JPH1097017A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material giving a very high contrast and high sensitivity image without deteriorating the physical properties of the film, excellent in rapid processability and giving a high sensitivity and high contrast silver image even when the amts. of a developing soln. and a fixing soln. replenished are reduced. SOLUTION: This silver halide photographic sensitive material has at least one silver halide emulsion layer on the substrate and contains at least one kind of hydrazine deriv. and polymer latex having a core-shell structure in the emulsion layer and/or other hydrophilic colloidal layer. The emulsion layer contains silver halide particles having >=70mol% silver chloride content and each of the particles has a surface layer having a lower silver chloride content than the interior and/or a local phase having a lower silver chloride content in the surface than in the interior.

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, and more particularly to a super-hard silver halide photographic light-sensitive material used in a photomechanical process.

[0002]

BACKGROUND OF THE INVENTION The addition of hydrazine compounds to silver halide photographic emulsions and developers is disclosed in U.S. Pat.
No. 727 (a developing solution combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (silver halide) It contains β-mono-phenylhydrazine of an aliphatic carboxylic acid as a stabilizer for the light-sensitive material), No. 2,419,975, and Mees.
Author, The Theory of Photographic Process, 3rd Edition (1
966), page 281 and the like. Among these,
In particular, U.S. Pat. No. 2,419,975 discloses obtaining a hard negative image by adding a hydrazine compound. The patent discloses that when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH such as 12.8, extremely hard photographic characteristics with a gamma (γ) exceeding 10 can be obtained. Is described. However, a strong alkaline developer having a pH close to 13 is liable to be oxidized by air and is unstable, and cannot withstand long-term storage or use. A silver halide photosensitive material containing a hydrazine compound,
There have been attempts to develop a high-contrast image by developing with a developer having a lower pH.

[0003] JP-A-1-179939 and JP-A-Hei-1
No. 179940, a process of developing with a developer having a pH of 11.0 or less using a sensitizing material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group. A method is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if the amount exceeds a certain limit, photosensitivity may be impaired, development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient high contrast cannot be exhibited. JP-A-60-140340
Discloses that addition of an amine to a silver halide photographic light-sensitive material increases the contrast. However, when developing with a developer having a pH of less than 11.0, sufficient high contrast cannot be exhibited. JP-A-56-1
JP 06244 discloses that an amino compound is added to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to the developing solution, the odor of the solution and stains due to adhesion to the equipment used,
Alternatively, there is a problem such as environmental pollution due to waste liquid, and it is desired to incorporate it into a photosensitive material, but sufficient performance has not been obtained by adding it to the photosensitive material.

In the hydrophilic colloid layer constituting the silver halide photographic light-sensitive material, generally, gelatin is often used as a bander. Such a hydrophilic colloid layer has drawbacks such as easy expansion and contraction in response to changes in humidity and temperature, and brittleness in a low humidity atmosphere. For the purpose of improving these drawbacks, a polymer latex is contained in a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, a protective layer, and a back layer.

For example, US Pat. No. 2,763,625,
2,852,382, JP-A-62-115,152.
JP-A-5-66,512 and JP-A-5-80,449
No., JP-B-60-15935, JP-B4-64058
No. 5,450,014 and the like disclose that a hydrophilic colloid layer contains a polymer latex composed of various monomers including alkyl acrylate and alkyl methacrylate. Also, Japanese Patent Publication No. 45-581
No. 9, No. 46-22507, JP-A-50-73625
Discloses that a polymer latex obtained by copolymerizing a monomer having an active methylene group with a monomer such as an alkyl acrylate is contained in a gelatin film to improve the strength of the latex-containing gelatin film when wet. .

However, when a high-contrast image is obtained by using a hydrazine derivative, there is a problem that by including these latexes, the gradation becomes soft and the film strength in a wet state cannot be sufficiently obtained. The improvement was desired.

On the other hand, in a silver halide photographic material requiring a rapid developing step, a silver chlorobromide emulsion having good developability is used as a silver halide emulsion constituting the light-sensitive material. It is known that a photosensitive material having good developability can be obtained by using a silver chlorobromide emulsion having a high silver chloride content.However, such a silver chlorobromide emulsion having a high silver chloride content is In particular, there was a disadvantage that the sensitivity was low in high-illuminance short-time exposure.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain an image with extremely high contrast and high sensitivity without deteriorating the physical properties of the film, to have excellent rapid processability, and to reduce the replenishment amount of the developing solution and the fixing solution. An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a high-sensitivity, high-contrast silver image even when lowered.

[0009]

An object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains silver chloride. Silver halide grains having a silver chloride content of at least 70 mol%, and a surface layer having a lower silver chloride content than the inside and / or a silver halide grain having a localized phase having a lower silver chloride content than the inside at the surface. A silver halide photographic material characterized in that said emulsion layer and / or other hydrophilic colloid layer contains at least one hydrazine derivative and a polymer latex having a core / shell structure.

The silver halide grains of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention are obtained by laminating one or more surface layers having a different halogen composition from the silver halide constituting the inside of the grain. And / or silver halide grains having a localized phase different from the inside on the surface. The silver halide of the grains is silver chlorobromide,
Any of silver chloroiodobromide may be used, but the average silver chloride content of the whole grains is 70 mol% or more, preferably 80 mol%.
That is all. The silver halide inside the grains has a constant halogen composition, preferably silver chlorobromide, silver chloroiodobromide or silver chloride having a silver chloride content of 85 mol% or more. The silver halide in the localized layer on the surface layer or surface of the grains is silver chlorobromide, silver chloroiodobromide, or silver bromide having a silver chloride content smaller than the internal halogen composition. The silver chloride content of silver chlorobromide or silver chloroiodobromide in the surface layer or localized phase may be constant or may continuously change toward the grain surface. The difference in silver chloride content between the inner and surface layers or the localized phase on the inner and surface layers is preferably at least 5 mol%, more preferably at least 10 mol%. The volume of the surface layer preferably accounts for 5 to 50%, more preferably 5 to 30% of the silver halide grains, and the volume of the localized phase on the surface is preferably 10 mol% or less. The silver halide grains of the present invention also include silver halide grains having a localized phase having a lower silver chloride content than the surface layer on the surface of a surface layer having a lower silver chloride content than the inside. The shape of silver halide grains is cubic,
Any of a tetrahedron, an octahedron, an irregular shape, and a plate shape may be used, but a cube is preferable. Average grain size of silver halide is 0.5 μm
The following is preferred, more preferably 0.1 to 0.4 μm, {(standard deviation of particle size) / (average particle size)} × 100
Is preferably 15% or less, more preferably 10% or less.
% Or less having a narrow particle size distribution. The photographic emulsion used in the present invention is Chimie et Physiq by P. Glafkides.
ue Photographique (Paul Montel, 1967), G.
Photographic Emulsion Chemistry (The F
orcal Press, 1966), Ma by VL Zelikman et al
king and Coating Photographic Emulsion (The Forcal
Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, described in JP-A-53-82408,
No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent varies depending on the type of the compound used, the target grain size, and the halogen composition.
It is preferably from 0 ^-5 to 10 ^-2 mol.

In the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
-36890 and 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445,
It is preferable to use the method of changing the concentration of the aqueous solution as described in 5-158124 to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Is preferred. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in silver halide grains, and are disclosed in JP-A-63-29603 and JP-A-2-3062.
As described in JP-A Nos. 36, 3-167545, 4-76534, 6-110146, and Japanese Patent Application No. 4-68305, they can be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III)
Complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, trizalatrodium (III) complex salts and the like can be mentioned. These rhodium compounds are used by dissolving them in water or a suitable solvent, and are generally used to stabilize the solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrochloric acid,
A method of adding bromic acid, hydrofluoric acid or the like, or an alkali halide (eg, KCl 3, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, and particularly preferably in the range of 5 × 10 ^-8 mol to 1 × 1 mol per mol of silver halide.
0 ^-6 mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1-285941.
And 2-20852, 2-20855, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] -n where M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counter ion is not important and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (CN) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (H ₂ O)] ^-2 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)) ^-2 [Ru (CN) ₆ ] ^-4 [Ru (CO) ₃ Cl ₃ ] ^-2 [Ru (CO) Cl ₅ ] ^-2 [Ru (CO) Br ₅ ] ^-2 [OsCl ₆ ] ^-3 [OsCl ₅ (NO)] ^-2 [Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN ) ₄ ) ^-4

The addition amount of these compounds is 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. The addition of these compounds was
At the time of manufacture of the emulsion and at each stage before coating the emulsion.
Can be carried out.
It is preferably incorporated into silver halide grains. these
The compound is added during silver halide grain formation to
For incorporation into silver halide particles, powder of metal complex or Na
The aqueous solution dissolved together with Cl and KCl is
Method to be added to a neutral salt or a water-soluble halide solution,
Or when silver salt and halide solution are mixed at the same time,
3 as a solution of 3
How to prepare silver halide grains or the amount required during grain formation
Of an aqueous solution of the metal complex of
You. In particular, powder or aqueous solution dissolved with NaCl and KCl
A preferred method is to add the solution to a water-soluble halide solution.
To add to the particle surface, immediately after particle formation or physical ripening
The required amount of metal during or at the end or during chemical ripening
An aqueous solution of the complex can also be charged to the reaction vessel.

Various compounds can be used as the iridium compound used in the present invention, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, and hexacyanoiridium.
These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl, NaC
l, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another iridium-doped silver halide grain during silver halide preparation.

The silver halide grains in the present invention may be doped with another heavy metal salt. In particular, doping of an Fe salt such as K ₄ [Fe (CN) ₆ ] is advantageously performed. Further, the silver halide grains used in the present invention may contain metal atoms such as cobalt, nickel, palladium, platinum, gold, thallium, copper, lead, and chromium. The amount of the metal is preferably 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of silver halide. Further, in order to incorporate the metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added at the time of preparing particles.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ° C or more.
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, for example, in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds,
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature and the size of silver halide grains during chemical ripening.
Changes under various conditions such as
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Unstable selenium compounds include JP-B-44-15748, JP-B-43-13489, and Japanese Patent Application No. 2-13097.
And compounds described in JP-A Nos. 2-229300 and 3-217798 can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in silver halide emulsion
It can be tested by the method described in No. 6739. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069,
3,772,031, UK Patent Nos. 235,211 and 1,121,496
No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, Japanese Patent Application No. 2-333819, No. 3-53693, No. 3-
131598, 4-129787, Journal of Chemical Society Chemical Communications (J.
Chem.Soc.Chem.Commun.) 635 (1980), ibid 1102 (1979),
ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc.P.
erkin.Trans.) 1,2191 (1980), edited by S. Patai,
The Chemistry of Organic Selenium
And Tellurium Campounds (The Chemistry of
Organic Serenium and Tellunium Compounds), Vol 1 (1
986) and Vol. 2 (1987). In particular, general formulas (II) and (III) in Japanese Patent Application No. 4-146739.
, (IV) are preferred.

[0025] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added by the method described in European Patent Publication No. EP293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (e.g., those having different average grain sizes, different halogen compositions, different crystal habits, different chemical habits, Those with different conditions) may be used in combination.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention are described in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (December 1978, p. 23) and Item 1831X (August 1979, p. 437) or cited in the literature. Have been. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected.
For example, A) for an argon laser light source, (I) -1 to (I)-described in JP-A-60-162247.
No. 8, compound I-1 to I-28 described in JP-A-2-48653, compound I-1 to I-13 described in JP-A-4-330434, U.S. Pat.
No.331 to Example1 to Example
Compound No. 14; compounds Nos. 1 to 7 described in West German Patent 936,071; B) For helium-neon laser light source, I-1 to I described in JP-A-54-18726.
-38 compound, I- described in JP-A-6-75322.
Compounds from 1 to I-35 and JP-A-7-287338
Compounds I-1 to I-34 described in JP-A-55-39818 (C).
To 20, described in JP-A-62-284343.
To I-37 and the compounds of I-1 to I-34 described in JP-A-7-287338; and D) For the semiconductor laser light source, the compounds of I-1 to I-37 described in JP-A-59-191332. -12 compound, JP-A-60-8084
Compounds of I-1 to I-22 described in No. 1;
Compounds I-1 to I-29 described in JP-A-335342 and I-1 to I-29 described in JP-A-59-192242.
-18 compound, E) for tungsten and xenon light sources of a plate making camera, compounds (1) to (19) represented by general formula [I] described in JP-A-55-45015; No. 7-346193, I-1 to I-9
Compound 7 and 4 described in JP-A-6-242547.
A compound of -A to 4-S, a compound of 5-A to 5-Q,
Compounds such as 6-A to 6-T are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

Two or more sensitizing dyes may be used in combination in the present invention. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The hydrazine derivative used in the present invention is
Compounds represented by the following general formula (N) are preferred. General formula (N)

[0032]

Embedded image

In the formula, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, A hydrazino group, G ₁ is —C
O- group, -SO ₂ - group, -SO- group,

[0034]

Embedded image

A represents a --CO--CO-- group, a thiocarbonyl group or an iminomethylene group; A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Or an unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (N), the aliphatic group represented by R ₁ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. . In the general formula (N), R
_The aromatic group represented by ₁ is a monocyclic or bicyclic aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group represented by R ₁ is a monocyclic or bicyclic aromatic or non-aromatic heterocyclic ring, which may be condensed with an aryl group to form a heteroaryl group. Examples include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. R ₁
Are preferably aryl groups. R ₁ may be substituted. Representative examples of the substituent include an alkyl group (including an active methine group), an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring and a quaternized nitrogen atom. A group containing a heterocyclic ring (eg, a pyridinio group),
A hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit),
Aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group,
Amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, group containing thiosemicarbazide group, hydrazino group, group containing quaternary ammonium group, mercapto group, (alkyl , Aryl, or heterocycle) thio group,
(Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano A nitro group, a phosphoric acid amide group, a group having a phosphate ester structure, a group having an acylurea structure, a group having a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure.
Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 20 carbon atoms), and alkoxy groups (preferably having 1 to 20 carbon atoms). 20), substituted amino group (preferably having 1 to 20 carbon atoms), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms) ), A ureido group (preferably having 1 to 30 carbon atoms), a carbamoyl group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) and the like. .

In formula (N), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. Is included. At least one nitrogen, oxygen,
And a 5- to 6-membered ring compound containing a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group, a quinolinio group,
And a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred. The alkoxy group has 1 to 8 carbon atoms
And the aryloxy group is preferably a monocyclic one, and the amino group is preferably an unsubstituted amino group, or an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a heterocyclic amino group. . R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Among the groups represented by R ₂ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl) is preferable. Group, pyridiniomethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methane) Sulfonamidophenyl group, o-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom or an alkyl group. When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Alternatively, a substituted amino group (eg, a dimethylamino group) is preferable. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group (for example, 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, Anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.) are preferred. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule and produces a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. Examples thereof include, for example, JP-A-63-2975.
No. 1 and the like.

A ₁ and A ₂ represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett having a sum of substituent constants of-
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (N) may be further substituted, and preferred examples include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (N) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (N) may have a built-in adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio, arylthio, thiourea, thioamide,
U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045 and JP-A-59-201045, such as mercapto heterocyclic groups and triazole groups. 201046, 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R ₁ or R ₂ in the general formula (N) may contain a plurality of hydrazino groups as substituents. Represents, for example, JP-A-64-86134
And compounds described in JP-A Nos. 4-16938 and 5-97091.

Next, in the present invention, a particularly preferred hydra
The gin derivative will be described. R₁Is a substituted phenyl group
Preferably, sulfonamide group, acylamino group, urethane
A ballast group,
A group containing a quaternary ammonium group,
A group containing a repeating unit of an ethyleneoxy group, alkyl,
Aryl or heterocyclic thio group, alkaline developing
Groups that can be dissociated in a physical solution (carboxyl group, sulfo group,
Silsulfamoyl group) or can form multimers
It is preferred that the hydrazino group is substituted. R₁Is
Most preferably substituted with a benzenesulfonamide group
A phenyl group, a substituent of the benzenesulfonamide group
Preferably has any of the groups described above.
New G₁Is preferably a --CO-- group or a --COCO-- group.
A —CO— group is preferred. R_TwoIs G₁Is -CO- group, water
A hydrogen atom, a substituted alkyl group or a substituted aryl group (substituent
Is an electron-withdrawing group or an o-hydroxymethyl group
Preferred) and G ₁Is a substituted amino group when is -COCO-
Is particularly preferred.

Specific examples of the compound represented by the formula (N) are shown below. However, the present invention is not limited to the following compounds.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8]

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized. A compound represented by (Chemical Formula 1) described in JP-B-6-77138.
Compounds described on pages 4 and 4. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP-A-6
Compounds represented by formulas (4), (5) and (6) described in JP-A-230497, specifically, compounds 4-1 to 4 described on pages 25 and 26 of the same publication. -1
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7. General formula (1) described in JP-A-6-289520
And compounds represented by formula (2), specifically, compounds 1-1) to 1-17) and 2-1) described on pages 5 to 7 of the same publication. Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3139
A compound represented by Chemical Formula 1 described in No. 51, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-561
Compounds represented by general formula (I) described in No. 0, specifically, Compounds 1-1 to 1-3 described on pages 5 to 10 of the same publication
8. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. JP-A-7-10442
Compounds represented by general formula (H) and general formula (Ha) described in No. 6, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in Japanese Patent Application No. 7-191007 characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, and particularly a compound represented by the general formula (A): , General formula (B), general formula (C), general formula (D),
Compounds represented by formulas (E) and (F), specifically, compounds N-1 to N-30 described in the publication. Japanese Patent Application No. 7
A compound represented by the general formula (1) described in 191007, specifically, compounds D-1 to D-5 described in the same publication
5.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve. It can be used by dissolving it in, for example. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto.

The addition amount of the hydrazine derivative of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol per mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

The silver halide photographic light-sensitive material of the present invention comprises
It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt, a disulfide derivative, and a hydroxylamine derivative to the silver halide emulsion layer or another hydrophilic colloid layer.

The nucleation accelerator used in the present invention includes
Examples include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. JP-A-7-77783, page 48, 2 lines to 37
Compounds described in the line, specifically, compounds A-1) to A-73) described on pages 49 to 58. Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formulas [Na] and [Nb] described in JP-A-7-104426.
Compounds of Na-1 to Na-22 and compounds of Nb-1 to Nb-12 described on pages 6 to 20. The general formulas (1), (2), (3) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formulas (4), (5), (6) and (7), specifically, the compounds of 1-1 to 1-19 described in the same specification, 2-1 to 2-22, 3-1 to 3-36, 4-1 to 4-5, 5-1 to 5-41, 6-1 to 6-58 and Compounds of 7-1 to 7-38.

The nucleation promoting agent of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator of the present invention is applied to a support.
The silver halide emulsion layer on the silver halide emulsion layer side or other
May be added to any of the hydrophilic colloid layers of
Silver colloid emulsion layer or hydrophilic colloid adjacent to it
It is preferably added to the metal layer. Nucleation accelerator of the present invention
The addition amount was 1 × 10 5 per mol of silver halide.^-6~ 2 × 10
^-2Mole is preferred and 1 × 10^-Five~ 2 × 10^-2Mole more
Preferably 2 × 10^-Five~ 1 × 10^-2Mole is most preferred
No.

The polymer latex having a core / shell structure of the present invention will be described below. The core constituting the latex of the present invention is specifically a polymer comprising one or more kinds of repeating units of various polymerizable ethylenically unsaturated monomers.

As such monomers, acrylic esters, methacrylic esters, vinyl esters, olefins, dienes, acrylamides, methacrylamides, vinyl ethers, and various other ethylenically unsaturated monomers are used. In addition, a monomer having two or more ethylenically unsaturated groups can be preferably used.

More specifically, examples of acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate. , Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-
Chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate,
Phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl Acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1 , 1-dichloro-2-ethoxyethyl acrylate and the like.

Examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, N-ethyl-
N-phenylaminoethyl methacrylate, 2- (3-
Phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate,
2- (2-methoxyethoxy) ethyl methacrylate,
2- (2-butoxyethoxy) ethyl methacrylate,
Allyl methacrylate and the like can be mentioned.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,
3-butadiene, 2-methyl-1,3-pentadiene,
1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1, 3-butadiene, 1-chlorobutadiene, 2-
Fluoro-1,3-butadiene, 2,3-dichloro-
1,3-butadiene, 1,1,2-trichloro-1,3
-Butadiene and 2-cyano-1,3-butadiene.

In addition to the above monomers, acrylamides such as acrylamide, ethyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, diacetone acrylamide and the like; Amides: for example, methacrylamide, ethyl methacrylamide, tert-butyl methacrylamide,
Benzyl methacrylamide, hydroxymethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide and the like;

Olefins: for example, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride and the like; styrenes: for example, styrene, methyl styrene, ethyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, Chlorostyrene,
Dichlorostyrene, bromostyrene, methyl vinyl benzoate, etc .; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether;

Others include butyl crotonate, hexyl crotonate, dimethyl itaconate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl Pyrrolidone, acrylonitrile, methacrylonitrile, methylenemalononitrile, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride,
Examples thereof include vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and styrene sulfonic acid.

In the core of the latex of the present invention, a monomer having at least two copolymerizable ethylenically unsaturated groups can be used. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples include trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

The monomers listed above may be used alone or in a combination of two or more. From the viewpoint of easiness of polymerization and easiness of forming a core / shell structure, among the above-mentioned monomer groups, acrylates, methacrylates, vinyl esters, conjugated dienes, Styrenes, 2
It is a monomer having at least two ethylenically unsaturated groups.
Among the core polymers described above, a particularly preferred embodiment is that the core polymer is produced by emulsion polymerization and exists in the form of a fine particle dispersion (latex) in an aqueous medium.

In such a dispersion, the core polymer is present in the form of fine particles. The particle size of the polymer affects the physical properties of the film mixed with gelatin, the stability of dispersion in water itself, and the ability to form a film. From the above points, the number average particle diameter of the core polymer is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less. And the lower limit is preferably 0.00001 μm or more.

The shell part of the core / shell latex of the present invention will be described below. The shell part of the present invention may be composed of any polymer, but is preferably a repeating unit derived from at least one ethylenically unsaturated monomer having an active methylene group represented by the following general formula (I). Is a polymer having General formula (I)

[0073]

Embedded image

In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X is R ₂ COCH ₂ COO—, NC
_{-CH 2 COO-, R 2 COCH 2} CO-, NC-CH
₂ CO- (R ₂ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, It represents the 12 substituent amino group), R ₉ -CO-C
H ₂ CON (R ₆ ) — (R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₉ represents 1 carbon atom.
X represents an active methylene group selected from substituted or unsubstituted primary or secondary alkyl groups, alkoxy groups having 1 to 12 carbon atoms, amino groups, and substituted amino groups having 1 to 12 carbon atoms; L is linked to alkylene aralkylene or arylene.

More specifically, R ₁ represents a hydrogen atom, a carbon atom having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl) or a halogen atom (for example, chlorine atom or bromine atom); It preferably represents a hydrogen atom, a methyl group or a chlorine atom. L represents a single bond or a divalent linking group, and is specifically represented by the following formula.

[0076]

Embedded image

L ¹ is -CON (R ₃ )-(R ₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms), -COO-, -NHCO
-, -OCO-,

[0078]

Embedded image

(R ₄ and R ₅ each independently represent a hydrogen, a hydroxyl, a halogen atom or a substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² represents L ¹ and X M represents 0 or 1; n represents 0 or 1; When n = 0, m = 0. L
^The linking group represented by ² is specifically represented by the following general formula.

[0080]

Embedded image

J ¹ , J ² and J ³ may be the same or different, and represent —CO—, —SO ₂ — and —CON (R ₆ ) —.
(R ₆ is a hydrogen atom, an alkyl group (1-6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon _{atoms)), - SO 2 N (} R 6) -
(R ₆ is as defined above), —N (R ₆ ) —R ₇ — (R ₆ is as defined above, R ₇ is an alkylene group having 1 to about 4 carbon atoms),
—N (R ₆ ) —R ₇ —N (R ₈ ) — (R ₆ and R ₇ are as defined above, R ₈ is a hydrogen atom, an alkyl group (having 1 to 1 carbon atoms)
6), a substituted alkyl group (1-6 carbon atoms; examples of the substituent include a halogen atom and an alkoxy group (methoxy, ethoxy, etc.)). ), -O-, -S-, -N (R
_{6) -CO-N (R 8} ) - (R 6, R 8 are as defined _{above), - N (R 6)} -SO 2 -N (R 8) - (R 6, R
₈ is as defined above), -COO-, -OCO-, -N (R
₆ ) CO _2- (R ₆ is as defined above), -N (R ₆ ) CO
— (R ₆ is as defined above) and the like.

P, q, and r represent 0 or 1. X ¹ ,
X ² , X ³ and X ⁴ may be the same or different from each other, and may be an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or phenylene having 6 to 20 carbon atoms. Represents an alkylene group which may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, methoxymethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decylmethylene. Examples of the aralkylene group include benzylidene. Examples include phenylene, methylphenylene, chlorphenylene, and methoxyphenylene.

X is a monovalent group containing an active methylene group, specifically, R ₂ COCH ₂ COO—, NCCH ₂ C
_{OO-, R 2 COCH 2 CO-,} NC-CH 2 CO-,
R ₉ -CO-CH ₂ CON (R ₆ )-can be mentioned. Here, R ₆ is the same as described above, and R 2 is
~ 12 substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, n-propyl, n-butyl, t-butyl,
n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl, etc.),
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms (e.g., phenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl, etc.) and an alkoxy group having 1 to 12 carbon atoms (e.g., methoxy, ethoxy, methoxyethoxy) , N-butoxy, etc.),

Cycloalkyloxy groups (eg, cyclohexyloxy), allyloxy (eg, phenoxy, p
-Methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.), an amino group, and a substituted amino group having 1 to 12 carbon atoms (eg, methylamino, ethylamino, dimethylamino, butylamino, etc.). Of the above, particularly preferred are substituted or unsubstituted primary or secondary alkyl groups having 1 to 12 carbon atoms.

R ₉ represents a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, or a substituted amino group having 1 to 12 carbon atoms; specific examples thereof are the same as described above R _2. Particularly preferred as R ₉ is a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms.

The active methylene group represented by X
Among them, a particularly preferable effect in the present invention is represented by R
_TwoCOCH_TwoCOO-, NCCH_TwoCOO-, R_TwoCO
CH _TwoCO-, NC-CH_TwoCO-.

Specific examples of the monomer having an active methylene group that gives a repeating unit constituting a shell in the latex of the present invention are specifically described below, but the present invention is not limited thereto.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamidoethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate

M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acrylamide M-10 2-propionylacetoxyethyl acrylate M-11 N- (2 -Propionylacetoxyethyl) methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide

M-13 ethyl acryloyl acetate M-14 acryloyl methyl acetate M-15 N-methacryloyloxymethyl acetoacetamide M-16 ethyl methacryloyl acetoacetate M-17 N-allyl cyanoacetamide M-18 2-cyanoacetyl ethyl acrylate

M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloylpiperazine M-22 ethyl-α-acetate Acetoxy methacrylate M-23 N-butyl-N-acryloyloxyethyl acetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene

In the polymer constituting the shell portion of the present invention, an ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer containing an active methylene group may be copolymerized. Examples of such monomers include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and other monomers constituting the core particles. Can be listed,
Of these, acrylic esters, methacrylic esters, vinyl esters, and styrenes are particularly preferred.

In the core / shell polymer latex of the present invention, the proportion of the monomer unit having an active methylene group in the shell polymer can be arbitrarily changed according to performance requirements, and is used in the range of 0.1 to 100% by weight. Can do things. However, when the copolymerization amount of the monomer unit having an active methylene group is increased, the above-mentioned various effects are increased. However, when the amount exceeds a certain amount, the effect may be saturated. %
Particularly preferred is 1 to 40% by weight.

The amount ratio of the core polymer and the shell polymer in the core / shell polymer latex of the present invention can be arbitrarily changed.
90-95 / 5, preferably 20 / 80-95
/ 5, particularly preferably 30/70 to 90/10. This means that if the core is too small, the effect of concentrating the active methylene monomer on the shell decreases, and if the shell is too small, it becomes difficult to form a clear core / shell structure. The particle diameter of the core / shell polymer latex is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less, similarly to the core polymer particles. And the lower limit is preferably 0.00001 μm or more.

As is well known in the art of core / shell latex formation technology in emulsion polymerization, a combination in which the polarity of the core polymer and the shell polymer are close to each other and are compatible with each other may result in a desired core / shell structure. May not be formed sufficiently. In order to form a more effective core / shell structure, it is preferable to select a polymer in which the polymer forming the shell and the polymer forming the core are hardly compatible.

One of the very useful aspects in this regard is to use a polymer having a conjugated diene monomer component as a core. When the conjugated diene monomer is used in a certain amount or more, the core particles have extremely low polarity, so that it is possible to form an effective core / shell structure with most of the monomers used for the shell portion. The standard for forming a core having such performance is that the conjugated diene monomer is contained in an amount of 25% or more by weight. As a preferred example, a styrene-butadiene copolymer (generally called SBR and solution-polymerized SBR) is used.
And emulsion polymerization SBR. As the solution-polymerized SBR, in addition to the random polymer, the above-mentioned block copolymer (for example,
Butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer)), butadiene homopolymer (for example, cis-1,4-butadiene,
Trans-1,2-butadiene, or a rubber in which these are mixed with a trans-1,4-butadiene structure), an isoprene homopolymer (an example of a three-dimensional structure is the same as a butadiene polymer), a styrene-isoprene copolymer (Random copolymer, block copolymer), ethylene-propylene-diene copolymer (diene monomers include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, etc.), acrylonitrile-
Butadiene copolymer, chloroprene copolymer, isobutylene-isoprene copolymer, butadiene-acrylate copolymer (acrylates such as ethyl acrylate and butyl acrylate) and butadiene-acrylate-acrylonitrile copolymer A polymer (the same as the acrylic ester described above) can be used.

An effective core / shell structure can also be formed by selecting a polymer having a large polarity difference between the polymer constituting the core and the shell. For example, poly (n-dodecyl methacrylate) core / poly (methyl acrylate) -Co-2-acetoacetoxyethyl methacrylate) shell or poly (ethyl acrylate) core / poly (styrene-co-2-acetoacetoxyethyl acrylate)
And the like. However, these are the core /
This shows that the effect of the shell polymer latex can be selected depending on the magnitude of the effect. Even in the case of a combination of polymers having similar polarities, the core / shell polymer latex of the present invention can be used for a non-core / shell type polymer latex. Shell latex exhibits better film strength properties.

Further, even when a monomer having close polarity is used for the core and the shell, the core is formed of the above-mentioned crosslinked monomer (a monomer having two or more ethylenically unsaturated groups in the molecule).
By performing three-dimensional cross-linking using a polymer, an extremely effective core / shell polymer latex can be obtained. As described above, in the present invention, it is possible to form a useful core / shell polymer latex structure irrespective of the type of monomer used.

The core / shell latex of the present invention has the glass transition temperature of the core or shell part, or both of the core part and the shell part, in terms of the brittleness improving effect when added to a gelatin film separately from the film strength characteristics. Tg) is 50 ° C
It is appropriate that the Tg of the core part is lower than the Tg of the shell part, more preferably the Tg of the core part is lower than 0 ° C. (the lower limit is −110 ° C.).
C), and the Tg of the shell part is preferably 0C or more (the upper limit is 150C).

The Tg of the polymer is described, for example, in "J. Brandrup,
Co-authored by EHImmergut. Polymer Hondbook, 2nd Edition, III
-139 to III-192 (1975) ", and in the case of a copolymer, it can be determined by the following formula.

[0101]

(Equation 1)

In the core / shell polymer latex of the present invention, the core polymer, the shell polymer, or both may be crosslinked. In this case, the molecular weight of the resulting polymer is infinite. The molecular weight of the polymer of the present invention in the case of non-crosslinking depends on the kind of the monomer and the synthesis conditions, but is in the range of 5,000 to 2,000,000, and the molecular weight may be adjusted by a chain transfer agent or the like depending on the purpose. Is also possible.

Preferred examples of the core / shell latex of the present invention are shown below, but the present invention is not limited thereto. The structure of each of the following latex compounds is described in the order of the core polymer structure, the structure of the shell polymer and the ratio of the core / shell, and the copolymer composition ratio and the core / shell ratio in each polymer are all expressed by weight percentage. .

P-1 to 12 core: styrene / butadiene copolymer (37/63) P-1 shell = styrene / M-1 (98/2) core /
Shell = 50/50 P-2 Shell = Styrene / M-1 (96/4) Core /
Shell = 50/50 P-3 Shell = Styrene / M-1 (92/8) Core /
Shell = 50/50 P-4 Shell = Styrene / M-1 (84/16) Core /
Shell = 50/50 P-5 Shell = Styrene / M-1 (68/32) Core /
Shell = 50/50 P-6 Shell = Styrene / M-1 (84/16) Core /
Shell = 67/33 P-7 Shell = Styrene / M-1 (84/16) Core /
Shell = 85/15 P-8 Shell = n-butyl acrylate / M-1 (96
/ 4) core / shell = 50/50 P-9 shell = n-butyl acrylate / M-1 (92
/ 8) core / shell = 50/50 P-10 shell = n-butyl acrylate / M-1 (84
/ 16) core / shell = 50/50 P-11 shell = methyl acrylate / M-7 (84/1
6) Core / shell = 50/50 P-12 shell = styrene / methyl acrylate / M-
3 (21/63/16) core / shell = 50/50

P-13, 14 core: styrene / butadiene copolymer (22/78) P-13 shell = styrene / M-2 (84/16) core /
Shell = 50/50 P-14 Shell = n-butyl acrylate / M-8 (84
/ 16) core / shell = 50/50

P-15-20 core: polybutadiene homopolymer (100) P-15 shell = styrene / M-1 (84/16) core /
Shell = 50/50 P-16 Shell = Ethyl acrylate / M-7 / Methacrylic acid (65/15/20) Core / Shell = 75/25 P-17 Shell = n-butyl acrylate / M-1 (84
/ 16) core / shell = 50/50 P-18 shell = n-butyl acrylate / M-2 (84
/ 16) core / shell = 50/50 P-19 shell = 2-ethylhexyl acrylate / M
-24 (84/16) core / shell = 50/50 P-20 shell = n-butyl acrylate / M-18
(84/16) core / shell = 50/50

P-21 to 23 Core: Polyisoprene homopolymer (100) P-21 Shell = styrene / acrylonitrile / M-1
(63/21/16) core / shell = 90/10 P-22 shell = methyl methacrylate / ethyl acrylate / M-2 / 2-acrylamido-2-methylpropanesulfonic acid sodium (15/65/15/5) core / Shell = 75 /
25 P-23 Shell = Styrene / M-1 (84/16) Core /
Shell = 20/80

P-24 to 26 core: styrene / butadiene copolymer (49/51) P-24 shell = styrene / butyl acrylate / M-
1 (26/60/15) core / shell = 50/50 P-25 shell = M-1 (100) core /
Shell = 90/10 P-26 Shell = Lauryl methacrylate / butyl acrylate / M-7 (30/55/15)
Core / shell = 40/60 P-27 core: acrylonitrile / styrene / butadiene copolymer (25/25/50) shell: butyl acrylate / M-1 (92/8) core /
Shell = 50/50 P-28 Core: Ethyl acrylate / butadiene copolymer (50/50
50) Shell: styrene / divinylbenzene / M-1 (79/5
/ 16) core / shell = 50/50

P-29 to 33 core: poly (n-dodecyl methacrylate) homopolymer P-29 shell = styrene / M-1 (92/8) core /
Shell = 50/50 P-30 Shell = Styrene / M-1 (84/16) Core /
Shell = 50/50 P-31 Shell = Ethyl acrylate / M-1 (96/4
) Core / shell = 50/50 P-32 shell = ethyl acrylate / M-1 (92/8
) Core / shell = 50/50 P-33 Shell = styrene / methyl acrylate / M-
3 (21/63/16) core / shell = 50/50

P-34 core: poly (n-butyl acrylate) homopolymer Shell: styrene / M-2 (84/16) core /
Shell = 50/50 P-35,36 Core: poly (ethylene glycol dimethacrylate / n-
(Butyl acrylate) copolymer (10/90) P-35 shell = styrene / M-1 (84/16) core /
Shell = 50/50 P-36 Shell = methyl acrylate / M-7 / methacrylic acid (65/15/20) core / shell = 75/25

P-37-40 Core: poly (ethylene glycol dimethacrylate / n-
(Butyl acrylate) copolymer (20/80) P-37 shell = styrene / M-1 (84/16) core /
Shell = 50/50 P-38 Shell = Styrene / M-1 (84/16) Core /
Shell = 75/25 P-39 Shell = Methyl acrylate / M-8 / 2-acrylamide-2-methylpropane sodium sulfonic acid (80/15/5) core / shell = 75/25 P-40 Shell = n-butyl Acrylate / M-1 (84
/ 16) core / shell = 50/50

P-41 to 43 core: polyvinyl acetate homopolymer (100) P-41 shell = styrene / M-1 (84/16) core /
Shell = 50/50 P-42 Shell = Styrene / divinylbenzene / M-24
(79/5/16) core / shell = 50/50 P-43 shell = n-dodecyl methacrylate / butyl acrylate / M-7 (30/55/15)
Core / shell = 40/60

P-44 to 46 Core: poly (divinylbenzene / 2-ethylhexyl acrylate) copolymer (10/90) P-44 shell = methyl acrylate / M-1 (84/1)
6) Core / shell = 50/50 P-45 shell = methyl acrylate / styrene / M-
1 (74/10/16) core / shell = 50/50 P-46 shell = M-1 (100) core /
Shell = 90/10 P-47-49 Core: Poly (divinylbenzene / styrene / 2-ethylhexyl acrylate) copolymer (10/23/67) P-47 Shell = methyl acrylate / M-1 (84/1)
6) Core / shell = 50/50 P-48 Shell = methyl acrylate / styrene / M-
1 (74/10/16) core / shell = 50/50 P-49 shell = ethyl acrylate / 2-hydroxyethyl methacrylate / M-5 (65/15/20)
Core / shell = 85/15

P-50 Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n-butyl acrylate) copolymer (20/20/60) Shell: Ethylene glycol dimethacrylate / styrene / n-butyl methacrylate / M- 1 (5/40/40/15)
Core / shell = 50/50 P-51 Core: poly (trivinylcyclohexane / n-butyl acrylate / styrene) copolymer (10/55/35) Shell: methyl acrylate / M-1 / 2-acrylamide-2- Sodium methylpropanesulfonate (88/7/5)
Core / shell = 70/30 P-52,53 Core: poly (divinylbenzene / styrene / methyl methacrylate) copolymer (10/45/45) P-52 shell = n-butyl acrylate / M-1 (84
/ 16) core / shell = 50/50 P-53 shell = n-dodecyl acrylate / ethyl acrylate / M-21 (60/30/10)
Core / shell = 50/50

P-54,55 core: poly (p-vinyltoluene / n-dodecyl methacrylate) copolymer (70/30) P-54 shell = methyl acrylate / n-butyl methacrylate / M-2 / acrylic acid ( 30/55/10/5)
Core / shell = 50/50 P-55 shell = n-butyl acrylate / M-19
(84/16) core / shell = 70/30

The core / shell polymer latex of the present invention can be easily prepared by subjecting an aqueous dispersion obtained by emulsion polymerization of a core latex polymer to emulsion polymerization while simultaneously adding or dripping monomers forming a shell. You can get it. The emulsion polymerization method is preferably carried out by emulsifying a monomer in water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) using at least one emulsifier, and using a radical polymerization initiator. Generally from 30 ° C. to about 100 ° C., preferably 40 ° C.
C. to a temperature of about 90.degree. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and optionally 0.1 to 10% by weight of an emulsifier with respect to the monomer to be polymerized. As the polymerization initiator, azobis compounds, peroxides,
Hydroperoxides, redox solvents and the like, for example, potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl-carbonate, 2,4-dichlorobenzyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicane Mil peroxide,
Examples include 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) hydrochloride, and a combination of potassium persulfate and sodium bisulfite.

Examples of the emulsifier include anionic, cationic and
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrisodium Methylene ammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, sodium dodecyl-diphenylether disulfonate, sodium 2-tetradecene-1-sulfonate, 3-hydroxytetradecane-1- Sodium sulfonate, gelatin, PVA, etc.
No.-6190, for example, an emulsifier and a water-soluble polymer. Among them, an anionic or nonionic surfactant and a water-soluble polymer are particularly preferable.

The addition of the monomer in the emulsion polymerization is preferably performed while dropping from the viewpoint of avoiding heat generation due to the polymerization and forming a clearer core / shell structure. Also, by the above initiator, emulsion polymerization in the presence of an emulsifier,
After the core latex particles are formed, when the shell monomer is polymerized, an emulsifier may be further added, or the polymerization may be performed without the emulsifier. In many cases, the addition of an emulsifier is necessary from the viewpoint of the stability of the produced polymer latex. However, if an excess emulsifier is present, particles other than the intended shell polymer alone may be by-produced. Therefore, it is preferable that the amount of the emulsifier added after the formation of the core polymer is suppressed to about 0.001 to 2% by weight based on the core particles, or not added at all.

In order to form a latex having an effective core / shell structure, the polymerization of the core particles at the time of addition of the shell-forming monomer is preferably as complete as possible, and the polymerization rate is 90% or more, preferably 95% or more. As described above, the content is particularly preferably substantially 100%.

The active methylene unit functions as a reactive group by improving the film strength of the polymer latex / gelatin composite film and improving various properties of the paint and adhesive latex. Therefore, the amount of active methylene units present on the latex surface is an important factor in performance. The core / shell latex of the present invention is useful in that basically active methylene units can be concentrated on the required latex surface. Further, by controlling other required functions in the core, for example, Tg of the whole latex, the ability to form a film and the physical properties (eg, brittleness) of the resulting film or a composite film with gelatin or the like can be controlled by the shell. Is also very useful in that it can be included independently.

The core / shell latex particles of the present invention include:
Although it can be obtained in the form of an aqueous dispersion by the above-mentioned emulsion polymerization method, it is also possible to obtain a fine particle powder while maintaining the core / shell structure. As a method of such powdering,
Lyophilization, aggregation using strong acids or salts, filtration, or aggregation by repeated freeze-thaw of latex solution,
A known method such as a filtration method can be used.

The addition amount of the polymer latex having a core / shell structure of the present invention is optional, but is preferably 5 to 400% by weight of gelatin in the hydrophilic colloid layer.
Preferably it is 10 to 200%.

Gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids may be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. In the present invention, the coated amount of gelatin as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less and the total hydrophilic colloid layer on the side having the silver halide emulsion layer is not more than 3 g / m ^2. total gelatin sex colloid layer and all hydrophilic colloid layers on the opposite surface is at 6 g / m ² or less, preferably 2.0 to 6.0 g / m ^2.

In the silver halide photographic light-sensitive material of the present invention, the swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer is 80.
To 150%, more preferably 90 to 1%.
It is in the range of 40%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material. Swelled for 1 minute, the swollen thickness (Δd) was measured, and the swelling ratio (%) = Δ
It is determined by the formula of d ÷ d0 × 100.

Examples of the support for the light-sensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate described in Japanese Patent Application No. 07-28188, and JP-A-3-131843. Syndiotactic polystyrene, polyethylene-coated paper and the like are used.

The processing agents such as the developing solution and the fixing solution and the processing method in the present invention will be described below, but it goes without saying that the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development start solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonic acid salts, and may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone or a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol is preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone and others. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like as p-aminophenol-based developing agents used in the present invention. Among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene-based developing agent is usually 0.1.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l to 0.5 mol / l. It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.1
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or p-aminophenol is used, the ascorbic acid derivative may be used in an amount of 0.01 to 0.5 mol / l, and the 1-phenyl-3-pyrazolidone or p-aminophenol may be used. The aminophenols are preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-93
The sugars described in 433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonate , Boric acid is used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular from 0.2 to
1.5 mol / l.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. Sulfite is used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more. However, if added in an excessive amount, it causes silver contamination in the developing solution.
It is desirable to use liters. Particularly preferably, 0.35 to
0.7 mole / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of additives other than those described above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol,
Examples thereof include methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these additives is usually 0.01 to 10 mmol per liter of developer, more preferably 0.1 to 10 mmol.
~ 2 mmol.

Further, various kinds of organic and
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As aminopolycarboxylic acids, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1
, 2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and other JP-A-52-25632, 55-67747, and 57-1
02624 and compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in, for example, US Pat. Nos. 3,214,454 and 3,794,591 and German Patent Publication 2,227,369, and Research Disclosure, Vol. 181, Item 18170 (1979).
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Other examples include the compounds described in Research Disclosure 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-121127 and JP-A-55-102127.
-4024, 55-4025, 55-126241, 55-65955, 55
-65956 and the aforementioned Research Disclosure 1817
0 and the like.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-46585, JP-B-62
849, compounds described in JP-A-4-362942, and triazines having at least one mercapto group (for example, JP-B-6-2383).
0, compounds described in JP-A-3-282457, JP-A-7-175178) and pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-) 2, 4-dimercaptopyrimidine, 2, 4, 6-trimercaptopyrimidine, etc.),
The same pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2
, 4, 6-trimercaptopyridine, the compounds described in JP-A-7-248587, etc.) and the same pyrazines (eg, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3, 5-trimercaptopyrazine, etc.) and the same pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3, 4, 6-trimercaptopyridazine, etc.), JP-A-7-175177 The compound described in U.S. Pat.
The polyoxyalkyl phosphonate described in 1, etc. can be used. These silver stain inhibitors can be used alone or in combination of two or more.
It is preferably from 0.05 to 10 mmol, more preferably from 0.1 to 5 mmol, per liter. As a dissolution aid, JP-A-61-2
The compound described in 67759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is from 9.0 to 12.0, particularly preferably from 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As cations in the developer, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishing amount of the developing solution was 39 per m ² of the light-sensitive material.
0 ml or less, preferably 325 to 30 ml, most preferably 180 to 60 ml. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration from the start solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution of the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are used as an aluminum ion concentration of 0.01 to 0.15 mol /
It is preferably contained in liters. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If necessary, a preservative (eg, sulfite, bisulfite, metabisulfite, etc.)
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / l to 1 mol / l, preferably 0.2 mol / l to 0.7 mol / l of phosphoric acid, succinic acid, adipic acid, etc., and compounds having aluminum stabilizing ability or water softening ability (for example, gluconic acid, iminodi Acetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediamine Acetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.1 mol / l
005 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene-based surfactants, and amphoteric surfactants described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-122535.
58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,216,459, JP-A-64-4739, JP-A-1-4739, JP-A-1-4739.
159645 and the mercapto compounds described in 3-101728,
The mesoionic compound described in 4-170539 and a thiocyanate can be included.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. The pH of the fixing solution is raised by the processing mixed with the developing solution. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less, preferably 6.7 or less for the non-hardened fixing solution.

The replenishment amount of the fixing solution is 50 per m ² of the photosensitive material.
0 ml or less, preferably 300 ml or less, more preferably 200 to 60 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, the washing including the stabilization processing is called washing, and the liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The amount of replenishment is generally but about 17 liters to about eight liter photosensitive material 1 m ^2, can also be carried out in less replenishing rate. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method of reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, means for preventing water scale may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method of energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, JP-A-4-18
980 or the like can be used.

In addition, a known water-soluble surfactant or antifoaming agent may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment is performed subsequent to the water washing treatment. Examples of such treatments are described in JP-A-2-201357, JP-A-2-132435,
A bath containing a compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains ammonium compounds, metal compounds such as Bi and Al, fluorescent brighteners, various chelating agents, membrane pH regulators,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. These waste liquids are described in, for example, Japanese Patent Publication No. 7-83867, US
It is also possible to dispose it after concentrating it into a liquid or solidifying it with a concentrating device as described in O.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of the liquid and the oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, the dry-to-dry processing
160 seconds is preferred, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C.
30-40 ° C is preferred. Washing temperature and time are 0-50 ℃
And preferably 40 seconds or less. According to the method of the present invention, development,
The fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. As the drying method, any known method can be used, and there is no particular limitation.
Heat roller drying and drying by far-infrared rays as disclosed in 4-15534, 5-2256 and 5-289294 may be used, and a plurality of methods may be used in combination.

When the developing and fixing agent in the present invention is a liquid agent, it is preferable to store it in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained. However, the solid processing agent will be described below. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

As the coating agent and granulation aid, known ones can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3
You can refer to the 13th line.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm.
³ , particularly preferably 1.0 to 5.0 g / cm ³ for tablets, and 0.5 to 1.5 g / cm ^{3 for} granules.

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-
32837, 4-78848, 5-93991, JP-A-4-85533,
4-85534, 4-85535, 5-134362, 5-97070, 5-
204098, 5-224361, 6-138604, 6-138605, Japanese Patent Application
7-89123 etc. can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid preparation is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, Japanese Patent Application 5-30664
Also, it is preferable to make it a foldable shape as disclosed in JP-A-7-5664 and JP-A-7-5666 to 7-5669, in order to reduce the storage space of the waste packaging material. These packaging materials
A screw cap, a pull top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function,
A method of dissolving with a dissolving apparatus having a dissolving portion and a portion for storing a completed solution as described in 7-235499 and replenishing from the stock portion, JP-A-5-119454, JP-A-6-19102,
A method of dissolving and replenishing by introducing a processing agent into the circulating system of an automatic developing machine as described in 7-261357, and inputting a processing agent according to the processing of the photosensitive material with an automatic developing machine having a built-in dissolving tank. Although there is a dissolving method and the like, any other known method can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method disclosed in JP-A-6-19102
And 6-95331.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line, line 11 to page 12, lower left line, line 5. Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardening agents described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, lower right line 2 to the lower right line 10 of the same publication, and the conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right line, line 1 to line 18, upper right line.

Solid disperse dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112.

Solid disperse dyes described in JP-A-2-294638 and JP-A-3-185773.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds IV-1 to IV-15 described in the publication.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

[0185]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of Emulsion A> 1 solution Water 1000 ml Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium thiosulfonate 6 mg 2 solutions Water 600 ml Silver nitrate 150 g 3 solutions Water 600 ml Sodium chloride 54 g K ₃ IrCl ₆ 0.25 mg (NH ₄ ) ₂ RhCl ₅ (H ₂ O) 0.06 mg Yellow blood salt 5 mg One solution kept at 38 ° C. and pH 4.5 is simultaneously stirred for 20 minutes while each of the second solution and the third solution is stirred for 20 minutes. Over 0, 0.
Nuclear particles of 18 μm were formed. Subsequently, the following liquids 4 and 5 were added over 8 minutes to grow to 0.20 μm, and the particle formation was completed. Liquid 4 200 ml Silver nitrate 50 g Liquid 5 water 200 ml Sodium chloride 15 g Potassium bromide 7 g Potassium ferrocyanide 5 mg Thereafter, water was washed by flocculation according to a conventional method, and 45 g of gelatin was added. pH 5.6, pAg
Adjusted to 7.5, sodium thiosulfonate 10 mg, sodium thiosulfinate 3 mg, sodium thiosulfate 1
mg and triphenylphosphine selenide 1mg, chloroauric acid 5
mg, and chemically sensitized to obtain the highest sensitivity at 55 ° C., 0.15 g of potassium iodide was added, 200 mg of 1,3,3a, 7-tetraazaindene was added as a stabilizer, and as a preservative, Phenoxyethanol was added. Finally, an average silver chloride content of 95% (internal silver chloride content of 1%)
Thus, a silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm and containing 0.08 mol% of silver iodide was obtained. (Variation coefficient 9%)

Preparation of Emulsions B to D By changing the content of sodium chloride and potassium bromide in the two and / or five solutions of Emulsion A, the silver chloride contents of the inside of the grains and the surface layer of the grains were changed as shown in Table 9. A modified emulsion was prepared.

Preparation of Emulsions EG After grain formation as in Emulsions A to D, 0.05
AgBr fine grains having a particle size of 1.mu.
Emulsions E to G having a silver bromide localized phase formed on the surface were prepared by adding 0 mol% equivalent.

[0188]

[Table 9]

Preparation of Coated Sample To the obtained emulsion, sensitizing dye (1) was added at 5.0 × 10 ⁻⁴ mol / mol Ag, and subjected to spectral sensitization. Furthermore, KBr 3.4 ×
10 ⁻⁴ mol / mol Ag, compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.0 × 10 ⁻⁴ mol / mol A
g, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) (nucleation accelerator) 6.0 × 10 ⁻⁴ mol / mol. Ag, compound (4)
Was added at 100 mg / m ² .
Next, the hydrazine derivative shown in Table 10 was 1.0 × 10 ⁻⁴ mol / mol Ag, the polymer latex was 300 mg / m ² , colloidal silica having a particle size of 10 μm at 20 wt% based on gelatin, and 4 wt% based on gelatin. was added to compound (5), Ag3.0g / m ² on a polyester support was coated to a gelatin 1.3 g / m ^2. On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (Gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Lower layer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2-benzald Kissim 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200mg / m ²

[0191]

Embedded image

[0192]

Embedded image

After the obtained sample was stored in an atmosphere of 25 ° C. and 55% RH for one week, the following (1) photographic performance and (2) wet film strength were evaluated. Table 10 shows the results. As is clear from Table 10, the sample of the present invention has high sensitivity, extremely high contrast, and strong wet film strength.

[0194]

[Table 10]

(1) <Evaluation of photographic performance> The sample was passed through an interference filter having a peak at 633 nm.
After exposing with a xenon flash light having an emission time of 10 ^-6 sec through a step wedge, and developing at 35 ° C. for 30 seconds with an automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd. using a developing solution A having the following composition. , Fixing, washing and drying. Sensitivity represents with the reciprocal of the exposure amount giving a density of 1.5, to calculate the relative value of the sensitivity of each sample in the case of the comparative sample was 100 and the S _1.5. The higher the value, the higher the sensitivity. Index (gamma) indicating the contrast of the image
From the point of Fog + 0.1 in the characteristic curve.
The points of + concentration 3.0 were connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.
1) / (log (exposure amount giving density 3.0) -log
(Exposure amount giving a density of 0.1)], indicating that the higher the gamma value, the harder the photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more. (2) Wet film strength After immersing the sample in distilled water at 25 ° C for 5 minutes, the radius was 0.3 mm.
The sapphire needle was pressed against the sample film surface, and the load of the needle was continuously changed while moving at a speed of 10 mm / sec to measure the load (g) when the film was broken.

Developer A Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenz Sodium imidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Add water to make 1 liter, adjust the pH to 10.5 with potassium hydroxide. The replenishment rate was 300 ml / m ² .

The fixing solution used had the following formulation. (Formulation of fixing solution) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g Add water to make 3 liters, and adjust to pH = 4.85 with sulfuric acid or sodium hydroxide. The replenishment rate was 250 ml / m ² .

Example 2 A coated sample was prepared in the same manner as in Example 1 except that the polymer latex shown in Table 10 was changed to the polymer latex shown in Table 11 when preparing a coated sample using Emulsion B of Example 1. Was prepared, exposed and developed. After storing the obtained sample in the same manner as in Example 1, the photographic properties and the wet film strength were evaluated in the same manner as in Example 1. Table 11 shows the results. As is clear from Table 11, the sample of the present invention has a very high contrast and a high wet film strength.

[0199]

[Table 11]

Example 3 A coated sample was prepared in the same manner as in Example 1 except that the polymer latex shown in Table 10 was changed to the polymer latex shown in Table 12 when preparing a coated sample using the emulsion E of Example 1. Was prepared, exposed and developed. After storing the obtained sample in the same manner as in Example 1, the following items were evaluated.

(1) Photographic Performance (Gamma Value) The procedure was the same as in Example 1. However, the evaluation of photographic properties was 670
This was performed by replacing the interference filter having a peak at nm. (2) Wet film strength This was performed in the same manner as in Example 1. (3) Brittleness After leaving the sample in an atmosphere of 25 ° C. and 10% RH for 2 hours, LS
In the same manner as in O6077 "Wedye brittleness test", the average value of the points where cracks first occurred on the side containing the silver halide emulsion layer was determined. (4) Adhesiveness The sample was cut into 4 cm x 4 cm pieces to form a set of two pieces at 35 ° C 8
After leaving for 3 hours in an atmosphere of 0% RH, the surface having the emulsion layer of the same set of samples was brought into contact with the opposite surface, and a load of 1 kg was applied and left for 24 hours in an atmosphere of 35 ° C. and 80% RH. did. Next, the load was removed, and the area of the portion where the surface having the emulsion layer was bonded to the surface on the opposite side was determined. (5) Mechanical stability of latex Malon mechanical friction test method (SHMaron, INUleritch
: Anal.Chem., 25, 1087 <1953>. 100 g of a sample latex having a concentration of 20 wt% was placed in a container, and a shearing force was applied thereto under the conditions of 1000 rpm, 10 kg, 5 min and 36 ° C., and the weight of the aggregate was determined.

The results are shown in Table 12. As is clear from Table 12, the sample of the present invention has a very high mechanical stability of the latex by setting the core portion to a low Tg and the shell portion to a high Tg, with ultra-high contrast and high wet film strength. It can be seen that the film has excellent film properties such as brittleness and adhesiveness.

[0203]

[Table 12]

Example 4 In preparing the coated sample of Example 1, 2.0 × 10 ^-4 mol of the sensitizing dye (2) was used per 1 mol of silver instead of the sensitizing dye (1).
A sample was prepared in the same manner as in Example 1 except that 7.0 × 10 ^-4 mol of the sensitizing dye (3) was added.

[0205]

Embedded image

The sample thus obtained was stored in the same manner as in Example 1 and evaluated in the same manner as in Example 1. However,
Evaluation of photographic properties was performed in the same manner as in Example 1 except that the interference filter having a peak at 488 nm was used. As a result, a photosensitive material for an argon laser scanner having high sensitivity, extremely hard photographic characteristics and strong wet film strength was obtained as in Example 1.

Example 5 The sensitizing dye (2) and the sensitizing dye were prepared at the time of preparing the coated sample of Example 4.
Instead of (3), sensitizing dye (4) was added to 8.0 × per mole of silver.
A sample was prepared in the same manner as in Example 4 except that 10 ^-5 mol was added, the compound (14) was added at 2.3 × 10 ^-4 mol, and the compound (15) was added at 1.4 × 10 ^-4 mol. The sample thus obtained was stored in the same manner as in Example 4 and evaluated in the same manner as in Example 4. However, the evaluation of photographic properties was performed by replacing the interference filter having a peak at 780 nm. As a result, Example 4
As a result, a photosensitive material for a semiconductor laser scanner having high sensitivity, extremely hard photographic characteristics, and high wet film strength was obtained.

[0208]

Embedded image

Example 6 The sensitizing dye (2) and the sensitizing dye were prepared at the time of preparing the coating sample of Example 4.
Instead of (3), sensitizing dye (5) per 7.0 mol of silver was used.
A sample was prepared in the same manner as in Example 4 except that 10 ^-4 mol was added. The sample thus obtained was stored in the same manner as in Example 4 and evaluated in the same manner as in Example 4. However, in the evaluation of photographic properties, exposure was performed with tungsten light at 3200 ° K. As a result, a photographic light-sensitive material having high sensitivity, extremely hard photographic characteristics, and high wet film strength was obtained as in Example 4.

[0210]

Embedded image

Example 7 Using the sample of Example 1, the photographic properties were evaluated in the same manner as in Example 1 by changing the replenishing amount of the developing solution as shown in Table 13. Table 13 shows the results. As is clear from Table 13, the sample of the present invention can maintain high sensitivity and a high gamma value even when the replenishment amount of the developer is reduced.

[0212]

[Table 13]

Example 8 The following developer B was used instead of the developer A used in Example 1.
The photosensitive material prepared in Example 1 was developed using C under the conditions of Example 1. However, the replenishment rate was 170 ml / m ² . Developer B Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfite 54.0 g Potassium carbonate 100.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.08 g 2,3,5,6 7,8-Hexahydro-2-thioxo 4- (1H) -quinazolinone 0.03 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium 0.15 g Hydroquinone 30.0 g 4-hydroxymethyl-4-methyl-1-phenyl- 3-Pyrazolidone 0.45 g Sodium erythorbate 3.0 g Add potassium hydroxide, add water to make 1 liter, and adjust the pH to 10.5.

Developer C Potassium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g Sulfurous acid Potassium 10.0 g 2-Sodium 2-mercaptobenzimidazole-5-sulfonate 0.15 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g Sodium erythorbate 30.0 g Add potassium hydroxide, add water To 1 liter and adjust the pH to 10.7.

Developer B was prepared from a solid storage form. In the method for producing the solid processing agent, the components of the developer were packed in a bag made of aluminum foil coated on a plastic substance in a solid state. The order of lamination is from the top, first layer Hydroquinone Second layer Other components Third layer Sodium bisulfite Fourth layer Potassium carbonate Fifth layer Potassium hydroxide pellets, evacuate by conventional method, evacuate the system Sealed.

As a result, the same results as in Example 1 were obtained using the developing solutions B and C.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer is a silver halide grain having a silver chloride content of 70 mol% or more, and a surface layer having a lower silver chloride content than the inside and / or having a silver chloride content lower than the inside on the surface. A halide comprising silver halide grains having a localized phase, wherein the emulsion layer and / or another hydrophilic colloid layer contains at least one hydrazine derivative and a polymer latex having a core / shell structure. Silver photographic photosensitive material. 2. The silver halide photograph according to claim 1, wherein the shell of the polymer latex having the core / shell structure has a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group. Photosensitive material. 3. The silver halide photographic material according to claim 1, wherein the Tg (glass transition temperature) of the core of the polymer latex having the core / shell structure is lower than the Tg of the shell. 4. An image forming method, wherein the replenishing amount of the silver halide photographic light-sensitive material according to claim 1, 2 or 3 is less than 200 ml per square meter of the light-sensitive material.