JPH06347935A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic emulsion giving a silver halide photographic sensitive material high in sensitivity and low in fog and superior in latent image stability and pressure resistance by incorporating a specified compound and silver halide grains chemically sensitized with a seleni um or tellurium sensitizer. CONSTITUTION:The silver halide photographic emulsion contains the silver halide grains chemically sensitized with the senenium or tellurium sensitizer and the compound represented by formula I or II in which each of R1-R4 is H or the like; each of R5-R8 is a substituent; each of L1 and L2 is a methine group, Z1 is an 0 atom or the like; Z2 is an atomic group necessary to form an imidazole ring; R9 is alkyl optionally substituted by a hetero atom, such as S, N or O; R10 is H or an alkylene group necessary to form a ring together with R9; and R11 is a monoor bi-cyclic aryl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved sensitivity, fog, latent image stability and pressure resistance. It relates to a silver halide photographic emulsion used.

[0002]

2. Description of the Related Art The spread of photography equipment such as cameras has been increasing in recent years, and the opportunity for photography using silver halide photographic light-sensitive materials has been increasing. Along with this, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials are also increasing.

Moreover, there is a tendency for silver halide photographic light-sensitive materials to be improved in performance in an increasingly complex and diverse manner.

In particular, in handling a silver halide photographic light-sensitive material in photographing, developing, etc., it is desired that the resistance to various pressures that are accidentally or inevitably applied be improved in terms of stability of photographic performance. ing.

Conventionally, as means for improving pressure resistance, for example, US Pat. No. 2,628,167, JP-A-50-116025 and JP-A-51-1.
No. 07129 describes a method of adding an iridium salt or a thallium salt at the time of forming silver halide grains. However, these methods have a problem that the sensitivity is lowered.

In JP-A-1-183644, a tabular plate containing a silver halide layer containing 3 mol% or more of silver iodide and having a completely uniform silver iodide distribution of the silver halide containing the silver iodide. Although a method of using a silver halide emulsion containing granular silver halide grains has been disclosed, it has been far from sufficient to meet the demand for further improvement of pressure resistance in recent years.

Further, a technique is known in which a plasticizer and other additives are added to a silver halide emulsion to be used to change the physical properties of a binder for dispersing silver halide grains,
For example, in JP-A-2-135335, the glass transition temperature is
A method of using a latex consisting essentially of a methacrylate polymer below 50 ° C. and an emulsion containing tabular silver halide grains is disclosed. However, this method is not a preferable method because it involves changes in other photographic performance due to changes in the physical properties of the binder, and the effect is not satisfactory, and the development of a superior technique has been desired. .

Further, a silver halide photographic light-sensitive material (hereinafter,
Stability over time is one of the other important characteristics of the "photosensitive material"), and above all, the stability from exposure to development, that is, latent image stability is an important item.

The latent image formed by the exposure of silver halide is unstable, and with the passage of time or due to heat or the like,
It regresses or is intensified, and it appears as a decrease or increase in sensitivity in terms of photographic performance.

The latent image stability depends on the production method and structure of silver halide, surface treatment, chemical and spectral sensitization methods, binder properties such as gelatin, type of hardener, pH of coating solution and silver. It is greatly affected by the ion concentration.

Various methods have been proposed for increasing the latent image stability. For example, a method using benzothiazolium described in JP-A 1-291250, a pyrogallol derivative described in JP-A 58-17431, tetrazaindenes described in JP-A 58-152235, and the like. Also, JP-A 1-2579
No. 47 discloses a tabular grain and a method for controlling the pH on the film surface.

However, even if these techniques are used, the latent image stability is not sufficiently improved, the sensitivity is lowered, and the fog is increased. Therefore, the development of further improved techniques has been desired.

[0013]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material having high sensitivity, low fog, and excellent latent image stability and pressure resistance. It is in.

[0014]

The above-mentioned object of the present invention is achieved by the following constitution.

Chemical sensitization with a selenium sensitizer and / or tellurium sensitizer, which contains a compound represented by the general formula (I) "Chemical formula 1" and / or the general formula (II) "Chemical formula 2" A silver halide photographic emulsion characterized by containing silver halide grains which have been subjected to.

That is, the present inventors have found that the styryl dye represented by the general formula (I) previously known as a supersensitizer is
It has been found that the latent image stability is also enhanced, but it further contains a styryl dye represented by the following general formula (I) and is chemically sensitized with a selenium sensitizer and / or a tellurium sensitizer. It was accidentally found that the silver halide emulsions are extremely pressure resistant.

The fact that a silver halide emulsion chemically sensitized with a specific selenium sensitizer or tellurium sensitizer is excellent in pressure resistance is shown in JP-A-5-23352 and JP-A-5-23355. However, these must use silver halide grains having a specific structure and shape.

Although the pressure resistance is improved by the technique disclosed in JP-A-5-45772, it has been insufficient in terms of obtaining a highly sensitive silver halide photographic light-sensitive material.

The present invention is not affected by the shape and size of the silver halide grains used, the internal structure, and the like, and can improve pressure resistance and simultaneously increase sensitivity. Furthermore, the fog is low and the latent image stability is excellent.

As a result of further studies thereafter, even when the compound represented by the general formula (II) was used instead of the general formula (I), the sensitivity was improved and the pressure resistance was improved to a lesser extent than the general formula (I). The obtained silver halide emulsion could be obtained.

The present invention will be described in more detail below.

First, the compound represented by the general formula (I) will be described.

In the general formula (I) "Chemical formula 1", R ₁ ,
Examples of the alkyl group represented by R ₂ , R ₃ and R ₄ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and dodecyl. These alkyl groups further include a halogen atom (for example, chlorine, bromine,
Fluorine, etc.), alkoxy groups (eg methoxy, ethoxy,
1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy, naphthyloxy etc.), aryl groups (eg phenyl, naphthyl etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl) , 2-ethylhexylcarbonyl), an aryloxycarbonyl group (eg phenoxycarbonyl, naphthyloxycarbonyl etc.), an alkenyl group (eg vinyl, allyl etc.), a heterocyclic group (eg 2-pyridyl, 3-pyridyl, 4-pyridyl, Morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl, etc.), alkynyl group (eg propargyl), amino group (eg amino, N, N-dimethylamino, anilino etc.), hydroxyl group, cyano group, sulfo group, carboxyl group A sulfonamido group (e.g., methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octyl sulfonylamino, phenylsulfonylamino, etc.) may be substituted by like.

Examples of the alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include vinyl and allyl.

Examples of the alkynyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include propargyl.

Examples of the aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ include phenyl and naphthyl.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ includes, for example, pyridyl group (eg 2-pyridyl, 3-pyridyl, 4-pyridyl etc.), thiazolyl group, oxazolyl group, imidazolyl group. Group, furyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group,
Examples thereof include a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group, and a tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups. It can be replaced by a group.

The substituent represented by R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group or an alkoxy group. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, carboxyl group, hydroxyl group, hydrogen atom, etc. . These groups can be substituted by the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ , and R ₄ and the groups shown as the substituents of the alkyl groups.

The ring formed by R ₁ and R ₂ is, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
Examples include rings such as pyrazine and indole.

Examples of the ring formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole and piperazine.

The ring formed by R ₅ and R ₆ and R ₇ and R ₈ is, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran,
Examples include rings such as pyrrole, pyrazine, and indole.

Examples of the ring formed by R ₁₂ and R ₁₃ include rings such as cyclopentane and cyclohexane.

The above rings can be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups mentioned as the substituents of the alkyl groups.

The methine group represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Examples thereof include an alkoxycarbonyl group and an aryloxycarbonyl group. These groups further include R ₁ , R ₂ , R ₃ ,
It can be substituted with the same groups as the alkyl group represented by R ₄ and the substituents of the alkyl group.

Specific examples of the compound represented by formula (I) (hereinafter referred to as the compound of the present invention) used in the present invention are shown below, but the present invention is not limited thereto.

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[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

Next, the compound represented by the general formula (II) will be described.

In the general formula (II) "Chemical formula 2", Z ₂ represents an atomic group necessary for forming an imidazole nucleus. R ₉ represents an alkyl group (the carbon chain may be replaced by a hetero atom such as S, N, O). R ₁₀ is a hydrogen atom or R
Represents an alkylene group necessary for connecting with ₉ to form a ring. R ₁₁ represents a bicyclic aryl group. Specific examples of the imidazole nucleus formed by Z ₂ are as follows.

Imidazole, 1-alkylimidazole,
1-alkyl-4-phenylimidazole, 1-alkyl-4,5-
Imidazoles such as dimethylimidazole. Benzimidazole, 1-alkyl Benzimidazole, 1-alkyl
-5,6-dichlorobenzimidazole, 1-tolyl-5-chlorobenzimidazole, 1-alkyl-5-bromobenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1
-Alkyl-5-fluorobenzimidazole, 1-alkyl
-5-Thiocyanite benzimidazole, 1-alkyl-5-
Acetyl-6-chlorobenzimidazole, 1-phenyl-5,
6-dichlorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-5-methylsulfonylbenzimidazole, 1-alkyl-5-methoxycarbonylbenzimidazole, 1-alkyl-5-ethoxycarbonyl Benzimidazole, 1-alkyl-5-
Benzimidazoles such as carboxybenzimidazole, 1-alkyl-5-benzoylbenzimidazole and 1-alkyl-5-acetylbenzimidazole. 1-alkylnaphtho [1,2-d] imidazole, 1-alkylnaphtho [2,1-d] imidazole, 1-alkylnaphtho [2,3-]
d] A naphthimidazole such as imidazole may be mentioned, and the carbon chain of the 1-alkyl group may be replaced by a hetero atom such as S, N or O.

The alkyl group represented by R ₉ may have its carbon chain replaced by a hetero atom such as O, N, S or may be branched and may have an unsaturated bond in the alkyl chain. good. More preferably, it has 10 or less carbon atoms and has an atom or a substituent such as sulfo, aryl, carboxy, amino, (primary, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl or cyano. (Eg, methyl group, ethyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
Benzyl group, phenethyl group, carboxyethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group, pt-butylphenoxyethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl Base,
Sulfophenethyl group, sulfobenzyl group, 2-hydroxy
-3-sulfopropyl group, ethoxycarbonylethyl group,
2,3-disulfopropoxypropyl group, sulfopropoxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanopropyl group, p-carboxyphenethyl group, ethoxycarbonylmethyl group, pivaloylpropyl group, propionylethyl group, Anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-
Ethylaminocarbonylpropyl group, allyl group, 2-butenyl group, 2-propynyl group, cyanoethyl group, etc.).

The aryl group represented by R ₁₁ is preferably a bicyclic aryl group, and specific examples include:
Examples thereof include phenyl group, naphthyl group, tolyl group, anisyl group, carboxyphenyl group, methoxycarbonylphenyl group, chlorophenyl group, xylyl group, thienyl group and furyl group.

When R ₁₀ is combined with R ₉ to form a ring, it is particularly preferable to form a 5-, 6- or 7-membered ring.

Specific examples of the compound represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0053]

[Chemical 12]

[0054]

[Chemical 13]

[0055]

[Chemical 14]

[0056]

[Chemical 15]

Specific synthetic examples of the compound (I) or (II) of the present invention are shown below, but other compounds can be easily synthesized by the same method.

Synthesis Example 1 (Synthesis of Exemplified Compound 4) 2-methylbenzothiazole (14.9 g), p-diethylaminobenzaldehyde (17.7 g), sodium hydride (hard oil 60)
%) 6 g and dimethylformamide 60 cc are added, and the mixture is allowed to stand at room temperature for 30
Reaction was carried out for a minute. The reaction solution was poured into water and the precipitated solid was filtered. The solid was dried and then recrystallized from methanol to obtain the desired product. Yield 19.4g (63%).

The amount of the compound of the present invention to be added is preferably 2 × 10 ⁻⁷ to 1 × 10 ⁻² mol, and more preferably 2 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of silver halide. Is preferred.

As a method for adding the compound of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol,
It can be dissolved in a water-soluble solvent such as dimethylformamide, or a mixture thereof, or diluted with water or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can also be used during the dissolution process.

Also, the compounds of the present invention were prepared according to US Pat. No. 3,469,98.
No. 7, etc., dissolved in a volatile organic solvent, and a solution obtained by dispersing this solution in a hydrophilic colloid is added to the emulsion. Water-insoluble as described in Japanese Examined Patent Publication No. 46-24185. A method is also used in which the dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to the emulsion.

Further, the compound of the present invention can be added to the emulsion in the form of a dispersion prepared by an acid solution dispersion method.

The compound (I) or (II) of the present invention may be added at any time during the period from the formation of silver halide grains to the coating, but it should be added particularly before the completion of chemical sensitization. Is preferred.

The selenium sensitizers used in the present invention include a wide variety of selenium compounds. For example, in this regard, U.S. Pat.Nos. 1,574,944, 1,602,592, 1,623,49
9, JP 60-150046, JP 4-25832, 4-10924
No. 0, No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, N, N, N'-trimethyl-N'-
Heptafluoroselenourea, N, N, N′-trimethyl-N′-
Heptafluoropropylcarbonyl selenourea, N, N,
N′-trimethyl-N′-4-nitrophenylcarbonyl selenoureas, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarbons Acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg tri-p-
Triselenophosphate, etc.) and selenides (dimethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenoketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. U.S. Patent No. 1,57
4,944, 1,602,592, 1,623,499, 3,297,4
66, 3,297,447, 3,320,069, 3,408,196
No. 3,408,197, 3,442,653, 3,420,670,
No. 3,591,385, French Patent No. 2,693,038, No. 2,093,
No. 209, Japanese Patent Publication No. 52-34491, No. 52-34492, No. 53-295
No. 57-22090, JP-A-59-180536, and 59-185330.
No. 59-181337, 59-187338, 59-192241,
No. 60-150046, No. 60-151637, No. 61-246738, JP-A No. 3-4221, No. 3-24537, No. 3-111838, No. 3-116132.
No. 3, No. 3-148648, No. 3-237450, No. 4-16838, No. 4-2
5832, 4-32831, 4-96059, 4-109240, and
4-140738, 4-140739, 4-147250, 4-149437
No. 4, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-
195035, British Patents 255,846, 861,984, HE
Spencer et al., Journal of Photographic Science, 31
, 158-169 (1983) and other research papers.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The temperature of chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. PH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

Tellurium sensitizers and sensitizing methods used in the present invention are described in US Pat. Nos. 1,623,499 and 3,320,0.
69, 3,772,031, 3,531,289, 3,655,394
No., British Patent No. 235,211, 1,121,469, 1,295,462
No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-
No. 20464 is disclosed. Examples of useful tellurium sensitizers include telluroureas, telluroamides and the like.

The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

In the present invention, a sulfur sensitizer may be used in combination with a selenium sensitizer or a tellurium sensitizer as the chemical sensitizer.

As the sulfur sensitizer applicable in the present invention, 1,3-diphenylthiourea, triethylthiourea,
Preferred examples include thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, sodium thiosulfate, and simple sulfur. As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Other examples of sulfur sensitizers include US Pat.
574,944, 2,410,689, 2,278,947, 2,728,6
68, 3,501,313, 3,656,955, etc., West German Application Publication (OLS) 1,422,869, JP-A-56-24937
The sulfur sensitizers described in JP-A No. 55-45016 and the like can also be used.

The addition amount of the selenium sensitizer and the tellurium sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using gold sensitization together. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, U.S. Patent Nos. 2,597,856, 5,049,484, and 5,
049,485, JP-B-44-15748, JP-A-1-147537, 4
Examples include gold complexes of organic compounds disclosed in No. 70650 and the like.

The above-mentioned various sensitizers can be added by adding them by dissolving in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent, or by adding gelatin, depending on the properties of the compound to be used. A method of mixing with a solution in advance and adding it may be a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

In the present invention, when the chemical sensitization is carried out in the presence of the silver halide adsorbing compound, the effect of the present invention is further enhanced. The silver halide-adsorptive compound is a sensitizing dye,
Antifoggants and stabilizers can be used.

As the sensitizing dye, a polymethine dye containing a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxonol dye, an oxonol, a merostyryl and a streptocyanine is used. Can be mentioned.

Examples of the antifoggants and stabilizers include tetrazaindenes and azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles and mercaptothiazoles. , Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines, mercaptotriazines, such as thioketo such as oxazolithion. Compounds, further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbi Mention may be made of the acid derivatives.

In the present invention, good results are often obtained by performing sensitization in the presence of a silver halide solvent.

Examples of the silver halide solvent used in the present invention include US Pat. Nos. 3,271,157, 3,531,2891, and 3,5.
(A) Organic thioethyls described in JP-A-74,628, JP-A-54-1019 and JP-A-54-158917, and
53-82408, 55-77737, 55-2982 and the like (b) thiourea derivatives, and (c) an oxygen or sulfur atom described in JP-A-53-144319 Examples thereof include silver halide solvents having a thiocarbonyl group sandwiched between nitrogen atoms, (d) imidazoles described in JP-A-54-100717, (e) sulfite, (f) thiocyanate, and the like.

The specific compounds are shown below.

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[Chemical 17]

Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferred amount is 5 mg to 1 mol of silver halide.
It is in the range of 1 g.

Known photographic additives which can be used when a color photographic light-sensitive material is constituted by using the silver halide photographic emulsion of the present invention are also described in the above Research Disclosure. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25 to 26 Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Color photographic light-sensitive using the silver halide photographic emulsion of the present invention Various couplers can be used in constructing the material, specific examples of which are described in Research Disclosure above. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Silver halide photograph of the present invention Additives used in constructing a color photographic light-sensitive material using an emulsion can be added by the dispersion method described in RD308119XIV.

When a silver halide photographic emulsion of the present invention is used to form a color photographic light-sensitive material, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pp. 647-8 and RD308119 XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K.

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, a color paper, a color positive film, and various color photographic sensitizers represented by color reversal paper. It can be preferably applied to materials.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pp. 28-29, RD18716 61.
Development can be carried out by a usual method described on page 5 and XIX of RD308119.

[0093]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In the following examples, the addition amount in the light-sensitive material is the number of grams per 1 m ² unless otherwise specified. The silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver.

Example 1 (Preparation of twinned seed emulsion T-I) By the method described below,
An emulsion with two parallel twin planes was prepared.

A ossein gelatin 80.0g potassium bromide 47.4g polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 0.48cc water 8000.0cc B silver nitrate 1200.0g water 1600.0cc C ossein Gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water 1600.0 cc D Ammonia water 470.0 cc Solution A and solution C were vigorously stirred at 40 ° C, and solution B and solution C were added by the double jet method in 7.7 minutes. Generated. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 30 ° C. over 30 minutes.
Further, the liquid D was added in 1 minute, followed by aging for 5 minutes. The concentration of potassium bromide during aging was 0.03 mol / liter, and the concentration of ammonia was 0.66 mol / liter.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they were hexagonal tabular grains having two twin planes parallel to each other.

The average grain size of the seed emulsion grains is 0.217 μm, 2
The parallel twin plane ratio was 75% in terms of the number ratio of all grains.

(Preparation of Emulsion EM-1 of the Present Invention) An octahedral twin monodispersed emulsion EM-1 having two parallel twin planes according to the present invention was prepared using the following seven kinds of solutions. .

(Solution A) Oscein gelatin 61.0 g Distilled water 1963.0 cc Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 2.5 cc seed emulsion (T-1) 0.345 mol 28 wt% ammonia solution 308.0cc 56wt% acetic acid aqueous solution 358.0cc 0.001mol methanol solution containing 1 mol of iodine 33.7cc distilled water to 3500.0cc (Solution B) 3.5N ammoniacal silver nitrate aqueous solution (however, pH was adjusted to 9.0 with ammonium nitrate) (Solution C ) 3.5N potassium bromide aqueous solution (Solution D) 3 wt% gelatin and silver iodide grains (average grain size)
0.05 μm) 1.40 mol fine grain emulsion (*) * The preparation method is shown below.

To 5000 cc of a 6.0 wt% gelatin solution containing 0.06 mol of potassium iodide, 2000 cc of an aqueous solution containing 7.06 mol of silver nitrate and 2000 cc of an aqueous solution containing 7.06 mol of potassium iodide were added for 10 minutes. The pH during the formation of fine particles was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

(Solution E) Fine grains composed of silver iodobromide grains (average particle size 0.04 μm) containing 2 mol% of silver iodide, prepared in the same manner as the silver iodide fine grain emulsion described in Solution D. Emulsion 3.68
However, the temperature during the formation of fine particles was controlled at 30 ° C.

(Solution F) 1.75N potassium bromide aqueous solution (Solution G) 56 wt% acetic acid aqueous solution Solution A kept at 70 ° C. in the reaction vessel was mixed with Solution B, Solution C and Solution D for 128 minutes. After the addition over a period of time, solution E was then added singly at a constant rate over a period of 7 minutes to grow a seed crystal to 0.806 μm.

Here, the addition rates of the solution B and the solution C were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and a large number of small particles other than the growing seed crystal were generated and Ostwald ripening was performed to increase the number. It was added at an appropriate addition rate so as not to disperse. The solution D, that is, the silver iodide fine grain emulsion supply, has a multiple structure by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the particle size (addition time) as shown in Table 1. A core / shell type silver halide emulsion was prepared.

By using solutions F and G, pAg and pH during crystal growth were controlled as shown in Table 1. Note that p
The Ag and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After grain formation, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, gelatin was then added and redispersed, and pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C. From the scanning electron micrograph of the obtained emulsion grains, the average grain size
It was confirmed to be an octahedral twin monodisperse emulsion having a distribution of 0.806 μm and a width of 12.0%.

[0108]

[Table 1]

EM-1 was divided into 25 parts, spectrally sensitized with the following sensitizing dyes (S-2) and (S-3) at 50 ° C., and chloroauric acid, ammonium thiocyanate and shown in Table 2. Chemical sensitization was performed with the sensitizer.

To these emulsions, the compound (I) or (II) of the present invention was added in an amount of 3.0 × 10 ^-5 mol per mol of silver halide to prepare 4-hydroxy-6-methyl-1,3,3a, 7-tetra The indene and 1-phenyl-5-mercaptotetrazole were added and the temperature was lowered to stabilize.

Each of the resulting silver halide emulsions (A)
To (Y), for each emulsion, the following cyan coupler (C-1) is further dissolved in ethyl acetate and dioctyl phthalate and emulsified and dispersed in an aqueous solution containing gelatin, and a spreader and a hardener. Samples 101 to 125 were prepared by adding a general photographic additive such as an agent to prepare a coating solution, coating the solution on the subbed cellulose triacetate support by a conventional method, and drying.

Samples 101 to 125 are each divided into two
Samples I and II were subjected to negative blue exposure through a wedge according to a conventional method, and immediately subjected to development processing according to the following processing steps. Further, in order to evaluate the pressure resistance of Sample II, each sample was bent along a cylinder having a diameter of 4 mm, and then similarly exposed and developed.

(Treatment process) Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780cc Bleach 45 seconds 38 ± 2.0 ℃ 150ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 60 Second 38 ± 5.0 ℃ 830ml Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher developer Replenisher Replenisher Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogen carbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg-Hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Add 1 liter of water and adjust the color developer to pH 10.06 and the replenisher to pH 10.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water The pH of the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixer and fixer replenisher Fixer replenisher Replenisher Water 800cc 800cc Ammonium thiocyanate 120g 150g Ammonium thiosulfate 150g 180g Sodium sulfite 15g 20g Ethylenediaminetetraacetic acid 2g 2g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2 Adjust the pH of the replenisher to 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher water 900 cc p-octylphenol 10 mol ethylene oxide adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UC-L-77 ) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The relative sensitivity is the relative value of the reciprocal of the received light amount that gives fog +0.1, and is shown as a value with the sensitivity of the sample 101 being 100.

Regarding the change in the density of the pressed part due to bending, in the fog density, the density of the pressed part and the density of the unpressurized part were measured with a microdensitometer to obtain the density change value of each sample. It was shown as a relative value of 100 (change in relative concentration of the pressure portion).

The results are shown in Table 2.

[0122]

[Table 2]

From Table 2, it can be seen that the sample using the silver halide emulsion of the present invention has higher sensitivity and excellent pressure resistance than the comparative sample.

Example 2 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material having the following compositions was prepared and used as Sample 201. Incidentally, the amount of additive is indicated in grams per photosensitive material 1 m ^2, a silver halide emulsion and colloidal silver are indicated in terms of silver value. Further, the sensitizing dye is shown by the number of moles per mole of silver halide contained in the same layer.

First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.16 UV Absorber (UV-1) 0.30 Gelatin 1.70 Second Layer: Intermediate Layer (IL-1) Gelatin 0.80 Third Layer: Low Sensitivity Red Sensitive Layer (RL) Silver iodobromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 1.2 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing dye (S-3) 2.0 × 10 ^-4 Sensitizing dye (S- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.30 Gelatin 0.55 Fourth layer: Medium sensitivity red sensitive layer (RM) Silver iodobromide emulsion (average grain size 0.40 μm) 0.48 Sensitizing dye (S-1) 1.5 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing dye (S─3) 2.5 × 10 ^-4 sensitizing dye (S─4) 1.5 × 10 ^-4 cyan coupler (C─1) 0.30 colored cyan coupler (CC─1) 0.05 high-boiling solvent (Oil─1) 0.40 peptidase Chin 0.60 Fifth Layer: High Sensitivity Red-Sensitive Layer (RH) silver iodobromide emulsion (A) 0.66 Sensitizing dye (S─1) 1.0 × 10 ^-4 Sensitizing dye (S─2) 0.2 × 10 ^-4 increase Sensitizing dye (S-3) 1.7 × 10 ^-4 Sensitizing dye (S- ⁴ ) 1.0 × 10 ^-5 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.01 DIR compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.15 Gelatin 0.53 Sixth layer: Intermediate layer (IL-2) Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer (GL) Silver iodobromide emulsion (average grain size 0.40 μm) 0.60 Iodine Silver bromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 0.6 × 10 ^-4 Sensitizing dye (S-5) 5.1 × 10 ^-4 Magenta coupler (M-1) 0.55 Colored magenta coupler ( CM-1) 0.17 DIR compound (D-2) 0.03 High boiling point solvent (Oil-2) 0.70 Gelatin 1.56 Eighth layer: High sensitivity green sensitive layer (GH) Silver iodobromide emulsion (average grain size 0.88 μm) 0.60 Sensitizing dye (S-6) 1.5 × 10 ^-4 Sensitizing dye (S-7) 1.5 × 10 ^-4 Sensitizing dye (S-8) 1.5 × 10 ^-4 Magenta coupler (M-1) 0.06 Magenta coupler ( M-2) 0.02 Colored magenta coupler (CM-2) 0.02 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.15 Gelatin 0.45 9th layer: Yellow filter layer (YC) Yellow colloidal silver 0.08 Formalin scavenger ( HS-1) 0.20 Color stain inhibitor (HS-2) 0.15 High boiling point solvent (Oil-2) 0.19 Gelatin 0.80 Layer 10: Low sensitivity blue sensitive layer (BL) Silver iodobromide emulsion (average grain size 0.40 μm) 0.18 Silver iodobromide emulsion (average grain size 0.30 μm) 0.35 Sensitizing dye (S-9) 5.1 × 10 ^-4 Sensitizing dye (S-10) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.58 Yellow coupler (Y-2) 0.30 High boiling point solvent (Oil-2) 0.15 Gelatin 1.20 11th layer: High-sensitivity blue-sensitive layer (BH) Odor Silver emulsion (average grain size 0.88 .mu.m) 0.45 Sensitizing dye (S─9) 3.0 × 10 ^-4 Sensitizing dye (S─10) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.10 High boiling solvent (Oil─ 2) 0.04 Gelatin 0.50 12th layer: 1st protective layer (Pro-1) Silver iodobromide emulsion (average grain size 0.07 μm) 0.30 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High Boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.25 Gelatin 0.80 13th layer: 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 polymethylmethacrylate (average particle size 3 μm) 0.02 gelatin 0.50 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, film hardeners H-1, H-2, dye AI -1, AI
-2 was added appropriately.

The structures of the compounds used to prepare the above samples are shown below.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate Su-1: dioctyl sodium sulfosuccinate Su-2: sodium tri-i-propylnaphthalene sulfonate HS-1: 1- (3-sulfophenyl) -3-methyl-5-imino-2
-Pyrazoline HS-2: 2-sec-octadecyl-5-methylhydroquinone H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: bis (vinylsulfonylmethyl) ether

[0128]

[Chemical 18]

[0129]

[Chemical 19]

[0130]

[Chemical 20]

[0131]

[Chemical 21]

[0132]

[Chemical formula 22]

[0133]

[Chemical formula 23]

Separately, the silver halide emulsions (G) to (O) prepared in Example 1 were added to the fifth layer of Sample 201 in an amount of 0.66 g per m ² and converted to Samples 202 to 210. Created. Divide each sample into 3 parts, I, II, III,
Sample I was subjected to wedge exposure according to a conventional method, and immediately subjected to the same development processing as in Example 1. Further, Sample II was subjected to wedge exposure in the same manner as Sample I, then left in an atmosphere of 55 ° C. and 20% RH for 3 days, and then subjected to the same development processing. Further, for the sample III, in order to evaluate the pressure resistance, each sample was bent along a cylinder having a diameter of 4 mm, and then similarly exposed and developed.

The sensitivity of each sample is expressed by the reciprocal of the exposure dose at which the red density gives an optical density of fog density + 0.15.
The sensitivity of Sample I of 201 was shown as a relative value with 100 as the sensitivity.

Regarding the density change of the pressed part due to bending, in the fog density, the density of the pressed part and the density of the unpressurized part were measured with a microdensitometer to obtain the density change value of each sample. It was shown as a relative value of 100 (change in relative concentration of the pressure portion).

The above results are shown in Table 3.

[0138]

[Table 3]

From Table 3, it can be seen that Samples 203 to 210 using the silver halide emulsion of the present invention are higher in latent image stability and pressure resistance than Comparative Samples 201 and 202.

[0140]

According to the present invention, it is possible to provide a silver halide photographic emulsion which gives a silver halide photographic light-sensitive material having high sensitivity, low fog, excellent latent image stability and pressure resistance.

Claims (2)

[Claims] 1. A silver halide grain containing a compound represented by the following general formula (I) and / or (II) and chemically sensitized with a selenium sensitizer and / or a tellurium sensitizer. A silver halide photographic emulsion characterized by containing a. [Chemical 1] [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ Each represents a substituent. L ₁ and L ₂ each represent a methine group, Z ₁ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₁₂ ) (R
₁₃₎ - or -N (R ₁₂₎ - a. R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₁₂ and R ₁₃ may be bonded to each other to form a ring. ] [Chemical 2] Z ₂ represents an atomic group necessary for forming an imidazole nucleus. R ₉ represents an alkyl group (the carbon chain may be replaced by a hetero atom such as S, N or O). R ₁₀ represents a hydrogen atom or an alkylene group necessary for forming a ring by bonding with R ₉ . R ₁₁ represents a bicyclic aryl group. 2. A silver halide grain containing a compound represented by the general formula (I) and chemically sensitized with a selenium sensitizer and / or a tellurium sensitizer. And a silver halide photographic emulsion.