JPH0561137A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material having sufficient film strength and reducible in drying time. CONSTITUTION:The photosensitive material is characterized by having at least one layer containing a polymer having a glass transition point lower than the temperature of drying after development processing and this polymer is represented by formula I in which R is H car a substituent; at least one of R1 and R2 is a substituent having at least one ether bond or both compound with each other to form a substituted heterocyclic group having a substituent with at least one ether bond: and A is a copolymerizable ethylenically unsaturated monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having improved rapid processability without impairing photographic characteristics.

[0002]

BACKGROUND OF THE INVENTION In general, a hydrophilic colloid film used for producing a photographic light-sensitive material is required not only to have no adverse effect on the photographic light-sensitive property but also to have a predetermined strength in terms of film physical properties. Therefore, conventionally, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer or a protective layer is coated on a support, a water-soluble polymer or polymer obtained by polymerizing various monomers in the hydrophilic colloid layer. Various attempts have been made to improve the physical properties of a hydrophilic colloid film formed by incorporating a latex, such as dimensional stability, scratch strength, flexibility, pressure resistance and drying property.

From this point of view, the use of acrylamide derivatives in JP-A-61-69061 and JP-A-61-151527, and the use of vinyl acetate polymer latex in US Pat. No. 2,376,005, The use of polymer latexes of alkyl acrylates in US Pat.
In 331 publication, the use of polymer latex such as n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile,
In Japanese Patent Publication No. 46-22506, alkyl acrylate,
Use of a polymer latex of acrylic acid or sulfoalkyl acrylate, and use of a polymer latex of 2-acrylamido-2-methylpropanesulfonic acid or the like have been proposed in JP-A-51-130217.

[0004]

[Problems to be Solved by the Invention] In recent years, the rapid processing of photographic light-sensitive materials has progressed, and the demands on the physical properties of the film have also increased. This rapid processing can be achieved mainly by shortening the development time and the drying time. Although it is possible to shorten the drying time by reducing the amount of binder in the film, it causes a bad influence on the film strength, and therefore there is a limit to the means for reducing the amount of binder. Further, when the water-soluble polymer or polymer latex proposed above was used as a binder, the drying time could not be shortened. That is, with the conventional binders, a photosensitive material having a sufficient film strength could be obtained, but the drying time after the developing treatment could not be shortened.

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which has a sufficient film strength and can be further shortened in drying time, and enables rapid processing.

[0006]

The above object of the present invention is to provide at least one layer containing a polymer represented by the following general formula (I) on a support, and temperature conditions for drying after development processing. Is at or above the thermal transition temperature of the polymer.

[0007]

[Chemical 2](In the formula, R represents a hydrogen atom or a substituent,₁and
R_TwoEach represents a hydrogen atom or a substituent, or R
₁And R ₂Combine with at least one ether bond
To form a heterocycle having a substituent having a substituent. However, R
₁And R₂At least one of the
A substituent having an ether bond or R₁And
And R₂Bind to form at least one ether bond
Forming a heterocycle having a substituent having. A is a copolymer
Represents possible ethylenically unsaturated monomers. ) The following
Ming will be described in more detail.

In the above general formula (I), R represents a hydrogen atom or a substituent, and the substituent is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.

R ₁ and R ₂ each represent a hydrogen atom or a substituent, or R ₁ and R ₂ are bonded to each other to form a heterocycle having a substituent having at least one ether bond. The substituent is preferably an alkyl group or a cyclic ether group, more preferably 1 carbon atom.
An alkyl group having 10 to 10, an alkyl group having an alkoxy group having 1 to 20 carbon atoms, an alkyl group having a cyclic ether group, or a cyclic ether group.

However, at least one of R ₁ and R ₂ is
A substituent having at least one ether bond, or R ₁ and R ₂ are bonded to each other to form a heterocycle having at least one substituent having an ether bond. The substituent having is preferably a cyclic ether group, an alkyl group having an alkoxy group having 1 to 20 carbon atoms, or a cyclic ether group.

The polymer represented by the general formula (I) used in the present invention includes monomers 1 to 10 represented by the following general formula.
0 mol% and copolymerizable ethylenically unsaturated monomer A
It is composed of 0 to 99 mol%.

[0012]

[Chemical 3] (In the formula, each of R, R ₁ and R ₂ has the same meaning as defined in the general formula (I).) The compound used in the present invention is obtained by copolymerizing two or more monomers represented by the above general formula with each other. It may also be composed of possible ethylenically unsaturated monomers A.

Specific examples of the monomer represented by the above general formula are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

In the general formula (I), the copolymerizable ethylenically unsaturated monomer represented by A is not particularly limited as long as it is copolymerizable with the above monomer, and may have a crosslinked structure. In the present invention, as the copolymerizable ethylenically unsaturated monomer, for example, acrylic acid ester, methacrylic acid ester, styrene derivative, vinyl acetate, acrylonitrile and the like are preferably used. Also, two or more kinds of copolymerizable ethylenically unsaturated monomers may be used.

The polymer represented by the general formula (I) has a thermal transition point, and changes from water-soluble to insoluble at that temperature as a boundary. Therefore, when the photosensitive material is developed and dried, by drying at a temperature equal to or higher than its thermal transition point,
The drying time can be shortened considerably. The thermal transition temperature of the polymer can be adjusted by the copolymerizable A. The polymer used in the present invention preferably has a heat transition temperature of 20 to 80 ° C, more preferably 30 to 60 ° C.

Since the polymer represented by the general formula (I) is generally water-soluble at room temperature, it can be added as an aqueous solution. Further, it may be crosslinked and contained in the form of particles. Further, it may be contained in the form of latex.

Specific examples of the polymer represented by formula (I) preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical formula 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

The measurement of the thermal transition temperature of the polymer is 1% by weight.
The temperature of the aqueous solution was measured using a spectrophotometer with an electronic cooling and temperature controller manufactured by Shimadzu Corporation, and the temperature was raised from the low temperature side at a rate of 1 ° C / min, and the transmittance at a wavelength of 500 nm was half the initial transmittance. Was defined as the heat transition temperature.

The polymer represented by the above-mentioned general formula (I) is, for example, a collection of polymer articles vol.47, No.6 (1990) p.467-p.4.
It can be synthesized with reference to the method described in 74.

In the present invention, the weight average molecular weight of the polymer is preferably 2,000 to 500,000, more preferably 3,000 to 100,000. The amount of the polymer added can be arbitrarily selected, but it is preferably 1 to 60% by weight, and particularly preferably 5 to 40% by weight of the total binder.

In the present invention, the above-mentioned polymer may be contained in any hydrophilic colloid layer in the photographic light-sensitive material, or may be contained in two or more layers, for example, a silver halide emulsion layer, an intermediate layer and a protective layer. , An antihalation layer, a back coat layer, an undercoat layer and the like.

In the present invention, gelatin is advantageously used as the hydrophilic colloid used together with the above-mentioned polymer, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, and cellulose derivatives. A hydrophilic colloid such as a synthetic hydrophilic polymer such as a single or copolymer can also be used.

As the gelatin, lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No.16, No. 16
The enzyme-treated gelatin as described on page 30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

Examples of the gelatin derivative include various types of gelatin such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. What is obtained by reacting a compound is used. Specific examples thereof include, for example, U.S. Pat.
4,928, 3,132,945, 3,186,846, 3,3
12,553, British Patent Nos. 861,414, 1,033,189, 1,005,784, and Japanese Patent Publication No. 42-26845.

As the protein, albumin, casein, etc., as the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc., and as the sugar derivative, sodium alginate,
Starch derivatives and the like are preferably used.

Examples of the graft polymer of the above-mentioned gelatin and other polymers include gelatin which is a homopolymer or homopolymer of acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene. What grafted the coalescence can be used. In particular, a polymer having a certain degree of compatibility with gelatin, for example, a graft polymer with a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. These examples are
U.S. Pat.Nos. 2,763,625, 2,831,767, 2,956,
No. 884, etc.

Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Copolymers and the like, for example, West German patent application (OLS) 2,312,70
No. 8, U.S. Pat. Nos. 3,620,751, 3,879,205, and JP-B-43-7561. The content of these polymers is preferably smaller than that of the polymer represented by the general formula (I).

Next, the silver halide grains used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention will be described. The grain size distribution of the silver halide grains may be monodisperse. Here, monodisperse refers to a dispersion system in which 95% of particles fall within ± 60% of the number average particle size, preferably within 40%. The number average grain size is the number average diameter of projected area diameters of silver halide grains. or,
It may be composed of an emulsion in which ultrathin tabular silver halide grains having a grain diameter of 5 times or more the grain thickness account for 50% or more of the total projected area. For details, see JP-A-58-127
No. 921, No. 58-113927, etc.

The silver halide grains contained in the light-sensitive silver halide emulsion layer in the present invention are preferably grains having a regular structure or morphology in which at least 80% by weight or the number of silver halide grains is regular. Here, a silver halide grain having a regular structure or morphology means a grain that does not include anisotropic growth such as twin planes and grows isotropically, and for example, a cube, a tetrahedron, a regular octahedron, a 12 Particles having a shape such as a face or a sphere may be used. The method for producing such regular silver halide grains is described in, for example, Journal of Photographic Science (J.Phot.Sci.). 5,332 (19
61), Berichte del Bunsenges Physik Hemi (Ber.Bunsenges.Phys.Chem.) 67,949 (1963), International, Congress of Photographic Science of Tokyo (Intern.Congres)
s Phot.Sci.Tokyo (1967)) and the like. In the production of monodisperse emulsions and / or emulsions having regular silver halide grains, Japanese Patent Publication No. 48-36890 and 52,
The methods described in JP-A-16364 and JP-A-55-142329 can be preferably used.

In the practice of the present invention, the silver halide grains used in the photosensitive silver halide emulsion layer are, for example,
The Theory of the Photographic P by TH James
rocess), 4th edition, published by Macmillan (1977), P.Glfki
Des, Chemie et Physique Photographique (Paul Montel, 1967), GFDuffin, Photographic Emulsion Chemistry, (Photographic Emulsion
Chemistry) (The Focal Press, 1966), VLZeli
Making and Coating Photographic Emulsion (Making and Coating Ph
otographic Emulsion), (The Focal Press, 1964
Year) and the like.

In order to control the growth of grains during the formation of silver halide grains, as a silver halide solvent, for example, ammonia, rodancali, rodanammon, and a thioether compound (eg, US Pat. Nos. 3,271,157 and 3,574,6) are used.
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
374), thione compounds (for example, JP-A-53-144319,
53-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used. Of these, ammonia is preferred. Two or more kinds of silver halide emulsions formed separately may be mixed and used. Further, in these silver halide grains or silver halide emulsions, at least among salts of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, platinum (soluble salts), It is preferable that one kind is contained. Its content is preferably 10 ⁻⁶ to 10 ⁻¹ mol per mol pAg. Particularly preferably, at least one of salts of thallium, palladium and iridium is contained. These may be used alone or as a mixture, and the addition position (time) is arbitrary. As a result, effects such as improvement of flash exposure characteristics, prevention of pressure desensitization, prevention of latent image extinction, and sensitization can be expected.

In the present invention, at least during the grain growth before chemical sensitization as described above, a mother liquor containing a protective colloid is added.
An embodiment in which pAg is 10.5 or more can be preferably adopted. It is particularly preferable to pass an atmosphere in which a very high bromine ion concentration of 11.5 or more is excessive even once. In this way, grains can be rounded by increasing the (111) plane. The ratio of the (111) plane of such particles to the total surface area is preferably 5% or more.

In this case, the rate of increase of the (111) plane (see 10.
It is preferable that the rate of increase (before the passage of a pAg atmosphere of 5 or more) is 10% or more, and more preferably
10 to 20%.

Regarding whether the outer surface of the silver halide grain is covered with the (111) plane or the (100) plane, or how the ratio is measured, a report by Akira Hirata, Bulletin of the Society was published.・ Scientific Photography of Japan N
o. 13, pages 5 to 15 (1963).

The above-mentioned pAg value is preferably set after the addition of about 2/3 of the total amount of silver to be added and before the desalting step. This is because it is easy to obtain a monodisperse emulsion having a narrow grain size distribution. The aging in an atmosphere having a pAg of 10.5 or more is preferably performed for 2 minutes or more.

In the present invention, the light-sensitive silver halide emulsion layer contains silver halide grains having a multi-layer structure consisting essentially of silver iodobromide, and any adjacent adjacent homogeneous silver halide grains are homogeneous. The difference in the average iodine content of the two layers having an iodine distribution (coating layer, or between the inner core and the coating layer) is 10 mol% or more, and the average silver iodide content of the outermost layer is
It is preferably 10 mol% or less and the silver halide grains are chemically sensitized.

Here, the particles having a multi-layered structure refer to particles in which a coating layer having an arbitrary halogen composition is provided on the outside of the inner core, and the coating layer may be a single layer or two or more layers, for example. It may be laminated with 3 layers or 4 layers, but preferably 5 layers or less. Silver bromide, silver iodobromide, and silver iodide are used as the silver halide of the inner core and the coating layer, but a mixture with a small amount of silver chloride may be used. Specifically, it may contain silver chloride in an amount of about 10 mol% or less, preferably about 5 mol% or less. The outermost layer is preferably substantially silver bromide or substantially silver iodobromide (iodine content is 10 mol% or less), and may contain less than several mol% of chlorine atoms. For example, in an X-ray light-sensitive material, silver iodide may cause problems such as development inhibition and infectious development. Therefore, in practice, the silver iodide content is preferably not more than a certain level. The silver iodide content is preferably 10 mol% or less, more preferably 7 mol% or less, and most preferably 0.1 to 3 mol% in the whole grain.

When the inner core is composed of silver iodobromide, it is preferably a homogeneous solid solution phase. More specifically, the homogeneity can be explained as follows. That is, when the X-ray diffraction analysis of the silver halide grain powder was conducted, the C
This means that the half width Δ2θ of the peak of the surface index [200] of silver iodobromide is 0.03 (deg) or less using u-Kβ X-ray. The use conditions of the diffractometer at this time are ωγ / r ≦ 10 when the scanning speed of the goniometer is ω (deg / min), the time constant is γ (sec), and the receiving slit width is r (mm). is there. The halogen composition of the inner core preferably has an average iodine content of 40 mol% or less,
More preferably, it is 0 to 20 mol%.

The difference in silver iodide content between two adjacent layers (any two coating layers or a coating layer and an inner core) is preferably 10 mol% or more, more preferably 20 mol% or more. , Particularly preferably 25 mol% or more.

The silver iodide content of the coating layers other than the outermost coating layer is preferably 10 to 100 mol%.

When the silver halide grains are composed of three or more layers and the coating layer is composed of silver iodobromide, it is not necessary that they are all homogeneous, but all layers are homogeneous silver iodobromide. Preferably. In the case of a negative type silver halide emulsion, it is preferable that such a coating layer (or internal nucleus) having a high silver iodide content is present below the outermost surface. In the case of a positive type silver halide emulsion layer, it may be inside or on the surface. The silver iodide content of the outermost coating layer is
It is preferably 10 mol% or less, more preferably 0
~ 5 mol%.

The silver iodide content of the inner core of the silver halide grains and the coating layer can be determined according to, for example, J. I. Goldstein
Stein), D.I. B. Williams “TEM /
X-ray analysis in ATEM "Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute), p. 651 (March 1977)
Can be determined by the method described in.

When the silver halide grains are composed of, for example, two layers, it is preferable that the inner core has a higher iodine than the outermost layer, and when it is composed of three layers, the coating layer other than the outermost layer or the inner core is preferably formed. It is preferable that the iodine content is higher than that of the outermost surface layer.

In the present invention, the silver halide grains contained in the photosensitive silver halide emulsion layer may be either positive type or negative type.

For chemical sensitization, for example, H. Frieser edited by Die Grundlagen der Photographischen Prozesse mit
Silberhalogeniden), Akademische Veragasellschaft 1968
The method described on pages 675 to 734 can be used. In the present invention, the spectral sensitizing dye can be added at any time from the time of silver halide grain formation to the chemical ripening or coating, but the final volume of the silver halide grains at the time of silver halide grain formation is 60%. It is desirable to add from 100% formation to the end of chemical ripening.

Examples of the spectral sensitizing dye preferably used in the present invention include "Chimie Photographigu" by P. Glafkides.
e) "(2nd edition, 1957: Paul Montol Paris (Pau
l Montel Paris)) Chapters 35-41 and Hamer (PM
Hamer) "The Cyanine and Related Compounds"
(Interscience), and US Pat. Nos. 2,503,776, 3,459,553, and 3,177,210.
Issue, Research Disclosur
e) Volume 176, 19643 (issued in December 1978) Paragraphs 23, IV, J. The sensitizing dyes may be used alone or in combination.

In the present invention, the sensitizing dye can be used in the same concentration as that used in a usual negative type silver halide emulsion. In particular, it is advantageous to use the dye at a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. About 1.0 × 10 ^{-5 to} 5.0 per mol of silver halide
It is preferably used in the range of ^{x10 -4} mol, and particularly preferably used in a concentration of about 4.0 x 10 ^{-5 to} 2.0 x 10 ^-4 mol per mol of silver halide.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,633).
No. 5,721), an aromatic organic acid formaldehyde condensate (for example, those described in US Pat. No. 3,743,510), a cadmium salt, an azaindene compound and the like.

The silver halide photographic light-sensitive material of the present invention comprises
In addition to the above-mentioned additives, matting agents, stabilizers, development accelerators, hardeners, surfactants, antifouling agents, lubricants, UV absorbers, formalin scavengers, color couplers, antistatic agents, and other photographic light-sensitive materials. Various useful additives can be used.

In the present invention, the photographic emulsion layer and other layers are
It is coated on one side or both sides of a flexible support usually used for photographic light-sensitive materials. As the support, paper laminated with α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer), flexible reflective support such as synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride Examples of the film include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, and polyamide, and flexible supports having these layers provided with a reflective layer, glass, metal, and ceramics. The support may be colored with a dye or a pigment. The surface of these supports is
Generally, an undercoating treatment is preferred in order to improve the adhesiveness to the photographic emulsion layer and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment. For more information, see Research Disclosure (Resear
chDisclosure), Vol. 176, page 25, "Supports".

The silver halide photographic light-sensitive material of the present invention comprises a black-and-white light-sensitive material for photography, a black-and-white light-sensitive material for X-rays, a black-and-white light-sensitive material for printing, a color reversal film, a color negative film, a color positive film and the like. It can be applied to color photosensitive materials and the like.

The development processing of the light-sensitive material of the present invention may be carried out, for example, by Research Disclos
ure) 176, pages 25-30 (RD-17, 643), various methods and processing solutions can be used. This development processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose.
The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Development processing temperature and time are interrelated and determined in relation to the total processing time. In the present invention, it is preferably 30 to 40 ° C, for example. In addition, depending on the case, various other developing methods (for example, thermal development) can be used.

For black-and-white photographic processing, the developing solution used may contain known developing agents. Examples of the developing agent include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), and aminophenols (such as N).
-Methyl-p-aminophenol) and the like can be used alone or in combination. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, etc., and further contains, if necessary, dissolution aids, color toning agents, development accelerators, surfactants, defoamers, hard water. A softening agent, a hardener, a viscosity imparting agent, etc. may be included.

As a special form of development processing, a method of incorporating a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution to perform development can be used. Hydrophobic developing agents can be prepared by various methods described in Research Disclosure No. 169 (RD-16928), US Pat. No. 2,739,890, British Patent No. 813,253, West German Patent No. 1,547,763, etc. Can be included inside. Such a development treatment may be combined with a silver salt stabilization treatment with a thiocyanate.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. As a color developing agent, various primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline,
3-methyl-4-amino-N, N-diethylaniline,
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β methanesulfoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like) are used. be able to.
In addition, L. F. A. Mason, Photographic Processing Chemistry
Chemistry), Focal Press, 1966, p226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-649.
You may use what is described in No. 33 grade.

The color developer may also be a development inhibitor such as a pH buffer such as an alkali metal sulfite, a carbonate, a borate and a phosphate, a bromide or an iodide and an organic antifoggant or an antifoggant. Agents and the like can be included. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler,
An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid type chelating agent, an antioxidant and the like may be contained.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), and copper (II), peracids, quinones, and nitroso compounds. For example, organic complex salts of ferricyanide compounds, dichromates, iron (III), cobalt (III), etc., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or A complex salt of an organic acid such as citric acid, tartaric acid, malic acid, persulfate, permanganate, nitrosophenol or the like can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) and irondiaminetetraacetate (I
II) Ammonium is particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixing liquid, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound having an effect as a fixing agent can be used. The fixer contains
A water-soluble aluminum salt may be included as a hardener.

In the present invention, the developed and fixed photographic light-sensitive material is washed with water and dried. Washing with water is performed to almost completely remove the silver salt dissolved by fixing, and for example, about 20 to
It is preferably carried out at 50 ° C.

After the development treatment, drying is carried out, but the drying temperature must be higher than the thermal transition temperature of the polymer used in the present invention. Drying is preferably performed at about 30 ° C. or higher, for example, 40 to 100 ° C., preferably about 40 ° C. or higher, and the drying time can be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 5 minutes. For example, dry air volume 6-14m ³ / mi
n, heater capacity of 2.0 to 4.0 kW (200 V) provides sufficient dryness.

[0072]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 [Preparation of Emulsion 1] 1) Preparation of seed emulsion 1 2 mol of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pH = 8, and pH = 2.0. Monodisperse cubic grains of silver iodobromide containing were prepared. The resulting reaction liquid was desalted at 40 ° C. using an aqueous solution of Kaolin Atlas's Demol Na and an aqueous solution of magnesium sulfate, and then redispersed by adding an aqueous solution of gelatin to obtain a seed emulsion.

2) Growth from Seed Emulsion 1 Using the above seed emulsion, grains were grown as follows. First, a seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method. During the addition, the pH was controlled to be 7.3 and pH = 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method.
Maintaining pAg = 9.0 up to 95% of target particle size, pH from 9.0
It was continuously changed to 8.0. Then, the pH was adjusted to 11.0 and the pH was maintained at 8.0, and the grains were grown to the target grain size. Subsequently, the pH was lowered to 6.0 with acetic acid to obtain 5,5'-dichloro-9.
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous was added at 400 mg / mol AgX, and desalted using Kao Atlas Co. demol Na aqueous solution and magnesium sulfate aqueous solution. , Gelatin aqueous solution was added and redispersed.

[0075]

[Preparation of Emulsion 2] 1) Preparation of seed emulsion 2 A 0.05 N potassium bromide aqueous solution containing hydrogen peroxide-treated gelatin, which was vigorously stirred at 40 ° C., was added an aqueous silver nitrate solution and hydrogen peroxide-treated gelatin. Add an equimolar amount of potassium bromide aqueous solution by the double jet method, lower the liquid temperature to 25 ° C over 30 minutes after 1.5 minutes, and then add
80 ml of ammonia water (28%) was added and stirring was continued for 5 minutes. After that, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then an aqueous gelatin solution was added and redispersed. The obtained seed emulsion had an average grain size of 0.23 μm and a coefficient of variation of 0.28.
It was a spherical particle.

2) Growth from Seed Emulsion 2 Using the above seed emulsion, grains were grown as follows. 75
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method to an aqueous solution containing ossein gelatin and propyleneoxy-polyethyleneoxydisuccinate-disodium salt vigorously stirred at ℃. During this period, the pH was kept at 5.8 and the pH was kept at 9.0. After the addition is complete,
Adjusted to 6.0, 5,5'-dichloro-9-ethyl-3,
Anhydrous of 3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt was added at 400 mg / mol AgX. After further desalting at 40 ° C. using an aqueous solution of Demol Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, gelatin aqueous solution was added and redispersed.

By this method, a tabular silver iodobromide emulsion (D) having an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0. Was prepared.

[Preparation of sample] Obtained emulsion (A),
(B), (C), (D) at 55 ℃, 5, 5 '
-Dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine anhydrous sodium and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 Anhydrous of'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt was added to 200:
(A) is 975 m per mol of silver halide in a weight ratio of 1.
g, (B) 600 mg, (C) 390 mg, and (D) 500 mg.

After 10 minutes, an appropriate amount of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-
6-Methyl-1,3,3a, 7-tetrazaindene was added at 3 × 10 ^-2 mol per mol of silver halide, and gelatin was added.
It was dispersed in an aqueous solution containing 70 g. Of the four ripened emulsions, (A), (B), and (C) were mixed at a weight ratio of 15:65:20 to prepare Emulsion-I, and (D) was used alone as Emulsion-II.
And

The following additives were added to each of Emulsion-I and Emulsion-II. The addition amount is indicated by the amount per mol of silver halide. 1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butylcatechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-dihydroxy Ammonium benzene-4-sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-Phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g

[0082]

[Chemical 15]

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

[Preparation Method of Dye Emulsion Dispersion] The following dyes
10 kg was dissolved in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate at 55 ° C. This is called an oil-based solution. On the other hand, anionic surfactant (A
270 liters of a 9.3% gelatin aqueous solution containing 1.35 kg of S) was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous solution were put into a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C. To the resulting dispersion, appropriate amounts of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane were added and the weight was adjusted to 240 kg with water.

[0085]

[Chemical 16]

The additives used in the protective layer liquid are as follows. The addition amount is shown as an amount per 1 liter of the coating liquid. Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate Matting agent with an area average particle size of 3.5 μm 1.1 g Silicon dioxide particles Matte with an area average particle size of 1.2 μm Agent 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₂ H ₂₅ CONH ( CH ₂ CH ₂ O) ₅ H 2.0 g

[0087]

[Chemical 17]

The emulsion layer has a silver conversion value of 1.7 g / side per side.
m ^2, the protective layer is such that 0.99 g / m ² as a weight with gelatin, at a speed per minute 90m by two slide hopper type coaters, glycidyl methacrylate 50 wt%, styrene 10 wt%, butyl methacrylate 40 weight %, A copolymer latex consisting of 3 kinds of monomers is diluted to a concentration of 10% by weight, and the obtained undercoat liquid is applied on a 175 μm polyethylene terephthalate film base.
An emulsion layer and a protective layer were simultaneously coated on both sides and dried in 2 minutes and 15 seconds to obtain sample 0.

Samples 1 to 4 and comparative sample A were prepared in the same manner as in sample 0 except that the polymer shown in Table 1 was replaced with 10% by weight of the gelatin in the emulsion layer and the gelatin in the protective layer. , B were obtained respectively. Comparative polymer A Comparative polymer B

[Sensitometry] The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corp.), and a tube voltage of 90 was applied.
The sensitivity was obtained by irradiating 0.05 second of X-ray with KVP and 20 mA and creating a sensitometric curve by the distance method. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0. The results are expressed as relative sensitivity when the sensitivity of Sample No. 0 is 100. The development is automatic developing machine SRX-50
1 (manufactured by Konica Co., Ltd.) using a developing solution and a fixing solution having the following composition, a developing temperature of 35 ° C., a fixing temperature of 33 ° C., and washing water of 3.5 liters per minute at a temperature of 18 ° C. Was processed for 45 seconds. [Processing process] Process processing temperature (℃) Processing time (sec) Replenishment amount Insertion-1.2 Development + crossover 35 14.6 33cc / 4-cut fixing + crossover 33 8.2 63cc / 4-cut water washing + crossover 18 7.2 3.51 / min Squeeze 40 5.7 Dry Table 1 8.1 Total-45.0 (Developer) Potassium sulfite 70 g Hydroxyethyl ethylenediamine triacetate trisodium 8 g 1,4-Dihydroxybenzene 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5- Mercaptotetrazole 0.01 g Sodium metabisulfite 5 g Acetic acid (90%) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4 g Potassium bromide 4 g 5-Nitro Benzimidazole (1 g, 1 liter) was made into an aqueous solution, and the solution was adjusted to pH 10.5 with sodium hydroxide. (Fixer) sodium thiosulfate-5-hydrate 4.5 g ethylenediaminetetraacetic acid disodium 0.5 g ammonium thiosulfate 150 g anhydrous sodium sulfite 8 g potassium acetate 16 g aluminum sulfate 10-18 hydrate 10 g sulfuric acid (50% by weight) 5 g Citric acid 1 g Boric acid 7 g Glacial acetic acid 5 g An aqueous solution of 1 liter was used to prepare glacial acetic acid as a pH 4.2 solution.

However, the dryness (change in weight) shown in Table 1,
The scratch strength and the devitrification property were evaluated by the following methods. [Dryness] Weight before development W ₁ of sample with width 35 mm and length 1000 mm
After drying, the weight W ₂ g was measured and the dryness was evaluated by 100 × (W ₂ / W ₁ ). [Scratch strength] After development, fixing and washing in the above-mentioned processing steps, a metal needle (φ; 0.
The film surface was scratched with 5 mils) and the minimum weight (scratch strength) with which scratches were made was examined. [Devitrification property] Visual evaluation was performed according to the following criteria. The devitrification property represents the gelatin compatibility of the polymer. A: No deterioration in transparency after development B: Very slightly milky white C: slightly milky white

[0092]

[Table 1]

Example 2 (Preparation of emulsion) The silver bromide content was 2 mol% as follows.
A silver chlorobromide emulsion of was prepared.

23.9 mg of pentabromorhodium potassium salt per 60 g of silver nitrate, an aqueous solution containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate were stirred in an aqueous gelatin solution at the same time for 25 minutes at 40 ° C. and averaged. Particle size 0.20
A μm silver chlorobromide emulsion was prepared.

6-Methyl-4- was added to this emulsion as a stabilizer.
Hydroxy-1,3,3a, 7-tetrazaindene 20
After adding 0 mg, it was washed with water and desalted.

To this, 20 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added, followed by sulfur sensitization. After sulfur sensitization, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7 was added as a stabilizer.
An emulsion was prepared by adding tetrazaindene and then making up to 260 ml with water.

(Preparation of Latex (L) for Emulsion Addition) Water
In 40 liters, 0.25 kg of KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo and ammonium persulfate
To a liquid added with 05 kg, while stirring at a liquid temperature of 81 ° C., under a nitrogen atmosphere, 4.51 kg of n-butyl acrylate and 5.49 kg of styrene.
A mixed solution of 0.1 kg of acrylic acid and acrylic acid was added over 1 hour, 0.005 kg of ammonium persulfate was added after that, the mixture was stirred for 1.5 hours, cooled, and adjusted to pH 6 with aqueous ammonia.

The latex solution thus obtained was used as GF manufactured by Whotman.
The mixture was filtered with a / D filter, and the weight was adjusted to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle size of 0.25 μ.

(Preparation of Silver Halide Emulsion Coating Solution) After adding 9 mg of the compound (A) to the above emulsion, the pH was adjusted to 6.5 with 0.5N sodium hydroxide solution, and then 360 mg of the compound (T). In addition, 5 ml of a 20% saponin aqueous solution, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, and 43 ml of the latex (L) for emulsion addition were added per mol of silver halide.
The compound (M) (60 mg) and a styrene-maleic acid copolymer water-soluble polymer (280 mg) as a thickener were sequentially added, and the mixture was adjusted to 475 ml with water to prepare a silver halide emulsion coating solution.

(Preparation of Coating Solution for Emulsion Protective Film) Water was added to gelatin to swell it and dissolve it at 40 ° C., then as a coating aid,
A 1% aqueous solution of compound (Z), compound (N) as a filter dye, and compound (D) were sequentially added, and the pH was adjusted to 6.0 with citric acid solution. A matting agent (amorphous silica having a particle size of 4.0 μm) was added to prepare a coating solution for emulsion protective film.

[0101]

[Chemical 18]

[0102]

[Chemical 19]

(Preparation of coating solution B-1 for backing layer) 36 g of gelatin was swollen in water, heated and dissolved, and then 1.6 g of compound (C-1), 310 mg of (C-2) as a dye, (C -3)
An aqueous solution of 1.9 g and compound (N) 2.9 g was added, and then saponin
11 ml of 20% aqueous solution, compound (C-4) as a physical property modifier
Was added, and a solution of 63 mg of the compound (C-5) in methanol was added. To this solution, 800 g of a water-soluble thickener styrene-maleic acid copolymer was added to adjust the viscosity, and the pH was adjusted to 5.4 using an aqueous citric acid solution. The reaction product of polyglycerol and epichlorohydrin: 1.5 g In addition, 144 mg of glyoxal was further added, and water was added to make 960 ml to prepare coating solution B-1 for backing layer.

[0104]

[Chemical 20]

[0105]

[Chemical 21]

(Preparation of protective film coating solution B-2 for coating protective film layer of backing layer) 50 g of gelatin was swelled in water and dissolved by heating, and then 2-sulfonate-bissuccinate (2
-Ethylhexyl) ester sodium salt 340 mg, sodium chloride 3.4 g, and glyoxal
1.1 g and 540 mg of mucochloric acid were added. Spherical polymethylmethacrylate having an average particle diameter of 4 μm was added as a matting agent to 40 mg / m ^2, and water was added to make 1 liter to prepare a protective film coating solution B-2.

Preparation of Comparative Sample G ₀ A polyethylene terephthalate film having a thickness of 100 μm after being biaxially stretched and heat-set was subjected to a corona discharge treatment of 8 W / (m ² · min) on both sides, and one surface was coated with the undercoating coating solution described below. B-3 as a subbing layer B-3 having a dry film thickness of 0.8 μm, and a subbing coating solution B-4 shown below on the side opposite to the subbing layer B-3 with a polyethylene terephthalate film sandwiched therebetween to give a dry film thickness. The undercoat layer B-4 was coated so as to have a thickness of 0.8 μm. Coating liquid B-3 Copolymer latex liquid (30% solid content) of butyl acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxyethyl acrylate 25% by weight 270 g Compound (C- 6) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water to 1 liter Coating solution B-4 Copolymer latex of 40 wt% butyl acrylate, 20 wt% styrene and 40 wt% glycidyl acrylate Liquid (solid content 30%) 270 g Compound (C-6) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Make up to 1 liter with water

Further, the undercoat layer B-3 and the undercoat layer B-4
8W / (m ² · min) corona discharge on top of the undercoat layer B
-3 on the undercoat layer B-5 as a subbing layer B-5, and the following coating solution B-6 on the undercoat layer B-4 as a dry film thickness of 0.1 μm. It was applied as an undercoat layer B-6 having an antistatic function so as to have a thickness of 0.8 μm. Coating solution B-5 Gelatin 10 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g Compound (C-8) 0.1 g Silica particles with an average particle size of 3 μm 0.1 g Water to make 1 liter Coating solution B -6 Water-soluble conductive polymer (C-9) 60 g Latex liquid containing compound (C-10) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (C-11) 12 g Polyethylene glycol (weight Average molecular weight 600) 6 g Make up to 1 liter with water

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

[0111] subjected to corona discharge of 25W / (m ² · min) on the subbing layer B-5, also, 8W / on the subbing layer B-6 (m ²
・ Min) corona discharge. Further, a backing layer (amount of coated gelatin 2.
0 g / m ² ) and B-2 to form a backing protective layer (coating gelatin amount 1.5 g / m ² ), and an emulsion layer using the above silver halide emulsion coating solution on subbing layer B-5. (Coated gelatin amount 2.0 g / m ² ) and an emulsion protective layer (coated gelatin amount 1.0 g / m ² ) were simultaneously coated in four layers using the coating solution for emulsion layer protective film and dried.

A comparative sample G ₀ was prepared as described above. The silver loading of comparative sample G ₀ is 3.5 g / m ² .

The amount of gelatin in the emulsion layer of Comparative Sample G ₀ was 10%.
5% by weight of gelatin in the emulsion layer protective film was replaced by the same polymer as the emulsion layer, in addition to the inventive polymer and comparative polymer used in Example 1 by weight%.
Furthermore, the backing layer also replaces the 10% by weight of the amount of gelatin in the same polymer as the emulsion layer, and except for replacing similarly 10% of gelatin in the protective layer in the same manner as in Comparative Sample G ₀ Sample G ₁ and ~ G ₄ was obtained respectively.

The prepared samples G _{0 to} G ₄ were subjected to wedge exposure and subjected to the following processing. (Processing conditions) Process Temperature (℃) Time (sec) Development 34 15 Fixing 34 15 Washing at room temperature 10 Drying 40 9 [Developer formulation] (Composition A) Water 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite ( 55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to make the pH of the used solution 10.9 Potassium bromide 4.5 g (Composition B ) Water 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% W / W aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg When the developer is used, the above composition A is used in 500 ml of water. , Composition B
Were dissolved in this order, and water was added to make 1 liter. [Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / V W aqueous solution) 8.1 ml (Composition B) Water 17 ml Sulfuric acid (50% W / W aqueous solution) 5.8 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / W aqueous solution) 26.5 g Water 500 ml when using fixer The above composition A and composition B were melted in this order, and water was added to make 1 liter. The pH of this fixer was about 4.3.

The above% W / W is (% weight) / (weight)
And% W / V represents (% weight) / (volume).

After the development processing, the dryness was compared.
Further, this was further fully dried for half a day under the humidity control conditions of 20 ° C. and 55% relative humidity, and then the scratching strength and devitrification property were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Regarding the degree of dryness, the following three grades were evaluated by actually touching the stickiness of the surface of each sample immediately after the drying treatment with a finger. ○ Well dried and not sticky △ Slightly sticky × Still sticky because it still feels damp

[0118]

[Table 2]

Example 3 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, each layer having the following constitution was formed into a polyethylene layer containing titanium oxide. A multi-layer silver halide color photographic light-sensitive material was prepared by coating on the side. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.6
To 7 g, additive (HQ-1) 0.67 g, anti-irradiation dye (AI-3), high boiling organic solvent (DNP) 6.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was dissolved in 20% surfactant (SU). -1) 10% gelatin aqueous solution containing 7 ml 22
Emulsified and dispersed in 0 ml using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, the second and fourth layers (H
-1) and (H-2) were added to the 7th layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

[Chemical formula 24]

[0126]

[Chemical 25]

[0127]

[Chemical formula 26]

[0128]

[Chemical 27]

[0129]

[Chemical 28]

[0130]

[Chemical 29]

(Method for preparing blue-sensitive silver halide emulsion) 40
In 1000 ml of 2% gelatin aqueous solution kept at ℃, the following (A
3) while controlling the liquid) and (B liquid) to pH = 6.5 and pH = 3.0.
Simultaneously added over 0 minutes, and further (C liquid) and (D
(Solution) was simultaneously added over 180 minutes while controlling pH = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For the control of pAg, a control solution having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution consisting of sodium chloride and potassium bromide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control solution is to mix solution A and solution B. In this case, 0.1 mol /
When mixing liter, C liquid, and D liquid, it was set to 1 mol / liter. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 ml. (Solution B) 10 g of silver nitrate was added to make 200 ml. (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 ml. (Solution D) 300 g of silver nitrate was added to make 600 ml.

[0132]

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B). Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS- 2 1 x 10 ^-4 mol / mol AgX

(Method for preparing green-sensitive silver halide emulsion)

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G). Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Method for preparing red-sensitive silver halide emulsion)

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained. Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0138]

[Equation 1] ri represents a particle size, and ni represents the number of particles having a particle size of ri.

[0139]

[Chemical 30]

[0140]

[Chemical 31]

[0141] The color light-sensitive material was prepared in the manner of a K _0, the sample was replaced with each polymer showing a 10% by weight of the amount of gelatin in each layer in the light-sensitive material shown in Table 5 K ₁ ~
It was set to K ₄ .

The produced samples were exposed to white light with a wedge and color-developed according to the following processing steps, and the dryness of each sample was compared.

The dryness of each sample was evaluated by rubbing the surface of each sample with a finger after the drying step and the degree of stickiness thereof was evaluated according to the following criteria. ○ Well-dried and not sticky △ Slightly sticky × Still sticky and sticky The above results are shown in Table 5.

[0144]

[Table 5]

The processing conditions are as follows. Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 70 ℃ 30 seconds Color developer Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5 g potassium bromide 0.02 g potassium chloride 2 g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 1 liter and adjust the pH to 10.10. Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1 liter and add potassium carbonate or Adjust to pH = 5.7 with glacial acetic acid. Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g O -Sodium phenylphenol 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1 liter and sulfuric acid. Alternatively, adjust to pH = 7.0 with potassium hydroxide.

The effects of the present invention were also obtained when the above-mentioned treatment liquids were used for the above samples K ₁ and K ₂ and the treatment steps were carried out as follows. Processing time Temperature Color development 10 seconds 35.0 ± 0.3 ℃ Bleach fixing 10 seconds 35.0 ± 0.5 ℃ Stabilization 10 seconds 30 to 34 ℃ Dry 30 seconds 70 ℃

Example 4 Polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side of the first layer, and each layer having the following constitution was coated on the support. A multilayer silver halide color photographic light-sensitive material was prepared. The coating liquid was prepared as follows.

First layer coating solution To 26.5 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 0.46 g of additive (HQ-1) and 10 g of high boiling organic solvent (DNP). 60 ml of ethyl acetate was added and dissolved, and this solution was emulsified and dispersed in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

[0151]

[Table 6]

[0152]

[Table 7]

Each photosensitive emulsion was prepared as follows. [Blue-sensitive silver chlorobromide emulsion] A silver chlorobromide emulsion having an average grain size of 0.7 μm and a silver bromide content of 90 mol% was optimally sensitized at 57 ° C. with sodium thiosulfate to give a sensitizing dye ( S-1) and Z-1 as a stabilizer were added. [Green-sensitive silver chlorobromide emulsion] A silver chlorobromide emulsion having an average grain size of 0.5 μm and a silver bromide content of 70 mol% was optimally sensitized at 59 ° C. with sodium thiosulfate to give a sensitizing dye ( S-2) and Z-1 as stabilizer were added. [Red-sensitive silver chlorobromide emulsion] Sodium thiosulfate, a sensitizing dye (S-3) and a phenol resin are used in a silver chlorobromide emulsion having an average grain size of 0.40 μm and a silver bromide content of 60 mol%. Optimally sensitized at C, Z-1 was added as a stabilizer.

[0154]

[Chemical 32]

[0155]

[Chemical 33]

[0156]

[Chemical 34]

[0157]

[Chemical 35]

[0158]

[Chemical 36]

[0159]

[Chemical 37]

[0160]

[Chemical 38]

[0161]

[Chemical Formula 39]

In the color paper obtained above,
As in Example 3, the present invention was prepared by replacing 10% by weight of gelatin for each layer with the polymer P-1 or P-12 of the present invention, and treating each sample according to the following processing steps after wedge exposure. The effect of was similarly confirmed.

The processing steps are shown below. Processing process Time Temperature Color development 3 minutes 30 seconds 33 ° C Bleach-fix 1 minute 30 seconds 33 ° C Water wash 2 minutes 33 ° C Color developer N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate 4.9 g Hydroxylamine sulfate 2.0 g Potassium carbonate 25.0 g Potassium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Benzyl alcohol 13 ml Diethylenetriamine pentaacetic acid 3.0 g Triethanolamine 10.0 g Diethylene glycol 10.0 g Add water to make 1 liter, PH 10 with sodium hydroxide.
Adjusted to 0. Bleach-fixing solution Ethylenediaminetetraacetic acid iron (III) ammonium salt 65 g Ammonium thiosulfate 100 g Sodium sulfite 10 g Sodium metabisulfite 3 g Water is added to make 1 liter, and the pH is adjusted to 7.0 with aqueous ammonia and acetic acid.

Example 5 In all the following Examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

One side (front surface) of the triacetylcellulose film support was subjected to an undercoating treatment, and then the support was sandwiched between the support and the surface opposite to the undercoating treatment surface (backside). Layers were created sequentially from the support side. Backside first layer Aluminasol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.1 g Diacetylcellulose 0.2 g Backside second layer diacetylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg On the surface of a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material-101. Sample 101 First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent ( OIL-2) 0.17 Gelatin 1.27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, Silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Dye-sensitizing agent (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (OIL) -1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8 .0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ^-4 Sensitizing dye (SD-2) 1.2 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler ( CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (OIL-1) 0.30 Gelatin 0.93 Fifth layer: high sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content rate) 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2 ) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (OIL-1) 0.14 Gelatin 0.91 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.20 Sensitizing dye (SD-4) 7.4 × 10 ^-5 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta Coupler (CM-1) 0.12 High boiling point solvent (OIL-2) 0.75 Gelatin 1.95 Eighth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion (average grain size 0.59 µm, silver iodide content 8.0 mol%) 0.87 increase Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-2) 0.50 Zera Chin 1.00 9th layer: High-sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-6) 1.4 × 10 ⁻⁴ Sensitizing dye ( SD-7) 1.4 × 10 ^-4 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (OIL-1) 0.27 High boiling point solvent (OIL-2) ) 0.012 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size) 0.27 μm, silver iodide content 2.0 mol%) 0.03 Sensitive dye (SD-8) 4.9 × 10 -4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling solvent (OIL-2) 0.30 Gelatin 1.20 13th layer: middle sensitivity blue-sensitive layer Silver iodobromide Silver halide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6 × 10 ⁻⁴ Sensitizing dye (SD-9) 7.2 × 10 ⁻⁵ Yellow coupler (Y -1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (OIL-2) 0.046 Gelatin 0.47 14th layer: high sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (OIL-2) 0.046 Gelatin 0.80 15 layers: First protective layer Silver iodobromide emulsion (average grain size 0.80 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV rays Suction agent (UV-2) 0.10 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (average) Grain size 2μm) 0.15 Polymethylmethacrylate (average grain size 3μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 Each silver halide emulsion in each photosensitive layer has a core / shell with a distribution of 20% or less. It was a monodisperse type emulsion. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate at 50 ° C. or higher to obtain a sensitizing dye, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 1-phenyl-5-
Mercaptotetrazole was added.

[0166]

[Chemical 40]

[0167]

[Chemical 41]

[0168]

[Chemical 42]

[0169]

[Chemical 43]

[0170]

[Chemical 44]

[0171]

[Chemical 45]

[0172]

[Chemical 46]

[0173]

[Chemical 47]

[0174]

[Chemical 48]

[0175]

[Chemical 49]

The above-mentioned photosensitive material 101 further comprises compounds Su-1, Su-2, a viscosity modifier, and a film hardener H-1, H.
-2, stabilizer ST-1, antifoggant AF-1, AF-
2 (weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ) is contained.

[0177]

[Chemical 50]

Sample 102 was prepared by substituting 10% by weight of gelatin for each layer in the light-sensitive material 101 described above with the polymers of the present invention and comparative polymers shown in Table 8.
Obtained as ~ 105 respectively.

Light-sensitive material-101 produced as described above
Each of ~ 105 was exposed to white light through a step wedge for sensitometry and processed under the following conditions. Treatment process Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780ml Bleach 45 seconds 38 ± 2.0 ℃ 150ml Fixed 1 minute 30 seconds 38 ± 2.0 ℃ 830ml Stability 60 seconds 38 ± 5.0 ℃ 830 ml Dry 1 min 55 ± 5.0 ℃-* Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used. Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl- N- (β-hydroxylethyl) aniline sulphate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid. Color development replenisher solution 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid. Bleached water 700 ml 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter and add ammonia water or glacial acetic acid. Use to adjust to pH 4.4. Bleach replenisher Water 700 ml 1,3 Diaminopropane iron (III) tetraacetate ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g pH adjusted to 4.0 with aqueous ammonia or glacial acetic acid Add after water to make 1 liter. Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter. Fixing replenisher liquid 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 with aqueous ammonia or glacial acetic acid, add water to make 1 liter. Stabilizer and stable replenisher water 900ml

[0181]

[Chemical 51] Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to 1 liter, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The dryness of the above samples was compared in the same manner as in Example 3. The results are shown in Table 8.

[0183]

[Table 8]

Example 6 Photosensitive Materials-101 to 105 prepared in Example 5 were the same as Photosensitive Materials-101 to 105 except that the backside first layer and the backside second layer were changed to the following compositions. The effect of the present invention was also obtained in the prepared light-sensitive material. Back side first layer

[0185]

[Chemical 52] Backside second layer Diacetylcellulose 107.6mg Aerosil 200 (particle size: about 0.2μm silica fine particles) 10.8mg (Nippon Aerosil Co., Ltd.) Citric acid half ethyl ester 6.4mg

[0186]

As described in detail above, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has a sufficient film strength and which further shortens the drying time and enables rapid processing.

Claims (1)

[Claims] 1. A support having at least the following general formula (I):
At least one layer containing a polymer represented by
And the temperature conditions for drying after development are
-Halogenation characterized by being above the thermal transition temperature
Silver photographic light-sensitive material. [Chemical 1](In the formula, R represents a hydrogen atom or a substituent,₁and
R₂Each represents a hydrogen atom or a substituent, or R₁
And R ₂Combine with at least one ether bond
To form a heterocycle having a substituent having a substituent. However, R
₁And R₂At least one of the
A substituent having an ether bond or R₁And
And R₂Bind to form at least one ether bond
Forming a heterocycle having a substituent having. A is a copolymer
Represents possible ethylenically unsaturated monomers. )