JPS60140344A - Method for dispersing hydrophobic photographic additive, and silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a dispersion superior in time lapse stability by mixing the first soln. of a high-boiling org. solvent dissolving a polymer polymerized in the presence of hydrophobic photographic additives, with the second soln. contg. a hydrophilic colloidal binder. CONSTITUTION:A hydrophilic colloidal binder contg. hydrophobic photographic additives is prepared by mixing the first soln. contg. a polymer polymerized at least in the presence of the hydrophobic photographic additives with the second soln. contg. the hydrophilic colloidal binder. A support is coated with the hydrophilic colloidal binder and photographic constituent layers are laminated to form a silver halide photosensitive material. As said hydrophobic additives, a hydrophobic coupler, a UV absorber, an antioxidant, etc., are enumerated. The high- boiling solvent substantially immiscible with water and having a b.p. of >175 deg.C at normal pressure is used for said solvent.

Description

[Detailed description of the invention]! BACKGROUND OF THE INVENTION The present invention relates to a method for well dispersing a hydrophobic photographic additive such as a coupler in a wood-philic colloid binder, and a method for dispersing a hydrophobic photographic additive such as a coupler in a wood-philic colloid binder, and a method for dispersing a dispersion obtained by such a method as a photographic constituent layer. This invention relates to a silver genide photographic material. For more details,
A method for obtaining a good dispersion by mixing a polymer polymerized in the presence of a hydrophobic photographic additive such as Kabuchi with a hydrophilic colloid binder, and a haptic having such a dispersion as a photographic constituent layer. This invention relates to silver oxide photographic materials.

Prior art and its problems Normally, in color photography, a color developing agent that is oxidized as a result of the reduction of silver halide grains in the development process, such as aromatic primary amines such as para-aminophenol derivatives and para-phenylenediamine derivatives, is used. Couplers that react with compounds to form dye images consisting of dyes such as indophenol, indoamine, azomethine, indoaniline, 7e/xazine, and 7enazine are used.

Such couplers include Fischer-type water-soluble couplers and silver halide compounds that are provided with water-soluble groups such as sulfonic acid groups and carboxyl groups to facilitate dispersion of these couplers in silver halide emulsions. There are hydrophobic couplers having a sufficiently bulky ballast group to prevent diffusion in the emulsion.

The water-soluble couplers not only cause the viscosity of the added photosensitive emulsion to change significantly over time, but also cause coating spots due to coupler precipitation, making it difficult to obtain silver halide photographic materials of uniform quality. It has the disadvantage that it is difficult to obtain vivid and robust dye images.

Various methods are known for dispersing hydrophobic couplers in silver halide emulsions with hydrophilic binders such as gelatin. For example, US Patent No. 2,269,158;
No. 272,191, No. 2,304,940, No. 241
No. 1.020, No. 2,522,027, No. 2.31S
O, No. 289, No. 2,772,163, No. 2,801
, No. 170, No. 2.801, 171, No. 2,852,
No. 382, No. 3,619.195, British Patent No. 1,15
1,590, German Patent No. 1.143,707, and Japanese Patent Publication No. 51-39853. The most typical method is to dissolve the coupler in a high-boiling organic solvent and mechanically disperse it in an aqueous gelatin solution in the presence of a surfactant using a homogenizer or colloid mill. . Solvents often used for this purpose include tricresol phosphate, diptyl heptalate, and the like. Examples using such solvents are described in US Pat. No. 2,033,027 and the like.

In the dispersion prepared by these methods, the oil droplets must be finely and uniformly dispersed in the silver halide emulsion layer, and even when the silver halide photographic light-sensitive material is stored for a long period of time. It is required that the additives in the oil droplets do not crystallize and precipitate. Therefore, the type of solvent or surfactant to be used is selected depending on the properties of the hydrophobic photographic additive, and at the same time, as a result of improving the dispersion equipment, etc., the particle size of the oil droplets can be reduced to about α5 microns. is now possible. However, the particle size of such fine dispersed particles tends to increase over time after dispersion. It is currently extremely difficult to suppress this increase in particle size after dispersion.

Furthermore, when such a dispersion is contained in a photographic constituent layer such as a silver halide photographic emulsion layer or a gelatin layer, these layers become soft due to the oily nature of the dispersed particles, making them less likely to be scratched or pressed. This has the disadvantage that the resistance to such external mechanical forces is reduced, resulting in a deterioration in the film quality of the silver halide photographic light-sensitive material. In order to improve the image sharpness of silver halide color photographic light-sensitive materials, efforts have been made to reduce the amount of gelatin as a binder as much as possible to make the photographic light-sensitive materials thinner. As the ratio increases, the physical strength of the film of the photographic light-sensitive material further deteriorates. By the way, it is known that when the weight ratio of the binder and dispersed particles (hydrophobic photographic additive and solvent) is held constant, the smaller the diameter of the dispersed particles, the better the physical strength of the film containing them. However, it is desirable that the particle size of the dispersed particles be as small as possible.

To overcome these drawbacks, it has been proposed to use vinyl polymers as dispersants instead of high-boiling organic solvents. For example, Japanese Patent Publication No. 48-30494 describes a method in which a vinyl pyrimer and a hydrophobic coupler are dissolved in a low-boiling water-immiscible solvent and dispersed together with gelatin. Furthermore, Japanese Patent Publication No. 51-39855 describes a method of mixing an emulsion-polymerized vinyl polymer with a hydrophobic coupler dissolved in a high-boiling point organic solvent and a low-boiling point water-immiscible solvent and dispersing it with gelatin. ing.

However, in all of these methods, the stability of the dispersion with the vinyl polymer is poor depending on the type of hydrophobic photographic additive dispersed, and there are problems with the stability of the emulsion polymerized vinyl polymer itself. A method of dissolving hydrophobic photographic additives in monomers in advance and emulsion polymerization was also devised, but this method had the disadvantage that as the proportion of hydrophobic photographic additives added increased, clumping was more likely to occur during emulsion polymerization. there were.

■ Purpose of the Invention The present invention has been made in view of the above circumstances, and therefore, the first object of the present invention is to provide a hydrophobic photographic additive with excellent stability over time and dispersibility in a hydrophilic colloid binder. A second object of the present invention is to provide a method for obtaining a dispersion of a hydrophobic photographic additive that has excellent stability over time and dispersibility, improves color development, and provides excellent image sharpness. An object of the present invention is to provide a silver halide photographic light-sensitive material.

■Specific Structure of the Invention The above-mentioned object of the present invention is to provide a first solution containing at least a polymer polymerized in the substantial presence of a hydrophobic photographic additive and a high-boiling organic solvent, and a first solution containing a hydrophilic colloid binder. The hydrophobic photographic additive is dispersed in the hydrophilic colloid binder by mixing with the solution of 2, and further, at least one photographic constituent layer containing such a dispersion is formed on the support. This can be achieved by using a silver halide photographic light-sensitive material.

In the present invention, hydrophobic photographic additives refer to hydrophobic additives that improve photographic performance, such as hydrophobic turnips, ultraviolet illuminants, antioxidants, optical brighteners, antifoggants, anti-staining agents, dyes, hardeners, etc. Refers to the various additives necessary to achieve the desired performance.

In the present invention, the first solution polymerized in the substantial presence of at least a hydrophobic photographic additive, but containing a reamer and a high-boiling organic solvent, refers to the hydrophobic photographic additive, the high-boiling organic solvent, A solution prepared by using a low boiling point organic solvent in which a polymerization initiator and a monomer are dissolved and reacted under conditions such as temperature and time that allow monomers to polymerize, or the above-mentioned hydrophobic photographic additive, polymerization initiator and A solution obtained by adding a high boiling point organic solvent to a monomer dissolved in a low boiling point organic solvent and reacting the monomer under conditions such as temperature and time that allow polymerization of the monomer. Therefore, it is considered that in this solution, the hydrophobic photographic additive is impregnated into the polymer molecules.

In the present invention, as described above, a first solution containing at least a polymer polymerized in the substantial presence of a hydrophobic photographic additive, a hydrophobic photographic additive, and a high-boiling organic solvent, and a hydrophilic binder are provided. to stably obtain a dispersion of fine particles with an average particle diameter of 3 μm or less, particularly 0.2 μm or less, by mixing with a second solution containing I can do it.

The dispersion of the present invention is obtained by further mixing and dispersing a first solution in which a hydrophobic photographic additive is impregnated into polymer molecules with a second solution containing a hydrophilic binder. It is considered that the hydrophobic photographic additive is directly impregnated into the polymer molecule. This dispersion is
For example, the stability of the dispersion over time is excellent compared to when a polymer made by polymerizing monomer alone is used as a dispersant, and there is a wide range of options for the range and order of hydrophobic photographic additives that can be impregnated.
In addition, the hydrophobic photographic additive can be dispersed in a large amount without reducing the physical strength of the silver halide emulsion layer or gelatin layer to which such hydrophobic photographic additive is added. Therefore, it has resistance to external mechanical forces such as scratches and pressure marks, and the color photographic material obtained by coating such a dispersion has good coloring properties of the coupler.

The polymer used in this invention can be prepared by suspension polymerization, solution polymerization, bulk polymerization, etc. in the presence of hydrophobic photographic additives. Preferably, a high boiling point organic solvent, which is a solvent for the hydrophobic photographic additive, is present during such polymerization. Since such polymers are dispersed in a woody binder as a dispersant for hydrophobic photographic additives, their solubility and swelling degree in water is extremely low, and their compatibility with hydrophobic photographic additives is extremely low. It is desirable that they have good compatibility.

The monomers polymerized in the presence of the hydrophobic photographic additive preferably in the simultaneous presence of a high-boiling organic solvent include:
For example, vinyl monomers can be mentioned. Such vinyl monomers include, for example, acrylic esters (eg, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, V-decyl acrylate, etc.), α-! l
Acrylic esters (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, etc.), acrylamide (e.g.,
ethyl acrylamide, butylacrylamide, hexylacrylamide, etc.), α-substituted acrylamide (e.g.
Vinyl halides (e.g., vinyl chloride, etc.), vinylidene halides (e.g., vinylidene chloride, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl 1' ctyl ether, etc.), styrene, α-substituted styrene (for example, α-methylstyrene, etc.), nuclear substituted styrene (for example, hydroxystyrene, polytetrarostyrene, methylstyrene, etc.), ethylene, propylene, butylene, butadiene, acrylonitrile, and the like. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a minor component of less than 50% as long as they have the above characteristics.

Examples of such other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, and the like.

Among the above vinyl monomers, 5 to 100% by weight of acrylate, methacrylate, vinyl ester, acrylamide, and methacrylamide monomers are particularly important.
, preferably in a composition of from 30 to 100% by weight.

Known methods can be used to synthesize polymers or copolymers using one or more of these vinyl monomers, such as those described in British Patent No. 1,21t059.
No., Special Publication No. 47-29195, No. 48-50.494
No. 961,595, U.S. Patent No. 3.227.
No. 672, Mr. 29 (No. L417, 5.24.5, 9)
The synthesis method described in No. 52 etc. can be used. The high-boiling organic solvent, type and amount of polymerization initiator, monomer concentration, polymerization temperature, reaction time, etc. used in the synthesis of the polymer of the present invention are well known and can be easily selected from a wide range depending on the type of monomer used. can do.

For example, polymerization of these vinyl monomers generally ranges from 20 to
It is carried out at a temperature in the range of 180°C, preferably 40SJ120°C. The polymerization reaction is usually carried out using a radical polymerization initiator in an amount of α05 to 5 by weight per 1 weight of heptamer to be polymerized. Examples of the polymerization initiator that can be used include azobis compounds, peroxides, hydrogen oxides, redox catalysts, etc., and specific examples include t-butyl peroctoate, benzyl peroxide, and methyl ethyl naton. Peroxide, azobisisobutyronitrile, etc. can be mentioned. The reaction time used for the polymerization may generally be from 5 to 20 hours, and the solvent used during the polymerization dissolves the monomer used in the polymerization, the polymer produced by the polymerization, and the hydrophobic photographic additive. Although solvents that do not dissolve only the polymer can also be used.

Alternatively, the system may be substantially free of solvent.

Examples of the solvent used in the polymerization of the present invention include:
Low-boiling organic solvents such as methanol, ethanol, butanol, methyl acetate, ethyl acetate, dioxane, and tetrahedron are preferred. The hydrophobic photographic additive to be present during the polymerization of the monomer of the present invention can be added to the monomer in an amount of 0.05 to 10 parts by weight per 1 part of the monomer. As the polymerization method, solution polymerization, bulk polymerization, suspension polymerization, etc. can be used in the present invention, and solution polymerization is particularly preferred.

Hydrophobic photographic additives used in the present invention include, for example, hydrophobic couplers, ultraviolet absorbers, antioxidants, optical brighteners, antifoggants, stain inhibitors, dyes,
Additives necessary for exhibiting photographic performance such as hardeners can be mentioned.

Further, the molecular weight of the polymer used in the present invention is usually 2. OO or more is used, preferably 4
Those in the range of 000 to 7 o, o o o are used.

Specific examples of monomers used in the present invention and their combinations will be described below.

t Butyl acrylate 2, Butyl acrylate-methyl methacrylate (molar ratio srs) 5 Ethyl acrylate 4. Ethyl acrylate 1 root - methyl methacrylate (molar ratio 18) 5, Ethyl ac 1 root - methyl methacrylate (molar ratio 3 near) 6, Ethyl acrylate - methyl methacrylate (molar ratio 4:6) 2 Ethyl acrylate - methyl methacrylate (molar ratio 5: 5) 8, ethyl acrylate methylmethac 1 route (molar ratio 6j4) 9
Ethyl acrylate to methyl methac 1 root (molar ratio 7:3) 10, ethyl acryto 1 root to methyl methac 1 root (molar ratio [2) 11, methyl methacrylate 12, ethyl acryto 1 root to ethyl methac 1 root (molar ratio 21) 16, Ethyl acrylate 1 root to ethyl methacrylate (molar ratio 5:5) 14, Ethyl acrylate -
Ethyl methacrylate (mole ratio 71) 15 Methyl acrylate-acrylic kuma (mole ratio 9N) 16 Butyl acrylate-acrylamide (mole ratio 9N) 1z Methyl acrylate-vinyl acetate (mole ratio 7:5) 18, Methyl acrylate-ethyl acrylate (mole ratio ratio 6:4)
19 Methyl ac 1 route - methyl methacrylate - vinyl acetate (molar ratio 4sse1) 20, Butylac 1 route - methyl methacrylate (mole ratio 2:8) 2t Butylacryto methyl methac 1 root (molar ratio ga 7)
) 22, butyl acrylate methyl metacoumarute (
Molar ratio 6:4) 25 Butyl acrylate - Methyl methacrylate (Molar ratio [2) 24, Butyl acrylate -
Acetoacetoxy methacrylate (molar ratio 8:2) The high boiling point organic solvent used in the present invention is substantially immiscible with water and has a boiling point of 175° C. or higher at normal pressure. These include those conventionally used as coupler solvents, and specifically, carboxylic acids such as those described in U.S. Patent No. 2.522.027 and U.S. Pat. Esters, phosphate esters, amides, ethers,
Examples include ketones. A preferred example is G-n-
Butyl 7-talate, diisooctyl 7-talate, dimethoxyethyl 7-talate, benzyl 7-talate, triphenyl phosphate, tricresyl phosphate, diphenylmotsbutyl phosphate, tributyl phosphate, tridecyl phosphate, dibutyl monohexyl phosphate, diphenyl mono-O-chlorophenyl phosphate The esters of talic acid and phosphoric acid are praised.

The mixing ratio of the high boiling point organic solvent, the hydrophobic photographic additive, and the monomer to be polymerized according to the present invention is as follows: hydrophobic photographic additive: high boiling point organic solvent: monomer to be polymerized = 1 j 0.01F 0.01~1:20420
preferably 1:0.1F0.1 to 14
The range is 10:10.

Examples of the dye image-forming coupler used as the hydrophobic photographic additive of the present invention include those belonging to phenol rust conductors, naphthol derivatives, 5-pyrazoline derivatives, pyrazole triazole derivatives, acylacetamide derivatives, and Things other than the above-mentioned derivatives can also be used in the present invention, and furthermore, colored couplers, DXR couplers, etc. can also be used.

Representative hydrophobic dye image-forming couplers are described, for example, in U.S. Pat.
No. 305, No. 2,322,027, No. 2,357,3
No. 94, No. 2.559.552, No. 2,374821
No. 2,433098, No. 2,455,170,
2,474,293, λ5iSOj No. 49, 2
．． 54 S, No. 687, No. 2,550,661, No. 2
, No. 589,004, No. 2,600,788, No. 2,
65th No. 134, No. 2,659,329, No. 2,71
No. 0,802, No. 2,72t798, No. 2,772,
No. 161, No. 2,801,170, No. 2,865,7
No. 51, No. 2,875,057, No. 2,895,82
No. 6, No. 2,899.445, No. 2,908,573
No. 2,920,961, No. 2,927,928, No. 4034.892, No. 5,062,655, No. 12 Su No. 269, No. 4148.062, No. 5.22
7.551, 22s No. 554, 3,265,5
No. 06, No. 3,511,476, No. 33, No. 344, No. 3.394071, No. 5,408,194, No. 409.459, No. 418,129, No. 3,4
19. ! S9j No. 441,414, No. 4447
．． No. 928, No. 5,459,552, No. 446B, 6
No. 66, No. 3,481,714, No. 831 to No. 451, No. 4519,429, No. 3,551,155, No. 3,551.156, No. 558,3119 to No.
55B, No. 700, No. 3,580,721, No. 58
No. 4322, No. 4584971, No. 5,591,58
No. 3, No. 461-504, No. 3,61-291, No. &676.137, Belgian Patent No. 697.122,
Special Publication No. 39-5547, No. 39-27565, No. 4
No. 2-11!105, No. 49-2175, JP-A-47
-26155, 48-59858, 4B-75
No. 147, No. 55-598, No. 55-32071,
It is described in No. 55-161239, No. 56-1938, etc.

Specifically, for example, the following hydrophobic couplers can be mentioned.

Yellow dye-forming coupler -3 -4 -6- 7- -10 -11 Magenta dye-forming coupler M-1 -2 -3 -4 -5 -7- 1 1,:1 -9 -10 Cyan dye-forming coupler - 2 -3 I -7 C-8 C-10 mti Mask formation lard coupler-1 L -3 -4 -7 DIR coupler (development inhibitor releasing coupler) -1 N-3 Hydrophobic photographic additive of the present invention Examples of the ultraviolet absorber used as the agent include those described in Japanese Patent Publication No. 42-21687, Japanese Patent Publication No. 48-5496, Japanese Unexamined Patent Application Publication No. 47-1026, and British Patent No. 1,293,982.

Some specific examples are listed below, but the present invention is not limited thereto.

-t'[J-2'[J-3-4 Examples of the antioxidant used as the hydrophobic photographic additive of the present invention include U.S. Pat. Compounds described in JP-A No. 2,835,579, JP-A-46-2128, and the like can be mentioned.

Some specific examples of antioxidants are listed below, but the present invention is not limited thereto.

O-2 Examples of the fluorescent brightener used as the hydrophobic photographic additive of the present invention include the compounds described in U.S. Pat. No. 3,630,738; As the dye used, for example, U.S. Pat.
, 651,494.

Next, a method for dispersing the hydrophobic photographic additive of the present invention in a hydrophilic colloid binder will be described.

In the present invention, it is preferable to polymerize by solution polymerization, and in that case, it is preferable to disperse the polymerized solution into a hydrophilic colloid binder as it is or by adding another solvent. Other polymerization methods involve dissolving a polymer containing at least a hydrophobic photographic additive in a low-boiling organic medium such as ethyl acetate, methanol, ethanol, or the like. At this time, a high boiling point organic solvent such as dibutyl chloride, tricresyl phosphate, etc. may be added to promote dissolution. The colloid is dispersed in a hydrophilic colloid according to the method using, for example, a mixer, homogenizer, colloid mill, ultrasonic disperser, etc. As the hydrophilic colloid, all those commonly used as binders for photography can be used. Specifically, gelatin, gelatin derivatives (
(e.g. acetylated gelatin, phthalated gelatin, succinated gelatin, etc.), hydrophilic polymers (e.g. poval, polyvinylpyrrolidone), and polymer latex (e.g.
Examples include polymethyl methacrylate, polyethyl acrylate, etc.).

Examples of surfactants used as dispersion aids include anionic surfactants,
For example, Special Publication No. 39-4293, No. 46-4547,
JP 55-88045, U.S. Patent No. 2,322,02
No. 7, No. 2.360,289, No. 2,801.170
No. 2,801,171, No. 2,9.49,360
German Patent No. 3,619,195, German Patent No. 1,143゜707, German Patent No. 2,045,414, German Patent No. 2,045,4
Items listed in No. 64, etc., or Special Publication No. 51-3
The one described in No. 9853 is used.

Also, amphoteric surfactants such as N,N-dimethyl-
N-dodecylbetaine, N-tetradecy A/-N, N-
Dipolyethylene-α-betaine or the like may also be used. Furthermore, the anionic surfactant or amphoteric surfactant may be used in combination with a nonionic surfactant.

As the nonionic surfactant, for example, German special tIf
Those described in No. 1,942,873 can be used.

The measurement of dispersed particle size in the present invention was mainly carried out using an electron microscope, but for the purpose of knowing the relative value of particle size in the same system, the turbidity value at a specific wavelength (for example, 670 nm) was used for convenience. It can be measured and used as a guide to particle size.

The dispersion of the present invention is mixed with a hydrophilic colloid binder or a silver halide photographic emulsion to prepare a photographic coating solution in the same manner as conventionally known dispersions.

Silver halide emulsions include silver bromide, silver iodide, silver chloride, and mixed silver halides, i.e., silver chlorobromide, silver iodobromide, and chloride iodobromide. A photographic emulsion consisting of silver can be used.

It is preferable that soluble salts be removed from the silver halide emulsion used in the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

As the binder for the silver halide emulsion layer according to the present invention, conventionally known binders can be used, such as gelatin, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, polyvinyl alcohol, polyvinylpyrrolidone, etc. , polymer nonelectrolytes such as polyacrylic acid amide, acidic polymer substances such as alginates, polyacrylic acid groups, polyacrylamide treated by Hoffmann rearrangement reaction, polymers such as copolymers of acrylic acid and N-vinylimidazole, etc. Ampholyte, US Pat. No. 4,21
Examples include crosslinkable polymers described in No. 5,195.

It may also contain a dispersed hydrophobic polymer substance, such as a latex such as butyl polyacrylate or ethyl polyacrylate. These binders can be used as a compatible mixture of two or more if desired.

A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

Note that when a gold compound is used, ammonium thiocyanate and sodium thiocyanate can be used together.1 As the sulfur sensitizer, a sulfur compound can be used in addition to activated gelatin.

As selenium sensitizers, active and inactive selenium compounds can be used.

Reduction sensitizers include stannous salts, polyamines, pithalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using optical sensitizers such as cyanine dyes such as monomethine dyes and trimethine dyes or merocyanine dyes alone or in combination. can be sensitized.

In addition to the above-mentioned additives, the silver halide photographic material of the present invention also contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, formalin scavengers, and others. Various additives useful in photographic materials are used.

The silver halide photographic light-sensitive material of the present invention is composed of photographic constituent layers including auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer in addition to the silver halide emulsion layer.

Supports include plastic films such as triacetyl cellulose, plastic laminated paper, baryta paper,
Conventionally known materials such as synthetic paper may be selected as appropriate depending on the intended use of the photographic material.

These supports are generally subjected to an undercoating process to strengthen the adhesion with the photographic emulsion layer. The silver halide color photographic light-sensitive material used as the silver halide photographic light-sensitive material of the present invention has a blue color on the support. Three types of silver halide photographic emulsion layers selectively spectrally sensitized to be sensitive to light, green light and red light are coated. These emulsion layers are generally coated with blue-sensitive, green-sensitive and red-sensitive emulsion layers in order from the exposed side.
A bleachable yellow filter layer is provided between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. Furthermore, other intermediate layers are provided between each emulsion layer, and a protective layer is provided as the outermost layer. Furthermore, in light-sensitive materials for color photographic paper, red-sensitive, green-sensitive, and blue-sensitive emulsion layers are generally applied in order from the exposed side, and each layer has a specific purpose, just as in light-sensitive materials for color negatives. A UV absorbing layer, an intermediate layer, a protection layer, etc. are provided respectively. These emulsion layers may be provided in a different arrangement from the above, and two or more types of photosensitive emulsion layers having different photosensitivity in substantially the same photosensitive region for each color light may be used. Good too.

After the silver halide photographic material of the present invention thus constructed is exposed to light, various photographic processing methods are used for color development. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component. Specific examples of this color developing agent include p
Typical examples include diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylamino Toluene hydrochloride, 2-amino-5-(N-ethyl-N
-)"y'cylamino)-)luene, 2-amino-5-
(N-ethyl-N-β-methanesulfonamidoethyl,
) Aminotoluene sulfate jJ[,4-(N-ethyl-N-
β-Methanesulfonamidoethylamino)aniline, 4
-(N-ethyl-N-β-human tetraxyethylamino)aniline, 2-amino-5-(N-ethyl-β-methoxyethyl)amine toluene, and the like. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with black and white developing agents such as hydroquinone and phenidone.

Furthermore, color developers generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or development regulators such as citradinic acid. etc. may be included.

The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. A color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff-Pase type precursor with an aromatic aldehyde rust conductor, a polyvalent metal ion complex precursor, a phthalic acid imide rust conductor precursor, and a phosphoric acid salt conductor precursor. Examples include rust conductor precursor, Seeger amine reactant precursor, and urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,59
No. 9, No. 2,507,114, No. 2.695,2
No. 34, No. 3,719,492, British Patent No. 803
, No. 783, JP-A-53-135628, No. 5
4-79035, Research Disclosure Magazine No. 15159, Research Disclosure No. 12146, and Research Disclosure No. 13924.

These aromatic primary-rmine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies depending on the type of photosensitive material, etc., but it is generally between 0.1 mol and 5 mol per mol of photosensitive silver halide, preferably 0.
．． It is used in a range of 5 mol to 3 mol. These color developing agents or their breakers can be used alone or in combination. To incorporate additives such as these developing agents or their precursors into photographic light-sensitive materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. and added. It can also be added as an emulsified dispersion using a high boiling point organic solvent such as tricresyl phosphate, Research Disclosure Magazine 14
They can also be added by impregnation into latex polymers as described in US Pat. No. 850.

The silver halide photographic material of the present invention is usually subjected to bleaching and fixing, or bleach-fixing and washing with water after color development. Many compounds are used as bleaching agents, among them iron (■), cobalt (■), tin (II),
polyvalent metal compounds such as, in particular, complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid,
Metal complex salts such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations.

1. Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Yellow coupler (Y-8) 1 (1, ethyl acrylate 49, methacrylate 1f and di-n-butyl phthalate) IF was dissolved in ethyl acetate 50-, and azobisisobutyronitrile 0 was added therein as a polymerization initiator. .2f was added and polymerized at 60°C for 10 hours. After the reaction was completed, the reaction product was concentrated to a concentration of 20. This concentrated solution was added to a 60°C aqueous solution containing 1 (l) of gelatin and 0.52 ml of sodium dodecylbenzenesulfonate, and the mixture was vigorously mechanically stirred with an ultrasonic homogenizer to obtain dispersion (I). Ta.

Dispersion (2) was obtained in the same manner as above except that dibutyl phthalate was omitted.

The relative particle diameters of the resulting dispersions CI) and 0 were measured, with the average particle diameter of dispersion (1) set as 100.

The results are shown in Table 1.

A mixture of each of these dispersions 20- and 0.8 f of 1,2-bisvinylsulfonylethane was added to a blue-sensitive silver iodobromide emulsion 15- prepared by a conventional method, and a mixture was added to a blue-sensitive silver iodobromide emulsion 15- prepared by a conventional method, and a mixture was added to a blue-sensitive silver iodobromide emulsion 15- prepared by a conventional method. It was coated on a support and dried. Samples corresponding to dispersions (I) and (2) are designated as samples (I) and (2), respectively.

Each of the samples (I) and 0 was exposed to light for sea urchin, . Further, the treatment liquid used in this treatment step was as shown below.

[Coloring liquid composition]

[Bleaching solution composition] [Fixing solution composition] [Stabilizing solution composition] Next, sensitometry was measured for the color images formed on the samples (■) and (■). The results are shown in Table 1, setting each characteristic of the sample as 100.

Table 1 From the results in Table 1, sample (I) of the present invention has the same relative velocity as comparative sample 0, but there is a significant improvement in the maximum concentration, a significant improvement in particle size, and good dispersibility. I understand that there is something.

Example 2 In the method for preparing dispersion (1) of Example 1, yellow coupler (Y-s) 10F was replaced with magenta coupler (M-t).
8f, ethyl acrylate) 4f, 5t.

A dispersion was obtained in the same manner except that 8F was used instead of 1F of di-n-butyl 7 tallate.

In addition, magenta coupler (M-i) 8f was added to a mixed solvent of dibutyl phthalate) 8F and ethyl acetate 6f at 65°C.
This coupler solution was stirred and added to a mixture at 50°C consisting of 150v of aqueous emulsion polymer containing 8f of 10 tisgelatin aqueous solution and 30f of ethyl acrylate, and then dispersed with a colloid mill. , a 1M dispersion was obtained.

These dispersions were mixed with a green-sensitive silver halide emulsion, coated on a support, and dried in the same manner as in Example 1 above. The obtained samples were designated as sample (111) and (IV
). Furthermore, samples (1■), (IV) t'
Sensitometry was measured on the color image formed by seven edge exposures. Each characteristic of sample (IV)
The results are shown in Table 2 with the value set as 0.

Table 2 From the results in Table 2, the sample of the present invention (Ill) is different from the comparative sample (Ill).
It can be seen that the capri is suppressed and the maximum density is improved compared to IV).

Example 3 Ultraviolet absorber (U-2) sf, butyl acrylate) 3F
, 2f of methyl methacrylate and 5f of tricresyl phosphate were dissolved in 30% of ethanol, 0.5f of azobisisobutyronitrile was added, and the mixture was polymerized at 60°C for 17 hours. After the reaction was completed, the reaction mixture was poured into 100 me water to obtain a polymer. After drying, it was dissolved in 20 ethyl acetate, added to 100 tnt of 10 thigelatin aqueous solution at 60°C, and the mixture was stirred and dispersed in a colloid mill. Dispersion M was obtained.

In the above method, a butyl acrylate-methyl methacrylate copolymer 5F (weight ratio of 3
A dispersion (VT) was obtained in the same manner except that: 2) was added.

The stability over time of the obtained dispersions (V) and (Vl) was measured based on the change in particle size. The results are shown in Table 3.

Table 3 From the results in Table 3, the dispersion M of the present invention is the comparative sample (VI)
It can be seen that the particle size is smaller than K, and the stability of the particle size over time is improved.

Patent applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] (1) by mixing a first solution containing a polymerized polymer and a high-boiling organic solvent in the substantial presence of at least a hydrophobic photographic additive and a second solution containing a hydrophilic colloid binder; a first solution containing a hydrophobic photographically added polymer and a high-boiling organic solvent, characterized in that the hydrophobic photographic additive is dispersed in a hydrophilic colloid binder, and a hydrophilic colloid binder; 1. A silver halide photographic light-sensitive material having at least one layer on a support as a photographic constituent layer of a hydrophilic binder containing a hydrophobic photographic additive obtained by mixing with a second solution.