (60% RH - 20% R Town (
RH: relative humidity) These results are shown in Table 2.

As is clear from Table 2, it can be seen that the dimensional stability of the silver halide photographic material containing the aqueous dispersion according to the present invention is significantly improved.

Example 3 The sample used in Example 1 was cut into 1 x 1 piece for each cut on the floor, and left for 3 days at a relative humidity of 20%.

Thereafter, each sample was folded using a folding tester with a slit interval of 2 m/m, and then developed in the same manner as in Example 11. After drying, the concentration of the pressure at the folded portion of each sample was measured using a Sakura Microdensitometer 8M (caliber 50 French, manufactured by Konishiroku Photo Industry Co., Ltd.). These results are shown in Table 3. As is clear from Table 3, it can be seen that the pressure resistance of the silver halide photographic material containing the aqueous dispersion according to the present invention is significantly improved.

Example-4 As a coupler, Q-(3-penzyl-2,4-dioxoimidazolidin-3-yl)-Q-pivaoyl-5-[
Q'-(2,4-di-ten-amylphenoxy)-butyrylamide] 20 parts of 2-chloroacetanilide, 10 parts of dibutyl phthalate, 30 parts of ethyl acetate
'Dissolved in the mixture.

Add this solution to Alkanol x C (trade name, manufactured by DuPont,
The mixture was added to a 5% gelatin solution 200 containing sodium alkylnaphthalene sulfonate as a dispersant and dispersed using a colloid mill to obtain a dispersion [A]. On the other hand, production example 1
To 100% of the aqueous dispersion of the present invention (polymer concentration 10%) synthesized in 2 and 3, 80% of each of tetrahydrofuran and acetone were added, and then 20% of ethyl acetate was added. At the same time, 20 portions of the coupler used in the dispersion [A] were added at once.

The coupler was then completely dissolved in 1 to 2 minutes to form a homogeneous colloidal liquid. The solvent was removed under reduced pressure using a rotary evaporator, and 10% of a 10% gelatin solution was added to obtain uniform dispersions [B], [C], and [D]. This [A]
, [B], [C], and [D] were mixed with a silver bromide photographic emulsion for color paper, and coated on a paper support having a polyethylene phthalate overcoat as shown in Table 4. Samples 1, 2, 3 and 4 were obtained.

Table 4 After each of the four samples was wedge exposed, they were developed at 31° C. for 3 minutes with a developer having the following composition, bleach-fixed, washed with water, and dried.

[Developer]

Photographic properties were measured for each sample obtained.

The results are shown in Table 5. Here, the sensitivity is sample 1 (dispersed by the protect method using dibutyl phthalate).
This is the relative sensitivity when the value is set to 100. Table 5 As is clear from Table 5, the silver halide photographic material using the aqueous dispersion according to the present invention exhibits almost the same excellent photographic properties as those using dibutyl phthalate.

At the same time, the dispersions [A], [B], [C], and [D] were left at room temperature (23qo) and under normal pressure for 2 days and observed under a microscope to check for the presence of precipitates and aggregates. , Dispersion [A] has many coupler precipitations and agglomerations, but dispersions [B], [C], and [D] have almost no precipitates or aggregates, and are protected using dibutyl phthalate. It was found that it has better stability than a dispersed one.

Furthermore, samples 1, 2, 3 and 4 subjected to the above development treatment
A light resistance test was conducted for 2 weeks under xenon lamp irradiation. D
Table 6 shows the results of measuring the residual rate of the color image in the M portion. As is clear from Table 6, even when using the same coupler, when using the aqueous dispersion according to the present invention (sample M.
, 3 and 4) have better light resistance than the case of protection dispersion with dibutyl phthalate (sample M.1).

Example 5 10 parts of 2-(Z-hydroxy-5'-octylphenyl)benztriazole, an ultraviolet absorber, was dissolved in a mixture of 10 parts of dibutyl phthalate and 50 parts of ethyl acetate.

This solution was mixed with 200ml of 5% gelatin solution containing alkanol xc as a dispersant and dispersed using a colloid mill to obtain a dispersion liquid [A]. On the other hand, the aqueous dispersions according to the present invention used in Example-4 (obtained in Production Examples 1, 3, and 5) each contained 100% [, 180%] of a mixed solvent of tetrahydrofuran:acetone = 1:1, and ethyl 25% of acetate was added, and 10% of the ultraviolet absorber used in the dispersion [A] was added while stirring.

Then, in 1 to 2 minutes, all the ultraviolet absorbers were dissolved and a uniform colloidal liquid was formed. The organic solvent was then removed under reduced pressure using a rotary evaporator and added to 100ml of a 10% gelatin solution to prepare dispersions [B], [C] and [D]. Next, dispersions [A], [B], [
C] and [D] were added to 40% 2.5% aqueous gelatin solution, and coated on a triacetate support to form samples 1 and 2.
, 3 and 4 were prepared.

The optical density of each sample was measured using a spectrophotometer at 37 m and 41 m.

The results are shown in Table 7. Table 7 As is clear from Table 7, the ultraviolet absorber dispersed in the aqueous dispersion according to the present invention (possibly due to the fineness of the dispersed particle size) has a high level of concentration in the ultraviolet light. It can be seen that the optical density in the visible region is low and exhibits sharp cutoff characteristics.

Example-6 4,4'-bis{1-(2,4,6-trichlorophenyl)-3-[3-(2
,4-Gten-amylphenoxyacetamide)benzamide]-pyrazoline-5-one}10 and DI
2-(1-phenyltetrazolyl-5-thio)-4-octadecylsuccinimide)indanone 1 as R substance
．． The mixture was dissolved in a mixed solvent of 10 parts of tricresyl phosphate and 30 parts of ethyl acetate, then added to 100 parts of a 5% gelatin solution containing alkanol Xc as a dispersant, and placed in a colloid mill according to a conventional method. Protect dispersion was performed to obtain a dispersion liquid [A].

On the other hand, the aqueous dispersion according to the present invention synthesized in Production Example 1 (
Add 10 parts of the magenta dye-forming coupler and 1.2 parts of the Dm substance to the top of 50 parts (solid content concentration 10%), and then add 30 parts of the mixed solvent of tricresyl phosphate:acetone = 1:1 while pushing the solution into the solution. When the solution was added, it became a homogeneous colloid solution within 1 to 2 minutes.

Next, the above solvent was removed under reduced pressure using a rotary evaporator, and 50% of 10% gelatin was added and dispersed to obtain a dispersion liquid [B]. The above dispersions [A] and [B] were mixed with silver iodobromide emulsion for line-sensitive color negatives, and the following 8.
Comparative samples and inventive samples were prepared by coating on triacetate supports as per the table.

Table 8: After wedge exposure, each of the obtained samples was developed according to a development process used for processing general color negative films, and the photographic properties were measured. Table 9 shows the results.

Note that the sensitivity is a relative sensitivity with the sensitivity of the comparison sample being 100. Table 9 As is clear from Table 9, the aqueous dispersion according to the present invention is D
It can be seen that it shows an excellent effect on the dispersion of the IR substance, and an even better effect on the graininess.

Claims (1)

[Scope of Claims] 1 A surfactant whose main component is a compound represented by the following general formulas [I], [II] and/or [III] and a monomer having a vinyl group are emulsion polymerized. Aqueous dispersion for photographic coating solutions. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a substituted or unsubstituted divalent organic group, M
_1 represents a hydrogen atom or a monovalent cation, n_1
represents 30 to 90 mol%, and n_2 represents 70 to 5 mol%. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_2 is a hydrogen atom or a lower alkyl group, M_
2, M_3, M_4 and M_5 each represent a hydrogen atom or a monovalent cation, n_3 is 30 to 95 mol%, n_4 is 70 to 0 mol%, and n_5 is 70 to 0 mol%.
represents. However, n_4+n_5 is 70 to 5 mol%. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_3 is a hydrogen atom or a lower alkyl group, M_6, M_7, M_8 and M_9 each represent a hydrogen atom or a monovalent cation, and n_6 is 30 to 70 mol% , n_7 represents 5 to 50 mol%, and n_8 represents 70 to 5 mol%. However, n_7+n_8 is 70 to 30 mol%. ]2
An aqueous photographic coating liquid according to claim 1, wherein the aqueous dispersion is a photographic coating liquid for coating as a part of a photographic element constituting a silver halide photographic light-sensitive material. dispersion liquid. 3. The aqueous dispersion for a photographic coating liquid according to claim 2, wherein the aqueous dispersion is a photographic coating liquid prepared by mixing a hydrophilic colloid solution such as gelatin. 4. A photographic coating liquid according to claim 2, wherein the aqueous dispersion is a photographic coating liquid obtained by impregnating polymer particles in the aqueous dispersion with a photographic hydrophobic substance. Aqueous dispersion. 5 Photographic hydrophobic substances include hydrophobic dye-forming couplers, fluorescent whitening agents, antifouling agents, hardeners, sensitizing dyes,
Lubricants, development inhibitor releasing substances, redox dye releasing agents (
DRR substance), a diffuse dye-releasing coupler, an ultraviolet absorber, and/or an antistatic agent,
An aqueous dispersion for a photographic coating liquid according to claim 4.