DE69434455T2 - Process for the preparation of a seed crystal emulsion - Google Patents

Description

The The present invention relates to a silver halide photographic material with excellent printing properties, which is an emulsion of tabular silver halide grains includes those made with improved manufacturability can be.

Of the technical trend in recent times of color photographic silver halide materials strives for high sensitivity, such as photosensitive through ISO1600 reproduced photographic materials for image capture, and after graininess sharpness and color reproducibility for photosensitive photographic materials for use with small format cameras, such as the 110 size system and the disk size system, and photographic photosensitive materials for use with Films equipped with a lens represented by "Utsurundesu Hi" and "Utsurundesu Panoramic" are sufficient. A further improvement of each of the different properties is required.

With With respect to these requirements, the use of tabular grains is intended for the increase of Sensitivity, e.g. by increasing the effectiveness of color sensitization through a sensitizing dye, improving the relationship between sensitivity and graininess and the increase of sharpness and opacity described in U.S. Patents 4,434,226, 4,414,310, 4,433,048, 4,414,306 and 4,459,353, in JP-A-58-113927 (the term "JP-A" as used herein) means an "unaudited published Japanese patent application ") and JP-A-59-119350 (corresponding to U.S. Patent 4,490,458).

Around Use of the properties of the tabular grains above Efforts have been made to make tabular grains in different size ranges adapt. In particular, tabular grains are in a large size range important to improve the relationship between sensitivity and graininess and have therefore been investigated.

Regarding the Prior art method for producing tabular grains can Reference may be made to JP-A-58-113927 (corresponding to US Pat 4,433,048), JP-A-58-113928 (corresponding to U.S. Patent 4,434,226), JP-A-58-127921 and JP-A-1-158426. These manufacturing methods are however disadvantageous in that it has a prolonged process time have that great for making tabular grains is required, and therefore have insufficient manufacturability. Furthermore, so produced are large tabular grains not necessarily satisfactory in terms of printing properties of photosensitive photographic materials containing these tabular grains contain.

When Process for the preparation of silver halide grains may be a so-called Crystal seed method can be used, i. a method which the growth of seed grains which have been prepared separately. In the application The crystal germination process can reduce the grain formation processes and the fluctuation of the production conditions can be achieved. Further allows the use of monodisperse seed crystal grains with the preparation of tabular grains an improved monodispersibility.

When Crystal seed process for the preparation of tabular grains is a Kornbildverfahren under Use of a spherical Seed crystal (aspect ratio: 1) in JP-B-3-46811 (the term "JP-B", as used herein means a "tested Japanese Patent Publication ") (corresponding to US Pat 4,798,775). However, the grains thus obtained have an aspect ratio of not more than 3.0 on. Therefore, this crystal germination method can not final aggregate with a high aspect ratio provide.

Furthermore JP-A-61-112142, JP-A-62-58237 and JP-A-55-142329 (corresponding to U.S. Pat US Pat. No. 4,301,241) uses a grain formation method using a multi-twin grain. This method is for manufacturing from tabular grains with a high aspect ratio suitable. However, this method is disadvantageous in that it, if a crystal germ, the desilvered and redispersed is not immediately grown, property fluctuations causes and thus an insufficient stability of the manufacturing conditions.

As mentioned above, can the prior art crystal germination methods do not produce stable production from tabular grains with a high aspect ratio realize and require therefore further improvements.

EP-A-359506 describes silver halide emulsions prepared by forming Silver halide crystals in a colloid dispersing medium, mixing this medium with aqueous solutions of silver salt and halides, adding a silver halide solvent to the medium, causing an increase in the size of the produced Gemini crystals and removing the water-soluble Salts and chemical and spectral sensitization of the emulsion.

JP-A-63-231334 describes highly sensitive silver halide light-sensitive materials, including the silver halide Contain silver iodide, which is used as a seed crystal.

EP-A-610 597, a document in accordance with Art. 54 (3) EPC a process for producing a tabular grain silver halide emulsion, which comprises growing a silver halide seed emulsion.

Further JP-A-3-196136 and JP-A-3-196137 (corresponding to EP-A-438791) a method which involves grain formation in the presence of a silver oxidizing agent includes. However, no examples have become known in which this method on the preparation of a seed crystal emulsion is applied.

It is therefore the object of the present invention, a method to provide a seed emulsion which has high Manufacturability, improved printing properties and the stable Preparation of tabular grains with a high aspect ratio allows.

The Object of the present invention will become apparent from the following detailed Description and examples more apparent. This task is solved by the method and the uses as defined in the appended claims.

preferred embodiments are in the subclaims Are defined.

The The present invention will be further described hereinafter.

The A process for preparing a silver halide emulsion from two main steps, i. the production of crystal seed grains and the growth of crystal seed grains.

Of the Step of producing seed crystal grains consists in the grain formation step, which includes nucleation, ripening and growth, and the subsequent desalting / washing step. If desired, cooling steps can be used or the subsequent cooling step be used. The seed crystal emulsion produced can be used for Preparation of a tabular Silver halide emulsion can be used.

Of the protruding step involving the growth of seed crystal grains includes a step for further growth of the grains in the presence of the above seed crystal grains, a desalting / washing step, a chemical sensitization step, etc.

The according to the present Crystal seed grains prepared according to the invention are further described hereinafter described.

The Silver oxidizing agent for use in the preparation of the seed crystal emulsion according to the present Invention is a compound that acts on metallic silver, to turn it into silver ions. Particularly effective is a compound the small particle size silver atoms used during the formation of silver halide grains By-product were formed, converted into silver ions. The so formed Silver ions can a difficult water soluble Silver salt, such as silver halide, silver sulfide and silver selenide, or a water-soluble one Silver salt, such as silver nitrate, form.

The Thiosulfonate is selected from the compounds represented by the formulas (I) to (III).

In the method for producing a seed crystal emulsion according to the present invention Invention will provide at least one of the foregoing silver oxidizing agents to the system during added to the production. The expression "during the production", As used herein, basically means that the addition of the oxidizing agent while every step is allowed. In particular, the addition is preferred while the formation of grains carried out. The addition is also preferred during desalting / washing step.

The Silver oxidizing agent may be previously introduced into the reaction vessel become. Preferably, the silver oxidizing agent becomes the system while at any suitable time in the grain forming step. alternative For example, the silver oxidizing agent may be preceded by an aqueous solution of a water-soluble one Silver salt or a water-soluble Alkali halide, which then used to form grains becomes. A still further preferred method is the silver oxidizing agent to the system in some batches with the progression of grain formation or in a continuous manner over a prolonged period add.

The amount of the silver oxidizing agent to be added is preferably in the range of 10 ^-7 to 10 ^-1 mol, more preferably 10 ^-6 to 10 ^-2 mol, most preferably 10 ^-5 to 10 ^-3 mol, per mol of silver halide.

The Incorporation of the silver oxidizing agent into the system during the Preparation of a seed crystal emulsion can be by any method that is usually achieved for addition of additives to a photographic emulsion is used. In detail, can if the silver oxidizing agent is a water-soluble compound is added to the system in the form of an aqueous solution at a suitable concentration become. If the silver oxidizing agent is a water insoluble or difficult water soluble Connection, it can be in the form of a solution in the system a solvent be added, which has no adverse effects on photographic Has properties, under suitable organic solvents, which are miscible with water, such as alcohol, glycol, ketone, ester and amide.

With further reference to the thiosulfone compounds represented by the above formulas (I) to (III), when R, R ¹ and R ² each represent an aliphatic group, it is a saturated or unsaturated, straight-chain, branched or cyclic aliphatic hydrocarbon group, preferably one C _1-22 alkyl group or a C _2-22 alkenyl or alkynyl group which may be further substituted with substituents.

Examples the above alkyl group include methyl, ethyl, propyl, butyl, Pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, Cyclohexyl, isopropyl, and t-butyl.

Examples The above alkenyl group includes allyl and butenyl. Examples The above alkynyl group includes propargyl and butynyl.

When R, R ¹ and R ² each represent an aromatic group, they may be a monocyclic or a fused aromatic group, preferably a C _6-20 aromatic group such as phenyl and naphthyl, which may be further substituted with substituents.

When R, R ¹ and R ² each represents a heterocyclic group, it may be a 3- to 15-membered ring group containing at least one member selected from the group consisting of nitrogen, oxygen, sulfur, selenium and tellurium, and at least one Contains carbon atom, preferably a 3- to 6-membered heterocyclic group such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, terrazole, triazole, benzotriazole, tetrazole, oxadiazole and thiadiazole.

Examples of substituents on R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyl), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, butylthio), an arylthio group (eg, phenylthio), an acyl group (eg, acetyl, propionyl, butyryl, valeryl), a sulfonyl group ( eg methylsulfonyl, phenylsulfonyl), an acylamino group (eg acetylamino, benzoylamino), a sulfonylamino group (methanesulfonylamino, benzenesulfonylamino), an acyloxy group (eg acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, an -SO ₂ SM- Group (in which M represents a monovalent cation) and a -SO ₂ R ¹ group (in which R ^{1 is} as defined above).

The divalent linking group represented by L may be an atom or an atomic group containing at least one of C, N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-, -CO-, -SO ₂ -, etc. may be used singly or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. If L is a divalent aliphatic group, its specific examples include a xylylene group and fol groups: (-CH ₂ ) - _n (n = 1 to 12), -CH ₂ -CH = CH-CH ₂ -, -CH ₂ C≡CCH ₂ -,

If L is a divalent aromatic group, including its specific ones Examples include a phenylene group and a naphthylene group.

These Substituents can further substituted with the above substituents.

M is preferably a metal ion or an organic cation. Examples such a metal ion include a lithium ion, a sodium ion and a potassium ion. Examples of the organic cation include Ammonium ion (e.g., ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (e.g., tetraphenylphosphonium) and a guanidyl group.

If the compound represented by the formula (I), (II) or (III) a polymer, it can be the following as its repeating unit Compounds (in which M and R are each as defined above) contain:

These Polymers can Homopolymers or copolymers with other copolymerizable monomers be.

Specific Examples of represented by the formula (I), (II) or (III) Compounds are summarized hereinafter in Table A, however, the present invention should not be construed as being limited thereto become.

The Synthesis of represented by the formula (I), (II) or (III) Connection can be easily made by any suitable method carried out as described or cited in JP-A-54-1019, in British Patent 972,211, in the Journal of Organic Chemistry, Tape. 53, p. 396 (1988) and in Chemical Abstracts, Vol. 59, 9776e.

At the most preferred among these compounds represented by the formula (I), (II) or (III) is one represented by the formula (I) represented compound.

Table A

• CH ₃ SO ₂ SNa (I-1)
• C ₂ H ₅ SO ₂ SNa (I-2)
• C ₃ H ₇ SO ₂ SK (I-3)
• C ₄ H ₉ SO ₂ SLi (I-4)
• C ₆ H ₁₃ SO ₂ SNa (I-5)
• C ₈ H ₁₇ SO ₂ SNa (I-6)

• C ₁₀ H ₂₁ SO ₂ SNa (I-8)
• C ₁₂ H ₂₅ SO ₂ SNa (I-9)
• C ₁₆ H ₃₃ SO ₂ Na (I-10)

• tC ₄ H ₉ SO ₂ SNa (I-12)
• CH ₃ OCH ₂ CH ₂ SO ₂ S · Na (I-13)

• CH ₂ = CHCH ₂ SO ₂ SNa (I-15)

• KSSO ₂ (CH ₂ ) ₂ SO ₂ SK (I-29)
• NaSSO ₂ (CH ₂ ) ₄ SO ₂ SNa (I-30 )
• NaSSO ₂ (CH ₂ ) ₄ S (CH ₂ ) ₄ SO ₂ SNa (I-31)

• C ₂ H ₅ SO ₂ -CH ₃ (II-1)
• C ₈ H ₁₇ SO ₂ SCH ₂ CH ₃ (II-2)

• C ₂ H ₅ SO ₂ SCH ₂ CH ₂ CN (II-5)

• C ₂ H ₅ SO ₂ SCH ₂ CH ₂ CH ₂ CH ₂ OH (II-18)

• CH ₃ SSO ₂ (CH ₂ ) ₄ SO ₂ SCH ₃ (II-21)
• CH ₃ SSO ₂ (CH ₂ ) ₂ SCH ₃ (II-22)

• C ₂ H ₅ SO ₂ SCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ SSO ₂ C ₂ H ₅ (III-2)

• C ₂ H ₅ SO ₂ SSSO ₂ C ₂ H ₅ (III-7)
• (n) C ₃ H ₇ SO ₂ SSSO ₂ C ₃ H ₇ (n) (III-8)

The according to the present Crystal seed grains prepared according to the invention are tabular grains having twin planes.

Of the Term "tabular grains" as used herein is a general term for grains with a twin plane or two or more parallel twin planes. The term "twin plane" as used herein means a (111) plane on both sides, on which ions on all Grid points are mirror images of each other.

The frequency The formation of twin planes during nucleation depends on different supersaturation factors from. In terms of Details may be found in JP-A-63-92942 Be referred.

If these supersaturation factors elevated are generally the sequential change of crystal form of formed grains a) octahedral regular grains, b) grains with a single twin plane, c) grains with two parallel twin planes (Task), d) grains with non-parallel twin planes and e) grains with three or more twin planes in this order. These different supersaturation factors will be so adjusted that the proportion of occurrence of grains c) in the end obtained grains falling into the area, which is defined by the effects of the present invention.

Other preferred conditions under which nucleation is carried out are described hereinafter. An aqueous solution of a water-soluble Silver salt or both an aqueous solution of a water-soluble Silver salt as well as an aqueous solution one while each of the halides to be added to nucleating each preferably contains a dispersant in an amount of 0.05 to 2.0 wt%. The Dispersant may be one commonly used photographic gelatin, preferably a low-gelatin Molecular weight, be. The temperature at which the nucleation carried out is, is 5 ° C to 60 ° C, preferred 15 ° C to 50 ° C. The Speed at which silver nitrate is added is preferred 0.5 g / min to 30 g / min per liter of the aqueous reaction solution.

The composition of the aqueous solution of a halide to be added is determined by the proportion of I ^- to Br ^- defined, in the range of not less than 4.5 mol% to not more than the intrinsic critical value, preferably not less than 4.5 mol% to not more than 10 mol%.

The concentration of foreign salts for the reaction in the reaction solution is preferably 0 to 1 mol / l. The pH of the reaction solution may be 2 to 10. The concentration of a silver halide solvent in the reaction solution is preferably 0 to 3.0 x 10 ^-1 mol / l.

The according to the present Invention prepared tabular Contains crystal germ emulsion Grains with an aspect ratio (Diameter expressed as the circle / thickness of silver halide grains) of not less than 2.0, preferably from not less than 2.0 to not more than 10.0, in particular from not less than 3.0 to not more than 8.0, in a proportion of not less than 50%, preferably not less than 70%, in particular not less than 85%, of all silver halide grains in the emulsion, calculated in terms of projected area. Of the average diameter of according to the present Invention prepared tabular Seed crystal grains is preferred not more than 0.5 μm, in particular not less than 0.2 μm to not more than 0.4 μm expressed as a ball. The mean diameter of the according to the present invention prepared tabular Seed crystal grains is preferably not more than 0.2 μm, in particular not more than 0.15 μm.

The according to the present Invention prepared tabular Seed crystal grains can Silver bromide, silver bromoiodide, silver chloride, silver bromochloride, Containing silver bromochloroiodide and silver chloroiodide.

The according to the present Invention prepared tabular Seed crystal grains either have at least two layers of essentially one Structure constructed by different halogen compositions a uniform halogen composition structure.

The Emulsion having a structure resulting in the halogen composition different from layer to layer, a layer with high Iodine content as the core and a low iodine layer as the outermost layer or vice versa.

The Particle size distribution is preferably monodisperse and has a coefficient of variation of not more than 20%.

The A method for producing tabular seed crystal grains according to the present invention Invention will be described hereinafter.

In The present invention includes the method of preparation tabular Crystal germ grains steps the simultaneous addition of an aqueous solution of a water-soluble Silver salt and an aqueous solution of a halide to an aqueous one Gelatin solution contained in a reaction vessel is, and the subsequent Tire the mixture to form tabular seed grains.

• 1) Die wirksame Gelatinekonzentration muss im Bereich von 0,8 Gew.-% bis 20 Gew.-%, bevorzugt von 1,0 Gew.-% bis 15 Gew.-%, bevorzugter von 1,0 Gew.-% bis 6 Gew.-%, liegen. Als Gelatine kann eine üblicherweise verwendete fotografische Gelatine verwendet werden. Eine Gelatinelösung mit einer hohen Konzentration (1,6 bis 20 Gew.-%) bei einer Temperatur von nicht höher als 35°C kann jedoch fest werden und kann somit kaum verwendet werden. Bei einer Temperatur so niedrig als nicht höher als 35°C kann Gelatine mit niedrigem Molekulargewicht (Molekulargewicht: 2000 bis 100000), modifizierte Gelatine, wie phthalatierte Gelatine, Gelatine, erhalten aus der Haut von Fischen, die im kalten Meer leben, kaum fest werden, und sie sind insbesondere erwünscht.
• 2) Als Zugabe-/Mischvorrichtung für Bewegung unter Beanspruchung wird bevorzugt eine Vorrichtung zur Submerszugabe verwendet, wie in der US-Patentschrift 3,785,777 (1974) und in der deutschen Offenlegungsschrift Nr. 2 556 888 beschrieben.
• 3) Die Geschwindigkeit, mit welcher ein Silbersalz und ein Halogenid zu dem System zugesetzt werden, beträgt 6 × 10^–4 mol/min bis 2,9 × 10^–1 mol/min pro Liter der wässrigen Gelatinelösung.
• 4) Als zu der wässrigen Lösung eines Silbersalzes oder eines Halogenids zuzusetzende Gelatine kann eine üblicherweise verwendete fotografische Gelatine verwendet werden. Die Konzentration von zuzusetzender Gelatine muss derart sein, dass die wässrige Lösung nicht fest werden kann und beträgt normalerweise 0,05 Gew.-% bis 1,6 Gew.-%. Falls eine Vorrichtung zum Erwärmen der wässrigen Lösung zusätzlich bereitgestellt wird, kann Gelatine in einer höheren Konzentration zugesetzt werden (etwa 20 Gew.-%).

Preferred conditions under which tabular seed grains are formed are as follows:

• 1) The effective gelatin concentration must be in the range of 0.8 wt% to 20 wt%, preferably 1.0 wt% to 15 wt%, more preferably 1.0 wt% to 6 % By weight. As the gelatin, a commonly used photographic gelatin can be used. However, a gelatin solution having a high concentration (1.6 to 20% by weight) at a temperature of not higher than 35 ° C may solidify and thus can hardly be used. At a temperature as low as not higher than 35 ° C, low molecular weight gelatin (molecular weight: 2,000 to 100,000), modified gelatin such as phthalated gelatin, gelatin obtained from the skin of fish living in the cold sea, can hardly become solid and they are particularly desirable.
• 2) As the adding / mixing apparatus for movement under stress, a submitter addition apparatus is preferably used as described in US Patent 3,785,777 (1974) and German Laid-Open Patent Publication No. 2,556,888.
• 3) The rate at which a silver salt and a halide are added to the system is 6 x 10 ^-4 mol / min to 2.9 x 10 ^-1 mol / min per liter of the aqueous gelatin solution.
• 4) As a gelatin to be added to the aqueous solution of a silver salt or a halide, a commonly used photographic gelatin can be used. The concentration of gelatin to be added must be such that the aqueous solution can not solidify and is normally 0.05% by weight to 1.6% by weight. If an apparatus for heating the aqueous solution is additionally provided, gelatin may be added at a higher concentration (about 20% by weight).

In In this case, low molecular weight gelatin (molecular weight: 2000 to 100000), modified gelatin, etc. hardly become solid, and they are therefore particularly desirable.

• 5) Die Konzentration von Br^– in der Reaktionslösung wird auf pBr 1,0 bis 2,5 gehalten.
• 6) Die Konzentration von Fremdsalzen zu der Reaktion in der Reaktionslösung beträgt 1,0 × 10^–2 bis 1 mol/l, bevorzugt 1 × 10^–1 bis 1 mol/l.

More preferable are the type, the concentration and the temperature of the gelatin to be added to the aqueous solution of a silver salt or a halide, the same as those of gelatin contained in the reaction vessel to keep these supersaturation factors uniform in the vicinity of the inlet allows a more even nucleation.

• 5) The concentration of Br ^- in the reaction solution is maintained at pBr 1.0 to 2.5.
• 6) The concentration of foreign salts to the reaction in the reaction solution is 1.0 × 10 ^-2 to 1 mol / l, preferably 1 × 10 ^-1 to 1 mol / l.

to Acceleration of the tire of the silver halide grains is a silver halide solvent usable. So it is e.g. Known excess halogen ions in the reaction vessel for accelerating of the tire. It is thus obvious that The tire can be accelerated by using only an aqueous solution of a Halides is introduced into the reaction vessel. Other ripening agents can be used. These ripening agents can be completely incorporated into a dispersing medium in the reaction vessel before Addition of the silver salt and the halide are mixed. alternative can these ripening agents into the reaction vessel with the addition of one or more halides, silver salts or deflocculants introduced become. These ripening agents can independently into the reaction vessel during the Addition of the halide and the silver salt are introduced.

When ripening agents other than the above halogen ions may be ammonia, Amine compound and thiocyanate, such as thiocyanate of alkali metal, especially sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, be used. The use of a thiocyanate ripening agent US Pat. Nos. 2,222,264, 2,448,534 and 3,320,069 taught. Furthermore, can known thioether ripening agents, as in US Pat. Nos. 3,271,157, 3,574,628 and 3,737,313 described, are used. In addition, thion compounds, as described in JP-A-53-82408 and JP-A-53-144319.

In The present invention is a step for the growth of thus obtained tabular seed grains involved.

In the step for the growth of grains is it desirable a silver salt solution and a halide solution to add to the system in such a way that the production is inhibited by new crystal germs. The size of emulsion grains can by appropriate selection the amount of crystal germ grain and the type and amount of solvent be set.

alternative For example, a method may be used which involves supplying a Part or all of the silver to be added during the growth of grains in Form of finely divided grains of silver halide as described in JP-A-62-99751.

Even though dependent of the method of using silver salt as defined herein can according to the present Invention prepared tabular Seed crystal grains according to one known processes for the preparation of tabular silver halide emulsion getting produced. In terms of of the process for preparing tabular silver halide emulsions can be referred to Duffin, "Photographic Emulsion Chemistry", Focal Press, New York, (1966), pages 66-72 and A.P.H. Tribelli, W.F. Smith, "Phot. Journal," 80 (1940), page 285. Better reference can be found in JP-A-58-113927, JP-A-58-113928 and JP-A-58-127921 become.

Another Reference can be made to Cleve, "Photography Theory and Practice" (1930), page 131, Gutoff, "Photographic Science and Engineering ", Volume 14, pages 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and U.S. Pat 4,439,520, British Patent 2,112,157 and Japanese Patent Applications Nos. 3-280961, 3-112259 and 3-119081 (corresponding to US Pat JP-A-4-330429, JP-A-318839 and JP-A-4-324440).

In In the present invention, it is essential that the tabular seed crystal grains for Desalting be washed to a newly prepared protective colloid dispersion to build. The washing temperature can be selected depending on the purpose and is preferably 5 ° C up to 50 ° C. The pH during the Washing can be dependent selected by the purpose be and amount preferably 2 to 10, more preferably 3 to 8. The pAg during the Washing can be dependent selected by the purpose be and is preferred 5 to 10. The washing process can be selected from noodle washing, Dialysis method using a diaphragm, centrifuge separation method, Coagulation sedimentation method and ion exchange method. The coagulation sedimentation method can be selected from the sulphate process, the organic solvent process, the water-soluble Polymer method and the gelatin derivative method.

The seed emulsion thus prepared is then cooled or frozen, if necessary. The location is preferably not higher than 5 ° C.

below describes the process which the growth of according to the present invention prepared tabular Seed crystal grains includes.

The Method involving the growth of seed crystal grains, consists of a procedure for further growth of grains in the presence of the above seed crystal grains, process for Desalting / washing, chemical sensitization etc. The amount of is to be used in the above method seed crystals arbitrary and amounts preferably not more than 1/10, more preferably not more than 1/20, especially not more than 1/25 of the molar amount of growth supplied Silver salt, calculated in terms of as a molar amount of silver. Although the seed crystal at any time between after the production of the seed crystal and before the growth of the seed Seed crystal arbitrarily selected so it can be used in the process prepared seed crystal preferably cooled for not less than 1 day before he is subjected to growth.

The Growth of germs in the presence of crystal seed grains can performed in the same way become as in the above production of the crystal nucleus.

The prepared tabular silver halide grains are further described hereinafter.

Of the Term "tabular grains" as used herein is a general term for grains with a twin plane or two or more parallel twin planes. The term "twin plane" as used herein means a (111) plane on both sides, of which ions are on all Grid points are mirror images of each other.

In the tabular Silver halide emulsion, the term "aspect ratio" means the ratio of the diameter of the Silver halide grain to the thickness of the silver halide grain, i. Divide the diameter of single silver halide grain his thickness. The term "grain diameter" as used herein indicates the diameter of the circle, which is the same area as the projected area of silver halide grain, observed under a microscope or Electron microscope. Therefore, the aspect ratio of not less than 3, that the diameter of the circle is not smaller is about 3 times the thickness of the grain.

The aspect ratio For example, it can be determined by a transmission electron micrograph a replica of an emulsion sample is obtained, at which then the diameter of individual grains, calculated expressed as a circle, and the thickness of the grains be measured. The thickness of the grains will be out of length of the shadow of the replica.

The tabular Silver halide emulsion comprises silver halide grains having an aspect ratio of not less than 3.0, preferably from not less than 3.0 to not more than 10.0, especially not less than 4.0 to not more than 8.0, in a proportion of not less than 50% not less than 70%, in particular not less than 85%, from all silver halide grains in the emulsion, calculated in terms of projected area. Of the average diameter of tabular silver halide grains is preferably not less than 0.8 μm, in particular not less than 0.8 μm to not more than 5 μm, in particular not less than 1.0 μm to not more than 3.0 μm, calculated expressed as a ball. The average thickness of tabular silver halide grains is preferred not less than 0.05 μm to not more than 0.5 μm.

The tabular Silberhalogenidkärner can Silver bromide, silver bromoiodide, silver chloride, silver bromochloride, Containing silver bromochloroiodide and silver chloroiodide.

The tabular silver halide grains can either one of at least two layers with substantially Structure constructed by different halogen compositions a uniform halogen composition structure to have.

The Emulsion having a structure resulting in the halogen composition different from layer to layer, a layer can have one high iodine content as the core and a layer with a low iodine content as the outermost layer or vice versa. The layer structure may be three or more Include layers. The iodine content preferably falls toward the outermost Layer.

The Properties of silver halide grains in the tabular silver halide emulsion can in be suitably regulated by different compounds in the system during the precipitate of silver halide grains be left. These compounds may be previously present in the reaction vessel to be left. Alternatively you can these compounds to the system with the addition of one or more Salts according to a customary used. By making a connection of Copper, iridium, lead, bismuth, cadmium, zinc, chalcogen, such as sulfur, Selenium and tellurium, gold and Group VIII precious metals, in the system while the precipitate of silver halide grains as disclosed in US Patents 2,448,060, 2,628,167, 3,737,313 and 3,772,031 and Research Disclosure (herein hereinafter referred to as "R. D. "), No. 13,452, Volume 134 (June 1975), may disclose the properties of silver halide grains be suitably regulated.

The Silver halide emulsion is preferred for reduction sensitization while the grain formation, between after the grain formation and before the chemical Sensitization different from the reduction sensitization is while chemical sensitization or after chemical sensitization subjected.

The Reduction sensitization can be selected from a method which involves the addition of a reduction sensitizer to a silver halide emulsion includes a process called silver ripening which grows silver halide grains or silver halide grains in an atmosphere from pAg as low as 1 to 7 ripen, and one as high-pH ripening a designated method which grows silver halide grains or silver halide grains in an atmosphere the pH is as high as 8 to 11 ripened. Two or more of these Procedures can be used in combination.

The above methods which include adding a reduction sensitizer is advantageous in that the degree of reduction sensitization can be regulated exactly.

As a reduction sensitizer, stannous salts, ascorbic acid and derivatives thereof, amines, polyamines, hydrazine derivative, formamidinesulfinic acid, silane compounds and borane compounds have been known. As the reduction sensitizer usable in the present invention, any of these known reduction sensitizers can be selectively used. Two or more of these compounds may be used in combination. Preferred examples of reduction sensitizers usable in the present invention include stannous chloride, thiourea dioxide, dimethylamine borane and ascorbic acid, and derivatives thereof. The amount of the reduction sensitizer to be added in the present invention must be selected depending on the production conditions of the emulsion, and is preferably 10 ^-7 to 10 ^-3 mol per mol of silver halide.

Of the Reduction sensitizer may be added to the system in the form of a solution a solvent, such as water, alcohols, glycols, ketones, esters and amides, during the Growth of grains be added. The reduction sensitizer may be added to the System added in the reaction vessel become. It is preferred to the system at any suitable time while growth of silver halide grains. alternative The reduction sensitizer may be previously aqueous solution a water-soluble Silver salt or a water-soluble Alkali halide, which then subjected to the precipitation of silver halide grains becomes. In another preferred example, the solution of Reduction sensitizer to the system in some batches or in a continuous manner over a prolonged period with the progress of growth of silver halide grains added become.

The silver halide emulsion to be used in the present invention may be a treatment for rounding grains, as in the European patents 96727B1 and 64412B1, or a surface modification be subjected, as in West German Patent 2,306,447C2 and JP-A-60-221320.

The Silver halide emulsion usually has a flat grain surface, can but preferably have a deliberately roughened grain surface, as required. Examples of such roughened grains include grains with an opening on a part of the crystal, like the top and center of a plane, as described in JP-A-58-106532 and JP-A-60-221320 and cluster grains such as in U.S. Patent 4,643,966.

The tabular grains in the emulsion to be used in the present invention preferably have a dislocation line. This offset may be selected from a displacement introduced linearly with respect to a particular direction in the crystal orientation of the grain, a curved Ver and a dislocation introduced into the entire part or a specific part of the grain, such as a dislocation which is inserted exactly in the edge of the grain.

The The emulsion to be used in the present invention may be either a so-called polydisperse emulsion having a width size distribution of silver halide grains or a monodispersed emulsion having a narrow size distribution of silver halide grains dependent be of the purpose. As a measure of size distribution of silver halide grains can the coefficient of variation of the diameter of circles, which the same area like the projected area of grains have, or be the diameter of balls which are the same Volume like that of grains to have. The monodisperse to be used in the present invention Emulsion is preferably an emulsion having a grain size variation coefficient of not more than 25%, more preferably not more than 20%, in particular not more than 15%.

The tabular Silver halide emulsion can be used for chemical sensitization, such as sulfur sensitization and gold sensitization become. The place on the emulsion grain, the chemical sensitization is subjected depends both on the composition, structure and shape of the emulsion grain as well as the purpose of the emulsion. A chemical sensitizer core can embedded in the interior of the grain, it can be flat in the surface of the grain Korns be embedded, or he may be on the surface of the Korns be formed. The effects of the present invention can be found in each of these configurations exercises especially in the case where a chemical sensitizer core in the neighborhood of the surface of the grain is formed. In other words, the effects of the present Invention with a surface latent image type emulsion are better exercised as with an emulsion of the internal latent image type.

The chemical sensitization can be carried out with an active gelatin, as in T.H. James, "The Theory of the Photographic Process ", 4th Edition, Macmillan (1977), pages 67-76. Chemical sensitization can also be done with sensitizers, such as Sulfur, selenium, tellurium, gold, platinum, palladium and iridium, individually or in combination, at a pAg of 5 to 10, a pH from 5 to 8 and a temperature of 30 ° C to 80 ° C, as described in R.D. No. 12008, Volume 120 (April 1974) and No. 13452, Volume 134 (June 1975), in U.S. Patents 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018 and 3,904,415 and British Patent 1,315,755 described.

When In the present invention, usable gold sensitizer can preferably a gold complex can be used (see US Pat 2,399,083).

Especially preferred among these gold sensitizers are potassium chloroaurate, Potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate and 2-Aurosulfobenzothioazolmethochiorid.

The content of such a gold sensitizer in the silver halide grain phase is preferably in the range of 10 ^-9 to 10 ^-3 mol, more preferably 10 ^-8 to 10 ^-4 mol, per mol of silver halide.

Examples a sulfur sensitizer usable in the present invention include thiosulfates, thioureas, thiazoles, rhodanines and others Compounds (as in US Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,656,955, 4,030,928 and 4,067,740). Especially preferred among these are sulfur sensitizers Thiosulfates, thioureas and rhodanines.

The optimum amount of the sulfur sensitizer may be selected depending on the grain size, chemical sensitization temperature, pAg, pH, etc., and is usually in the range of 10 ^-7 to 10 ^-3 mol, preferably 5 x 10 ^-7 to 10 ^{. 4} mol, more preferably ^{5x10 -7} to 10 ^-5 mol, per mol of silver halide.

The chemical sensitization temperature may be suitably in in the range of 30 ° C up to 90 ° C be determined. The pAg can be suitably adjusted in the Range of not less than 5 to not more than 10 set become. The pH may be suitably in the range of not less than 4.

In In the present invention, the above chemical sensitization from sensitization with a metal, such as iridium, platinum, Rhodium and palladium (as in US Patents 2,448,060, 2,566,245 and 2,566,263), a selenium sensitization with a Selenium compound or tellurium sensitization with a tellurium compound be accompanied.

The chemical sensitization may occur in the presence of a chemical Sensitization help performed become. As such, usable in the present invention chemical sensitizer can use a compound which is known to inhibit the veil and the Sensitivity during of chemical sensitization, such as azaiden, azapyridazine and azapyrimidine. Examples of chemical sensitizers U.S. Patent Nos. 2,131,038, 3,411,914 and 3,554,757, in JP-A-58-126526 and in Duffin, "Photographie Emulsion Chemistry", pp. 138-143.

The Silver halide emulsion may have a spectral sensitization with be subjected to a methine dye or other dyes. Examples of a spectral type to be used in the present invention Sensitizing dye includes a cyanine dye, a Merocyanine dye, a complex cyanine dye, a complex Merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxonol dye. Particularly suitable Among these dyes are a cyanine dye, a merocyanine dye and a complex merocyanine dye. Every kernel, usually called basic heterocyclic nucleus used for cyanine dyes can be applied to these dyes. Examples of suitable cores that can be applied to these dyes include a pyrrole nucleus, an oxazoline nucleus, a thiazole nucleus, a Pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and a by condensation of one or more alicyclic hydrocarbon rings core obtained by the nucleus or by condensation of a or more aromatic hydrocarbon rings obtained at the core Core, e.g. an indolink, a petrol, an indolk, a benzoxazole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, a naphthol thiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus and a quinoline nucleus. These nuclei can be substituents on carbon atoms contain.

Examples suitable cores based on the merocyanine dye or the complex merocyanine dye can be applied, include those with a Ketomethylenstruktur, such as a 5- or 6-membered heterocyclic Core, e.g. a pyrazoline-5-onkernel, a thiohydantoin core, a 2-thiooxazolidine-2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus.

These Sensitizing dyes can used singly or in combination. In particular, will often a combination of sensitizing dyes for the purpose of Used supersensitization. Typical examples of such Combination are disclosed in US Pat. Nos. 2,688,545, 2,977,229, 3,397,060, US Pat. 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707, in British Patents 1,344,281 and 1,507,803 and in JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

In Combination with these sensitizing dyes can be a dye, which itself has no spectral sensitizing effect, or a substance that essentially does not absorb visible light, but has a supersensitizing effect, incorporated into the emulsion become.

These Dyes can the emulsion is added in each stage of the preparation of the emulsion which has hitherto been known to be applicable. In general he can between the completion be added to the chemical sensitization and the coating. As described in U.S. Patents 3,628,969 and 4,225,666, it can be added simultaneously with the chemical sensitizer be a spectral sensitization and chemical sensitization to effect at the same time. Alternatively, as described in JP-A-58-113928 be added before chemical sensitization, or he can before completing the precipitate of silver halide grains be added to initiate the spectral sensitization. Further, the above compound can be used as described in U.S. Patent 4,225,666 taught to be added intermittently, i. a part of the connection can be added before chemical sensitization, and the Remainder of the compound may be added after chemical sensitization become. As taught in U.S. Patent 4,183,756, it may in every stage during the formation of silver halide grains be added.

These dyes can be used in an amount of 4 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide.

When Protective colloid for use in the preparation of a silver halide emulsion and a binder for other hydrophilic colloid layers may advantageously be gelatin be used. Other hydrophilic colloids can be used.

Examples the above hydrophilic colloids used in the present invention include a protein such as a gelatin derivative, a graft polymer of gelatin with other compounds of high Molecular weight, albumin and casein, a cellulose derivative, such as Hydroxyethylcellulose, carboxymethylcellulose and a sulfuric acid ester of cellulose, a sugar derivative such as sodium alginate and a starch derivative, and various high-performance synthetic hydrophilic compounds Molecular weight, such as homopolymer and copolymer, e.g. a polyvinyl alcohol, a partial acetal of polyvinyl alcohol, a poly-N-vinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, a polyacrylamide, a polyvinylimidazole, a polyvinylpyrazole.

When The above gelatin can be used with both lime-processed gelatin as well as with acid processed gelatin or enzyme processed gelatin as in Bull. Soc. Sci. Photo, Japan, No. 16, page 30 (1966) described. Further, a hydrolyzate of gelatin or a product the enzymatic decomposition of gelatin.

The Use of a low molecular weight gelatin with a Molecular weight of not more than 70,000 during nucleation is in particularly desirable in the present invention.

on the other hand For example, the photographic light-sensitive material may contain a support, on which at least one blue-sensitive layer, at least a green sensitive Layer and at least one red-sensitive layer are provided, which may optionally comprise a non-photosensitive layer, wherein the Photosensitive layer in the manner mentioned above containing prepared silver halide emulsion. The number of silver halide emulsion layers and light-insensitive layers and the order of arrangement These layers are not subject to any particular limitation. In a typical embodiment For example, the silver halide photographic material comprises a support which is provided with at least one photosensitive layer, which consists of a plurality of silver halide emulsion layers, which is essentially the same color sensitivity and different Have photosensitivity. The photosensitive layer is a photosensitive layer unit having a color sensitivity for blue light, green Light and red light. In the color photographic multilayer silver halide material these photosensitive layer units are normally in the order red-sensitive layer, green-sensitive layer and blue-sensitive Layer, viewed from the carrier out, arranged. However, the order of arrangement may be optional be reversed dependent of the purpose. Alternatively, two photosensitive Layers with the same color sensitivity can be arranged wherein at least one photosensitive layer or photosensitive Layers with a different color sensitivity in between can be arranged.

A photosensitive layer or photosensitive layers, such as different intermediate layers, can be between these photosensitive Silver halide layers and the top layer and the bottom one Layer be provided.

These Interlayers can Couplers, DIR compounds or the like as disclosed in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038 described. These intermediate layers may further contain a color stain preventing agent as usual is used.

The a plurality of silver halide emulsion layers, each having a photosensitive Layer unit can form preferably in a bilayer structure, i. an emulsion layer with high sensitivity and an emulsion layer with lower Sensitivity, as in West German Patent 1,121,470 and in British Patent 923,045. In general these layers are preferably arranged in such an order that the photosensitivity to the support becomes lower. Farther For example, a light-insensitive layer may be provided between these silver halide emulsion layers be. As in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543 described, may be an emulsion layer with low sensitivity away from the wearer be provided while an emulsion layer with high sensitivity closer to the carrier can be provided.

In one embodiment of such an arrangement, a low sensitivity blue sensitive layer (BL), a high sensitivity blue sensitive layer (BH), a high sensitivity green sensitive layer (GH), a low sensitivity green sensitive layer (GL), a red sensitive layer with high sensitivity (RH) and a low sensitivity red sensitive layer (RL) in this order from the side farthest from the support. In another embodiment, BH, BL, GL, GH, RH and RL may be different in order from those of the carrier farthest side. In a further embodiment, BH, BL, GH, GL, RL and RH may be arranged in this order from the farthest side of the carrier.

As in JP-B-55-34932 a blue-sensitive layer, GH, RH, GL and RL in that order from that of the wearer farthest side. Alternatively, like in JP-A-56-25738 and JP-A-62-63936, a blue-sensitive one Layer, GL, RL, GH and RH in this order from that of the carrier farthest side.

As described in JP-B-49-15495, a layer arrangement such that the topmost layer is a silver halide emulsion layer with the highest Sensitivity, the middle layer is a silver halide emulsion layer with a sensitivity lower than that of the uppermost layer and the lowest layer is a silver halide emulsion layer with a sensitivity lower than that of the middle one Layer is. In such a layer arrangement, the photosensitivity becomes to the carrier lower. Even if the layer structure has three layers different light sensitivities, an emulsion layer with medium sensitivity, an emulsion layer with high sensitivity and an emulsion layer with low sensitivity in this order from that of the wearer distant side arranged in a color-sensitive layer be as in JP-A-59-202464 described.

alternative can in the above three-layer structure, an emulsion layer with high sensitivity, an emulsion layer with low sensitivity and an intermediate sensitivity emulsion layer or a Low sensitivity emulsion layer, an emulsion layer with medium sensitivity and a high-density emulsion layer Sensitivity in this order from that removed from the carrier Be arranged side. In the case of a four or multi-layer structure For example, the arrangement of layers can likewise be changed in a similar manner.

Around to improve color reproducibility becomes a donor layer (CL) for an intermediate image effect with a spectral sensitivity distribution, which is different from the photosensitive main layers, such as BL, GL and RL, preferably adjacent or in proximity to them Main layers, as disclosed in U.S. Patents 4,663,271, 4,705,744 and 4,707,436; and JP-A-62-160448 and JP-A-63-89850 described.

As described above different layer structures and arrangements depending on the purpose of the photosensitive material.

In silver halide grains to be used in the present invention from the tabular ones above grains are different, are described hereinafter. An in the photographic emulsion layer to be incorporated suitable silver halide in the photosensitive type to be used in the present invention photographic material is silver bromoiodide, silver chloroiodide or Silver bromochloroiodide, the silver iodide in an amount of about 30 contains mol% or less. Particularly suitable is silver bromoiodide or silver chloroiodide, the each silver iodide in an amount of about 2 mol% to about 10 mol% contains.

Silver halide grains in The emulsions for use in the present invention may include grains which a regular crystal form, like cubes, Have octahedron and tetradecahedral, or those that have an irregular crystal form have, like sphere and plate, those that have a crystal defect, like twin plane, or those that have a composite of these crystal forms have, be.

The silver halide grains can either fine grains of about 0.2 μm or smaller in diameter or larger grains with a diameter the projected area of up to about 10 μm be. The emulsion may be either a monodisperse emulsion or a polydisperse emulsion.

The Preparation of the photographic silver halide emulsion prepared by the tabular one above grains containing emulsion used in the present invention can be may be carried out by any suitable method, as described in Research Disclosure No. 17643 (December, 1978), pages 22-23, "I. Emulsion Preparation and Types ", no. 18716 (November 1979), page 648 and no. 307105 (November 1989), Pages 863-865, P. Glafkides, "Chimie et Physique Photographique ", Paul Montel (1967), G.F. Duffin, "Photographie Emulsion Chemistry", Focal Press (1966) and V.L. Zelikman et al., "Making and Coating Photograph Emulsion ", Focal Press (1964).

In the present invention, monodisperse emulsions can be used as described in US Pat 3,574,628 and 3,655,394 and in British Patent 1,413,748, preferably used in the present invention.

Tabular grains with an aspect ratio of about 3 or more, according to a Procedures have been prepared which is different from the manufacturing process according to the present Invention, can used in the present invention. The production such tabular Grains can be carried out in a simple manner by any suitable method, as in Gutoff, "Photographic Science and Engineering ", Volume 14, pages 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.

The single silver halide crystals to be used in the present invention can either a homogeneous structure or a heterogeneous structure composed from a core and an outer shell, which are different in the halogen composition have, or you can have a layered structure. Furthermore, the grains can be a silver halide with a different halogen composition or one of silver halide different compound, e.g. Silver thiocyanate, lead oxide, etc., through have fused an epitaxial connection. Mixtures of grains with different crystal forms can also be used.

The silver halide emulsion usable in the present invention can be of the face sheet latent image type, in which latent images, mainly on the surface of grains internal latent image type in which latent images are formed mainly inside of grains be formed, or of the type in which latent images both on the surface as well as inside grains be formed. The emulsion must be a negative type emulsion be. If the emulsion is of the internal latent image type, it can be a core / shell type internal latent image emulsion as in JP-A-63-264740. A method for producing a such core / shell type internal latent image emulsion is disclosed in JP-A-59-133542 described. In this emulsion, the thickness of the shell depends on Development process, etc., and is preferably in the range from 3 to 40 nm, in particular from 5 to 20 nm.

The silver halide emulsion to be used in the present invention is usually the physical ripening, the chemical ripening and subjected to spectral sensitization. In these steps additives to use are described in Research Disclosure Nos. 17643, 18716 and 307105, such as listed below in tabular form.

In The photosensitive material may have two or more types photosensitive silver halide emulsions described in at least a property of grain size, grain size distribution, Halogen composition, grain shape and sensitivity different are mixed in the same layer as above called.

Surface- silver halide grains, as disclosed in U.S. Patent 4,082,553, veiled inside silver halide grains, as described in U.S. Patent 4,626,498 and in JP-A-59-214852, or colloidal silver preferably in a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer be incorporated. The term "inside or surface-fogged silver halide grains" as used herein means "silver halide grains (emulsion), the even (non-imagewise) can be developed independently whether they are in the exposed part or not exposed Part were present on the photosensitive material. "Process for the preparation from inside or surface-veiled silver halide grains are described in US Patent 4,626,498 and JP-A-59-214852.

silver halides, the core of internally veiled silver halide grains in front Core / shell type can form have the same or different halogen compositions. Inside- or surface-fogged silver halide grains can Silver chloride, silver bromochloride, silver bromoiodide and silver bromochloroiodide contain. The size of this fogged silver halide grains is not subject to any particular restriction and its mean grain size is preferably in the range from 0.01 to 0.75 μm, in particular from 0.05 to 0.6 μm. The crystal form of these grains is not subject to any special restrictions and may be regular. These emulsions can be polydisperse, but are preferably monodisperse (silver halide grains, from which are at least 80 percent by weight or percent by numbers, have grain diameters in the range of ± 30% of the mean grain size fall).

In the present invention, light-insensitive finely divided silver halide grains are preferably used. Non-photosensitive finely divided silver halide grains are silver halide grains used in the imagewise exposure for taking color images are not exposed so that they are essentially not developed in the development process. Preferably, these silver halide grains are not previously fogged.

These have light-insensitive finely divided silver halide grains a silver bromide content of 0 to 100 mol% and may optionally Silver chloride and / or silver iodide, preferably 0.5 to 10 mol% of silver iodide.

These have light-insensitive finely divided silver halide grains preferably has an average diameter of 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm, calculated expressed as the diameter of the circle with the same area as the projected area of the circle Grain.

These light-insensitive finely divided silver halide grains can be used in the same way as usual photosensitive silver halide are prepared. In this Case needs the surface the photosensitive finely divided silver halide grains neither be chemically sensitized spectrally. Before the addition of Emulsion to a coating solution However, it is preferred to use a known stabilizer such as triazole, azaindene, Benzothiazolium or mercapto compound and zinc compound to the Added emulsion. Colloidal silver may be preferred in the layer, which incorporates these finely divided silver halide grains.

The coated amount of silver in the light-sensitive material of the present invention is preferably in the range of 6.0 g / m ² or less, most preferably 4.5 g / m ² or less.

Known photographic accessories, which can be used in the present invention are also described in the three Research Disclosures cited above, as tabulated below.

Around a deterioration of photographic properties due to of formaldehyde gas can inhibit a compound in the photosensitive Material to be incorporated, which is capable of with formaldehyde too react and solidify it, as in US patents 4,411,987 and 4,435,503.

The contains photosensitive material preferably a mercapto compound as described in US patents 4,740,454 and 4,788,132 and JP-A-62-18539 and JP-A-1-283551.

The contains photosensitive material preferably a fogging agent, a development accelerator, a silver halide solvent or a compound for releasing precursors thereof as in JP-A-1-106052 described, independently from the amount of developed silver produced during development.

The photosensitive material preferably contains a dye which has been dispersed by a method as described in Published Unexamined International Patent Application No. WO88 / 04794 and Published Unexamined International Patent Application No. 1-502912, or a dye as described in U.S. Pat EP 317,308A in U.S. Patent 4,420,555 and JP-A-1-259358.

The Photosensitive material may contain various color couplers. Specific examples of the color couplers are in the patents described in the above-cited Research Disclosures No. 17643, VII-C to G and No. 307105, VII-C to G are described.

preferred Yellow couplers include those disclosed in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023 and 4,511,649, in JP-B-58-10739, in the British patents 1,425,020 and 1,476,760 and European Patent Publication 249473A are described.

preferred Magenta couplers include 5-pyrazolone compounds and pyrazoloazole compounds. Especially preferred are those described in US patents 4,310,619, 4,351,897, 3,061,432, 3,725,064, 4,500,630, 4,540,654 and 4,556,630, in the European Patent 73636, JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034 and JP-A-60-185951, in Research Disclosures No. 24220 (June 1984) and 24230 (June 1984) and published in the unaudited interantional Patent Application No. WO88 / 04795.

cyan coupler include naphthol and phenolic couplers. Preferred are those which in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, in West German Publication No. 3,329,729, in the European Patent Publications 121365A and 249453A and JP-A-61-42658. Further can Pyrazoloazole couplers as in JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556 and imidazole couplers as described in U.S. Patent 4,818,672 described, are used.

typical Examples of polymerized dye-forming couplers are in US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910, in the British Patent 2,102,137 and European Patent Publication 341188A.

couplers which is a dye with moderate diffusibility preferably include those described in U.S. Patent 4,366,237, in British Patent 2,125,570, in European Patent 96570 and in West German Laid-Open Publication No. 3,234,533 are.

Colored couplers to correct unnecessary Absorptions of the developed dye preferably include those in R.D. No. 17643, VII-G, R.D. No. 307105, VII-G, in U.S. Pat 4,163,670, 4,004,929 and 4,138,258, in JP-B-57-39413 and in British Patent 1,146,368. Furthermore, preferred Coupler for correction of unnecessary Absorption of the developed dye by a fluorescent Dye which is released upon coupling, as in the US patent 4,774,181, and couplers containing as release group a Dye precursor group which are used to react with a developing agent a dye capable is used as described in U.S. Patent 4,777,120 become.

The Photographic photosensitive material may preferably include compounds included for releasing a photographically usable residue capable of coupling are. Preferred examples of DIR couplers which are a development inhibitor are described in the patents described in R. D. 17643, VII-F and R.D. 307105, VII-F, in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Patents 4,248,962 and 4,782,012.

bleach accelerator releasing couplers as described in R.D. Nos. 11449 and 24241 and JP-A-61-201247, are effective for reducing the time spent on the processing step with bleaching ability required are. When these couplers are in a photosensitive Incorporated incorporated material containing the above-mentioned tabular silver halide grains in particular, in a remarkable way its effect. couplers for imagewise releasing a nucleating agent or a Development accelerator at the time of development, preferably include those described in the British patents 2,097,140 and 2,131,188 and JP-A-59-157638 and JP-A-59-170840 are. Further preferred are compounds which undergo a redox reaction with the oxidation product of a developing agent for release a fogging agent, a development accelerator, a silver halide solvent or the like as disclosed in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687 described.

In addition to the above couplers, the photographic material may further contain competing couplers as described in U.S. Patent 4,130,427, poly equivalent couplers as described in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds as described in JP-A-60-185950 and JP-A-62-24252, couplers for release a dye capable of returning to its original color upon release, as described in European Patent Publications 173302A and 313308A, couplers capable of releasing a ligand, as described in U.S. Patent 4,553,477, couplers useful for releasing a leuco dye as described in JP-A-63-75747 and couplers capable of releasing a fluorescent dye, as described in U.S. Patent 4,774,181.

The Incorporation of the couplers for use in the present invention in the photosensitive material may after any suitable known Dispersion method performed be like an oil-in-water dispersion process and a latex dispersion method.

Examples of high-boiling solvents, those in the above oil-in-water dispersion process are to be used are described in US Patent 2,322,027. Specific examples of high-boiling organic solvents with a boiling point of 175 ° C or higher at atmospheric pressure, in the oil-in-water dispersion process can be used include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, Bis (1,1-diethylpropyl) phthalate), phosphoric or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate), amides (e.g., N, N-diethyldodecanamide, N, N-diethyl laurylamide, N-tetradecylpyrrolidone), Alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g., bis (2-ethylhexyl) sebacate, dioctylazerate, glycerol tributylate, Isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (e.g., paraffin, dodecylbenzene, diisopropylnaphthalene). As auxiliary solvent can be an organic solvent with a boiling point of about 30 ° C or higher, preferably 50 ° C up to about 160 ° C, be used. Typical examples of such an organic solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The Method and effects of the above latex dispersion method and specific examples of latexes to be used in immersion are in the US patent 4,199,363 and in West German Offenlegungsschriften No. 2,541 274 and 2 541 230.

The color photographic light-sensitive material preferably contains various antiseptic agents or antifungal agents, such as Phenethyl alcohol and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole, as described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941.

The The present invention can be applied to various color photographic materials be applied. Typical examples include color negative films for general Purposes or for cinematographic purposes, color reversal films for slides or television, Color papers, color positive films and color reversal papers.

suitable Carrier, which can be used in the present invention are in the above-cited R.D. 17643 (page 28), R.D. 18716 (right column, page 647 to left column, page 648) and R.D. 307105 (Page 897).

In the photosensitive photographic material, the total thickness of all hydrophilic colloidal layers on the emulsion side is preferably in the range of 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, especially 16 μm or less. The film swelling T _1/2 is preferably in the range of 30 seconds or less, more preferably 20 seconds or less. The film thickness is determined after two days storage at a temperature of 25 ° C and a relative humidity of 55%. The film swelling T _1/2 can be determined by a method known in the art, for example by means of a swelling meter of the type as described in A. Green et al., Photographic Science and Engineering, Vol. 19, No. 2, pp. 124- 129 described. T _1/2 is defined as the time required to reach half of the saturated film thickness, wherein the saturated film thickness is 90% of the maximum swollen film thickness achieved when the photosensitive material is exposed to a color developer at a temperature of 30 ° C is processed over 195 seconds.

The film swelling T _1/2 can be adjusted by adding a film hardener to gelatin as a binder or by changing the aging conditions after the coating. The percentage swelling of the photosensitive material is preferably in the range of 150 to 400%. The percentage swelling can calculated from the maximum swollen film thickness determined as described above, according to the equation: (maximum swollen film thickness - film thickness) / film thickness.

The photographic light-sensitive material preferably contains a hydrophilic Colloidal layer (hereinafter referred to as "backside layer") with a total dry thickness of 2 microns up to 20 μm, on the side different from the emulsion layer side. The backside layer contains preferably an above-mentioned light-absorbing agent, a Filter dye, an ultraviolet absorbing agent, an antistatic agent Agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid surfactant Medium, etc. The backside layer preferably has a percentage swelling of 150 to 500%.

The Photosensitive photographic material can be a development according to a usual Methods as described in R.D. 17643 (pages 28-29), R. D. 18716 (left column to right column on page 651) and R.D. 307105 (pages 880-881) described.

Of the in the development of photosensitive photographic material color developer to be used is preferably an alkaline aqueous solution which as the main component, an aromatic primary amine as a color developing agent contains. As such a color developing agent, an aminophenol compound can be effectively used be used. In particular, preferred are p-phenylenediamine compounds used. Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides and p-toluenesulfonates thereof. Especially preferred among these compounds is 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate. These Connections can in combination of two or more thereof according to the purpose of use be used.

Of the contains the above color developer usually a pH buffer, such as carbonate, borate and phosphate an alkali metal, or a development inhibitor or a fog inhibitor, such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and Mercapto compounds. If desired, the above color developer may further contain various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfates, hydrazines (e.g. N, N-biscarboxymethylhydrazine), phenyl semicarbazides, triethanolamine and catecholsulfonic acids, organic solvents, such as ethylene glycol and diethylene glycol, development accelerator, such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, color forming couplers, competing couplers, auxiliary developing agents, such as 1-phenyl-3-pyrazolidone, viscosity-providing agents, various Chelati sierungsmittel, illustrated by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic cyclohexanediamine, hydroxyethyliminodiacetic, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid and Ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof).

If the photosensitive photographic material reversed It usually becomes a black and white development subjected to color development. The black and white developer can be known black and white developing agents, such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), and Aminophenols (e.g., N-methyl-p-aminophenol) alone or in combination contain.

The color developer or black-and-white developer usually has a pH of 9 to 12. The replenishment rate of the developer is usually 3 liters or less per m ² of the photosensitive material, although depending on the type of the color photographic material to be processed. The replenishment rate can be reduced to 500 ml / m ² or less by lowering the bromide ion concentration in the supplement. If the replenishment rate is reduced, the area of the processing container in contact with air is preferably reduced to inhibit the evaporation and air oxidation of the processing solution.

The area of the photographic processing solution in contact with air in the processing vessel may be represented by an opening rate as defined by the following equation: Opening rate = [area of the processing solution in contact with air (cm 2 )] / [Volume of processing solution (cm 3 )]

The opening rate as defined above is preferably in the range of 0.1 or less preferably from 0.001 to 0.05. Examples of methods of reducing the opening rate include a method of applying a cover such as a floating lid to the surface of the processing solution in the processing container, a method as described in JP-A-1-82033 using a movable lid , and a slot development method as described in JP-A-63-216050. The reduction in the opening rate is preferably carried out in the color development and black-and-white development steps as well as in all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The replenishment rate may also be reduced by a measure for suppressing the accumulation of the bromide ion in the developing solution.

The Color development time is usually between 2 minutes and 5 Minutes set. By performing the color development at a high temperature and a high pH with a highly concentrated color developing agent, the processing time be further reduced.

The photographic emulsion layer which has been color-developed becomes usually subject to bleaching. The bleaching can be done at the same time with fixing (i.e., bleach-fixing), or these two Steps can carried out separately become. To speed up the processing can be a bleaching Follow with bleach-fix. Further, any embodiment wherein two in series associated bleach-fix baths be used, an embodiment, wherein fixation precedes bleach-fix, and an embodiment wherein the bleach-fixing is followed by bleaching, arbitrarily according to selected for the purpose become. Bleaching agents to be used include compounds of polyvalent ones Metals, e.g. Iron (III), peroxides, quinones and nitro compounds. Typical examples of these bleaching agents are organic complex salts of iron (III) with e.g. Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycoletherdiaminetetraacetic or citric acid, Tartaric acid, malic acid, etc. Among these are aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetato-iron (III) complex salts and 1,3-diaminopropanetetraacetato-iron (III) complex salts, preferably in terms of acceleration of processing and environmental protection. In particular, aminopolycarboxylic acid iron (III) complex salts both in a bleach solution as well as in a bleach-fix solution usable. The pH of a bleaching solution or a bleach-fixing solution which is one Aminocarboxylic acid Eissen (III) complex salt contains is usually in the range of 4.0 to 8. For acceleration Processing can be at an even lower level pH is carried out become.

The Bleach, the bleach-fix or pre-bath thereof, if he wishes, contain a bleach accelerator. Examples of usable Bleach accelerators include compounds that are a mercapto group or a disulfide group as described in US Pat 3,893,858, West German Patents 1,290,812 and 2 059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623 and JP-A-53-28426 and Research Disclosure No. 17129 (July, 1978), thiazolidine derivatives, as described in JP-A-50-140129, thiourea derivatives, such as in JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735 and U.S. Patent 3,706,561 described iodides, as in West German Patent 1,127 715 and JP-A-58-16235 described, polyoxyethylene compounds, as in the West German patents 966,410 and 2,748,430, polyamine compounds as in JP-B-45-8836 describes Compounds as disclosed in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940, and bromine ions. Prefers among these compounds are compounds which are a mercapto group or disulfide group due to their large accelerating effects. Especially are in US Patent 3,893,858, in West German Patent 1,290,812 and compounds described in JP-A-53-95630 prefers. The compounds described in U.S. Patent 4,552,834 are also preferred. These bleach accelerators can be used in the photosensitive material is incorporated. These bleach accelerators are particularly effective for the bleach-fixing of color photosensitive materials for image pickup.

The bleach solution or bleach-fix solution contains preferably an organic acid in addition to the aforementioned compounds for inhibiting bleach discoloration. A Particularly preferred organic acid is a compound with an acid dissociation constant (pKa) from 2 to 5. In particular, acetic acid, propionic acid, hydroxyacetic acid, etc. prefers.

Examples of fixing agents as contained in the fixing solution or bleach-fixing solution include thiosulfates, thiocyanates, thioethers, thioureas and a large amount of iodides. The thiosulfates are normally used. In particular, ammonium thiosulfate can be used to the fullest extent. Furthermore, thiosulfates are preferably used in combination with thiocyanates, thioether compounds, thio ureas, etc. used. As the preservative of the fixing or bleach-fixing bath, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds may preferably be used as described in European Patent Publication 294,769A. The fixing solution or bleach-fixing solution preferably contains aminopolycarboxylic acids or organic phosphonic acids for stabilizing the solution.

In the present invention is preferably a compound having a pKa value from 6.0 to 9.0, preferably an imidazole, such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole, preferred to the fixing solution or bleach-fix solution in an amount of 0.1 to 10 mol / l added to their pH adjust.

The Total time for the desilvering step is needed in the development process, is preferably as short as possible, as long as there is no failure of desilvering. The desilvering time is preferably in the range of 1 to 3 minutes, more preferably from 1 to 2 minutes. The processing temperature is within the range from 25 ° C up to 50 ° C, preferably from 35 ° C up to 45 ° C. In the preferred temperature range, the desilvering rate be improved, and the discoloration after processing can be effectively inhibited.

In the desilvering step, the movement is preferred as far as possible intensified. Specific examples of such intensifying Motion method include a method as in JP-A-62-183460 which describes the ejection of the processing solution the surface the emulsion layer in the photosensitive material comprises a method as described in JP-A-62-183461, which is the improvement the movement effect comprises by a rotating device, a method which improves the movement through Moving the photosensitive material in contact with the emulsion surface with a wiper blade provided in the bath, so that a turbulence on the emulsion surface occurs, and a method which the increase the circulated total amount of processing solution. Such a the Motion enhancing process can be effective on the bleaching bath, the bleach-fix or fixer are used.

The Improvement of the movement effect can be considered to the supply of a bleaching agent, a fixing agent or the like accelerate into the emulsion film, resulting in an improvement the desilvering rate leads. The aforementioned motion enhancing devices can be more effective work when a bleach accelerator is used, giving the bleach accelerating effect considerably elevated and turns off the inhibition of fixation by the bleach accelerator.

The to be used in the processing of the photosensitive material automatic developing machine is preferred with a photosensitive Material transporting device equipped as in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. Such a transporting device can the amount of being towed by a bath in the following bath processing solution considerably reduce what a high effect of inhibition of deterioration the properties of the processing solution results. This effect is considerable effective for reducing the processing time or the amount of Supplement, which is required in every step.

It is common that the silvered color photographic silver halide material thus subjected to washing and / or stabilization. The amount of water to be used in the washing can be selected from a wide range depending on the characteristics of the photosensitive material (eg, the kinds of materials such as copper, etc.), the end use of the photosensitive material, the temperature of the washing water, the number of washing containers (number of washing tanks) Stages), the supplementary system (eg countercurrent system or DC system) and other various factors. Among these factors, the relationship between the number of washing containers and the amount of water in a multi-stage countercurrent system can be obtained according to the method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, pp. 248-253 (May 1955) is. According to the multistage countercurrent system described in the above publication, although the required amount of water can be considerably reduced, bacteria would grow due to an increase in the retention time of the water in the container, and floating bacterial masses would adhere to the photosensitive material. In order to solve this problem, in the processing of the photosensitive coloring material, the method of reducing calcium and magnesium ion concentrations described in JP-A-62-288838 can be used very effectively. Further, it is also effective to use isothiazolone compounds or thiabenzazoles as described in JP-A-57-8542, chlorine type bactericides, eg, chlorinated sodium isocyanurate, benzotriazole and bactericides described in Hiroshi Horiguchi, "Bokinbobaizai no kagaku", edited by Sankyo Shuppan (1986 ), Eisei Gijutsu Gakkai (ed.), "Biseibutsu no mekkin, sakkin, bobigijutsu", Kogyogijutsukai (1982) and Nippon Bokin Bobi Gakkai (ed.), "Bokin bobizai jiten" (1986).

The Wash water has a pH of 4 to 9, preferably 5 to 8 when processing the photosensitive material. The temperature of the water and the washing time from broad areas, dependent of the characteristics and the end use of the photosensitive Materials selected are, but are usually in the temperature range of 15 to 45 ° C and in the time range of 20 seconds to 10 minutes, preferably in the temperature range of 25 to 45 ° C and in the time range of 30 seconds to 5 minutes. The photosensitive Material can be processed directly with a stabilizer in the washing step become. For stabilization can the known techniques as in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

the The washing step mentioned above can in some cases a Stabilization follow. Thus, e.g. a stabilizing bath that a dye stabilizer and a surface active agent such as in a final bath for photosensitive color materials are used for image acquisition, be used. Examples of such a dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, Hexamethylenetetramine and aldehyde bisulfite adducts. This stabilizing bath may also contain various chelating agents or antifungal agents contain. The accompanying the overflowing Supplement of the Wash baths and / or stabilizing baths can be used in other steps, such as desilvering, to be reused.

In a processing using an automatic developing machine will the concentration - if the above-mentioned various processing solutions of Concentration due to evaporation subject - preferred corrected by the addition of water.

The Photosensitive photographic material can be a color developing agent to simplify and speed up processing. Such a color developing agent is preferably in the form of different precursors used when contained in the light-sensitive material is. Examples of such precursors include indoaniline compounds as disclosed in U.S. Patent 3,342,597 described Schiff base compounds, as in US Patent 3,342,599 and in R. D. 14850 and R. D. 15159, and aldol compounds, as described in R.D. 13924, metal complexes as in US Pat 3,719,492, and urethane compounds as in JP-A-53-135628 described.

The Photosensitive photographic material may optionally be different 1-phenyl-3-pyrazolidones to speed up the color development. Typical examples Such compounds are disclosed in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438 described.

With With respect to the photosensitive photographic material, the different processing solutions at a temperature of 10 ° C up to 50 ° C used. The standard temperature range is normally 33 ° C to 38 ° C. A higher temperature range but can be used to speed up processing, which reduces the processing time. In contrast, a lower temperature range can be used to adjust the picture quality or the stability the processing solutions to improve.

Techniques and inorganic and organic materials useful in the preparation of the color photographic light-sensitive material are described in the following parts of JP-A-3-161745: 1st layer structure: Page 28, lower left column, line 1 to page 29, upper right column, line 7 2. Silver halide emulsion: Page 29, upper right column, line 8 to page 30, upper right column, line 12 3. Yellow coupler: Page 30, bottom right column, line 5 to line 11 4. Magenta coupler: Page 30, bottom right column, line 12 to page 31, line 3 5. cyan coupler: Page 31, lower left column, line 4 to line 16 6. Polymer coupler: Page 31, lower left column, line 17 to upper right column, line 1 7. Functional coupler: Page 31, upper right column, line 2 to lower right column, line 5 8. Antiseptic / antifungal agent: Page 32, upper right column, line 10 to line 17 9. formalin catcher: Page 30, lower left column, line 16 to line 20 10. Other accessories: Page 35, lower right column, line 19 to page 36, upper right column, line 14 and page 30, upper right column, line 13 to lower left column, line 15 11. Dispersion method: Page 31, lower right column, line 8 to page 32, upper right column, line 9 12. Carrier: Page 32, lower left column, line 4 to line 6 13.Thick / physical properties of the film: Page 32, lower left column, row 7 to lower right column, row 10 14. Color development method: Page 32, lower right column, line 15 to page 33, lower right column, line 16 15. Desilvering process: Page 32, lower right column, line 17 to page 35, upper left column, line 16 16. Automatic developing machine: Page 35, lower left column, line 17 to upper right column, line 5 17. Washing / stabilizing method: Page 35, upper right column, line 6 to lower right column, line 15

The Silver halide photographic material can also be applied to heat-developable photosensitive photographic materials are applied, as in US Patent 4,500,626 and JP-A-60-133449, JP-A-59-218443 and JP-A-61-238056 and European Patent Publication 210 660A2.

If the photographic silver halide material on a film unit with Lens is applied as described in JP-B-2-32615 and JP-B-U-3-39784 (the term "JP-B-U" as used herein) means a "tested Japanese Utility Model Publication "), it can be its Exercise effects more easily.

The The present invention will be further described in the following examples. however, the present invention should not be construed as being limited thereto become.

EXAMPLE 1

(Preparation of a seed crystal emulsion Em-1)

A 1 M aqueous solution of silver nitrate and a 1 M aqueous solution of potassium bromide and potassium iodide (92/8 in molar ratio) were added to a solution of 6 g of low molecular weight inert gelatin (average molecular weight: 50,000) and 2.5 g ³ / added potassium bromide in 1 liter of distilled water at a flow rate of 50 cm min for 40 seconds, the latter was stirred at a temperature of 30 ° C. Subsequently, the pAg of the emulsion thus obtained was adjusted to 8.5. To the emulsion was then added 20 g of an inert gelatin. The emulsion was then heated to a temperature of 65 ° C. The emulsion was then ripened with 50 g of ammonium nitrate and 100 cm ³ of a 1 M aqueous solution of sodium hydroxide 30 minutes to the formation of tabular nuclei. To the emulsion was then added 8 g of glacial acetic acid. 100 cm ³ of an aqueous solution of 1 M silver nitrate and an aqueous solution of 1 M potassium bromide were added to the emulsion in an equimolar amount at a rate which was close to the critical growth rate to effect shell formation. Thus, tabular silver bromide grains were grown to obtain emulsion Em-1. In this method, the silver potential with respect to a saturated calomel electrode was kept at +10 mV. The amount of silver nitrate used for grain growth was 135 g in total.

The emulsion Em-1 thus obtained was then desalted by ordinary flocculation subject to proceedings. Gelatin was then added to the emulsion. The pH and pAg values of the emulsion were then adjusted to 6.0 and 8.5, respectively. The emulsion was then cooled.

Em-1 was an emulsion of tabular silver halide grains with a diameter of 0.18 μm, calculated as a sphere, and a coefficient of variation of 27%, comprising grains an aspect ratio of not less than 3.0 in a proportion of 92% of all silver halide grains, calculated as projected area.

(Preparation of Crystal Seed Emulsions Em-2 to Em-10)

The Seed emulsions Em-2 to Em-7 were prepared in the same way as Em-1, except that compound I-2 or I-16 to the system just before the formation of the shell in a crowd, like shown below in Table 1 was added to the To cause grain formation.

The Seed emulsion Em-8 was prepared in the same manner as Em-1 with the exception that the connection I-16 to the system shortly before the beginning of the formation of grains was added in an amount as indicated in Table 1, to cause grain formation.

The Seed emulsion Em-9 was prepared in the same manner as Em-1 with the exception that the compound I-16 to the system during the Addition of gelatin after desalting in an amount as in Table 1 was added to effect grain formation.

The Seed emulsion Em-10 was prepared in the same manner as Em-1 prepared with the exception that the compound I-16 to the system just before the start of shell formation and during the addition of gelatin after desalting in an amount as indicated in Table 1, was added to effect grain formation.

(Preparation of Crystal Seed Emulsions Em-11 and Em-12)

The Seed emulsion Em-11 was used as an emulsion of tabular silver halide grains having a Diameter of 0.18 μm, calculated as a sphere, and a coefficient of variation of 19%, comprising grains of one aspect ratio of not less than 2.0 in a proportion of 5% of all silver halide grains, calculated from pressed as projected area, prepared in the same way as Em-1, except that the Silver potential during the shell formation changed to +40 mV has been.

Em-1 bis Em-10: Körner mit einem Aspektverhältnis von nicht weniger als 3,0 liegen in einem Anteil von 92% sämtlicher Silberhalogenidkörner in der Emulsion vor, berechnet ausgedrückt als projizierte Fläche. Durchmesser: 0,18 μm (berechnet ausgedrückt als Kugel) Variationskoeffizient: 27% Em-1 bis Em-12: Körner mit einem Aspektverhältnis von nicht weniger als 2,0 liegen in einem Anteil von 5% sämtlicher Silberhalogenidkörner in der Emulsion vor, berechnet ausgedrückt als projizierte Fläche. Durchmesser 0,18 μm (berechnet ausgedrückt Kugel Variationskoeffizient: 19% Seed emulsion Em-12 was prepared in the same manner as Em-11, except that compound I-16 was added to the system shortly before the start of shell formation in an amount as shown in Table 1. Table 1

Em-1 to Em-10: Grains having an aspect ratio of not less than 3.0 are present in a proportion of 92% of all silver halide grains in the emulsion, calculated in terms of projected area. Diameter: 0.18 μm (calculated as a sphere) Coefficient of variation: 27% Em-1 to Em-12: Grains having an aspect ratio of not less than 2.0 are present in a proportion of 5% of all silver halide grains in the emulsion, calculated in terms of projected area. Diameter 0.18 μm (calculated in terms of sphere coefficient of variation: 19%

(Preparation of Em-1-1)

An aqueous solution (1350 ml) containing 20 g of deionized gelatin and Em-1 cooled as a seed crystal emulsion one day after preparation in an amount of 0.03 mol, calculated as silver, became at a temperature of 75 ° C, and its pH was adjusted to 5.5. Then, an aqueous solution of silver nitrate (AgNO ₃ : 115 g) and an aqueous solution of halide (KI content: 2.0 mol% per KBr content) were added to the emulsion at an accelerated flow rate by a double jet method for 32 minutes so that seed crystal grains were grown at a speed close to the critical growth rate. In this method, the silver potential with respect to a saturated calomel electrode was kept at -25 mV. Subsequently, an aqueous solution containing 8.0 g of potassium iodide was added to the emulsion. An aqueous solution of silver nitrate (AgNO ₃ : 53 g) and an aqueous solution of potassium bromide (KBr: 37 g) were then added to the emulsion by a double jet process. The resulting emulsion was then desalted by a usual flocculation process. Gelatin was then added to the emulsion. The emulsion was then adjusted to pH 5.5 and pAg 8.8 to obtain an Em-1-1 emulsion. Em-1-1 was an emulsion of 0.78 μm diameter tabular silver halide grains, calculated as spheres, and a variation coefficient of 22% comprising grains of an aspect ratio of not less than 4.0 in an amount of 86% of all the silver halide grains contained therein, expressed in terms of projected area.

(Preparation of Em-1-2 and Em-1-3)

 A Emulsion Em-1-2 was prepared in the same manner as Em-1-1 with the exception that Em-1, which has been refrigerated for 90 days after manufacture was when crystal germ emulsion was used.

A Emulsion Em-1-3 was prepared in the same manner as Em-1-1 with the exception that Em-1, the day after manufacture chilled and then dissolved at a temperature of 75 ° C for 8 hours, was used as a seed crystal emulsion.

The grains in these emulsions had the same properties as those in Em-1-1.

(Preparation of Em-2-1 to Em-10-1, Em-2-2 to Em-10-2, Em-2-3 to Em-10-3)

The Emulsions Em-2-1 to Em-10-1 were prepared in the same manner as Em-1-1 except that Em-2 to Em-10 are seed emulsions were used.

The Emulsions Em-2-2 to Em-10-2 were prepared in the same manner as Em-1-2 except that Em-2 to Em-10 are seed emulsions were used.

The Emulsions Em-2-3 to Em-10-3 were prepared in the same way as Em-1-3 except that Em-2 to Em-10 are seed emulsions were used.

The grains in these emulsions had the same properties as those in Em-1-1.

(Preparation of Em-11-1 and Em-12-1)

The Emulsions Em-11-1 to Em-12-1 were prepared in the same manner like Em-1-1 with the exception that Em-11 to Em-12 as seed emulsions were used. In this process, the silver potential became while the formation of grains on -40 mV kept. Em-11-1 and Em-12-1 were each an emulsion of tabular silver halide grains with a diameter of 0.78 μm, calculated expressed as a ball, and a coefficient of variation of 32%, comprising grains Aspect ratio of not less than 4.0, accounting for 71% of all its content silver halide grains, calculated expressed as a projected area.

(Preparation of Em-11-2, Em-11-3, Em-12-2 and Em-12-3)

The Emulsions Em-11-2 and Em-12-2 were prepared in the same manner as Em-1-2 made with the exception that Em-11 to Em-12 as seed emulsions were used. In this process, the silver potential became while the formation of grains on -40 mV kept.

The Emulsions Em-11-3 and Em-12-3 were prepared in the same manner as Em-1-3 was prepared with the exception that Em-11 to Em-12 as seed emulsions were used. In this process, the silver potential became while the formation of grains on -40 mV kept.

The grains in these emulsions had the same properties as those in Em-11-1.

The emulsions thus prepared were each subjected to gold and sulfur sensitization as follows. These emulsions were each heated to a temperature of 60 ° C. To these emulsions were successively added a sensitizing dye A having the formula shown hereinafter, a fog inhibitor A, sodium thiosulfate, chloroauric acid, potassium thiocyanate and N, N-dimethylselenourea in amounts of 6.8 × 10 ^-4 mol / mol Ag, 1.2 × 10 ^-4 mol / mol Ag, 8.5 × 10 ^-6 mol / mol Ag, 1.7 × 10 ^-5 mol / mol Ag, 1.2 × 10 ^-3 mol / mol Ag and 0.5 × 10 ^{- 5} mol / mol Ag were added so that they were each subjected to optimal chemical sensitization. The term "subjected to optimum chemical sensitization" as used herein means that the emulsion is subjected to chemical sensitization such that the sensitivity reaches the highest value when the thus chemically sensitized emulsion is exposed to light for 1/100 second.

On a triacetylcellulose support, various layers having the following formulations were successively applied from the support side. In this way, Samples 101 to 136 were prepared using the above chemically sensitized emulsions as emulsion layers. (1) emulsion layer Emulsion: different emulsions (2.4 × 10 ^-2 mol / m ² , calculated as silver) hereinafter indicated coupler (1.2 × 10 ^-3 mol / m ² ) tricresyl (1.10 g / m ² ) gelatin (2.30 g / m ² ) (2) protective layer Sodium salt of 2,4-dichloro-6-hydroxy-S-triazine (0.08 g / m ² ) gelatin (1.80 g / m ² )

The Samples 101 to 136 thus obtained were then each at a temperature from 40 ° C and a relative humidity of 70% for 14 hours. Part of each of these samples immediately became the following Subjected to exposure and development processes. The other part from each of these samples was heated at a temperature of 40 ° C and a stored 40% relative humidity for 30 days, and then each These obtained samples the subsequent exposure and development process subjected. Exposure was through a gel filter SC50, available Fuji Photo Film Co., Ltd., and a continuous wedge for 1/100 Seconds, and the color development process was carried out in the following manner.

Farbentwickler (Einheit: g) Diethylentriaminpentaessigsäure 2,0 1-Hydroxyethyliden-1,1-diphosphonsäure 3,0 Natriumsulfit 4,0 Kaliumcarbonat 30,0 Kaliumbromid 1,4 Kaliumiodid 1,5 mg Hydroxylaminsulfat 2,4 4-[N-Ethyl-N-β-hydroxyethylamino]-2-methylanilinsulfat 4,5 Wasser bis auf 1,0 l pH 10,05 These samples thus processed were each measured for density by means of a green filter.

color developer (Unit: g) diethylenetriaminepentaacetic 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 sodium 4.0 potassium carbonate 30.0 potassium 1.4 potassium iodide 1.5 mg Hydroxylamine 2.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water up 1.0 l pH 10.05

bleach

wash solution

Tap water was passed through a mixed bed column filled with a H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm & Haas) and an OH type anion exchange resin (Amberlite IR-400, manufactured by Rohm & Haas) so that the calcium and magnesium ion concentrations were each reduced to 3 mg / L or less. To the solution was then added 20 mg / L of dichlorinated sodium isocyanurate and 1.5 g / L of sodium sulfate to obtain a washing solution. The pH range of the solution was 6.5 to 7.5. stabilizing (Unit: g) 37% formalin 2.0 ml Polyoxyethylene p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium 0.05 Water up 1.0 l pH 5.0-8.5

The Sensitivities of these samples were each determined as the reciprocal value of the exposure, represented by lux · second, which is a fog density plus 0.2 both relative to that of Sample 101 as 100 as well as that of the sample, which is a fresh Contains crystal germ emulsion (i.e., the number represented by the Em number at the end thereof 1), than 100 results.

The Results of the evaluation of samples 101 to 136 are in the tables 2 and 3 below.

Table 2

(Samples 101 to 103 and 131 to 133 are comparative samples, while the other samples are according to the present invention.) Note 1: Sensitivity relative to that of Sample 101 as 100. Note 2: Sensitivity relative to that of each sample containing tabular grains prepared from fresh seed crystal emulsion as 100. Note 3: Sensitivity relative to that of the above reference samples according to Note 2.

The shown in Table 2 show that the emulsion production process according to the present Invention provides an emulsion of tabular grains with extremely small variation properties at different storage conditions of seed emulsion, provide high sensitivity and improved durability can.

EXAMPLE 2

at In the preparation of Em-1-1 of Example 1, the process was carried out increased by a factor of 70 or 490. The The emulsions obtained were designated as "Em-101-1" and "Em-201-1". In these methods, devices were used a scale used by a factor of 70 and 490 (factor 4.12 and 7.88 in length) were enlarged, the geometrically similar had been built to the manufacturing device that in example 1 was used.

For Em-10-1 Example 1 was a similar one Magnification to Received Em-110-1 and Em-210-1- performed.

These Emulsions then became gold and sulfur sensitization in the same manner as in Example 1. From these Emulsions, Samples 201-204 were prepared.

These Samples were then evaluated in the same manner as in Example 1. The results are shown in Table 3.

Table 3

The shown in Table 3 show that the emulsion production process according to the present Invention, an emulsion of tabular grains with a low dependence of the scale magnification result can.

EXAMPLE 3

One Photosensitive multilayer color material was used as sample 301 by applying different layers to one with an underlayer prepared cellulose triacetate film support, wherein the layers the following compositions had:

(Composition of photosensitive Layer)

Materials to be incorporated into the various layers are classified into the following categories:
ExC: cyan coupler, ExM: magenta coupler, ExY: yellow coupler, ExS: sensitizing dye, UV: ultraviolet absorber, HBS: high boiling organic solvent, H: gelatin hardener.

The amount of silver halide and colloidal silver applied is given in g / m ² , calculated as silver. The amount of coupler, additive and gelatin applied is expressed in g / m ² . The amount of sensitizing dye applied is expressed in number of moles per mole of silver halide in the same layer. (Sample 301) 1st layer: antihalation layer Black colloidal silver 0.18 expressed as silver gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 2nd layer: intermediate layer Silver bromoiodide emulsion G 0.065 in terms of silver 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0,020 UV-1 0,060 UV-2 0,080 UV-3 0.10 HBS-1 0.10 HBS-2 0,020 gelatin 1.04 3rd layer: Red-sensitive emulsion layer with low sensitivity Silver Bromide Emulsion A 0.30 expressed as silver Silver bromoiodide emulsion B 0.30 expressed as silver ExS-1 7.2 × 10 ^-5 ExS-2 2.2 × 10 ^-5 ExS-3 3.5 × 10 ^-4 ExC-1 0.17 ExC-3 0,030 ExC-4 0.10 ExC-5 0,020 ExC-7 0.0050 ExC-8 0,010 Cpd-2 0,025 HBS-1 0.10 gelatin 0.87 4th layer: Red sensitive emulsion layer with medium sensitivity Silver bromoiodide emulsion D 0.68 expressed as silver ExS-1 3.5 × 10 ^-4 ExS-2 2.0 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0,060 ExC-3 0.0070 ExC-4 0,090 ExC-5 0,025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 gelatin 0.75 5th layer: Red-sensitive emulsion layer with high sensitivity Silver bromoiodide emulsion EM-301 1.75 expressed as silver ExS-1 2.2 × 10 ^-4 ExS-2 1.3 × 10 ^-4 ExS-3 2.8 × 10 ^-4 ExC-1 0.18 ExC-3 0,045 ExC-6 0,020 ExC-8 0,025 Cpd-2 0,050 HBS-1 0.20 HBS-2 0.10 gelatin 1.15 6th layer: intermediate layer Cpd-1 0.10 HBS-1 0.50 gelatin 1.10 7th Layer: Green Sensitive Emulsion Layer with Low Sensitivity Silver bromoiodide emulsion C 0.35 expressed as silver ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0,010 ExM-2 0.33 ExM-3 0.086 ExY-1 0,015 HBS-1 0.30 HBS-3 0,010 gelatin 0.73 8th Layer: Green Sensitive Emulsion Layer with Medium Sensitivity Silver bromoiodide emulsion D 0.80 expressed as silver ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0,030 ExY-1 0,018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90 9th layer: green sensitive emulsion layer with high sensitivity Silver Bromide Emulsion E 1.45 expressed as silver ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0,010 ExM-1 0,030 ExM-4 0,040 ExM-5 0.019 Cpd-3 0,040 HBS-1 0.25 HBS-2 0.10 gelatin 1.44 10th layer: yellow filter layer Yellow colloidal silver 0.030 in terms of silver Cpd-1 0.16 HBS-1 0.60 gelatin 0.60 11th Layer: Blue-sensitive emulsion layer with low sensitivity Silver bromoiodide emulsion C 0.18 expressed as silver ExS-7 8.6 × 10 ^-4 ExY-1 0,020 ExY-2 0.22 ExY-3 0.50 ExY-4 0,020 HBS-1 0.28 gelatin 1.10 12th Layer: Blue-sensitive emulsion layer with medium sensitivity Silver bromoiodide emulsion D 0.40 expressed as silver ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0,050 ExY-3 0.10 HBS-1 0,050 gelatin 0.78 13th Layer: Blue sensitive emulsion layer with high sensitivity Silver bromoiodide emulsion F 1.00 expressed as silver ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0,070 gelatin 0.86 14th layer: First protective layer Silver bromoiodide emulsion G 0.20 expressed as silver UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 15th layer: second protective layer H-1 0.40 B-1 (diameter: 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter: 1.7 μm) 0.10 B-3 0.10 S-1 0.20 gelatin 1.20

Around the durability, the processability, the pressure resistance, the mold resistance, the bacterial resistance, the antistatic properties and the coating properties of the material were W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt incorporated into the various layers.

The Formulations of the silver bromoiodide emulsions A to G are described in U.S.P. Table 4 below.

• (1) wurden die Emulsionen A bis F einer Reduktionssensibilisierung mit Thioharnstoffdioxid und Thiosulfonsäure während der Herstellung der Körner gemäß einem Beispiel in JP-A-2-191938 (entsprechend der US-Patentschrift 5,061,614) unterworfen,
• (2) wurden die Emulsionen A bis F einer Goldsensibilisierung, Schwefelsensibilisierung und Selensensibilisierung in Gegenwart des spektralsensibilisierenden Farbstoffs, wie mit Bezug auf die verschiedenen lichtempfindlichen Schichten angegeben, und Natriumthiocyanat gemäß einem Beispiel in JP-A-3-237450 (entsprechend EP-A-443453) unterworfen,
• (3) wurde die Herstellung von tafelförmigen Körnern unter Verwendung einer Gelatine mit niedrigem Molekulargewicht gemäß einem Beispiel in JP-A-1-158426 durchgeführt und
• (4) wurden die tafelförmigen Körner und die regelmäßigen Kristallkörner mit einer Kornstruktur unter einem Hochvolt-Elektronenmikroskop betrachtet, um eine Übergangslinie festzustellen, wie in JP-A-3-237450 (entsprechend EP-A-443453) beschrieben.

In Table 4

• (1) Emulsions A to F were subjected to reduction sensitization with thiourea dioxide and thiosulfone acid during the preparation of the grains according to an example in JP-A-2-191938 (corresponding to US Pat. No. 5,061,614),
• (2) The emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye as mentioned with respect to the various photosensitive layers, and sodium thiocyanate according to an example in JP-A-3-237450 (corresponding to EP-A-). 443453),
• (3) The preparation of tabular grains using a low molecular weight gelatin according to one example has been carried out in JP-A-1-158426 and
• (4) The tabular grains and the regular crystal grains having a grain structure under a high-voltage electron microscope were observed to detect a transition line as described in JP-A-3-237450 (corresponding to EP-A-443453).

The Em-301 used in the 5th layer was an emulsion prepared in the same manner as Em-1-1 of Example 1, except that the sensitizing dye to be used by ExS-1 in an amount of 2.2 × 10 ^-4 mol / mol Ag, ExS-2 was replaced in an amount of 1.3 × 10 ^-5 mol / mol Ag and ExS-3 in an amount of 2.8 × 10 ^-4 mol / mol Ag.

The Samples 302 to 309 were each prepared in the same manner as the Sample 301 was prepared with the exception that in the 5th layer to be incorporated Em-301 was replaced by an emulsion prepared by Replacing the sensitizing dye in the same manner as for Em-301 based on the emulsions for Example 1, given in Table 5.

The thus prepared photosensitive color photographic material samples 301 to 309 were irradiated with light in the same manner as in Example 1 exposed and then by means of an automatic developing machine in processed as shown below, until the accumulated Amount of the supplement the bleaching solution reached three times the container capacity.

(Processing Method)

The Bleach-fix and wash steps were in a countercurrent process carried out, in which the wash water flows backwards from the bath (2) to the bath (1). The overflowing solution the bleaching bath was complete introduced into the bleach-fix (2).

The carried over Amount of the bleach-fix bath in the washing bath was 2 ml per liter in a 35 mm wide photosensitive photographic material sample.

The different processing solutions had the following compositions:

color developer

bleach solution

bleach

Wash solution (same for both the processing solution as well as the supplement)

Tap water was passed through a mixed bed column filled with a strongly acidic H-type cation exchange resin (Amberlite IR-120B manufactured by Rohm & Haas) and a strongly basic OH-type anion exchange resin (Amberlite IRA-400) Calcium and magnesium ions concentrations were each reduced to 3 mg / L or less. To the solution was then added 20 mg / L of dichlorinated sodium isocyanurate and 150 mg / L of sodium sulfate to obtain a washing solution. The pH range of the solution was 6.5 to 7.5. Stabilizing solution (equal for both the processing solution and the replenisher) (Unit: g) 37% formalin 1.2 ml Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.4 ethylene glycol 1.0 Water up 1.0 l pH 5.0-7.0

The Sensitivities of the different samples are reproduced by the reciprocal value of the exposure, which is a fog density and a fog density plus 0.1 on the characteristic curve of a Cyan dye results, relative to those of the samples 301, 304th and 307 as 100.

These Samples were at a temperature of 40 ° C and a relative humidity stored at 40% for 30 days and then in the same manner as above described. The results are shown in Table 5.

Table 5

(Samples 301 to 303 are comparative samples while the other samples are according to the present invention) Note 1: The sensitizing dyes used were changed as indicated in the description. Note 2: Sensitivity relative to that of Sample 301 as 100. Note 3: Sensitivity relative to that of each sample containing tabular grains prepared from fresh seed crystal emulsion, greater than 100. Note 4: Sensitivity relative to that of the above reference samples according to Note 3.

The Results given in Table 5 show that the photosensitive photographic materials with an emulsion of tabular grains with a small variation of properties under different storage conditions the crystal germ emulsion, a high sensitivity and improved Durability include.

Sensitizing dye A

Veil inhibitor A

pimp

ExC-1

ExC-2

ExC-3

ExC-4

ExC-5

ExC-6

ExC-7

ExC-8

ExM-1

ExM-2

ExM-3

ExM-4

ExM-5

ExY-1

ExY-2

ExY-3

ExY-4

ExY-5

ExF-1

Cpd-1

Cpd-2

Cpd-3

UV-1

UV-2

UV-3

UV-4

UV-5

HBS-1: tricresyl

HBS-2: Di-n-butyl phthalate

HBS-3

ExS-1

ExS-2

ExS-3

ExS-4

ExS-5

ExS-6

ExS-7

S-1

H-1

B-1

B-2

B-3

B-4

B-5

B-6

W-1

• C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ N ⊝ (CH ₃ ) ₃

W-2

W-3

As mentioned above, discloses the process for preparing the silver halide seed emulsion according to the present invention Invention improved manufacturability and exercises a considerable Effect of providing a photographic silver halide material with an excellent relationship of sensitivity / graininess and improved printing properties.

The The present invention further provides a tabular silver halide emulsion ready with a dramatically improved stability in the manufacturing process can be produced. About that In addition, according to the present Invention a photosensitive photographic material having a high sensitivity and excellent durability Use of such an emulsion can be provided.

Claims (8)

A process for producing a seed emulsion comprising nucleation, ripening, growth and desalting / washing, said method comprising the use of at least one silver oxidizing agent selected from the compounds represented by the following formula (I), (II) or (III): R-SO ₂ SM (I) R-SO ₂ SR ¹ (II) R-SO ₂ SL _m -SSO ₂ -R ² (III) wherein R, R ¹ and R ² , which may be the same or different, each represents an aliphatic group, an aromatic or a heterocyclic group, M represents a cation, L represents a divalent linking group, m represents 0 or 1 represented by the formulas (I), (II) and (III) can each be a polymer comprising, as a repeating unit, a divalent group derived from the structures represented by the formulas (I), (II) and (III) and R, R ¹ , R ² and L may be optionally joined together to form a ring. A method as claimed in claim 1, which the simultaneous addition of an aqueous solution of a water-soluble Silver salt and an aqueous solution of a halide to an aqueous one Solution of a contained in a reaction vessel Low molecular weight gelatin and then ripening the mixture for the formation of tabular seed grains includes. A method as claimed in claim 2, wherein the composition of the aqueous solution of a halide by the ratio of I ^- to Br ^- is defined, which is not within the range of not less than 4.5 mol% up to more than the specific critical value. A method as claimed in claim 1, which the simultaneous addition of an aqueous solution of a water-soluble Silver salt and an aqueous solution of a halide to an aqueous one Solution of a contained in a reaction vessel Low molecular weight gelatin and then ripening the mixture for the formation of tabular seed grains includes. A method as claimed in claim 4, wherein the composition of the aqueous solution of a halide by the ratio of I ^- to Br ^- is defined, which is not within the range of not less than 4.5 mol% up to more than the specific critical value. Use of according to one of claims 1 to 5 prepared crystal seed emulsion for preparing a tabular silver halide emulsion. Use of a compound represented by the following formulas (I), (II) or (III): R-SO ₂ SM (I) R-SO ₂ SR ¹ (II) R-SO ₂ SL _m -SSO ₂ -R ² (III) for stabilizing a seed crystal emulsion. A method as claimed in claim 1, wherein the Compound of formula (I), (II) or (III) during the preparation of the seed emulsion is added.