JPH03259244A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably obtain an action of hardening gelatin and photographic characteristics by incorporating at least one kind of alkaline agent in an aldehyde type hardener. CONSTITUTION:At least one kind of alkaline agent is incorporated in the aldehyde type hardener contained in at least one of hydrophilic colloidal layer of the photographic sensitive material formed on a support. As this alkaline agent to be used for the hardener stabilizer, usually used alkalis, that is, aqueous solutions of alkali metal and ammonium hydroxides and salts, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium sulfate or sodium sulfite, ammonium carbonate sodium phosphate, are used, and they are not especially limited, so long as it is alkaline, thus permitting the gelatin hardening action and the photographic characteristics to be both stably maintained.

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a method for curing a hydrophilic colloid layer of a silver halide photographic light-sensitive material containing gelatin, and more particularly to a silver halide photographic light-sensitive material whose curability is improved using an aldehyde-type compound containing an alkaline agent. be. [0002]

[Background of the invention]

BACKGROUND OF THE INVENTION Many compounds have been widely known as curing agents for curing gelatin used as a binder in silver halide photographic light-sensitive materials to enhance the heat resistance, mechanical strength, etc. of the gelatin layer. [0003] Example Eva C, E, K, MEES, T, H, JAM
Written by ES, THE THEORY OF THE PH0
TOGRAPHIC PROCESS pages 56-57 (19
76) 3rd edition Macmillan Publishing
Aldehyde-type compounds such as formaldehyde, glyoxal, and glutaraldehyde described in G. Co., Inc. (New York), or Japanese Patent Publication No. 1983-1986
Dichloro-5-) riazine type described in No. 51, etc., Japanese Patent Publications No. 13563/1980, 73122/1982, 57257/1983, 41221/1983, U.S. Patent No. 3,490, 911 Vinyl sulfone type compounds described in US Pat. No. 3,288,775 and others, compounds with reactive halogens described in US Pat.
A large number of compounds are disclosed, such as compounds having reactive ethylenically unsaturated bonds as described in No. 86, mucohalogen acids, aziridine series, and epoxies. [00041] However, when these conventionally known curing agents are used in photographic light-sensitive materials, there are disadvantages such as a decrease in photographic properties such as a decrease in photosensitivity and the occurrence of fog. Many of them have some kind of drawbacks, such as long-term changes in the degree of curing over time, which is called the phenomenon of "unevenness" or "posterior hardening," and bad interactions with other types of additives. [00051 Among these, compounds with rapid curing reactivity to gelatin and high crosslinking efficiency are effective for improving post-hardening, but in general, curing agents with excellent curing reactivity are not suitable for silver halide photographic sensitization. It has the disadvantage of deteriorating the development progress of the material, which leads to a decrease in photosensitivity. Another problem is that quick-acting curing agents generally have an active cross-linking reaction with gelatin, so if they are added directly to the coating solution, they can cause a gelation phenomenon, causing fatal coating failures such as unevenness and trailing. . [0006] Therefore, most fast-acting curing agents are not added at the time of preparing the coating liquid, but are added in-line to the coating liquid during the coating process. [00071 Therefore, it is required to be stable under various conditions such as storage, temperature, time, stirring, etc.). [00081 1- However, some curing agents, including the above-mentioned aldehyde-type compounds, are chemically unstable, easily polymerized or depolymerized during storage, and have low water solubility. There are many things that deteriorate and precipitate. [0009] In particular, with aldehyde-type curing agents, the material itself is unstable when stored after production, and as a result, the cross-linking reaction to the amino groups of gelatin fluctuates (-easy, stable, and has excellent film physical properties and photographic properties). Therefore, it is strongly desired to develop a silver halide photographic material using a stable curing method using an aldehyde curing agent.[0010]

[Purpose of the invention]

Therefore, a first object of the present invention is to provide a silver halide photographic material in which gelatin curing action and photographic properties can be stably obtained by using an aldehyde type curing agent. [0011] A second object of the present invention is to provide a silver halide photographic light-sensitive material using a curing method that is fast-acting and has little potash post-curing property. Other objectives will become apparent from the description below. [0012]

[Structure of the invention]

As a result of intensive studies, the present inventors have found that the above object can be achieved by the following method, and have completed the present invention. [0013] That is, in a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing an aldehyde type curing agent on a support, the aldehyde type curing agent contains at least one kind of alkaline agent. This was easily achieved by using a silver halide photographic light-sensitive material that contains silver halide. The present invention will be explained in detail below. [0014] As an organic hardening agent for photography, aldehyde compounds such as formaldehyde are excellent hardening agents because they are fast-acting hardening agents, have good water solubility, are highly pure, have high chemical reactivity, and are relatively inexpensive. It is considered one. [0015] However, formaldehyde solutions are unstable upon storage and generate formic acid and paraformaldehyde. It is also known that when stored in an aqueous solution, a dissociation reaction occurs depending on the storage temperature, time, and pH. [0016] Such a change in the degree of polymerization changes the degree of crosslinking to gelatin-amino groups, resulting in lot-to-lot variation in the degree of curing of the photosensitive material. [0017] The hydrophilic colloid layer of a silver halide photographic light-sensitive material referred to in the specification refers to all the layers constituting the silver halide photographic light-sensitive material, for example, substantially the photosensitive silver halide emulsion layer. Silver halide emulsion layers, photosensitive silver halide, protective layers for emulsion layers, interlayers, filter layers, ultraviolet absorbing layers that have photosensitivity of 1 to 1 or 12 do not directly contribute to image formation. layer, antihalation layer, antistatic layer, barrier/
-layer, timing layer, release layer, mordant layer, scavenger layer, backing layer, protective layer of the backing layer, or subbing layer of the photographic material element. As the binder used in these hydrophilic colloid layers in the present invention, gelatin is most preferably used, but gelatin may be treated with so-called alkali-treated gelatin, which is treated with lime or the like during the derivation process from collagen. , or so-called acid-treated gelatin that involves treatment with hydrochloric acid etc., amino groups, imino groups as functional groups contained in gelatin molecules,
Reacts with a hydroxyl group or a carboxyl group and is treated and modified with a reagent;
: For example, phthalated gelatin, succinated gelatin, 1-.
Any gelatin derivatives commonly used in the industry, such as so-called gelatin derivatives such as limerized gelatin, and modified gelatin, can be used. [0018] Mag: Many synthetic or natural polymers can also be used in combination with these gelatins. These polymers 6 and 7 can be used, for example, in Riza-di Fusukuro-De V-(RD) No. 18716 (1979) 2.
Examples include those listed in the left column on page 6. [001,9] The aldehyde type curing agent according to the present invention 7 refers to all compounds conventionally known as photographic curing agents, such as aldehyde, acetyldehyde, acrolein, glyoxal, Examples include rifucinaldehyde, glutaralanide, dialdehyde starch, etc., which are easily available as commercial products. The alkaline agents used as agents may be any of the usual ones, such as alkali metal salts, lamb salts, etc.
There are no particular limitations as long as they exhibit alkalinity in aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium sulfite, ammonium carbonate, and sodium phosphate. [0021] The amount of these alkaline agents used as a stabilizer in the aldehyde type curing agent according to the present invention varies depending on the type and amount of the aldehyde type curing agent, usage conditions, storage conditions, etc., but usually aldehyde type sand 1 to 10 per mole of curing agent
00 mg, preferably 10 to 500 mg,
More preferably, 30 to 100 mg is sufficient to achieve the effects of the present invention. [0022] The aldehyde type curing agent containing the above-mentioned alkaline agent according to the present invention can be dissolved in water or a hydrophilic organic solvent such as methanol, ethanol, acetone, methyl cellosolve, etc. alone or in a mixed solvent with water. can be used. Particularly preferred is water or a mixed solvent of water and methanol. [0023] The aldehyde type curing agent containing the above-mentioned alkaline agent according to the present invention has a finished pH of 4.0 to 10 as a curing agent solution.
．． It may be in the range of 0, preferably 5.5 to 9.0
[0024] The curing agent solution of the present invention may contain two or more aldehyde curing agents, and may also contain other known photographic curing agents or Photographic additives may also be included. [0025] The amount of the aldehyde type curing agent containing the above-mentioned alkaline agent according to the present invention is determined based on the amount of gelatin contained in the hydrophilic colloid layer.
It may range from 0.1 mg to 10 g per g, preferably 1
The effects of the present invention are well exhibited at mg to 5 g, more preferably from 10 mg to 3 g. [0026] The addition time may be any time during the production or coating process of the constituent layers of the silver halide photographic light-sensitive material, but it is preferably added in-line at the time of coating the hydrophilic colloid layer. [0027] In the most preferred embodiment of the present invention, an alkaline agent is added to the curing agent powder or solution to adjust the pH to 4 to 10.
By adjusting the hardening agent within this range, it is possible to prevent variations in performance due to lot variations in the curing agent. [0028] The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochlorobromide, etc., but those with particularly high sensitivity are preferred. Silver iodobromide is preferable in that it can be used. [00291 The silver halide grains in the photographic emulsion are cubic, octahedral, 1
A polyhedral crystal such as a tetrahedron (all grown isotropically), a polyhedral crystal such as a sphere, a twin crystal with planar defects, or a mixture thereof, or a composite. It may be a type. The grain size of these silver halide grains is
The particles may be fine particles of 0" μm or less to large particles of up to 20 μm. [00301] The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure - The Ya = (RD) No. 17643
(January-February 1978)・Pages 22-23 1-・Emuls:ion Prepar″atic
n and 'cypes) and the same (RD) No,
18716 (January-January, 1979), page 648. [0031,] The emulsion of the silver halide photographic light-sensitive material according to the present invention is, for example, 1. by James “i” het, heor
y of tlie photography Y)
roc, ess 4th edition, Macrn i 1]
The method described in published by Ansha (1977, pp. 38-104),
G, F, ]) auffin “Photography, Emulsion Chemistry J
”Photographic emulsion Ch
emistry”,, Focal ptess?
Published (1966) by P. G1afkides.
ique photographjq+ie Pau
i Montel Graduation JJ (1967)
Written by V. L. Zelii <man et al. [Preparation of photographic emulsions 1
4 and coating-1”Making and coattin
g photography emu'l;ion
It is prepared by the method described in Focal press 'ft (1964). [0032] That is, solution conditions such as neutral method, acidic method, ammonia method,
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell method, and combination methods thereof. [0033] A preferred embodiment of the present invention is a monodispersed emulsion in which silver iodide is localized inside the grains. A monodispersed emulsion as used herein means that at least 95% of the grains in terms of number or weight are within ±40% of the average particle diameter, preferably within 2303 mm, when the average grain diameter is not measured by a conventional method. They are silver halide grains. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. [0034] The crystal structure of the silver halide may have different silver halide compositions inside and outside. [0035] The emulsion as a preferred embodiment of the present invention is a core/shell type monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer. The silver iodide content of the high iodide portion is 20 to 40 mol%, particularly preferably 20 to 30 mol%. Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
No. 55-142329, No. 58-49938, British Patent No. 1.413.748, US Patent No. 3.574.628
No. 3.655.394. [0036] As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. Note that methods for obtaining the core/shell emulsion include, for example, British Patent No. 1.027.146 and US Patent No. 3.505.0.
No. 68, No. 4.444.877, JP-A-60-143
This is detailed in publications such as No. 31. [0037] The silver halide emulsion used in the present invention may be tabular grains with an aspect ratio of 3 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness.
9.520 No. 4. ．． No. 433.048, 4. A,
Emulsions can be prepared by methods described in publications such as No. 14.310 and No. 4.434.226. [00383 Above 1. :? , = The emulsion may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. good. These emulsions are treated with cadmium salts, lead salts, zinc salts, thallium salts,
Iridium salts or complex salts thereof, rhodium salts, iron salts, complex salts thereof, etc. may also be used. The emulsion may be washed to remove soluble salts by a water washing method such as a Nurdel water washing method, a flocculagecon sedimentation method, or an ultrafiltration method. Preferred water washing methods include, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or a method using an agglomerating polymer agent exemplified G3 as described in JP-A No. 63-158644. ．． G
A particularly preferable desalting method is a method using a method such as No. 8. [00393] In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of known additives include compounds described in Research Disclosure No. 1-7643 (January-February 1978) and Research Disclosure No. 1-8716 (November 1979). The following table lists the types of compounds and their descriptions in these two research disclosures. [00403 Additive RD-17643RD-18716
Page Classification Page Classification Chemical sensitizer 23III648-Upper right sensitizing dye
23 IV 648 right-64
9 Left development accelerator 29 XXI
648-Top right antifoggant 24 VI
649-Lower right stabilizer //// Color stain prevention agent 25 VII 65
0 Left-Right Image Stabilizer 25// Ultraviolet Absorber 25-26 VIII
649 Right-650 Left Filter Dye //// Brightener 24 V Hardener 26 X 651
Left coating aid 26-27 XI
650 Right Surfactant 26-27 XI
650 Right plasticizer 27
0 right binder 26 IX 6
Examples of supports that can be used in the photosensitive material according to the present invention include those described in the left column of page 28 of RD-17643 and page 647 of RD-18716.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc., in order to improve the adhesion of the coating layer. . The emulsion according to the present invention can then be coated on one or both sides of the support thus treated. The present invention is applicable to all silver halide photographic materials, and is particularly suitable for high-sensitivity black and white photographic materials. [0042] When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is desirable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention. [0043] The penetrating radiation herein refers to high-energy electromagnetic waves, and means X-rays and gamma rays. [0044] In addition, the fluorescent intensifying screen refers to, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a fluorescent intensifying screen whose main component is a rare earth compound activated with delbium. . [0045] [0045] Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.2 μm were used as cores, and iodine particles containing 30 mol% of silver iodide were used as cores. Silver bromide was grown at pH 9.3, pAg 7.5, and then equimolar amounts of potassium bromide and silver nitrate were added at pH 7°8°pAg 8.9. , an average grain size of 1-021-02 such that silver iodobromide grains have an average silver iodide content of 2.3 mol.
57-z, 0.987-zrn(B), 0.60/
Preparation of monodisperse emulsion grains of 1rn(C) 1.7':. The emulsion is desalted to remove excess salts using a conventional flocculation method. That is, the mixture was kept at 40° C., and an aqueous solution of a formalin condensate of naphthalenesulfonic acid sulfur/sulfur/cum and magnesium sulfate was added to cause coagulation. ] - After removing the clear liquid, pure water up to 40°C was further added, and an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed. [0047] Next, particles (A), (B), and (C) were each treated with ammonium thiocyanate salt at a concentration of 1.9 XiO per mole of silver.
3 mol, and appropriate amounts of chloroauric acid, hypo, and spectral sensitizing dyes A and B described below at a weight ratio of 200:1, with a total amount of 800 mg per mol of silver halide, and chemical ripening was carried out. 1-5 minutes before completion, 200 mg of potassium iodide was added per mole of silver7, and then 4-hydroxy-
6-Methyl-1,3,3a, 7-chitrazaindene was stabilized at 3 x 102 moles, and three types of emulsion grains were mixed in descending order of size: (A) 25%, (B) 40%, and (C) 35%. Then, the additives listed below and lime-treated gelatin were added to prepare an emulsion coating solution. [0048] The spectral sensitizing dyes used for sample preparation are as follows. [0049] Sensitizing dye (A) 5.5'-dichloro-9-ethyl-3,3'-di(3
-Sulfopropyl)oxacarbocyanine sodium salt anhydride sensitizing dye (B) 5.5'-di(butoxycarbonyl) -1,1'-
The additives used in the anhydride or emulsion solution (photosensitive silver halide coating solution) of diethyl-3,3'-di(4-sulfobutyl)benzimidazolocarbocyanine sodium salt are as follows. The amount added is expressed per mole of silver halide. [0050] 1.1-dimethylol-1-bromo-1-nitromethane 65m. t-butyl-catechol 400m
g Polyvinylpyrrolidone (molecular weight 10,000)
1.0g styrene-maleic anhydride copolymer
2.5g trimethylolpropane
10g diethylene glycol 5
g Nitrophenyl-triphenylphosphonium chloride 50mg1
．． Ammonium 3-hydroxybenzene-4-sulfonate 4g
Sodium 2-mercaptobenzimidazole-5-sulfonate 15m
g04H90CH2CH(OH)CH2N(CH2CO
OH) 21g 1-phenyl-5-mercaptotetrazole 50mg [0051]

[0052] The additives used in the protective layer solution are as follows. The amount added is shown per coating liquid 1-1. [00531 Lime-treated inert gelatin 68° acid-treated gelatin 2g isoamyl-
Sodium n-decyl sulfosuccinate 1g Polymethyl methacrylate - 1.1g Matting agent with an area average particle size of 3°5 μm
Matting agent with silicon dioxide particles area average particle size 1.2μm 065g
Ludox AM (manufactured by DuPont) (colloidal silica) 30g 2mg in 04F9803 [0054]

[0055] Apart from the above various additives, a curing agent solution according to the present invention was prepared as follows [0056] ■) Preparation of formaldehyde curing agent solution Commercially available 37% formaldehyde was mixed with different lofts. We prepared 5 types, each with A. B, C, D, and E. 300 as formaldehyde
mg, diluted with water, and added as an alkali agent according to the present invention as shown in Table 1 below to prepare a formaldehyde hardening agent solution. [0057] 2) Preparation of glyoxal curing agent solution Five different lots of commercially available 40% glyoxal were prepared, F and G, respectively. H, I, and J. 300 mg of glyoxal was collected, diluted with water, and added as an alkaline agent according to the present invention as shown in Table 1 below to prepare a glyoxal curing agent solution. [0058] The obtained solution was added as a curing agent solution to the coating solution for a protective layer as shown in Table 1. [0059] Then, an emulsion layer was formed on one side on a polyethylene terephthalate film base having a thickness of 175 μm that had been subjected to subbing treatment. The amount of gelatin is 20rng/dm', the amount of silver is 30mg, /
drn'''', the -yp radiation amount of the protective layer is 12rng/
An emulsion layer and a protective layer were simultaneously coated on both sides of the base in order from the support so that the coating amount was dm2. If the moisture content of the film is 100% or more under drying conditions, ■) 830℃, W
B At 13°5°C, film moisture content is below 00% 3
00% or more was dried at DB 32°C and WB 22°C to obtain a sample. [00603 The obtained sample was left for 2 days at a temperature of 25° C. and a relative humidity of 48% 1-. [0061] Next, the curability and photographic performance of the coating films were measured in the following manner. [0062] (Measurement of melting point of membrane) Sample strip was kept warm at 50°C /:: 1.5% of caustic soda
Immersion in aqueous solution1. The time taken for the layer to start melting was measured and determined as the melting point of the film. [0063] (Photographic performance) Use the standard light B described in the "New Edition, Lighting Data Book" as a light source, and use an exposure time of 0.1 seconds and 3 degrees Oems, and use a non-filter to ensure the same amount of light on both sides of the film. exposed to light. The above sample was prepared using a 5RX-501 automatic processor (Konica Co., Ltd.).
The sensitivity of each sample was determined by processing with XD-3R developer for 45 seconds. The sensitivity was determined by the reciprocal of the amount of light required for the blackening density to increase by 1.0, and the sensitivity of sample No. 3 was expressed as a relative sensitivity of 100 and I~. [0064] The results obtained are shown in Table 1 below. -1, shown in Table 1--2. [0065]

[Table 1] [0066]

[Table 2] [00673] The apparent molecular weights of formaldehyde (HCHO molecular weight 30) and glyoxal (Ol-(C-CHO molecular weight 58)) vary depending on the conditions during production, the storage conditions after production, the number of H stored, etc. [0068] The apparent molecular weight was measured by the freezing point depression method, and the measurement solution was 1
-3° using a 0x diluted solution, and the formaldehyde concentration was measured by the iodometric titration method (JIS K8872).
Glyoxal was measured by a neutralization titration method using hydrochloric acid after Canitzaro reaction with an alkali. [0069] A-E of formaldehyde and F-J of glyoxal
The measured values are shown in Table 2. [0070]

[Table 3] [0071] Example 2 The 20 samples used in Example 1 were heated at a temperature of 25°C and a relative humidity of 4.
The samples were stored under 8% 2B for 3 and 5 days, and changes in the dura mater over time were examined. [0072] The melting points of the films in the table were measured in the same manner as in Example 1. The results obtained are shown in Table 3-1.3-2 below. [00733

[Table 4] [0074]

[Table 5] [0075]

【Effect of the invention】

According to the present invention, it was possible to prevent variations in performance due to lot variations in aldehyde type curing agents. [0076] As a result, a silver halide photographic material with stable curing action on gelatin and stable photographic properties could be obtained.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer containing an aldehyde type hardener on a support, wherein the aldehyde type hardener contains at least one alkaline agent. A silver halide photographic material comprising: