JPS6280641A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf stability by incorporating at least one kind of specified compound, a high b.p. solvent and hydrophobic additives into a hydrophilic colloidal layer in the form of drops of oil. CONSTITUTION:This silver halide photographic sensitive material contains at least one kind of compound represented by formula I, a high b.p. solvent and hydrophobic additives in at least one hydrophilic colloidal layer in the form of drops of oil. In the formula I, R is 1-20C alkylene, typically methylene. Any org. solvent having >=150 deg.C b.p under ordinary pressure may be used as the high b.p. solvent but phthalic ester is preferably used. The typical hydrophobic additives include a dye forming coupler.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material in which the dispersion stability of an oil-soluble additive is improved by using a cyclic ether compound. .

[Prior Art] Silver halide light-sensitive materials contain many additives, and color photographic light-sensitive materials in particular include dye-forming couplers, colored couplers, DIR couplers, and DI.
Among the R compounds, printing stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds are included.

The hydrophobic compound is usually dissolved in a high boiling point organic solvent with a boiling point of about 150° C. or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and a surfactant is added to a new aqueous binder such as an aqueous gelatin solution. After emulsification and dispersion using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, the oil is added as oil droplets into the desired hydrophilic colloid layer and exposed to light. It is coated on a support together with silver halide.

As a high boiling point Nada solvent, U.S. Patent No. 2,322,02
No. 1, No. 2,533,514, No. 2,835,579
No. 3,287.134, No. 2,353,262
No. 2,852,383, No. 3.554,755
No. 3,676.137, No. 3,676.14
No. 2, 3,700,454@, 3,748,141
No. 3,779,765, No. 3,837,863, British Patent No. 958,441@, No. 1,222,753
No., OL No. 82,538,889, Japanese Unexamined Patent Publication No. 1973-10
31@, No. 49-90523, No. 50-23823, No. 51-26037, No. 51-27921, No. 5
No. 1-27922, r6151-26035, same 51
-26036, 50-62632, 53-15
No. 20, No. 53-1521@, No. 53-15127,
No. 54-119921, No. 54-119922,
No. 55-25057, No. 55-36869, No. 56
-19049, ff5G-81836, special public show 4B
-29060 etc.

Phenol derivatives, phthalate alkyl esters, phosphate esters, citrate esters, benzoate esters,
Organic solvents having a boiling point of 150° C. or higher, such as alkylamides, fatty acid esters, and trimesic acid esters, are used.

In particular, phthalate ester compounds, phenol compounds and phosphate ester compounds are usefully used.

Oil droplets containing hydrophobic additives such as couplers are required to stably exist as fine particles in the hydrophilic colloid layer.

It is known that oil droplet components such as high-boiling point solvents have a significant impact on oil droplet dispersibility (particle size and stability of the dispersion state), the effectiveness of hydrophobic additives, and storage stability. Improvements are desired. For example, it is required that oil droplets containing a dye-forming coupler have good dispersibility and that they do not adversely affect the color-forming dye, its storage stability, and hue.

In recent years, the use of a large number of functional materials in photographic materials has brought about significant technological progress. This means that the types and types of hydrophobic additives that can be added to hydrophilic colloids have increased. However, over time, the oil droplets are destroyed, the oil component oozes out, and the gloss deteriorates.Additionally, oil droplets are added using only conventional solvents such as phthalate ester compounds, phenol compounds, and phosphate ester compounds. However, dispersion stability is not always fully satisfied, and improvements in dispersion stability are desired.Other means commonly used to improve dispersion stability include the use of surfactants.
This can be solved by increasing.

However, increasing the amount of surfactant j increases fog when the emulsion stagnates, softens the tone, and has a large influence on photographic properties, which is undesirable.

Although an epoxy compound similar to the epoxy compound used in the present invention is described in the specification of Japanese Patent Publication No. 58-45017, the compound of the general formula [1] of the present invention is not suggested;
The effects of the present invention are not stated.

Moreover, the effect as in the present invention was not obtained.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material in which the storage stability of oil droplets containing a hydrophobic additive in a hydrophilic colloid layer is improved.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support,
At least one hydrophilic colloid layer has the following general formula [1
], a high boiling point solvent, and a hydrophobic additive are contained in the form of oil droplets.

General formula [1] In the formula, R represents an alkylene group having 1 to 20 carbon atoms.

Typical alkylene groups for R include methylene, ethylene, propylene, 1,2-propylene, hexylene, nonylene, octadecylene, and the like.

Next, exemplary compounds of the compound of general formula [I] will be shown, but the present invention is not limited thereto.

The following margins are exemplified compounds R (1) -CH2- (2) -CH2CH2- <3> -(C
) -2Hs (4) -CH- Ha (5) -CH2CH- (6-(CH2)) The high boiling point solvent used in the present invention is particularly limited as long as it is an organic solvent with a boiling point of 150°C or higher at normal pressure. However, preferably used high boiling point solvents are phthalate compounds, phenol compounds and phosphoric acid ester compounds.

Examples of the phenolic compound advantageously used in the present invention include those represented by the following general formula []I].

General formula [Ir] In formula [I], R5 and R6 each represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 20 carbon atoms (e.g., methyl group, [-butyl group, t-pentyl group, group, t-octyl group, dodecyl group, pentadecyl group, etc.). R7 is a linear or branched alkyl group having 1 to 20 carbon atoms (e.g., methyl group, t-butyl group, t-pentyl group, (-octyl group, dodecyl group, pentadecyl group, etc.), or a cycloalkyl group ( For example, cyclopentyl group, cyclohexyl group, etc.) However, the total number of carbon atoms of the groups represented by R5, R6 and R7 is 6 to 24.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula []II].

General formula [I[I] In the formula, R8 and R9 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R8 and R9 is 2 to 36. More preferably, the total number of carbon atoms is 6 to 24.

In the present invention, R8 and R9 of the general formula [I[[]
The alkyl group represented by is linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, These include a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by R8 and R9 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, allyl group, etc. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. As substituents for alkyl groups and alkenyl groups,
Examples include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, and the like. Examples of substituents on the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

Examples of phosphoric acid esters advantageously used in the present invention include those represented by the following general formula [IV].

General Formula [IV] In the formula, Rlo, R++ and R+2 each represent an alkyl group, an alkenyl group or an aryl group. However, Rho
, the total number of carbon atoms in the groups represented by R11 and R+2 is 3
~54.

In the present invention, Rho, R++ of the general formula [IV]
The alkyl group represented by and R+2 is linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
These include undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and the like.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably Rho, R++ and R12 are alkyl groups, such as n-butyl group, 2-ethylhexyl group, n-octyl group, 3.5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec -decyl group, 5ec-dodecyl group, t-octyl group, etc.

Examples of the alkenyl group include ethylene group, allyl group, and butene group, and examples of the aryl group include phenyl group, tolyl group, and xylyl group.

Examples of high boiling point solvents of general formulas [I] to [IV] are shown below, but the present invention is not limited thereto.

Below margin A'-I A・-2
A"-3A'-4 A'-5A'-6 A'-7A'-8 A"-9A'-1O A'-11A'-12 A'-13A'-14 A'-15A'-16 A '-17A'-18 C2H3 2Hs CI"i"i3 A'-21A'-22 A'-23A'-24 A'-27A'-28 A'-33A'-34c2H.

A・-35A'-36 A・-37A'-38 A'-41 A'-42 A'-43 A'-44 A'-56 Below margin In the silver halide photographic light-sensitive material of the present invention, the high boiling point solvent is , preferably used at a ratio of 1 to 5 times the total weight of the hydrophobic compound, more preferably 0.1 to 3 times the total weight of the hydrophobic compound.
Used twice. The high boiling point solvent and the hydrophobic compound do not need to be used alone, and multiple types of each may be used.

In the present invention, the compound of general formula [I] is characterized by being present in the high boiling point solvent as oil droplets, and is added in a weight ratio of 5% or more, preferably 10% or more to the high boiling point solvent used. Things are good.

Further, the weight ratio of the compound of general formula [I] to the high boiling point solvent is preferably 500% or less, more preferably 400% or less, from the viewpoint of dispersion stability.

The compound of general formula [I] improves the dispersion stability of oil droplets containing a hydrophobic additive when used in combination with a high boiling point solvent. The hydrophobic additive is not particularly limited as long as it is added to the silver halide photosensitive material by being included in oil droplets. Usually, the compound is an organic compound having a solubility in water of 10% by weight or less.

Typical hydrophobic additives include dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners,
These include DDR couplers, DRR compounds, dye developers, and the like.

In the present invention, containing as oil droplets means adding a hydrophobic additive such as a coupler to a high-boiling organic solvent with a boiling point of about 150°C or more and a solubility in water of 10% or less, as necessary.
and/or dissolved in a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After making an oil-in-water emulsion and dispersion, it is added to the desired hydrophilic colloid liquid, coated on a support, and dried in the same state as the high-boiling organic solvent is contained in the layer. It means that it is contained.

In the present invention, the method of incorporating the hydrophobic additive and the compound of the general formula [I] together with a high-boiling point solvent into the silver halide photosensitive material as oil droplets is not particularly limited, but the above-mentioned oil-in-water emulsion dispersion method is used. Things are good.

The compound of general formula [I] may be purchased as a commercial product, or it may be obtained by synthesizing a corresponding compound having a double bond in advance and then oxidizing the double bond with an oxidizing agent (for example, hydrogen peroxide). You can also do it.

The silver halide photographic light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support. The oil droplets containing the boiling point solvent and the hydrophobic additive may be contained in at least one layer behind the silver halide emulsion or in at least one layer of the non-photosensitive hydrophilic colloid layer.

The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. You can use any one you like.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling l)H and/or DAQ in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) for at least 1 second to add metal ions to the interior of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1
sclosure (hereinafter abbreviated as RD) No. 17643 π
It can be carried out based on the method described in Section.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of (100) planes to (111) planes can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion was separately formed 2F! ! The above silver halide emulsions may be mixed and used.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal inkstone compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, polar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or to maintain stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and the hydrophilic colloid layer thereof in the light-sensitive material of the present invention are hardened by using one or more hardeners that bridge binder (or protective colloid) molecules and increase film strength. be able to.

A hardening agent can be added to the processing solution to harden the photosensitive material to such an extent that it is not necessary to add a hardening agent, but it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in section △ of RD 17643.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-encapsulant, in which 4 molecules of silver ions must be reduced in order to form 1 molecule of dye, 2 molecules of silver ions are reduced.

It may be either 2-equivalent or 2-equivalent. The dye-forming coupler is a colored coupler that has a color correction effect and a development inhibitor by coupling with an oxidized form of a developing agent.
Development accelerator, bleaching accelerator, developer, silver halide solvent,
Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitizers are included. Among these,
A coupler that releases a development inhibitor during development and improves image sharpness, release properties, and image graininess is called a DrR coupler. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a doxy group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron 9-dynamic reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Further, as for the inhibitor, one having excellent release diffusibility and one having less diffusibility can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Among compounds, image stabilizers, color antifoggants, optical brighteners, etc., hydrophobic compounds can be used in various ways such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. The compound can be added in a dispersed manner using a method, and this can be appropriately selected depending on the hydrophobization of the coupler and the chemical structure of the compound. For the oil-in-water emulsion dispersion method or the oil-in-water dispersion method for adding oil droplets of the present invention, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150. It is dissolved in a high-boiling point organic solvent of ℃ or above using a low-boiling point and/or water-soluble organic solvent as necessary, and a hydrophilic binder such as a gelatin solution is mixed with a surfactant using a stirrer, a homogenizer, It may be emulsified and dispersed using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

As the high boiling point solvent, R solvents such as phenol derivatives, phthalate alkyl esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc., which do not react with the oxidized form of the developing agent, are used. .

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nidoethane, and benzene, and examples of water-soluble organic solvents include: Acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol monophenyl ether,
Examples include phenoxyethanol.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be dissolved in hydrophilic colloids as an alkaline aqueous solution. It can also be introduced into

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsions WII of the light-sensitive material (between the same color sensitivity and/or between the different color sensitivity F!J), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent deterioration and noticeable graininess.

The color capri-preventing agent may be included in the emulsion itself, or
The intermediate ffIII may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image.

The hydrophilic colloid layer of the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent capri and image deterioration due to ultraviolet rays due to discharge caused by charging of the photosensitive material due to friction or the like.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RQ 176.
The compound is a compound described in Section XXI, Section B-0 of No. 43, and the development retardant is a compound described in Section XXI, Section E of No. 17643@. A black and white developing agent and a developer or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section 1 of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These dyes and/or emulsion layers may contain dyes that flow out of the light-sensitive material or are bleached during development.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be used to reduce gloss of the light-sensitive material, improve buildability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

Slip a! for photosensitive materials! Lubricants can be added to reduce chafing.

Antistatic agents can be added to photosensitive materials to prevent static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in R077643 Xm.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development, hardening, sensitization, etc.). ) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Paper laminated with ethylene/butene copolymer), flexible reflective supports such as synthetic foods, semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of 2000, flexible supports made of these films with reflective layers, glass, scrap metal, ceramics, etc.

The hydrophilic colloid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. It may be coated through one or more subbing layers to improve properties such as hardness, hardness, antihalation, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The light-sensitive material of the present invention falls within the spectral region 1! to which the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. Can be exposed using magnetic waves. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, X-rays, and gamma rays. Any known light source can be used, such as light emitted from a phosphor excited by alpha rays or the like.

The exposure VF bar can not only use an exposure time of 1 millisecond to 1 second, which is normally used in a camera, but also an exposure shorter than 1 microsecond, for example, an exposure time of 100 nanoseconds to 1 microsecond using a cathode ray tube Yaxenon flash lamp. However, exposures longer than 1 second are also possible.

The exposure is 3! ! ! It may be performed continuously or intermittently.

Any known method can be used for developing the photosensitive material of the present invention. If an image is to be produced by the reversal method, a black and white negative development process is first carried out, and then a white exposure is given or a color development process is carried out by processing with a bath containing a fogging agent.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods are also available, such as a spray method in which the processing solution is supplied in the form of a wA mist, or a method in which the material is brought into contact with a carrier impregnated with the processing solution. A method such as the Kuep method, a method of performing a viscous development process, etc. may also be used.

In order to obtain a silver image using the photosensitive material of the present invention, black and white development processing is performed after exposure. Black and white development processing is a development process,
A fixing process and a washing process are performed. When a stopping process is performed after the development process or a stabilizing process is performed after the fixing process, the washing process may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the photosensitive material, and the developing process may be performed using only an alkaline solution. A development process using a lithium developer as a developer may be performed.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. Alternatively, a bleach-fixing process can be carried out using a 1-bath bleach-fix solution, or a monobath process using a 1-bath development, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also carry out the process.

In combination with these treatment steps, a pre-hardening treatment step, its neutralization step, a stop window @ treatment step, a post-hardening treatment step, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed with an activator solution, or a monobath treatment may be performed using a seven activator solution. Processing can be applied.

Among these processes, typical processes are shown below.

(These treatments are carried out as a final step, one of a water washing process, a water washing process, and a stabilization process.) - Color development process - bleaching process - constant fixation process - color development process - bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

Examples of the present invention will be shown below to describe the present invention in more detail, but the present invention is not limited thereto.

The following couplers and additives were used in the examples.

Coupler (A) Cl coupler (B) Coupler (D) Additive (A) Coupler (A) Cl coupler (B) Coupler (D) Additive (A) Coupler (C) 25 (1), 25 g of exemplified compound (1), and 25 g of high-boiling solvent A'-27. Ethyl acetate 20 (h12
Dissolved in hot water.

Add this solution to 5g of sodium dodecylbenzenesulfonate.
After adding it to 1000.4 of a 5% gelatin aqueous solution containing 1,000.4% of the gelatin solution, an oil-in-water dispersion 1 was prepared using a homogenizer. Half a m of the dispersion was added to 1000 d of red-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion (containing 60 g of silver), and N,N',N''-triacryloyl 6H-8 was added as a hardener. - Add a 2% methanol solution of triazine and coat it on a polyethylene coated paper support so that the coated silver ω is 0.4 (1/t2, coated gelatin) is 1.50/12, and then A protective layer was provided on top so that the amount of gelatin applied was 1 (+/W2) to prepare sample 1. Similarly, the components to be dissolved in acetate ethyl acetate were prepared as shown in Table 1.
Samples 2 to 4 were created using 4.

4f created as above! ! The sample was left unexposed and processed according to the following processing steps to obtain a blank sample.

<Processing process> Processing time Processing temperature Color development 3.5 minutes 33℃ bleach fixing 1.5 minutes 33℃ water washing
Dry for 3 minutes at 33℃
Composition of color developing solution at 80℃〉 Pure water
700tf benzyl alcohol
15d diethylene glycol 15 residue hydroxylamine sulfur M salt 2gN-ethyl-N
-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.49 Potassium carbonate 30° Potassium bromide
0.49 potassium chloride
o, sg potassium sulfite
Add 2g of pure water to make 12 (DH=10.2
) <Bleach-fix solution composition> Ethylenediaminetetraacetate iron ammonium 610 Ethylenediaminetetraacetate R2 Ammonium 5g Ammonium thiosulfate 125K Sodium metabisulfite 13a Sodium sulfite
Add 2.1g water to make 11 pH = 7
．． A glossiness deterioration test was conducted under various conditions on the white background sample obtained.

The deterioration conditions were as follows, and a gloss meter manufactured by Tokyo Denshoku Co., Ltd. was used to measure the glossiness, and the results were shown in Table 2 immediately after the treatment and after the deterioration test #.

Deterioration condition A; 85℃ without humidification 10 days; 75℃
80% R8 10 days C; Table 1 shows the results of measuring changes in the particle size of oil droplets after storage for several days.

The number of particles of 25μ or more per 0.75 cc of the dispersion was measured using a light scattering method.

From Table 1 below, it can be seen that the deterioration of dispersibility is improved by adding the compound of general formula [I] to the oil-in-water type dispersed particles.

Table 2 As shown in Margin Table 2 below, under conditions where the gloss level decreases in the comparative samples, the decrease in gloss level is improved in the samples of the present invention.

Example 2 In the same manner as in Example 1, the components shown in Table 3 were dissolved in 200% ethyl acetate to create oil-in-water dispersions 5 to 8. A portion of each of the dispersions was added to a green-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 1000xt2 (containing 60 g of silver), and N was added as a hardener.

A 2% methanol solution of N',N''-triacryloyl 6H-8-triazine was added to the polyethylene-coated paper support with a coated silver amount of 0.40/f and a coated gelatin amount of 1.5 (1/f). Samples 5 to 8 were prepared by applying a protective layer on top of this layer so that the amount of gelatin applied was 1 (+/f).

These samples were treated in the same manner as in Example 1, and the gloss deterioration test was conducted in the same manner as in Example 1. The results are shown in Table 4. Further, in the same manner as in Example 1, dispersion stability tests were conducted on dispersions 5 to 8, and the results are shown in Table 3.

From Table 3 below, it can be seen that the deterioration of dispersibility is improved by adding the compound of general formula (I) to the oil-in-water type dispersed particles.

Table 4 As shown in Margin Table 4 below, under conditions where the glossiness of the comparative sample decreases, the sample of the present invention improves the decrease in glossiness.

Example 3 In the same manner as in Example 1, the components shown in Table 5 were dissolved in 200 ml of ethyl acetate to form oil-in-water dispersions 9 to 1.
2 was created. A drop of each of the dispersions was added to 1000 d of blue-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion (containing 60 mol% silver).
a) and a 2% methanol solution of N,N',N"-triacryloyl 6H-8.-triazine as a hardening agent, and the amount of coated silver was 0.4 g/ Samples 9 to 12 were prepared by coating the gelatin in an amount of 1.5 g/f and further providing a protective layer on top of this layer so that the amount of gelatin in the coating was 1 g/f.

These samples were treated in the same manner as in Example 1, and the gloss deterioration test was conducted in the same manner as in Example 1. The results are shown in Table ◯. Further, in the same manner as in Example 1, dispersion stability tests were conducted on dispersions 9 to 12, and the results are shown in Table 5.

From Table 5 below, it can be seen that the deterioration of dispersibility is improved by adding the compound of general formula [I] to the oil-in-water type dispersed particles.

Table 6 As shown in Table 9, under the conditions where the glossiness of the comparative sample decreases, the sample of the present invention improves the decrease in glossiness.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (voluntary) November 21, 1985 Patent application No. 221328/20 Name of invention Silver halide photographic light-sensitive material 3, person making amendment Related Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishi Rokueta Shin Kogyo Co., Ltd.
Co-educational Keio 4, agent 〒102

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one hydrophilic colloid layer on a support, at least one of the compounds represented by the following general formula [I] is added to the at least one hydrophilic colloid layer. 1. A silver halide photographic material characterized by containing a high boiling point solvent and a hydrophobic additive in the form of oil droplets. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R represents an alkylene group consisting of 1 to 20 carbon atoms.