JPH05333465A - Silver halide photographic sensitive material and image forming method using the same - Google Patents

Abstract

PURPOSE:To enhance rapid processing aptitude and to improve pressure resistance and storage stability by coating the side of a support with a binder in a specified range of the amount of the total binder to be used and incorporating a specified polymer compound in a layer on the same side. CONSTITUTION:One of the constituent layers of the silver halide photographic sensitive material contains the polymer compound composed repeating units each having 1,2,4-triazo-[1,5-a]-pyrimidine residue represented by formula I in which R<1> is H lower alkyl; L is a divalent bonding group; and X is the univalent residue of the above-mentioned repeating unit. The total coating amount of the binder can the side of the support on which the one layer contains the polymer is in the range of 1.7-2.5g/m<2> and one of the constituent layers has a silver to binder ratio of >=1.2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and an image forming method using the same, and particularly to the pressure characteristics of a photographic light-sensitive material having a reduced binder content, which is excellent in rapid processing suitability. It relates to a technique for improving.

[0002]

2. Description of the Related Art Various forces are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is rolled up in a cartridge, bent, pulled, or rubbed against the carrying part of the camera when loaded in the camera. On the other hand, a sheet-shaped film such as a printing photosensitive material or a direct medical X-ray sensitive material is often bent because it is directly handled by a person. Also, in the bright room transport equipment and high-speed changer, it comes into strong contact with metal and rubber.
In addition, all sensitive materials are subject to great pressure during cutting and processing. When various forces are applied to the photographic light-sensitive material in this manner, pressure is applied to the silver halide by using gelatin or a polymer substance which is a holder (binder) of the silver halide grains as a medium.
It is known that when pressure is applied to silver halide grains, blackening and desensitization that do not correspond to the amount of exposure occur.
B. Mather. J. Opt. Soc. Am., 38. 1054 (1948), P. Faele
ns andP.de Smet.Sci. et Ind. Phot., 25. No 5. 178
(1954) P.Faelens, J.Phot.Sci. 2.105 (1954) and so on.

Therefore, it is strongly desired to provide a photographic light-sensitive material which is not affected by these pressures in photographic properties. On the other hand, silver halide photographic light-sensitive materials require complicated and many processes from photographing to obtaining an image. While it is desirable to speed up the process during this time, it is desirable to reduce the amount of binder in the light sensitive material for this purpose. That is, since the amount of the binder is reduced, the processes such as development, fixing and drying are speeded up. The binder here is used as a binder and a protective colloid for a photographic emulsion, and gelatin is generally used, but other hydrophilic colloids can also be used. However, the above-mentioned pressure property deteriorates as the amount of binder decreases. This deterioration is 1,2,4- which is a typical stabilizer for silver halide photographic light-sensitive materials.
It is promoted by triazolo [1,5-a] pyrimidines such as 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene. Therefore, a stabilizer that does not deteriorate pressure resistance has been desired.

As will be described later, 1,2,4-triazolo [1,5], which is a problem in a light-sensitive material having a reduced amount of binder.
-A] Deterioration of pressure due to pyrimidines is
By polymerizing 4-triazolo [1,5-a] pyrimidines, it was improved while keeping the storage stability.
An example of a polymer compound containing a repeating unit containing a residue of 1,2,4-triazolo [1,5-a] pyrimidines is disclosed in JP-A-57-211142, which is suitable for rapid processing. It does not correspond. Further, there are other examples of polymerizing a compound known as a stabilizer, for example, US Pat. Nos. 3,576,638 and 3,3.
Nos. 598,599, 3,598,600, and 4,134,768 each contain tetrazole, thiazole, imidazole, and 1-phenyl-5-mercaptotetrazole residues which are repeatedly contained in a high concentration. Molecular compounds are disclosed. Further, JP-A-62-949 discloses an example of a polymer compound containing an oxadiazole ring, a thiadiazole ring, a selenadiazole ring or a triazole ring as a repeating unit. In any case, it is suitable for rapid processing. It does not correspond.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a silver halide photographic light-sensitive material having a low binder content, excellent suitability for rapid processing, and good pressure and storability. To get a way to form.

[0006]

The object of the present invention is (1).
Was achieved by (4). (1) At least one of the constituent layers contains a polymer compound containing a repeating unit having a residue of 1,2,4-triazolo [1,5-a] pyrimidines, and the polymer of the support described above. A silver halide photographic light-sensitive material characterized in that the total coating amount of the binder coated on the side containing the compound is 1.7 g / m ² or more and 2.5 g / m ² or less. (2) The silver halide photographic light-sensitive material described in (1) above, wherein at least one of the constituent layers has a silver / binder ratio of 1.2 or more.

(3) 1,2,4-triazolo [1,5-
a] The halogenated compound according to 1 or 2 above, wherein the polymer compound containing a repeating unit having a residue of a pyrimidine is a polymer compound containing a repeating unit represented by the general formula (I). Silver photographic light-sensitive material.

[0008]

[Chemical 2]

(4) An image forming method using the silver halide photographic light-sensitive material described in 1 above, wherein the time from the start of processing to the end of drying is 35 seconds or less.

The general formula (I) will be described in more detail. R ¹ is a hydrogen atom or a lower alkyl group, and the lower alkyl group is preferably one having up to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, hexyl group). R
¹ is particularly preferably a hydrogen atom or a methyl group. L is a divalent linking group, but preferably has a total carbon number of 1 to 20. Among such linking groups, the following formula (L-
Those represented by I) or (L-11) are preferred.

[0011]

[Chemical 3]

In the formula, Q represents --O-- or --NR ^2- (wherein R ² represents a hydrogen atom or a lower alkyl group, and the lower alkyl group preferably has up to 6 carbon atoms). Z is an alkylene group (preferably having up to 10 carbon atoms. An amide bond, an ester bond or an ether bond may be interposed in the middle of the alkylene group. For example, a methylene group, an ethylene group, a propylene group, -CH ₂ OCH.
_{2 -, - CH 2 CONHCH 2} -, - CH 2 CH 2 CO
_{OCH 2 -, - CH 2 CH} 2 OCOCH 2 -, - CH 2
NHCOCH ₂ — or the like) or arylene group (preferably having 6 to 12 carbon atoms, such as p-phenylene group)
Represents. Particularly preferred divalent linking groups as L include the following.

[0013]

[Chemical 4]

X is 1,2,4-triazolo [1,5-
a] represents a monovalent group of pyrimidines. The 1,2,4-triazolo [1,5-a] pyrimidines preferably have 5 to 25 total carbon atoms. Among them, the following formula (X-
Those represented by I), (X-II) or (X-III) are preferable.

[0015]

[Chemical 5]

In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, an unsubstituted or substituted alkyl group (preferably a methyl group having up to 12 carbon atoms such as a methyl group or ethyl group). Group, propyl group, hexyl group, hydroxyethyl group, carboxyethyl group, chloropropyl group,
Benzyl group, 2- (methoxycarbonyl) ethyl group, cyanopropyl group, trichloromethyl group, etc., unsubstituted or substituted aryl group (preferably phenyl group having 6 to 12 carbon atoms, naphthyl group, p-tolyl group) Group, p
-Chlorophenyl group, o-carboxyphenyl group, etc.), substituted amino group (for example, dimethylamino group,
Acetylamino group).

Unsubstituted or substituted carbamoyl group (eg, carbamoyl group, methylcarbamoyl group, etc.), hydroxyl group, --OM group (M represents an alkali metal ion or ammonium ion), cyano group, halogen (chlorine, bromine). Represents an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butoxycarbonyl group, etc.), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), and R ⁴ and R ⁵ may form a ring (for example, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, etc.). R ³
At least one of R ⁶ to R ⁶ is a hydroxyl group or —O
It is preferably an M group. Particularly preferred as X 1,
Monovalent groups of 2,4-triazolo [1,5-a] pyrimidines include the following.

[0018]

[Chemical 6]

The polymer compound containing a repeating unit represented by the general formula (I) of the present invention generally has the following general formula (I
It is obtained by homopolymerizing the unsaturated monomer represented by I) or by copolymerizing the unsaturated monomer represented by the general formula (II) with an ethylenically unsaturated monomer copolymerizable with the monomer.

[0020]

[Chemical 7]

In the formula, R ¹ , L and X have the same meanings as described in the general formula (I). Specific examples of the monomer represented by the general formula (II) are listed below.

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

Among the above specific examples, II-1, 2, 3, 7,
The 8 and 11 monomers are particularly preferred. Such a general formula (I
The monomer represented by I) is generally a 1,2,4-triazolo [1,5-a] pyrimidine derivative having a carboxy group or a hydroxy group in its side chain (for example, US Pat.
35, 581) and an unsaturated monomer having an amino group, a hydroxy group or a carboxy group. The polymer compound of the present invention has the general formula (II)
The above monomer may be polymerized alone, or may be a copolymer of the monomer of the general formula (II) and one or more ethylenically unsaturated monomers copolymerizable therewith.

Examples of ethylenically unsaturated monomers in the preferred polymers of the invention are ethylene, propylene, 1-
Butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, potassium vinylbenzene sulfonate, sodium vinylbenzyl sulfonate, N,
N, N-trimethyl-N-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinyl Pyridinium chloride,
N-vinylacetamide, N-vinylpyrrolidone, 2-
Methyl-3-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, allyl acetate).

Ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, maleic acid), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg n- Butyl acrylate, n-hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N, N- Diethylaminoethyl methacrylate, N, N, N-triethyl-N-methacryloyloxyethylammonium-p-toluenesulfonate, N, N- Ethyl -N- methyl -N- methacryloyloxyethyl ammonium -p- toluenesulfonate, dimethyl itaconate, maleic acid mono benzyl ester).

Amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg acrylamide, N,
N-dimethyl-N'-methacryloyl propane diamine acetate betaine, N, N-dimethyl-N'-acryloyl propane diamine propionate betaine, N,
N-dimethylacrylamide, N-methylolacrylamide, N- (N, N-dimethylaminopropyl) acrylamide, N, N, N-trimethyl-N- (N-acryloylpropyl) ammonium-p-toluenesulfonate, 2-acrylamide 2-methylpropanesulfonic acid soda, acryloylmorpholine, 2-acrylamido-2-methylpropanesulfonic acid sodium, methacrylamide) and the like.

Among these ethylenically unsaturated monomers, vinylbenzenesulfonic acid salts, vinylbenzenesulfinic acid salts, monoethylenically unsaturated esters of aliphatic acids or their saponification products, 2-acrylamido-2-methylpropane. Sodium sulfonate, N-vinylpyrrolidone,
Ethylenically unsaturated monocarboxylic acid esters (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate), ethylenically unsaturated monocarboxylic acid amides (eg, acrylamide, methacrylamide) and the like are preferable.

The degree of polymerization of the polymer compound of the present invention may be arbitrarily selected, but the molecular weight is preferably in the range of 5 × 10 ^{3 to} 3 × 10 ⁶ , particularly 10 ⁴ to 10 ⁶ . When a copolymer with an ethylenically unsaturated monomer is used, the copolymerization ratio may be arbitrarily selected, but at least the molar percentage of the repeating unit represented by the general formula (I) is 0.1 mol% or more, particularly 1 The effect of the present invention can be obtained as long as it is a copolymer having a mol% or more. Specific examples of the polymer compound of the present invention are listed below. In addition, x and y represent mol%, and a specific mol% is shown by a compound number.

[0032]

[Chemical formula 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

The homopolymerization of the monomer represented by the general formula (II) and the copolymerization with other ethylenically unsaturated monomers are described, for example, in Ronald L. Schnaar, Yuan Chuan described in Biochemistry, page 1535 (1975). Lee et al., Journal of Polymer Science; Polymer Chemistry E
Anthony Wi, ddition, page 2155 (1976)
nston, Glenn R. Mclaughlin et al.

Die Makromolekule Chemie, Volume 177, 683
Hans-Georg Batz, Johan, pp. 1976.
na Koldehotf et al., Angewante Chemie; Internat.E
ddit. 1103 (1972) Hans-Georg Batz.
Giselner Franzmann.Helmut Ringsdorf et al., Poly
mer, p. 462 (1972), P. Ferruti, AB.
It is performed according to the method of ettelli, Angelino Fere and others.

The polymer compound of the present invention is added to at least one of the constituent layers of the photographic light-sensitive material. A silver halide emulsion layer is most preferable as the layer to be added. There is no particular limitation on the timing of addition, and it may be added at any time, for example, during emulsion production or during emulsion coating, depending on the purpose of use.
Examples of layers other than the silver halide emulsion layer to which the polymer compound of the present invention can be added include various auxiliary layers such as an overcoat layer, an undercoat layer, an intermediate layer and a filter layer. The polymer compound of the present invention may be added in the form of a latex. The size of the latex is not particularly limited, but the equivalent spherical diameter is preferably 0.01 μm to 3 μm. Especially 0.03
It is preferably from 1 μm to 1 μm.

The polymer compound of the present invention may be used alone as the sole stabilizer, or may be used in combination with other known stabilizers. For example, 1,2,4-triazolo [1,5-a]
Pyrimidines, especially 4-hydroxy-6-methyl-1,
The combined use of 3,3a, 7-tetrazaindene and the polymer compound of the present invention, in principle, has the same mechanism for stabilizing silver halides, and therefore enables stronger stabilization without harmful side effects. Further, when it is necessary to use a large amount of 1,2,4-triazolo [1,5-a] pyrimidines, there is a problem of a decrease in spectral sensitivity, an outflow to a processing solution,
This is preferable from the viewpoint that stains and the like due to accumulation can be eliminated without lowering the stabilizing effect.

Therefore, the amount of the polymer compound of the present invention to be used is not particularly limited and can be selected from a wide range. Generally, 1,2,4-triazolo [1,5-a] contained in the polymer compound is used. It is used in the range of 10 ^-8 mol to 10 ^-3 mol, and particularly 10 ^-7 mol to 5 × 10 ^-4 mol per m ^{2 of} the support in terms of the number of pyrimidine residues. The weight of the polymer compound is about 0.02 mg to about 2 g, particularly about 0.2 mg to about 1 g, and about 60 per 1 mol of silver halide per 1 m ^{2 of the} support.
It is used in the range of mg to about 200 g, especially about 300 mg to about 100 g.

Examples of the stabilizer used in combination with the polymer compound of the present invention include 1,2,4-triazolo [1,5-a] mentioned above.
Besides pyrimidines, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzo Thiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
As an antifoggant or stabilizer such as mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; a thioketo compound such as oxazoline thione; benzenethiosulfonic acids; benzenesulfinic acid; Many known compounds may be mentioned.

As the binder or protective colloid for the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. These are collectively referred to as a binder. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. You can

As the gelatin, lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Phot. Japan, No.
The enzyme-treated gelatin as described on pages 16 and 30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are US Pat. Nos. 2,614,928 and 3,132,945.
Issue 3, Issue 3,186,846, Issue 3,312,553
No., British Patents 861,414, 1,033,189
No. 1,005,784, Japanese Patent Publication No.
No. etc.

The gelatin / graft polymer may be a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, their derivatives such as esters and amides, acrylonitrile and styrene. What grafted can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable.
Examples of these are US Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956,884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German Patent Application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. These are collectively referred to as a binder. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. You can

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Phot. Japan, No.
The enzyme-treated gelatin as described on pages 16 and 30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are US Pat. Nos. 2,614,928 and 3,132,945.
Issue 3, Issue 3,186,846, Issue 3,312,553
No., British Patents 861,414, 1,033,189
No. 1,005,784, Japanese Patent Publication No.
No. etc.

As the gelatin / graft polymer, gelatin is a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and acrylonitrile and styrene. What grafted can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable.
Examples of these are US Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956,884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German Patent Application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer, if desired, and is preferably provided with a protective layer. In order to achieve the object of the present invention, Dry to Dry 35 seconds or less, the photosensitive material of the present invention needs to reduce the total amount of the binder applied per one side of the support. That is, the amount of the binder on the side having the hydrophilic colloid layer including the photosensitive silver halide emulsion layer is 1.70 to 2.50 g /
It is in the range of m ² . If the photosensitive emulsion layer is present only on one side of the support, the amount of gelatin on that side is required to be within the above range, and when there is no hydrophilic colloid layer other than the photosensitive emulsion layer, The amount of gelatin in the functional emulsion layer is within the above range. More preferably, the amount of binder is
Range of 1.80 to 2.4 g / m ² , especially 1.9 to 2.3 g
A range of / m ² is preferred. Melting of the sensitive material of the present invention
The time is preferably set to 8 minutes or more and 45 minutes or less.

The melting time referred to in the present invention means a silver halide light-sensitive material cut into 1 cm × 2 cm.
It means the time until at least one silver halide emulsion layer constituting the silver halide photographic light-sensitive material begins to melt when immersed in a 1.5% by weight sodium hydroxide aqueous solution at a temperature of ℃. When the amount of the binder is reduced as described above, the pressure property deteriorates, which is a serious problem in product design. Further, such deterioration becomes a problem even if the silver / binder ratio of at least one of the emulsion layers constituting the light-sensitive material is 1.2 or more. Under such circumstances, the addition of a stabilizer such as 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene further aggravates the pressure deterioration. We have found that polymerizing such a stabilizer causes almost no deterioration in pressure.

The amount of the polymer compound of the present invention used is the same as mentioned above, but the amount of 1,2,4-triazolo (1,5-a) pyrimidines required (the amount required for the monomer) is required. On the other hand, in polymer compounds,
Even if about 10 times the amount of 2,4-triazolo (1,5-a) pyrimidine residue residue (converted into a polymer amount) was added, the deterioration of the pressure property was slight. In order to obtain a sufficient stabilizing effect, the amount of polymer is preferably several times to 10 times the amount of the required monomer.

Next, the emulsion grains used in the present invention will be described. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the present invention. The average grain size (diameter when converted into spheres of the same volume) of silver halide grains in the photographic emulsion is not particularly limited, but is preferably 3 μm or less. The particle size distribution may be narrow or wide. The silver halide grains in photographic emulsions are regular, such as cubic and octahedral.
It may have a different crystal body, or may have an irregular crystal system such as a sphere or a plate. It may be composed of a mixed system of particles of various crystal systems. The silver halide grains may have different layers in the inside and the surface, or may have a uniform phase. Further, the particles may be such that a latent image is formed on the surface or particles inside the particles.

The photographic emulsion used in the present invention is P. Glfkid.
es Chimie et Physique Photogr-aphique (Paul Mont
published by el, 1967), by GF Duffin Photographic Emulsi
onChemistry (The Focal Press, 1966), VLZeli
By kman et al Making and Coating Photographic Emulsi
on (The Focal Press, 1964) and the like. That is, the acidic method,
The neutral method, the ammonia method, or the like may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In addition, JP-A 1-1
No. 83644, No. 1-18345, No. 1-18341
As described in No. 7, fine grains of silver halide may be added to grow the grains. At this time, the size of the ultrafine particles is 0.2 μm or less, preferably 0.1 μm or less,
In particular, it is preferably 0.05 μm or less.

Two or more kinds of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together. Further, a sensitizing dye for spectral sensitization may coexist. In addition, a silver halide solvent such as thiocyanate, thioether compound, thiazolidineethione, 4-substituted thiourea, ammonia and crown ether may be present at the time of grain formation. The present invention can be used in a negative emulsion forming a surface latent image or a direct spot emulsion.
Examples of the latter emulsion include an internal latent image type emulsion and a pre-fogged direct inversion type emulsion.

The silver halide emulsion used in the present invention is usually subjected to physical ripening, desalting and chemical ripening after grain formation and then used for coating. Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 3,271,1).
57, JP-A-51-12360, and JP-A-53-82.
408, JP-A-53-144319, JP-A-54-
No. 100717, when subjected to physical ripening in the presence of thioethers and thione compounds described in JP-A No. 54-155828, etc., a single crystal having a regular crystal form and a nearly uniform particle size distribution is obtained. A dispersion emulsion is obtained. In order to remove the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method or ultrafiltration method is used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, primary tin salt, amines) , A hydrazine derivative, formamidinesulfinic acid, a silane compound); a reduction sensitization method; a metal compound (for example, a gold complex salt, Pt,
A noble metal sensitization method using a group VIII metal of the periodic table such as Ir, Pd, Rh, and Fe) can be used alone or in combination.

The light-sensitive material of the present invention may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.).

Active halogen compounds (2,4-dichloro-
6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonyl) Methyl) ether or vinyl-based polymer having a vinyl sulfonyl group in the side chain) is preferable because it rapidly cures a hydrophilic colloid such as gelatin and provides stable photographic characteristics.

N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate and the like) are also fast and excellent in curing rate.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes.

That is, a pyrroline nucleus, an oxazoline nucleus,
Thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine as a nucleus having a ketomethylene structure. 5 such as nucleus and thiobarbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensation (For example, US Pat. No. 3,743,
No. 510), a cadmium salt, an azaindene compound, and the like. U.S. Pat. No. 3,615,6
No. 13, No. 3,615, 641, No. 3, 617, 29
The combinations described in No. 5 and No. 3,635,721 are particularly useful. The sensitizing dye may be added during or during each step of grain formation, grain growth, desalting, chemical sensitization, or after chemical sensitization.

The silver halide photographic emulsion used in the present technology may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be included.
That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole. , Benzotriazoles, nitrobenzotriazoles,

Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes. (In particular, 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes, pentaazaindenes, etc .; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide) Many compounds described above can be added.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as required. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive, blue-sensitive layer, green-sensitive and red-sensitive layers or blue-sensitive, red-sensitive and green-sensitive. Further, an arbitrary emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The graininess may be further improved as a three-layer structure.

Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having different color sensitivity may be inserted between certain emulsion layers having the same color sensitivity. A sensitivity layer may be improved by providing a reflective layer of fine grain silver halide under the high sensitivity layer, especially the high sensitivity blue sensitive layer. Generally, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used in some cases. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports such as plastic films, papers and cloths commonly used in photographic light-sensitive materials or rigid supports such as glass, ceramics and metals. Applied to the body. Useful as flexible supports are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers. (For example, polyethylene, polypropylene, ethylene / butene copolymer)
It is a paper coated or laminated with the above.

The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

The developing solution used in the present invention may contain a known developing agent. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, a dissolution aid, a color tone agent, a development accelerator (for example,
A quaternary salt, hydrazine, benzyl alcohol), a surfactant, an antifoaming agent, a water softener, a hardener (eg, glutaraldehyde), a viscosity imparting agent and the like may be contained.

As the fixing liquid, those having a generally used composition can be used. Thiosulfate as a fixing agent,
In addition to thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The development processing method by the automatic processor in the present invention includes:
U.S. Pat. Nos. 3,025,779 and 3,515,5
No. 56, No. 3,573,914, No. 3,647,
It is preferable to use a roller-conveying type automatic processor described in, for example, No. 459 and British Patent No. 1,269,268.

The developing temperature is 18 ° C to 50 ° C, especially 3 ° C.
The temperature is preferably 0 ° C. to 45 ° C., and the developing time is preferably 8 seconds to 40 seconds, particularly preferably 8 seconds to 25 seconds. The total development processing steps from the start of development to the fixing, washing, and drying are 30 seconds to 200 seconds, particularly 40 seconds to 100 seconds.
Seconds are preferred. There are no particular restrictions on various additives, developing methods, exposure methods, etc. of the light-sensitive material of the present invention, Research Disclosure Magazine 176 items 17643 (December 1978) and 184 items 18431 (August 1979). Can be referred to. The light-sensitive material of the present invention is suitable for rapid processing because the amount of binder is reduced. Especially Dry to Dr
y Excellent processability for 35 seconds or less. Moreover, no special treatment liquid is required for this treatment. As shown in the examples, it is only necessary to increase the transport speed of the automatic developing machine.

[0074]

The present invention will be described in more detail with reference to the following examples. (Preparation of octahedral pure silver bromide grains (grain 1)) To 1 liter of water was added 0.35 g of potassium bromide and 20.6 g of gelatin, and 5
40 cc of silver nitrate aqueous solution (0.28 g of silver nitrate) and potassium bromide aqueous solution were added to the solution kept at 0 ° C. while stirring.
0 cc (0.21 g of potassium bromide) was simultaneously added by the double jet method for 10 minutes. 200 silver nitrate solution
cc (1.42g as silver nitrate) and aqueous potassium bromide solution 200
cc (1.06 g as potassium bromide) was added simultaneously over 8 minutes. After this, 27 cc of potassium bromide aqueous solution (potassium bromide 2.
7 g) was added. After this, an aqueous silver nitrate solution and an aqueous potassium bromide solution were again added by the control double jet method. The added silver nitrate aqueous solution is 1 liter (silver nitrate 140
In step g), the flow rate was set to 2 cc / min at the start of the addition, and the addition was linearly accelerated to complete the addition in 70 minutes. An aqueous potassium bromide solution was simultaneously added while controlling the control potential to pAg = 8.58. Then, the temperature was lowered to 35 ° C. to remove soluble salts by the sedimentation method. The temperature was again raised to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and sodium polystyrene sulfonate (0.35 g) as a thickener.
8 g was added, and the pH was adjusted to 6.0 with an aqueous sodium hydroxide solution. Thus, monodisperse pure silver bromide octahedral grains 1 having a diameter of 0.62 μm were prepared.

(Preparation of octahedral silver iodobromide grains (grain 2))
0.35 g of potassium bromide and 20.6 of gelatin in 1 liter of water
To the solution added with g and kept at 50 ° C, 40cc of an aqueous solution of silver nitrate (0.28g as silver nitrate) and 40cc of an aqueous solution of potassium bromide (0.21g of potassium bromide) are simultaneously added by the double jet method for 10 minutes while trying to stir. did. Subsequently, 200 cc of an aqueous silver nitrate solution (1.42 g as silver nitrate) and 200 cc of an aqueous potassium bromide solution (1.06 g as potassium bromide) were simultaneously added over 8 minutes. After this, 27cc of aqueous potassium bromide solution
(2.7 g of potassium bromide) was added (the steps up to this point are the same as those of the particle 1). After this, an aqueous silver nitrate solution and an aqueous potassium bromide solution were again added by the control double jet method. The added silver nitrate aqueous solution was 1 liter (140 g of silver nitrate), and the flow rate was 2 cc / min at the start of the addition, and the addition was linearly accelerated to complete the addition in 70 minutes. Control potential is pA
While controlling so that g = 8.58, a mixed aqueous solution of potassium iodide and potassium bromide was simultaneously added. The amount of potassium iodide consumed here was 0.4 mol% with respect to the total silver amount. Subsequently, a 1% potassium iodide aqueous solution was added over 1 minute. The amount of potassium iodide consumed at this time was 0.1 with respect to the total amount of silver.
It was mol%. Then, the temperature was lowered to 35 ° C. to remove soluble salts by the sedimentation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.0 with an aqueous sodium hydroxide solution. Thus, monodisperse silver iodobromide octahedral grains 2 having a diameter of 0.64 μm and a silver iodide amount of 0.5 mol% were prepared.

(Preparation of pure silver bromide tabular grains (grain 3))
A 0.49% by weight gelatin solution containing 0.1 mol of potassium bromide was added to 1.94 liters by a double jet method while stirring to obtain 0.39M silver nitrate solution as well as 0.39M.
And 30 ml of potassium bromide solution were added over 30 seconds. During this time, the gelatin solution was kept at 40 ° C.
After the addition was completed, the temperature was raised to 75 ° C. After heating, 22 g of gelatin and 94 cc of 0.39 M silver nitrate solution were added. After 10 minutes to 65 minutes, 1.47M silver nitrate solution 7 was added.
00cc accelerated flow rate (end flow rate is 2 at start
0.5 times). During this period, pBr was kept at 2.86. After this, the emulsion is cooled to 35 ° C., washed by conventional flocculation method, and then pH at 40 ° C.
It was adjusted to 6.0 and pAg 8.6. 88% of the grains thus obtained were occupied by tabular grains, and the coefficient of variation was 15%. The average D circle (diameter corresponding to the circle of the projected area) of the particles was 1.22 μm, and the average thickness was 0.17 μm. Data on particle size was obtained from electron micrographs.

(Preparation of surface iodine type tabular grains (grain 4)) In 1 liter of water, 4.5 g of potassium bromide, 20.6 g of gelatin, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) Addition of _2.5 cc of 5% aqueous solution of ₂ OH and stirring in a container kept at 60 ° C while stirring 37 cc of silver nitrate aqueous solution (3.43 g of silver nitrate), 2.97 g of potassium bromide and 0.363 g of potassium iodide. 33 cc was added by the double jet method in 37 seconds. Then, an aqueous solution of 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C. to 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at the same temperature, 14 cc of 100% acetic acid solution was added.
Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while keeping the pAg at 8.5. Next, 10 ml of a 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were added in an amount of 0.2 mol% based on the total amount of silver. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus the total silver iodide content is 0.46
Mol%, average projected area diameter 1.10 μm, thickness 0.16
Monodisperse tabular grains having a diameter of 5 μm and a variation coefficient of diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution.

(Chemical sensitization) For the above particles 1 and 2,
Chloroauric acid salt, sodium thiosulfate and ammonium thiocyanate were added for optimal gold-sulfur sensitization, and then the following sensitizing dye (A) was added at 590 mg / Ag mol.

[0079]

[Chemical 17]

Further, the grains 3 and 4 were chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 500 mg of the sensitizing dye (A) were added. Furthermore, 1.1 g of an aqueous calcium chloride solution was added. Subsequently, 3.3 g of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C.
In this way, preparation of particles 1 to 4 was completed.

(Preparation of emulsion coating layer) The following chemicals were added to chemically sensitized emulsions 1 to 4 per mol of silver halide to prepare coating solutions. -2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72mg-trimethylolpropane 9g-dextran (average molecular weight 39,000) 18.5g-potassium polystyrene sulfonate (average molecular weight 60) 10,000) 1.8 g-Compound (E-1) 3.4 mg-Compound (E-2) 10.9 mg-Gelatin and hardener (1,2-bis (vinylsulfonylacetamide) ethane) Table-1 description Adjusted to the volume swelling rate

[0082]

[Chemical 18]

In addition to the above chemicals, in the case of coating liquid type A, the following chemicals were added. 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 0.2 g In the case of coating liquid type B, the following chemicals were added. -Compound 13 of the present invention 11.2 g In the case of coating liquid type C, the following chemicals were added. -Compound 14 of the present invention 7.0 g In the case of coating liquid type D, the following chemicals were added.・ 10.7 g of Compound 15 of the present invention

(Preparation of Surface Protective Layer Coating Liquid) In the case of the surface protective layer coating liquid X, preparations were made so that the respective components had the following coating amounts.・ Gelatin 0.966 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.023 ・ Compound (P-1) 0.013 ・ Compound (P-2) 0.045 ・ Compound (P-3) 0 0.0065 compound (P-4) 0.003 compound (P-5) 0.001 polymethylmethacrylate (average particle size 3.7 μm) 0.087 proxel 0.0005 (adjusted to pH 7.4 with NaOH) In addition, the following compounds were further added to the above coating liquid and the pH was adjusted to 7.4, to obtain a surface protective layer coating liquid Y.・ 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 0.015 g / m ²

[0085]

[Chemical 19]

(Preparation of Support) (1) Dye D- for Undercoat Layer
Preparation of 1 The following dye was ball milled by the method described in JP-A-63-197943.

[0087]

[Chemical 20]

6.7 ml of water (434 ml) and Triton X-200® surfactant (TX-200®).
% Aqueous solution (791 ml) was placed in a 2 liter ball mill. 20 g of dye were added to this solution. 400 ml of zirconium oxide (ZrO) beads (2 mm diameter) were added and the contents were crushed for 4 days. After this, 12.5% gelatin 16
0 g was added. After defoaming, the ZrO beads were removed by filtration. When observing the obtained dye dispersion,
The particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size is 0.37 μm.
It was m. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained.

(2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoat liquid having the following composition was applied at an amount of 5.1 cc / m ² . Was applied by a wire bar coater so as to obtain the above, and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained 0.04 wt% of the dye having the following structure.

[0090]

[Chemical 21]

-Butagen-styrene copolymer latex solution (solid content 40%, butadiene / styrene weight ratio = 31/36 79 cc-2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20. 5cc ・ Distilled water 900.5cc * In latex solution, as an emulsifying dispersant

[0092]

[Chemical formula 22]

A second undercoat layer having the following composition was applied on each of the above-mentioned first undercoat layers one by one so that the coating amount would be the amount described below, and 150 on each side by a wire bar coater system. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0094]

[Chemical formula 23]

(Preparation of Photographic Material) On the support prepared as described above, the emulsion layer and the surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per side is 1.75.
It was set to g / m ² . The swelling ratio determined by the freeze-drying method using the amount of coated gelatin and liquid nitrogen is adjusted by the gelatin added to the emulsion layer and the hardener, the amount of coated binder per side is 2.20 g / m ² , and the swelling ratio is 220%. Set to. Thus, photographic materials 1 to 20 were obtained.

(Measurement of swelling ratio) This photographic material was treated at 25 ° C. 60
The swelling ratio of the hydrophilic colloid layer was measured after 7 days under the condition of% RH. The dry film thickness (a) was determined by a scanning electron microscope of the section. The swollen film thickness (b) is 2 for photographic materials.
It was determined by observing with a scanning electron microscope after freeze-drying with liquid nitrogen a state of being immersed in distilled water at 1 ° C. for 3 minutes. The swelling rate is [(a)-(b)] / (a) × 100.
Calculated as (%).

(Evaluation of Photographic Performance) The photographic material was exposed for 0.05 seconds from both sides using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. After the exposure, the following processing was performed to evaluate the sensitivity. Sensitivity is photographic material 1
Is indicated by the reciprocal of the ratio of the exposure amount giving a density of 1.0 in addition to the fogging.

(Processing) <Automatic developing machine> ... SRX-501 manufactured by Konica Corporation
(The drive motor and gears were modified to increase the transport speed. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid treatment 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 2 g Compound (D-1) 0.6 g Water is adjusted to 1 liter (adjusted to pH 10.60).

[0099]

[Chemical formula 24]

<Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid).

When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above concentrated developer solution, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above fixing solution concentrate and 800 ml of water Processing speed …… Dry to Dry 30 seconds Development temperature ………… 35 ℃ Fixing temperature ………… 32 ℃ Drying temperature ………… 45 ℃ Replenishment amount ……… ...... Developer 22ml / 10x12 inch Fixer 30ml / 10x12 inch

(Evaluation of Dryness) Under the same conditions as the evaluation of photographic performance, the dryness of the film when each photographic material having a size of 4 pieces was continuously processed was sensory-evaluated by touch. The film was processed continuously with the short pieces oriented in the transport direction. The results are summarized in Table 1. ◎ Even after the 30th sheet, the film appears warm and dry. There is no problem at all. ○ Even on the 30th sheet, the film is completely dry. The temperature when touched was about the same as the film left at room temperature. △ The film is slightly cold at the 30th sheet, but the continuously processed film does not adhere and is practically acceptable. × At the 30th sheet, the film is wet and undried.
The films adhere to each other.

(Evaluation of pressure property) Photographic materials 1 to 20 were replaced by 2
After conditioning the humidity for 1 hour under the conditions of 5 ° C. and 25% RH, it was bent 180 degrees along the stainless pipe having a diameter of 6 mm under the same conditions. The bending speed was 180 degrees / sec, and then the original state was restored in the next 1 second. Thirty minutes after the bending, the same treatment as that used for evaluating the photographic properties was performed.
After this, increase the density of the blackened area along the stainless steel pipe (excluding the emulsion original fog and base density)
Was measured with a Macbeth densitometer. The results are shown in Table 1.

(Evaluation of Storage Stability) A coated sample was placed in a closed container having a saturated aqueous solution of sodium nitrate at the bottom (the sample does not come into contact with the aqueous solution). Add this solution at 50 ° C for 5
It was aged for a day (at this time, the humidity in the container was kept at 68%). After that, the same processing as that used for the evaluation of photographic properties was performed, and the increase in density of the fogged portion was measured. The results are shown in Table 1.

[0105]

[Table 1]

As shown in Table 1, as the silver halide grains, octahedral pure silver bromide grains (grain 1), octahedral silver iodobromide grains (grain 2), pure silver bromide tabular grains (grain) 3) and surface iodine type tabular grains (grain 4) were used. Sample No. 1,
As can be seen from Nos. 5, 9, and 13, grains 3 and 4 are silver halide grains having poorer pressure resistance. As a surface protective layer, X of No. 1 to 16 and Y of No. 17 to 20 are 4-hydroxy-6-methyl-1,3,3a, 7-tetraaza which is not polymerized in the protective layer. Contains indene and contributes to increased sensitivity and storage stability, but has little effect on pressure. The emulsion coating layers B, C and D containing the polymerized tetraazaindenes of the present invention were used.
It can be seen that Nos. 2 to 4, 6 to 8, 10 to 12, and 14 to 16 are excellent in pressure property and storage stability, although the sensitivity is slightly lowered as compared with those containing no tetraazaindenes. ..

Claims (4)

[Claims] 1. In at least one of the constituent layers, 1, 2,
The total coating amount of the binder containing a polymer compound containing a repeating unit having a residue of 4-triazolo [1,5-a] pyrimidines and coated on the side of the support containing the polymer compound is A silver halide photographic light-sensitive material characterized in that it is 1.7 g / m ² or more and 2.5 g / m ² or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver / binder ratio of at least one of the constituent layers is 1.2 or more. 3. 1,2,4-Triazolo [1,5-a]
The halogenated compound according to claim 1 or 2, wherein the polymer compound containing a repeating unit having a pyrimidine residue is a polymer compound containing a repeating unit represented by the general formula (I). Silver photographic light-sensitive material. [Chemical 1] 4. An image forming method using the silver halide photographic light-sensitive material according to claim 1, wherein the time from the start of processing to the end of drying is 35 seconds or less.