JPS5832370B2 - squirrel beetle - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a lithium-type silver halide photographic light-sensitive material, and more particularly to a method for producing a lithium-type silver halide photographic light-sensitive material with improved pressure sensitivity characteristics.

When pressure is applied to a coated layer of a photographic material by bending the material extremely or rubbing its surface with a protrusion, the photographic sensitivity of that portion often increases or decreases.

This is a phenomenon called "pressure mark" or "scratch mark" that seriously damages photographic images.

Therefore, the sensitivity of photographic materials to pressure (pressure sensitivity)
It is desired to reduce the occurrence of pressure marks and scratch marks.

Generally, photographic light-sensitive materials for forming line drawings and halftone images contain cadmium salt in order to increase photographic sensitivity and contrast. is eluted and causes environmental pollution.

Therefore, it is desirable that photographic materials do not contain cadmium salts.

However, photographic materials that do not contain cadmium salts not only have low photographic sensitivity and contrast, but also tend to generate the pressure marks and scratch marks mentioned above.

On the other hand, such photographic materials are developed with so-called infectious developers, and it is well known that the presence of polyoxyethylene compounds improves the dot quality and contrast.

However, it has been found that when a polyoxyethylene compound is contained in a photographic light-sensitive material, the number of desensitizing pressure marks and scratch marks increases, and this is particularly noticeable in photographic light-sensitive materials that do not contain cadmium salts.

In order to reduce the pressure sensitivity of photographic materials, water-soluble polymers, dispersions of water-insoluble polymers such as latex,
Alternatively, it has been proposed to use hygroscopic substances such as alcohol and glycerin as gelatin plasticizers.

Gelatin plasticizers reduce pressure marks that occur when photographic materials are bent, but do not reduce scratch marks that occur when minute protrusions rub the coated surface.

Moreover, gelatin plasticizers often cloud the processed gelatin film or make it easier to adhere to the surface of the photosensitive material.

Therefore, an object of the present invention is, firstly, to provide a method for producing a photographic material with improved pressure sensitivity characteristics, and secondly, to provide a method for producing a photographic material with improved pressure sensitivity characteristics.
Thirdly, to provide a method for manufacturing a photographic material in which the generation of pressure marks and scratch marks is prevented, and thirdly, to provide a method for producing a photographic material with improved pressure sensitivity characteristics and in which the generation of pressure marks and scratch marks is prevented. To provide photographic materials.

The above object of the present invention is achieved by adding a water-soluble iridium compound during ripening of a silver halide photographic emulsion, and further adding a hydroxytetrazaindene compound and a polyoxyethylene compound and coating the emulsion on a support.

Generally, the manufacturing process of silver halide photographic emulsion is (1)
Precipitate formation of silver halide, (2) Progress of physical ripening (first ripening), (3) Removal of excess salts (desalting step), (4)
) It can be roughly divided into four steps: the progression of chemical ripening (secondary ripening).

In the method of the present invention, the water-soluble iridium compound is
It is added to the emulsion during the ripening and/or second ripening process.

When an iridium compound is added in this step, the iridium compound exists at or near the surface of the silver halide crystal, and exhibits a coexistence effect with the hydroxytetrazaindene compound and polyoxyethylene compound that are added later.

In other words, if a water-soluble iridium compound is added during silver halide precipitation, it will exist inside the silver halide crystal, and if it is added during the desalting process, it will flow out with the washing water, so it will not be present in the silver halide crystal. unable to exist,
Therefore, the desired effect of the present invention cannot be obtained.

The water-soluble iridium compound used in the present invention is a water-soluble iridium salt or a water-soluble iridium complex salt, such as a trihalogenated iridium salt, a tetrahalogenated iridium salt, a hexahalogenoiridium (III) salt, a hexahalogenoiridium (IV ) includes acid salts, etc.

Specific examples of these include IrCl3, IrBr3, ■
r■3, IrCl4. IrBr4°R3 (IrC16)
, Na3 (I rCla ), Li, 3 (IrCl
6 ], (NH4)a (I rc16 ], K3(I
rBr6 ], Na5 (IrBr6 ), K2CIrC
16] Na2 CI rc16], Li2 CI r
c16 ], (NH4)2 (I rc16 ), R2
[■rBr6], Na2 (IrBr6), CIr
(NH3)a ) (OH)a, (I r (NH3)
a ] (NOa ) 3, (I r (N'Hs ) 6
) C13, (I r (NH3)6 ) Br s, and the like.

Water-soluble iridium compounds are known to be added to photographic emulsions for various purposes, and these prior patents can be followed for specific examples of the compounds.

However, since all of these prior patents have purposes different from the present invention, they must be clearly distinguished from the present invention.

As such prior art, U.S. Patent No. 2,566,245
No. (stabilizer), No. 2566263 (stabilizer), No. 2448060 (sensitizer), No. 3318702 (
Sensitizer), No. 3320068 (Sensitizer), No. 33
No. 26690 (sensitizers), "British Journal of Photography (vol. 59, no. 106, p. 147)" (sensitizers), and Special Publication No. 43-4935 (tone softening prevention agent). .

In the present invention, the water-soluble iridium compound is preferably added in an amount of 10@-6 to 10@-4 mol per mol of silver halide.

If the amount is less than 10@-7 mol, the effect will be small, and if the amount is more than 10@-4 mol, undesirable effects such as a decrease in photographic sensitivity will occur.

Therefore, the range of the amount of iridium compound added is important in the present invention.

After the water-soluble iridium compound is added, a hydroxytetrazaindene compound and a polyoxyethylene compound are further added.

Although the order of adding the sinus compounds is not particularly limited, it is more practical to add the hydroxytetrazaindene compound first.

The hydroxytetrazaindene compound is preferably added at the end of the second ripening or just before coating, and must be added after the water-soluble iridium compound is added.

In the present invention, hydroxytetrazaindene compounds include compounds represented by the following general formula (2).

General formula I [wherein R1 and R2 are hydrogen atoms, alkyl groups (e.g., methyl, ethyl, propyl, butyl, etc.: methyl, ethyl, furoyl, butyl substituted with hydroxyl groups, carboxyl groups, etc.), or aryl group (for example, phenyl group; alkyl group such as methyl, ethyl, propyl, butyl, halogen atom such as chlorine, bromine, iodine, phenyl group substituted with hydroxyl group, etc.), n is 1 or 2
represents.

]Hydroxytetrazaindene compounds exhibit significant interactions when combined with the above-mentioned water-soluble iridium compounds and their addition timing and polyoxyethylene compounds, but hydroxytetrazaindene compounds always exhibit these interactions. The type is not particularly limited.

Hydroxytetrazaindene compounds are disclosed in US Pat. No. 2,716,062, US Pat. No. 2,784,091, British Patent No. 98
Although it is described in No. 1470, specific examples include: Compound ■ 4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene Compound ■ 4-Hydroxy-1,3,3a, 7-Tetrazaindene compound ■ 4-Hydroxy-6-phenyl-1,3,3a,7-tetrazaindene compound ■ 4-Methyl-6-hydroxy-1,3,3a,7-tetrazaindene compound ■ 4 -Hydroxy-6-benziroot 3,3a,7-tetrazaindene compound ■ 2-Methyl-4-hydroxy-6-butyroot 3,3a
・7-tetrazaindene compound ■ 4-hydroxy-6-carboxymethyl-1, 3, 3a
・7-tetrazaindene compound ■ 2-hydroxymethyl-4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene compound ■ 2-(4-chloro-2-meth-phenoxymethyl)
-4-Hydroxy-1,3,3a,7-tetrazaindene compound

Among the compounds represented by the above general formula, 4-hydroxy-1,3,3a,7-tetrazaindenes are particularly preferred,
In particular, compound (I) is practically advantageous.

The amount of the hydroxytetrazaindene compound added is 10-4 to 10-2 mol, especially 5X, per 1 mol of silver halide.
10' to 5 x 10-3 mol is preferred.

These compounds, like other photographic additives, are added to the silver halide emulsion by conventional methods.

For example, it is possible to dissolve the photographic material in a solvent (such as water or an alkaline aqueous solution) that does not have a harmful effect on the final photographic light-sensitive material, and add this solution to the photographic emulsion at the end of the second ripening or just before coating. can.

In the present invention, a polyoxyethylene compound is a compound having 5 or more ethylene oxide groups, including polyoxyethylene and water, aliphatic alcohols, glycols,
It includes condensation products with fatty acids, aliphatic amines, phenols, dehydrated cyclic compounds of hexitol derivatives, and block copolymers of polyoxyethylene and polyoxypropylene.

U.S. Patent 2400 for polyoxyethylene compounds
No. 532, No. 3142568, No. 3259540,
No. 3288612, No. 3294537, No. 3294
No. 540, No. 3345175, No. 3516830,
It is described in detail in No. 3567458.

The molecular weight of the polyoxine ethylene compound used in the present invention is preferably 300 to 50,000, particularly preferably 800 to 20,000.

When the polyoxyethylene compound is a block copolymer of polyoxyethylene and polyoxypropylene, the block copolymer is preferably represented by the following general formula (2).

General formula ■ [In the formula, Y is an organic residue with a valence of 2 or more, m is an integer of 2 or more [
The values of X and m are (C3H60) The molecular weight of m is approximately 800
~3500), E represents a polyoxyethylene chain comprising about 10-90% by weight of the block copolymer, and R represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group. .

] Among the general formula (2), it is particularly desirable to use a block copolymer represented by the general formula (2).

General formula ■ [In the formula, b is an integer from 16 to 57, a and C are each a+
c represents an integer from 7 to 295, and the polyoxyethylene group constitutes 10 to 90% by weight of the block copolymer.

] ※※ Specific examples of polyoxyethylene compounds are as follows, but the compounds used in the present invention are not limited to these.

The polyoxyethylene compound can be added to the photographic emulsion in the same manner as the hydroxytetrazaindene compound described above.

In this case, the polyoxyethylene compound is silver halide 1
about 0.01 to 1.01, especially 0.05 to 0.5 per mole
1 is preferred.

Since the silver halide photographic emulsion obtained by the method of the present invention is a high contrast photographic emulsion, it is necessary to contain at least 60 mol % of silver chloride.

Since the contrast increases as the amount of silver chloride increases, 75 mol % or more is particularly preferred for practical purposes.

Accordingly, the silver halide used in the present invention is selected from silver chloride, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

When containing chlorine ions other than silver chloride, silver bromide is 40 mol% or less (especially 25 mol% or less), silver iodide is 8 mol% or less.
It is preferably mol% or less (especially 5 mol% or less).

The shape of the silver halide grains can be any shape, such as cubic, octahedral, or a mixed crystal shape.

In addition, the particle size is generally about 0.04 to 1μ, but practically it is 0.7μ or less, especially 0.1 to 0.7μ.
A range of μ is preferred.

These silver halide grains are produced according to known and commonly used methods.

Of course, it is also useful to use the so-called single jet method, double jet method, controlled double jet method, or the like.

Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, British Patent No. 635,841, and U.S. Patent No. 362,231.
It may also be of a so-called conversion type as described in No. 8.

Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.

These photographic emulsions are from “TheT” by Mees
theory of Photographic Pr
ocess” (The.

Theory of Photographic Process), Ma
Published by CM i 11ac; P, Grafikide
“Chimie Pho” by P. Grafkide
It can be prepared by various methods such as the generally accepted neutral method and acidic method, which are also described in "Shimmy Photographic", published by Paul Mante 1 (1957), etc.

Photographic silver halide emulsions contain hydrophilic colloids.

Examples of hydrophilic colloids include gelatin, colloidal albumin, casein, carboxymethyl cellulose,
Cellulose derivatives such as hydroxyethylcellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives or moieties thereof. Examples include hydrolyzates.

If desired, compatible mixtures of two or more of these colloids are used.

The most commonly used of these is gelatin, but gelatin can be partially or completely replaced with synthetic polymeric substances, and it is also possible to use so-called gelatin derivatives, i.e. amino groups as functional groups contained in the molecule. , imino groups, hydroxyl groups, and carboxyl groups are treated and modified with a reagent that has groups that can react with them, or they are replaced with graft polymers bonded with molecular chains of other polymeric substances. It's okay.

Reagents for making gelatin derivatives include, for example, isocyanates, acid chlorides, acid anhydrides as shown in US Pat. No. 2,614,928, and US Pat. No. 3,118,76.
Acid anhydrides as shown in No. 6, Special Publication No. 39-551
Bromoacetic acids shown in No. 4, Japanese Patent Publication No. 42-26845
phenyl glycidyl ethers as shown in US Pat. No. 3,132,945, N-ruvinyl sulfonamides as shown in British Patent No. 861,414, maleimides as shown in US Pat. No. 3,186,846. Compounds, acrylonitriles as shown in U.S. Pat. No. 2,594,293, U.S. Pat. No. 3,312,55
Polyalkylene oxides shown in No. 3, Special Publication No. 4
Examples thereof include epoxy compounds as described in US Pat. No. 2,26845, acid esters as shown in US Pat. No. 2,763,639, and alkanesultones as shown in British Patent No. 1,033,189.

In addition, the branched polymer grafted onto gelatin has been developed in US Patent No. 27
No. 63625, No. 2831767, No. 2956884
No. or ' Polymer Letters5.5
95 (1967)”, “Phot, Sci.

Eng 9.148 (1965)” “J.

Polymer Sci, A-L9.3199
(1971) etc., there are many descriptions such as acrylic acid, methacrylic acid or their esters, amides,
A wide variety of derivatives such as nitrile or polymers or copolymers of what are commonly called vinyl monomers such as styrene can be used.

In embodiments of the invention, the photographic emulsion layers and other layers used also contain synthetic polymeric compounds, such as latex-like water-dispersed vinyl compound polymers, especially compounds that increase the dimensional stability of the photographic material. They may be included alone or in mixtures (of different types of polymers), or in combination with hydrophilic water-permeable colloids.

There are many types of polymers, such as U.S. Pat.
No. 76005, No. 2739137, No. 2853457, No. 30626
No. 74, No. 3142568, No. 3411911, No. 3488708, No. 3516830, No. 35256
No. 20, No. 3635715, No. 3607290, No. 3645740, British Patent No. 1186699, No. 1
307373, etc.

Among these descriptions are alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate. Copolymers and homopolymers selected from acrylates, alkoxymethacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride are commonly used.

In some cases, when these vinyl compounds are subjected to emulsion polymerization, a so-called graft-type emulsion polymerization latex carried out in the coexistence of a hydrophilic protective colloid polymeric substance may be used.

The above silver halide emulsion can also be chemically sensitized by regular washing.

Chemical sensitizers include, for example, US Pat. No. 2,399,083;
No. 2540085, No. 2597856, No. 25979
Sulfurization occurs by reacting with gold compounds such as chloroauric acid salts and gold trichloride as shown in No. 15, and silver salts as described in U.S. Pat. A sulfur compound that forms silver.

U.S. Patent No. 2487850, U.S. Patent No. 2518698, U.S. Patent No. 2
No. 521925, No. 2521926, No. 269463
Examples include stannous salts, amines, and other reducing substances as described in No. 7, No. 2983610, and No. 3201254.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.

These compounds are 3-methyl-benzothiazole, ■-
A large number of compounds have been known for a long time, including phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts.

An example of a compound that can be used is “The
T heory of thePhotograph
ic Process (3rd edition, 1966), as well as U.S. Patent No. 1758576.
No. 2110178, No. 2131038, No. 21
No. 73628, No. 2697040, No. 2304962
No. 2324123, No. 2394198, No. 26
No. 94716, No. 2697099, No. 2708162
No. 2728663-5, No. 2476536, No. 2824001, No. 2843491, No. 30525
No. 44, No. 3137577, No. 3220839, No. 3226231, No. 3236652, No. 32516
No. 91, No. 3252799, No. 3287135, No. 3326681, No. 3420668, No. 36223
No. 39, British Patent No. 403789, British Patent No. 1173609, British Patent No. 1200188, etc.

Photographic emulsions can be subjected to spectral sensitization or superchromatic sensitization, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like.

These color sensitization techniques have been known for a long time, and are disclosed in, for example, U.S. Pat.
No. 34, No. 3672897, No. 3703377, No. 2688545, No. 2912329, No. 33970
No. 60, No. 3615635, No. 3628964, British Patent No. 1195302, No. 1242588, No. 12
No. 93862, German Patent Publication (OLS) 20303
No. 26, No. 2121780, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 10773-1973, U.S. Pat.
No. 32, No. 3617295, No. 3635721, No. 3694217, British Patent No. 1137580, No. 12
It is also described in No. 16203.

The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

Hardening of the emulsion can be carried out according to conventional methods.

Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, and bis(2-
chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5 triazine, and others U.S. Patent No. 3288
No. 775, No. 2732303, British Patent No. 974723
No. 1167207, etc., compounds containing reactive halogens, divinyl sulfone, 5-
Acetyl 3-diacryloyl hexahydro-■・3
・5-triazine and other compounds with reactive olefins as shown in U.S. Patent No. 3,635,718, U.S. Patent No. 3,232,763, British Patent No. 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. N-methylol compounds such as those shown in US Pat. No. 31,034
Incyanates as shown in US Pat. No. 37, etc., aziridine compounds as shown in US Pat. No. 3,017,280, US Pat.
Acid derivatives as shown in US Pat. No. 94, No. 2,725,295, etc., carbodiimide compounds as shown in US Pat. No. 3,100,704, US Pat. No. 3,091
Eioxy compounds as shown in US Pat. No. 537, inoxazole compounds as shown in US Pat. No. 3,321,313 and US Pat. , dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chrome light pan and zirconium sulfate.

Moreover, instead of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, and primary aliphatic ditroalcohols may be used.

A surfactant may be added alone or in combination to the above photographic emulsion.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, improving photographic properties, antistatic, antiadhesive, etc.

These surfactants include natural surfactants such as saponins,
Higher alkylamines, pyridine, other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfate ester groups, phosphoric ester groups, amino acids, aminosulfonic acids, and sulfuric or phosphoric acids of amino alcohols. It is divided into amphoteric active agents such as esters.

Examples of surfactant compounds that can be used include U.S. Pat. No. 2,271,623, U.S. Pat.
No. 9891, No. 3201253, No. 3475174, German Patent Publication (OLS) No. 1942665, British Patent No. 1077317, "Synthesis of Surfactants and Their Applications" by Ryohei Oda et al. (Sekishoten 1964 edition) and "Surface Active Agents" by A. W. Perry (Interscience Publications, Inc., 1958 edition); "Encyclopedia of Surfaces, Active Agents, Volume 2" by J. P. Cislini (Chemical Publishing Co., Ltd., 1964 edition) ) etc. is written on the bottom.

Certain quaternary ammonium salts, 3-pyrazolidone compounds (see U.S. Pat. No. 3,518,085) and U.S. Pat.
The compounds shown in No. 45175 can be added to photographic emulsions for the purpose of accelerating development and improving dot quality, contrast and development latitude.

The photographic emulsion is coated on a flexible support that does not undergo significant dimensional changes during processing.

Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate phthalate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, and polycarbonate, which are commonly used in photographic materials. There are films and other laminates of these materials.

When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer.

Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

An antihalation layer or a filter layer can be provided below or above the emulsion coating layer according to the invention.

The silver halide photosensitive material obtained according to the present invention is processed by a conventionally known processing method.

For example, an infectious developer is used for development.

Such an infectious developer basically consists of dihydroxybenzene (
It consists of a developing agent), an alkali, a small amount of sulfite, and a sulfite ion buffer.

Dihydroxybenzene as a developing agent is appropriately selected from those well known in the field of photography.

Specific examples include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, but hydroquinone is particularly practical. It is true.

These developing agents may be used alone or in combination.

The sulfite ion buffer is used in an amount effective to keep the sulfite concentration in the developer solution low, and includes aldehyde bisulfite alkali adducts such as formalin sodium bisulfite adduct, and ketone-bisulfite alkali adduct such as acetone sodium bisulfite adduct. adduct, sodium bis(2-
such as hydroxyethyl) aminomethane sulfonate,
Examples include carbonyl bisulfite-amine condensation products.

The alkali makes the developer alkaline, more preferably pH 9.
Added to above.

The developer may further contain an organic antifoggant such as 5- or 6-nitroindazole, penztriazole, ■-phenyl-5-mercaptotetrazole, an amine compound, and an organic compound such as triethylene glycol, dimethylformamide, methanol, or ethylene glycol monoalkyl ether. Various additives conventionally known to those skilled in the art, such as solvents, can be included.

U.S. Patent No. 30388 discloses a method for processing a photographic material obtained by the method of the present invention and a processing agent therefor.
No. 01, No. 3512981, No. 3573914, No. 3625689, No. 3615524, No. 36001
No. 74, No. 3294540, No. 3516524, British Patent No. 1163724, etc.

For processing, US Pat. No. 3,025,779 and US Pat. No. 3,028,024
No. 3122086, No. 3156173, No. 32
A roller conveyance type continuous processing device such as that described in No. 24356 can be used.

As described above, the present invention improves pressure characteristics by making an iridium compound exist near the surface of a lithium-type silver halide crystal, and then adding a hydroxytetrazaindene compound and a polyoxyethylene compound. .

Even if an iridium compound is present on the silver halide crystal surface, the pressure sensitivity characteristics will not be improved much if a hydroxytetrazaindene compound is not used in combination, and even if a hydroxytetrazaindene compound is used alone, it will not be used in conjunction with an iridium compound. In this case, no sufficient effect will be seen.

Moreover, the degree of this improvement is remarkable when a polyoxyethylene compound is added.

That is, according to the present invention, in a lithium-type photographic material using a polyoxyethylene compound, the pressure sensitivity characteristics are significantly improved only when an iridium compound and a hydroxytetrazaindene compound are used in combination.

The lithium-type photographic material according to the present invention has improved pressure characteristics and can prevent pressure marks and scratch marks from occurring without using cadmium salts that have been commonly used in the past.

Further, according to the present invention, it is possible to provide a lithium-type photographic material having high sensitivity, high contrast, and excellent halftone dot quality.

Furthermore, this photosensitive material has a wide exposure and development latitude,
It also has improved storage stability over time and has various excellent advantages.

Examples of the present invention are shown below.

Example 1 An emulsion was prepared according to the following recipe.

■Liquid gelatin 20g Potassium bromide 3g Sodium chloride 81 Potassium iodide 1z Water 60Qcc ■Liquid silver nitrate water 10 (100CC) ■Liquid potassium bromide sodium chloride water 9g 24g oocc ■Liquid gelatin water 0P oocc ■Liquid hexachloroiridium Tripotassium (0.05%) 2cc ■Liquid chloroauric acid (0.1%) 2CC Potassium thiocyanide (1%) 5cc ■While keeping the solution at 60℃, add the ■solution and ■solution simultaneously for 10 minutes. After aging at the same temperature for 20 minutes, the mixture is precipitated with a gelatin flocculant and washed with water.

After the precipitate was redispersed, solutions (1), (2) and (2) were sequentially added and the mixture was aged at 60°C for 60 minutes (emulsion A).

For comparison, a V solution, ie, an emulsion in which only the iridium compound was removed, was also prepared from the above formulation (emulsion B).

Hydroxytetrazaindene compound (
Compound ■) was mixed with 3QCC in a 1% aqueous solution per mole of Ag, and polyoxyethylene compound (compound E) was mixed with Ag 1
A 1% aqueous solution per mole was prepared with and without 10cc added, and appropriate amounts of color sensitizer, hardener, coating aid, etc. were added, coated and dried on a polyethylene terephthalate base, and a protective layer was further applied. The samples shown in Table 1 were prepared by coating.

The pressure sensitivities of the eight types of samples obtained were compared using the following method.

First, a needle with a spherical tip with a radius of curvature of 0.05 mm was
0'? The emulsion surface of the film is scratched at a constant speed while applying a thin line of pressure.

These films were then exposed to light for 5 seconds through an exposure wedge using a 500 W tungsten bulb with a voltage of 80'V and light passing through a dark color temperature conversion filter (5400°K).

The direction of the concentration gradient of the exposure wedge is made to match the direction in which linear pressure is applied.

After exposure, the film was developed for 3 minutes at 20° C. using the following Lith developer, fixed by a conventional method, washed with water, and dried, and then the appearance of pressure marks was examined.

Developer solution Sodium carbonate (monohydrate) 5o1 Formaldehyde, hydrogen sulfite adduct Potassium bromide Hydroquinone Sodium sulfite Add water 51 1 81 2g 1 Pressure marks are made by tracing the area where linear pressure is applied with a microphotometer. On the other hand, the density was measured using an ordinary densitometer in the area where no pressure was applied, and quality was judged based on the difference in sensitivity and gradation between these two characteristic curves.

The results thus obtained are shown in Table 2 and FIG.

The specific sensitivity indicates a value when the sensitivity of the unpressurized part of Sample 1 prepared according to the present invention is set as 100.

Comparing Samples 7 and 8 to which neither a water-soluble iridium salt nor a hydroxytetrazaindene compound was added, in Sample 8 to which no polyoxyethylene compound was added, the pressurized area was desensitized and the tone was softened.

The desensitization was even more remarkable in Sample 7 to which a polyoxyethylene compound was added.

Although a hydroxytetrazaindene compound is added, in sample 5.6 which does not contain an iridium salt, when compared with sample 7.8, sensitivity and γ increase in samples 7, 5.8 and 6, respectively. Desensitization of the pressurized area is considerably prevented, but not sufficiently.

Similarly, sample 3.4, which also contains iridium salt but does not contain a hydroxytetrazaindene compound, is more prevented from desensitizing the pressurized area than sample 7.8.
Compared to Samples 5 and 6, when the polyoxyethylene compound is absent, the tone becomes significantly softer (Sample 4), and when the polyoxyethylene compound is present, the desensitization is remarkable (Sample 3).

On the other hand, among the samples in which an iridium salt and a hydroxytetrazaindene compound were used together, in sample 2, in which no polyoxyethylene compound was added, desensitization due to pressure was almost prevented, but softening was not completely prevented. It's not peeling off.

Only sample 1, in which a polyoxyethylene compound was also added, ie, the sample according to the invention, was completely prevented from desensitizing and softening due to pressure.

Example 2 An emulsion was prepared according to the following recipe.

Liquid I gelatin 2 (1 Sodium chloride 41 Potassium iodide 2'iI' Water
400CC ■Liquid silver nitrate water 100g 00CC ■Liquid potassium bromide sodium chloride water 18g 51 000CC ■Liquid hexachloroiridium dipotassium (0.05%) cc ■Liquid gelatin water 50g oocc ■Liquid chloroauric acid (0.1%) ) 2.5 cc potassium thiocyanide (1%) 5 cc liquid at 64℃
While stirring at a constant temperature, liquids (1) and (2) were added simultaneously over 10 minutes, and the mixture was aged at the same temperature for IO minutes, then liquid (2) was added, and the mixture was further aged for 5 minutes.

Add a gelatin flocculant to this, settle, and wash with water.

After redispersing the sediment, add solution V and solution ① sequentially to 62
Aged for 70 minutes at °C (emulsion C).

Furthermore, an emulsion in which only the iridium compound, i.e., the iridium compound was removed, was also prepared from the above formulation (emulsion D).

Hydroxytetrazaindene compound (compound 1) was added to these two emulsions in a 1% aqueous solution per mol of Ag at 35%
cc, and polyoxyethylene compound (compound A) as A
14 cc of ■% aqueous solution per 1 mole was prepared with both added, only one added, and neither added, and appropriate amounts of color sensitizer, hardening agent, coating aid, etc. were added. , was coated on a polyethylene terephthalate base, dried, and further coated with a protective layer to prepare the samples shown in Table 3.

The eight types of samples obtained were bent by a radius of curvature of 1.2 degrees with the emulsion side facing inside, then exposed and developed under the same conditions as in Example 1, and the bent portions were bent. The concentration was measured by microtracing and the results shown in Table 4 were obtained.

The specific sensitivity was determined by the same method as in Example 1.

As in Example 1, only the material according to the present invention completely prevents desensitization and softening due to pressure, and is excellent in pressure resistance.

[Brief explanation of the drawing]

FIG. 1 shows characteristic curves of photographic materials produced by the method of the present invention and the comparative method. 1 is the characteristic curve of the present invention, 2 to 8 are comparative characteristic curves, and the numbers correspond to the samples of Example 1. In FIG. 1, the broken line shows the characteristic curve of the unpressurized part, and the solid line shows the characteristic curve of the pressurized part.

Claims (1)

[Claims] 1. In the first and second ripening steps of a silver halide photographic emulsion containing at least 60 mol% silver chloride, 10'' to 10-4 mol of a water-soluble iridium compound is added per mol of silver halide, and hydroxytetra 1. A method for producing a lithium-type photographic material, which comprises adding a zainden compound and a polyoxyethylene compound and coating it on a support.