JPH0640202B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material.

[Background of the Invention]

Generally, mechanical stress is often applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, in the case of a negative film for general photography, when it is wound in a cartridge or loaded on a camera, stress such as bending or pulling for frame advance is applied.

On the other hand, in the case of a sheet-shaped film such as a photosensitive material for printing or a direct medical roentgen photosensitive material, a person often handles the film directly by hand, and a stress such as bending or bending often occurs.

Further, cutting and processing steps are indispensable in the process of commercializing all light-sensitive materials, and at that time, large stress is applied.

As described above, various stresses are applied to the photographic light-sensitive material, whereby stress is applied to the silver halide grains through gelatin which is a holder (binder) of silver halide grains and a plastic film which is a support. It is generally known that when stress is applied to silver halide grains, the photographic performance of photographic light-sensitive materials changes. For example, KB Mather "Journal of Optical
Society of America "(KB Mather, J.Opt.So
c.Am.) 38 , 1054 (1948), P. Faelenls and P.de, Smet.Sci.et.Ind.Pho.
t.) 25 , No.5,178 (1954) P. Farrens "Journal Photographic Science" (P.Faelens.J.Pho
t.Sci. 2 , 105 (1954) and so on.

When stress is applied to the light-sensitive material, desensitization occurs in that portion, which causes sensitization or fog, which significantly deteriorates image quality. As a result, there is a risk that, for example, an X-ray sensitive material may cause a misdiagnosis, and an urgent improvement is required.

Therefore, it is strongly desired to provide a photographic light-sensitive material whose photographic performance is less affected by these stresses.

As described above, when stress is applied to the light-sensitive material, pressure is applied to the particles through the holding body or support of the particles, and the photographic performance is changed. As a means, conventionally, a method of containing a plasticizer such as a polymer or an emulsion, a method of reducing the silver halide / gelatin ratio of a silver halide emulsion, or the like to prevent pressure from reaching the grains is known. .

For example, US Pat. No. 738,618 describes heterocyclic compounds.
Alkyl phthalate in 38,637, alkyl ester in 738,639, polyhydric alcohol in U.S. Pat.No. 2,960,404, carboxyalkyl cellulose in 3,121,060, and paraffin in JP-A-49-5017. Japanese Patent Publication No. 53-28086 discloses a method of using a carboxylic acid salt and an alkyl acrylate and an organic acid.

However, in the method of adding a plasticizer, the mechanical strength of the emulsion layer is lowered, so that the amount used is limited, and increasing the amount of gelatin causes various problems such as a slower development processing speed. Even if the method is used, it is difficult to achieve a sufficient effect. Therefore, it is desired that the particles themselves have strong pressure resistance.

By the way, for example, when pressure is applied to an emulsion formed by adding silver nitrate to a solution containing gelatin, potassium bromide and potassium iodide, the photosensitivity is remarkably lowered, which is extremely inconvenient in practical use. Therefore, the property of desensitizing to light when such stress is applied is formed by adding pure silver bromide or a solution of silver nitrate and a halide by the double jet method so as not to re-nucleate. This property is improved with perfectly uniform silver iodobromide grains. However, on the other hand, the particles become remarkably easily fogged against stress, which is not preferable in practice.

On the other hand, Japanese Laid-Open Patent Publication No. 53-22408 discloses that the development activity can be increased and the sensitivity can be enhanced by a laminated silver halide grain having a plurality of shells on the outside of the inner core. Publication No. 43-13162, Journal of Photographic Science (J.Photo.Sci.) 24 , 198 (197
There is a description in 6) etc.

However, the silver halide grains obtained for these purposes do not necessarily improve the pressure characteristics, and problems such as desensitization and fogging due to stress still occur. For example, JP-A-53-22408 describes a laminated type silver halide grain composed of pure silver bromide (internal core) / silver iodobromide (containing iodine / mol%) / pure silver bromide. However, since fog is strongly generated due to pressure, there is a problem similar to the above-described conventional completely uniform silver iodobromide emulsion from the viewpoint of pressure characteristics.

Silver halide grains having a coating layer formed by substituting the outermost layer of silver halide grains with halogen are West German Patent No. 2932650,
JP-A-52-2417, JP-A-51-17436, and JP-A-52-11927
It is described in the official gazette. These silver halide grains have an effect of accelerating the fixing speed, but on the contrary, they are not preferable in practical use as a negative working emulsion because they inhibit development and cannot provide sufficient sensitivity.

Further, a positive type (internal latent image type) silver halide grain having a plurality of coating layers on the outside of the inner nucleus by halogen substitution is known, and US Pat. Nos. 2,592,250 and 4,075,0
The details are described in JP-A No. 20 and JP-A-55-127549. These silver halide grains are often used for internal latent image type direct positive light-sensitive materials for diffusion photography, etc., and because they have naturally too high internal sensitivity, they can be used as negative emulsions. Can not.

Sensitizing the surface of silver halide grains of this type is also described in West German Patent 2,932,650, but the use of such a silver halide emulsion does not improve the pressure characteristics.

For example, in the above-mentioned JP-A-55-127549, almost 100% of the inner core is converted to silver iodide by converting chlorine in the inner core (core) into bromine and bromine into iodine, and then Although a silver halide emulsion coated with silver iodobromide is described, it cannot be used because pressure desensitization is strongly generated. Even if the grain surface is subjected to a sensitizing treatment to be a negative type, pressure desensitization still occurs strongly, so that it is not practical.

Therefore, as a technique for improving these pressure characteristics, JP-A-59
There are core-shell type emulsions described in JP-A-178447 and JP-A-60-35726. As shown in FIG. 2, the structure of this silver halide grain has an inner core 4, a first coating layer 5 containing a high concentration of iodine on the outside thereof, and a low concentration of iodine on the outside thereof. It has a second coating layer 6 made of silver iodide or pure silver bromide. Although it is possible to improve the pressure characteristic to some extent by using these techniques, it is not sufficient yet. Therefore, it is desired to further improve the pressure characteristics and obtain silver halide grains having further pressure resistance.

That is, the object of the present invention is to solve the above-mentioned problems and to provide a silver halide grain having pressure resistance, whereby the sensitivity change due to stress is reduced, and pressure blackening, pressure desensitization and pressure fog are reduced. An object is to provide a good silver halide photographic light-sensitive material.

[Structure and Action of Invention]

The silver halide photographic light-sensitive material of the present invention contains silver halide grains as schematically shown in FIG. That is, the silver halide grains in the present invention are silver chloroiodide bromide,
It has an internal core 1 of silver iodobromide or silver bromide. On the outside of the inner core 1, a first coating layer formed by an iodine substitution method or by reacting iodine ions with silver ions at a ratio of 25 mol% or more with respect to all halogen ions at the time of forming the first coating layer. Have two. A second coating layer formed on the outside of the first coating layer 2 by reacting with silver ions under the condition that the bromine ion / iodine ion ratio is 10 mol% or more and more bromine ions are present than when the first coating layer was formed. Have three. The second
On the outer side of the coating layer 3, there is a third coating layer 4 formed by reacting with silver ions under the condition that the ratio of iodine ions and bromide ions is 12 mol% or more and iodine ions are smaller than when the second coating layer is formed. . Further, the average aspect ratio of the silver halide grains is less than 8: 1, and the light-sensitive material of the present invention is configured to contain such silver halide grains.

The silver halide grain has an internal nucleus, and the internal nucleus is a portion forming the central portion inside the grain. The inner core may be composed of silver chloroiodobromide, silver iodobromide, or silver bromide.

When iodine is contained in the inner core of the particles in the present invention, the iodine content is preferably 20 mol% or less.

In the present invention, in the case of the internal core, the preferable proportion of silver occupied by each part of the grain is preferably 40 mol% or less of the total grain, and particularly preferably 0.5 mol% to 20 mol%. In the first coating layer, it is preferably 10 mol% or less, particularly preferably 0.0005 mol% to 4 mol%. In the second coating layer, it is preferably 30 mol% or less, particularly preferably 1 mol% to 10 mol%. In the third coating layer, it is preferably 30 mol% or more, particularly preferably 40 mol% or more.

The first coating layer of the silver halide grains can be formed by an iodine substitution method or a method of reacting iodine ions with silver ions to newly coat the inner nucleus with a layer.
The iodine substitution method is a method of forming a coating layer by adding an aqueous solution of an iodine compound or the like after the formation of the inner nucleus and substituting the inner nucleus surface with iodine.

In the present invention, when the second coating layer and the third coating layer of particles are formed, the above-mentioned ratio of added iodine ion and bromine ion is the same as the iodine ion and bromine ion of the halogen solution when forming each coating layer. The ratio is defined as the standard. If the ratio of bromine ion to iodine ion at the time of forming the first coating layer and the second coating layer and the second coating layer and the third coating layer is not within the range of the present invention, no improvement in pressure resistance can be seen, or the inner layer and the outer layer. When the ratio of iodine ions and bromine ions during formation is too large (for example, the first coating layer iodine ions 10
0%, bromine ion 0%, second coating layer iodine ion 0%,
In the case of 100% bromine ion), fog often increases and sensitivity is lowered, which is not preferable. As an addition method, iodine ions and bromine ions may be mixed in advance and added, or they may be added individually.

The inner core and the first to third coating layers in the particles of the present invention may contain 1 mol% or less of chloride ion or a metal other than silver as the average content of each layer.

Although the particles of the present invention have three coating layers outside the inner core, more coating layers may be formed. In that case, in order to maintain the excellent pressure resistance of the silver halide grains, it is desirable to form the silver halide grains with a solution having a smaller iodine ion ratio than the third coating layer. However, in reality, even if the layer structure is increased in the first layer to the third layer or more, the performance is not so improved, and the manufacturing cost is increased, which is not so useful.

The silver halide grains of the present invention have an average aspect ratio of 8: 1.
Is less than. Here, the aspect ratio means the ratio of the diameter of a circle having an area equal to the projected area of a particle to the thickness of the particle. The thickness is represented by the distance between two parallel major faces of a silver halide grain. The average aspect ratio is the average value of the aspect ratios of the entire photosensitive particles. The use of particles having an average aspect ratio of less than 8: 1 improves pressure characteristics such as pressure fog.

The size distribution of the silver halide grains of the present invention is arbitrary, but monodisperse is more preferable. Here, the monodisperse refers to a dispersion system in which 95% of particles have a size within ± 60% of the number average particle size, preferably within ± 40%. Here, the number average particle diameter refers to the number average diameter of the projected area diameters of the particles.

The ratio of the grains in the emulsion layer containing the silver halide grain size of the present invention contained in the layer is arbitrary, but is preferably 40% or more in terms of silver amount based on the total silver halide grains,
It is particularly preferably 90% or more.

Next, a method for producing an emulsion containing silver halide grains of the present invention will be described. First, after forming an inner nucleus composed of silver chloroiodobromide, silver bromide or silver iodobromide (iodine content of 10 mol% or less), silver iodobromide or a coating method is applied on the inner nucleus. A first coating layer made of silver iodide is formed, and a second coating layer made of silver iodobromide having a halogen composition different from that of the first coating layer is provided on the first coating layer. A third coating layer made of silver iodobromide or silver bromide having a halogen composition different from that is provided. In this production method, the iodide content of the first coating layer is set to 20 mol% or more than the inner core, and the silver content of the first coating layer is 10% or less of the entire silver halide grains. To do.

The inner core of the silver halide grain of the present invention is produced by P. Glafkides by Chamie et Physi (Chamie et Physi).
gue Ptotographigue, Paul Montel) 1967, GF Duffin, Photography Emulsion Chemistry, published by The Focal Press
(Photographic Emulsion Chemistry, The Focal Press) 19
1966, Buj El Zlikmann et al. (VL Zelikman et al)
By Making and Coating Photographic Emulsion, published by The Focal Press (Makin
g and Coating Photographic Emulsion, The Focal Pres
s) It can be prepared using the method described in 1964 or the like. Specifically, any of the acidic method, the neutral method, the ammonia method and the like may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Further, a method of forming particles in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced (so-called controlled double jet method) can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

When preparing the inner nucleus of the silver halide grain, the halogen composition is preferably uniform. Therefore, when the inner core is silver iodobromide, it is preferable to use the double jet method or the control double jet method. When the inner core is silver bromide, the one-sided mixing method is preferable.

The pAg for preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 7
Is ~ 11. Further, a silver halide solvent is preferably used so that the grain formation time can be shortened. For example, a silver halide solvent such as ammonia or thioether can be used.

The shape of the inner core may be a plate, a sphere, a twin system, or may be an octahedron, a cube, a tetradecahedron or a mixed system.

The inner core may be polydisperse or monodisperse, but monodisperse is more preferable.

In addition, in order to make the particle size uniform, US Pat.
No. 6, JP-B-48-36890, JP-A-52-16364 and the like, a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the grain growth rate, U.S. Pat.
As described in JP-A No. 242,445, JP-A-55-158124, etc., it is preferable to grow rapidly within a range not exceeding the critical degree of supersaturation by using a method of changing the concentration of the aqueous solution. By using such a method, since re-nucleation is not caused and each silver halide grain is uniformly coated,
It can be preferably used also when introducing the 1st and 2nd coating layers mentioned below.

During the process of forming the internal nucleus or physical ripening of silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt,
An iridium salt or its complex salt, a rhodium salt or its complex salt, an iron salt or an iron complex salt, etc. may coexist.

The first coating layer of the silver halide grain of the present invention may be formed by subjecting the formed inner core to a desalting step, and then a usual iodine substitution method, or a method of reacting iodine ion and silver ion to coat the layer. Can be provided by.

The iodine substitution method can be carried out, for example, by adding an aqueous solution mainly containing an iodine compound (preferably potassium iodide) after the inner core is formed, preferably an aqueous solution having a concentration of 10% or less. At this time, 0.01 to the number of moles of silver in the completed grains
Add 30 mol% iodine compound. At this time, pA
It is preferable that g is 5 to 12. For this,
It can be carried out by the method described in US Pat. Nos. 2,592,250, 4,075,020, JP-A-55-127549 and the like. At this time, in order to reduce the difference in iodine distribution between the particles of the first coating layer, it is desirable to adjust the concentration of the aqueous iodine compound solution to 10 ^-2 mol% or less and to add it for 10 minutes or more.

As a method for newly coating the inner nucleus with silver halide, a so-called simultaneous mixing method in which an aqueous solution of halide and an aqueous solution of silver nitrate are simultaneously added, or a control double jet method can be used. For details, refer to JP-A-53-22408, JP-B-43-13162, and Journal Photographic Science (J.Photo.S).
ci., 24, 198 (1976) and the like.

At this time, it is 0 with respect to the number of moles of silver in the completed grains.
Add an iodine compound in an equimolar amount or more (up to about twice as much) as 01 to 30 mol% silver nitrate and optionally a halide aqueous solution containing silver bromide.

The pAg for forming the first coating layer is the reaction temperature,
Although it varies depending on the kind and amount of the silver halide solvent, those described above are preferably used in the same manner.

As a method for forming the first coating layer, a simultaneous mixing method or a control double jet method is more preferable.

The second coating layer of the silver halide grain of the present invention is a mixture of silver halide having a halogen composition different from the halogen composition of the first coating layer, which is simultaneously mixed outside the inner core having the first coating layer on the surface. Alternatively, it is provided by a method such as coating with a control double jet method.

Regarding these methods, the method of providing the first coating layer described above is similarly used.

When introducing the second coating layer, the halogen composition of the second coating layer is different from the halogen composition of the first coating layer. Second
Since the coating layer may be difficult to precipitate on the surface of the first coating layer, it is necessary to consider the change in the critical supersaturation degree. Further, it is preferable to increase the number of moles added per unit time along with the increase in the total surface area of the particles.

Regarding the iodine content of the first coating layer of the silver halide grain of the present invention, for example, JI Goldstein (Goldstei
n), DB Williams, "X-ray analysis in TEM / ATEM," Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute), Item 651 (March 1977). It can also be determined by the method described in.

The third coating layer of the silver halide grain of the present invention comprises a silver halide having a halogen composition different from the halogen composition of the second coating layer on the outside of the second coating layer having the second coating layer on its surface. Similar to the case of providing the second coating layer, it can be provided by a method of coating by a double jet method or a control double jet method.

In order to remove soluble salts from the emulsion after the formation of the precipitate of the third coating layer or after the physical composition or, if necessary, from the emulsion after the formation of internal nuclei or after the formation of the first and second coating layers, gelatin is gelatinized. It is possible to use the Maidel washing method performed by Further, a precipitation method (flocculation) using an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid), or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) can be used.

The grain surface of the silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, Etch Freezan H.
Frieser), Die Grundlagen der Photographischen Prosess m.
it Silberhalogeniden, Akademische Verlagageacllsch
aft) The method described in 1968, 675 to 734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include US Pat.
10,689, 2,278,947, 2,728,668, 3,656,955,
4,032,928 and 4,067,740. As reduction sensitizers, primary tin salts, amines, hydrazine derivatives,
Formamidinesulfinic acid, silane compounds and the like can be used, and specific examples thereof are US Pat. No. 2,487,850.
No. 2,419,974, 2,518,698, 2,983,609, 2,98
3,610,2,694,637, 3,930,867, 4,054,458. In addition to gold complex salts, complex salts of metals of Group VIII of the Periodic Table such as platinum, iridium and palladium can be used for noble metal sensitization, and specific examples thereof are described in US Pat.
No. 9,083, No. 2,448,060, and US Pat. No. 618,061. These compounds can be used alone or in combination.

The silver salt particles of the present invention can be used in combination of two or more of these chemical sensitization methods.

The coated silver amount is arbitrary, but preferably 1000 mg / m ² or more 150
200 mg / m ² or less is but more preferably 2000 mg / m ² or more,
It is 10000 mg / m ² or less.

Further, the photosensitive layer containing the particles may be present on both sides of the support.

Gelatin is advantageously used as the binder or protective colloid of the photographic light-sensitive material of the present invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, protein compartments such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymers such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. be able to.

In addition to lime-processed gelatin, acid-processed gelatin and bulletin-society-scientific
Photography of Japan (Bull.Soc.Sci.Phot.J
apan) No. 16, page 30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. As a gelatin derivative,
Obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds Things are used.

The photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the production process of the light-sensitive material, storage during storage or photographic processing, and stabilizing the photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, eg triazaindene , Tetraazaindenes (especially 4-
Hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; benzenethiosulfonic acid,
Many compounds known as antifoggants or stabilizers such as benzenesulfinic acid, benzenesulphonic acid amide and the like can be added.

Particularly preferred antifoggants and stabilizers are disclosed in JP-A-58 / 58
-158631, 58-200232, 58-203432, 58-2070
40, 58-224349, 59-34530, 59-166941,
58-217928, 60-76743, JP-B-50-40665, 5
2-28660 No. USP-2628167 etc. are mentioned. These compounds can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration,
Various surfactants may be included for various purposes such as increasing contrast and sensitizing.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars Agents; alkyl carboxylates, alkyl sulfonates,
Alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl Anionic surfactants containing an acidic group such as carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group such as phosphoric acid ester; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid ester , Alkyl betaines, amine oxides and other amphoteric surfactants; alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Among them, as a preferable example, in the polyalkylene compound system, JP-A-58-158630, JP-A-52-203435 and JP-A-58-208743 are used.
It is preferable to use the compounds described in U.S. Pat.

Further, as a preferable fluorine-containing surfactant, JP-A-60
-164738 is mentioned. These compounds can be used alone or in combination.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and the like. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. With sensitizing dye,
Since the dye itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light, a substance exhibiting supersensitization may be included in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resea
rch Disclosure) Volume 176 17643 (December 1978) Page 23 IV
, Page J.

It is particularly preferable to use the compounds disclosed in JP-B-43-22184 and JP-B-51-31228.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (diethylolurea, methyloldimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3.5-triacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4- Dichlor
-6-Bidroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), etc. can be used alone or in combination.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.
For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination with methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. can be used.

The matting agent has an average particle size of 0.5 μm to 15 μm, preferably
Those having a thickness of 1.5 μm to 5 μm can be used. Various materials can be used as the material of the matting agent, but it is preferable to use a fluorine-containing matting agent such as polymethylmethacrylate, silicon dioxide, titanium oxide, glass or Teflon, or an alkali-soluble matting agent.

In the photographic emulsion tank of the photographic light-sensitive material of the present invention, a color-forming coupler, that is, a color is formed by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. It may also contain a compound. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, pivaloylaceanilides). , Etc., and cyan couplers include naphthol couplers, phenol couplers, and the like. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. Further, it may be a colored coupler having a color correcting effect, or a coupler (so-called DIR coupler) which releases a development inhibitor upon development. In addition to the DIR coupler, a color-free DIR coupling compound which is colorless as a product of the coupling reaction and releases a development inhibitor may be contained.

In carrying out the present invention, the following anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Examples of anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used alone or in combination. These UV absorbers may be fixed in the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hexoxonol dyes and merocyanine dyes are useful.

The light-sensitive material of the present invention comprises a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative as an antifoggant,
You may contain an ascorbic acid derivative etc.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Generally, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer. However, different combinations can be used in some cases.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. As the coating method, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used. U.S. Patents 2,681,294 and 2,7
The methods described in 61,791 and 3,526,528 are advantageous methods. The support is preferably a cellulose ester film such as a cellulose triacetate film, a polyester film such as a polyethylene terephthalate film, or a paper coated with an α-olefin polymer.

The photographic light-sensitive material of the present invention is not limited to a black-and-white light-sensitive material such as a direct or indirect Xray light-sensitive material, a lith light-sensitive material, a black-and-white photographing light-sensitive material, a color negative light-sensitive material, a color reversal light-sensitive material, a color light-sensitive material such as color paper, and the like. Can also be used for

Photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure 176 No. 28-30
Any of various methods and various processing solutions as described on page (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. Treatment temperatures are usually between 18 ° C and 50 ° C, but may be below 18 ° C or above 50 ° C.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl, -3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), etc. are used alone or in combination. be able to. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, and the like, and further contains a dissolution aid, a color tone agent, a development accelerator, a surfactant, if necessary.
A defoaming agent, a water softener, a hardener, a viscosity imparting agent and the like may be included.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thionitrate and thiocyanate, an organic sulfur compound known to be effective as a fixing agent can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (eg, “Journal of Society of Motion Picture and Television Engineers”) “(Journal of the Society
of Motion Picture and Television Engineers ”) 61
Vol. (1953), pp. 667-701); developed with a developer containing a black-and-white developing agent to produce a negative silver image, then at least one uniform exposure or other suitable fog treatment. And the subsequent color development to obtain a positive dye image (so-called color reversal method); the photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and the dye is bleached using this as a bleaching catalyst. A method (so-called silver dye bleaching method) or the like is used.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are various primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N). -Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl
N-β-methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

"Photographic Processing Chemistry" by LFA Mason
(Photographic Processing Chemistry, Focal Press) 196
6 years, pp. 226-229, U.S. Pat.Nos. 2,193,015 and 2,592,36
No. 4, JP-A-48-64933 and the like may be used.

The color developer may further contain a pH buffering agent, a development inhibitor or an antifoggant. If necessary, water softener, preservative, organic solvent, development accelerator, dye forming coupler, competitive coupler, fogging agent, auxiliary developing agent, viscosity imparting agent, polycarboxylic acid chelating agent, antioxidant May be included. These may be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitrone compounds are used.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives can be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506, JP-B-45-8836, and the thiol compounds described in JP-A-53-65732.

〔Example〕

Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the following examples.

Example 1 (Preparation of Inner Core) While controlling at 60 ° C., pAg = 8, and pH = 2.0, a double jet method was used to obtain an iodine odor having an average particle size of 0.30 μm containing 2.0 mol% of silver iodide having an average particle size of 0.3 μm A monodisperse cubic crystal emulsion of silver halide emulsion was obtained. From the electron micrograph of this emulsion, the generation rate of twin grains was 1% or more in number.

After desalting these particles, add silver nitrate solution and pAg at 60 ℃.
= 3, pH = 6, and silver ripening was performed for 70 minutes.

(Preparation of comparative grains) For 30 g of silver in the above internal core emulsion, potassium iodide
A 1.0% aqueous solution was added to 50 cc with sufficient stirring for 10 minutes to form a first coating layer, and then 700 cc of water, 14 g of gelatin and 0.1% of 3,4-dimethyl-4-thiazoline-2-thione were added. While mixing 50cc of aqueous solution of metal and stirring in a container kept at 45 ° C, keep 2.6N ammoniacal silver nitrate solution and 2.0N potassium bromide solution constant at pAg 9.0, and add ammoniacal silver ion The pH was changed from 9.0 to 8.0 in proportion to, and 0.85 μm particles (I) having the second coating layer were prepared.

(Preparation of particles having a third coating layer) After the first coating layer was provided in the same manner as the preparation of the comparative particles, the second coating layer was prepared by adding 2.0 N potassium bromide and an aqueous potassium iodide solution to the first layer.
The solutions were mixed at the mixing ratios shown in the table, and this solution and 2.6N ammoniacal silver nitrate were mixed for 15 minutes by the double jet method while maintaining the pAg of 9.0 to prepare particles having a 0.51 μm second coating layer. did.

Subsequently, a third coating layer was formed under the same conditions and under the same solution as that for forming the second coating layer of the comparative particles to prepare 0.85 µ particles (II) to (VIII). All of these were cubic monodisperse emulsions with 98% of the grains falling within ± 40% of the number average grain size. (The ratio of the projected area of the obtained particles to the pressure, that is, the aspect ratio is 1: 1).

Excessive water-soluble salts were removed from each of the obtained particles by the coagulation-precipitation method, and ammonium thiocyanate, chloroauric acid and hypo were added to perform gold-sulfur sensitization.

Then, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and a usual stabilizer, thickener and the following compounds were added to prepare an emulsion coating preparation.

・ Trimethylolpropane ・ Nitron ・ Copolyer fine particles of styrene and butadiene An aqueous solution containing the following compounds was prepared as a protective layer liquid.

The emulsion thus prepared was coated with a slide hopper coater at 150 m / mim so that the silver amount would be 4.8 g / m ² and the protective layer would be 1.1 g / m ² as the gelatin amount.
It was dried in 170 seconds to obtain samples No. 1 to No. 8.

Each sample was subjected to wedge exposure at 3.2 CMS, and developed for 90 seconds with an XD-90 developing solution using a QX-1200 automatic developing machine manufactured by Konishi Rokusha Kogyo Co., Ltd., and the sensitivity of each sample was determined. Sensitivity is expressed as a relative value with sample No. 1 set to 100, by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0 by exposure.

Two pieces of each of the obtained samples were kept at a constant temperature and humidity of 25 ° C. and a relative humidity of 35% for about 12 hours, and under this condition, the radius of curvature was 2 cm.
Then, it was bent about 280 °.

One of the two sheets was developed 3 minutes after folding and was left unexposed. The difference between the density of the blackened portion and the fog density caused by bending at this time was set as ΔD _{1 and used} as a standard for pressure blackening. That is, the smaller this value, the better the pressure blackening resistance.

The other one of the two sheets was exposed and developed using an optical wedge 3 minutes after bending. The darkening density of each wedge of this sample was measured, and the density difference between the desensitized portion caused by bending at the density 1.0 ± 0.1 portion and the portion not bent was ΔD _2, and each density D ₂ With ΔD ₂
And the average value ΔD ₂ / D ₂ was calculated, and this value was used as a guide for pressure desensitization. That is, the smaller this value, the better the pressure desensitization resistance.

The results of this pressure blackening and pressure desensitization are shown in Table 2.

In Table 2, the sensitivity of the comparative sample (Sample No. 1) is 10
The sensitivity represented by the relative sensitivity when 0 is set, and the fog density excluding the base density are also shown.

As shown in Table 2, the samples (Sample No. 5 to No. 7) of the present invention having the third coating layer are comparative samples (Samples No. 1 to No. 4) formed only to the second coating layer. It is understood that the fog is lower than that of, and the pressure resistance such as pressure blackening and pressure desensitization is improved without deteriorating the sensitivity. Also, the sample
No. 8 is a case where the formation of the third coating layer cannot be performed under the condition that the amount of iodine ions is 12 mol% or more less than that when the second coating layer is formed which is the condition of the present invention. In this case, the pressure resistance is deteriorated.

Example 2 (Preparation of Comparative Grains) The internal core grains prepared in Example 1 were grown as seed crystals in the following amount in an amount corresponding to 2 mol% of all silver halide used for growth in the emulsion. .

That is, the seed crystals were dissolved in a solution 8.5 containing protected gelatin and ammonia which was kept at 40 ° C., and the pH was adjusted with glacial acetic acid.

Using this solution as a mother liquor, 3.2N ammoniacal silver ion aqueous solution and 3.0N halide aqueous solution were added by the double jet method, followed by stirring and mixing.

In this case, the pH of the mother liquor was set to 9.7 and the pAg was set to 7.7, and layers having various silver iodide concentrations as shown in Table 3 were formed inside. An emulsion containing 5 types of particles A to E provided with a first coating layer having an average particle size of 0.39 μm was prepared.

Further, using the emulsions A to E thus obtained, pAg
A mixture solution of potassium bromide and potassium iodide having a molar ratio of KBr: KI of 86%: 14% at a pH of 7.7, pH 9.5 and 40 ° C was mixed with an aqueous solution of silver nitrate for 24 minutes. Average particle size with coating layer
0.46 μm A-2 to E-2 were prepared. Further, as a third coating layer, a 3.0N mixed aqueous solution of potassium bromide and potassium iodide prepared in Emulsions A-2 to E-2 at a molar ratio of potassium bromide and potassium iodide as shown in Table 4 was used. The pH was 9.5 to 8.0 and pAg was
Average particle size 0.96μm while continuously changing from 7.7 to 11.5
25 kinds of emulsions of tetradecahedral grains were obtained. (The ratio between the projected area and the thickness of the particles, that is, the aspect ratio is 1: 1 in each case).

These emulsions were chemically ripened in the same manner as in Example 1 to prepare the same additives and protective layer liquids, and the same coating and drying were conducted to obtain samples No. 9 to No. 33.

These samples were evaluated in the same manner as in Example 1 and the results are shown in Table 5. However, the sensitivity was expressed as relative sensitivity with sample No. 14 as 100.

As is clear from Table 5, a sample using the silver halide grains formed up to the third coating layer under the conditions of the present invention (Sample No. 1
No. 9 to No. 21, No. 24 to No. 26, No. 29 to No. 31) have the third coating layer, but the forming conditions are lower in fog than the comparative sample other than the present invention, and the sensitivity is high. It can be seen that pressure resistance such as pressure blackening and pressure desensitization is improved without any damage.

Example 3 (Preparation of Inner Core) A pure silver bromide monodisperse cubic emulsion having an average grain size of 0.18 μm was obtained by the double jet method while controlling at 50 ° C., pAg8.2 and pH3.0. From the electron micrograph of this emulsion, the generation rate of twin grains was 1% or less in number.

The particles were desalted to obtain internal core particles.

(Preparation of comparative grains) For 30 g of silver in the upper inner core emulsion, potassium iodide
45% 0.5N aqueous solution and 55% 0.5N potassium bromide aqueous solution were mixed, and 0.51N ammoniacal silver nitrate solution was simultaneously mixed for 30 minutes under conditions of pAg 7.3 and pH 10.0, and an average particle size of 0.23 Particles having a first coating layer of μm were prepared. Then shown in Table 6
A 1.0 N potassium iodide and potassium bromide mixed aqueous solution and a 1.02 N ammoniacal silver nitrate solution were added at 40 ° C. and pAg 8.3 from pH 10.0.
Simultaneous mixing while continuously changing to 9.0, average particle size 0.2
Particles with a 9 μm second coating layer were prepared. Continued,
A solution of 3.1N potassium bromide 99.9% and sodium chloride 0.1% was mixed with a 3.3N ammoniacal silver nitrate solution.
℃, pAg was changed from 8.3 to 10.2 and pH was changed from 9.0 to 7.8 continuously, and a third coating layer with an average particle size of 0.62 μm was provided 14
Emulsions containing the monodisperse grains were obtained. This emulsion was prepared by using the same sensitizer as in Example 1 with optimum chemical ripening and additives to prepare an emulsion coating solution.

The protective layer was the same as in Example 1 and was applied and dried under the same conditions to obtain samples 34 to 38. These samples were tested in Example 1.
The same evaluations as above and the results are shown in Table 6.

As shown in Table 6, the samples of the present invention (Sample Nos. 36 and 37) are
It can be seen that the pressure resistance such as pressure blackening and pressure desensitization is good without fog being low and sensitivity being kept.

Example 4 Inner core grains prepared in the same manner as in Example 1 were grown as described below with an amount corresponding to 3 mol% of all silver halide used for growth in the emulsion as a seed crystal.

That is, the seed crystal was dissolved and dispersed in a solution 8.5 containing protected gelatin and ammonia which was kept at 40 ° C., and pH was adjusted with glacial acetic acid.

Using this solution as a mother liquor, 3.2N ammoniacal silver ion aqueous solution and 3.0N halide aqueous solution (mixed solution of 65 mol% potassium bromide and 35 mol% potassium iodide) were added by the double jet method, and stirred and mixed. I did.

At this time, the pH was 9.7 and the pAg was 7.7, and the grains were grown. The ratio of silver in the first coating layer to the total amount of the finished grains was 5 mol%, 9 mol%, 13 mol%, 17 mol% and four types of Particles with one coating layer were prepared and subsequently pH 9.0, pAg8.0, 40
A mixture solution of potassium bromide and potassium iodide having a molar ratio of KBr; KI of 86:14 at a temperature of ℃ was mixed with an aqueous solution of silver nitrate, and the ratio of the first coating layer + the second coating layer to all the particles was The second coating layer was formed so as to be 22 mol%. In addition to the four types of particles thus formed up to the second coating layer, a third coating layer was prepared by adding a mixed aqueous solution of potassium bromide and potassium iodide having a molar ratio of KBr: KI of 99.5%: 0.5% to an aqueous solution of silver nitrate. The mixture was mixed by the double jet method at 40 ° C. for 20 minutes. It was produced at pH 9.0 and pAg8.0 for the first 12 minutes and thereafter at pH 8.0 and pAg 11.7.

The thus obtained emulsion containing grains having four kinds of third coating layers was chemically ripened in the same manner as in Example 1 to prepare the same additives and protective layer liquid, and the same coating and drying were carried out. Samples A, B, C and D were obtained.

These samples were evaluated in the same manner as in Example 1, and the results are shown in Table 7. However, the sensitivity was expressed as relative sensitivity with sample A set to 100.

As shown in Table 7, Samples C and D in which the proportion of the first coating layer is 10 mol% or more are samples A and B in terms of pressure blackening.
Because of further deterioration, the proportion of silver occupied by the first coating layer is preferably less than 10 mol% with respect to the total silver of the particles.

〔The invention's effect〕

As described above, by using the silver halide photographic light-sensitive material of the present invention, pressure resistance is improved, sensitivity change due to stress is reduced, and good photographic performance with less pressure blackening, pressure desensitization and pressure fog is obtained. be able to.

[Brief description of drawings]

FIG. 1 is a sectional view showing the structure of the silver halide grains of this example. FIG. 2 shows a conventional example. 1 ... inner core, 2 ... first coating layer, 3 ... second coating layer, 4 ... third coating layer.

Claims (2)

[Claims] 1. A silver halide grain has an inner nucleus made of silver chloroiodobromide, silver iodobromide or silver bromide, and iodine-dispersing means or iodine ion is first coated on the outside of the inner nucleus. It has a first coating layer formed by means of reacting with silver ions at a ratio of 25 mol% or more with respect to all halogen ions at the time of layer formation, and is provided outside the first coating layer from the time of forming the first coating layer. Also has a second coating layer formed by reacting with silver ions under the condition that the ratio of bromine ions to iodine ions is 10 mol% or more and the amount of bromine ions is large, and the second coating layer is formed outside the second coating layer. The ratio of iodine ion and bromide ion is more
Includes a silver halide grain having a third coating layer formed by reacting with silver ion under the condition of less than 12 mol% iodine ion, and having an average aspect ratio of the silver halide grain of less than 8: 1 A silver halide photographic light-sensitive material. 2. A grain of the first coating layer, wherein the first coating layer of the silver halide grain comprises silver iodobromide, silver chloroiodobromide having the highest iodine content, or silver iodide. The ratio to the total silver is less than 10 mol% in terms of molar ratio, and the second coating layer contains silver halide grains formed under the condition that the ratio of bromine ions is higher than that of iodine ions. The silver halide photographic light-sensitive material according to claim 1.