JPS61123833A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a high sensitivity at a whole visible range and a broad exposure latitude and an excellent gradation by forming at least two emulsion layers conyg. a core / shell type silver halide (AgX) having a low and a high silver iodide concns. and also contg. coloring matters of a sensitizer having a specific combination respectively. CONSTITUTION:The titled material is prepared by forming on a substrate at least two emulsion layers of AgX contg. the core/shell type AgX particles in which the AgI content of the core part is higher than that of the shell part. One of the prescribed layers contains 0.1-3.0mol% a low iodine concn. and also contains a combination of the prescribed coloring matters shown y formulas I, III and IV wherein R1, R2 and R6-R9 are each an alkyl group, Y3 is each a hydrogen atom, an alkyl group, Z3-Z5 are each an atom capable of forming a heterocyclic ring, X<->1, X<->3 and X<->4 are each an acid anion, (l), (n), (p) are 0 or 1. Another one of the prescribed layers contains the AgX having 3.0-7.0mol% a high iodine concn., and also contains a combination of the prescribed coloring matters shown by formula II wherein Z1 and Z2 are each S or Se, Y1 and Y2 are each a hydrogen atom, a halogen atom or an alkyl group, R3-R5 are each an alkyl group, (m) is 0 or 1, and formulas III and IV. The titled material has an excellent reproducibility of a tone in addition to the prescribed properties.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material that is spectrally sensitized to have high sensitivity and a wide exposure latitude. This invention relates to an orthopanchromatically spectrally sensitized black and white photographic material that exhibits little desensitization of silver's inherent sensitivity.

[Prior Art] Many spectral sensitization methods using a combination of two or more sensitizing dyes are known as techniques for producing silver halide photographic emulsions.

It is also well known to improve exposure latitude by mixing emulsions of different photographic properties or silver halide compositions, or by providing them as separate photosensitive layers.

As is well known, spectral sensitization technology is influenced by the chemical structure of the sensitizing dye, the silver halide composition of the silver halide emulsion, crystal habit, crystal form, silver ion concentration, EIH, etc. It is also greatly influenced by various photographic additives, including stabilizers that coexist.

In general, as the amount of sensitizing dye added to the emulsion increases, the sensitivity of the spectral sensitized portion increases, but the blue light sensitivity region inherent to silver halide usually becomes desensitized, especially in panchromatic and J- Agglomerated bottle type dyes have great desensitization properties. Desensitization of the inherent sensitivity of silver halide by such a sensitizing dye leads to a decrease in blue light sensitivity for photography, which is an undesirable phenomenon for photosensitive materials.

In addition, in recent years, there has been a demand for silver halide photographic materials that have photographic properties whose reproducibility is not affected by the type of light source used during photography, and for this reason, blue light, green light Many techniques have been developed for spectrally sensitizing silver halide emulsions so that they can be appropriately sensitized to red light and are known as spectral sensitization methods.

The purpose of such spectral sensitization is not only to simply increase the spectral sensitivity of the silver halide emulsion, but also to ensure that the spectral sensitization wavelength range is appropriate, as well as to prevent reactions with other additives. have no properties, and do not cause deterioration of photographic characteristics.
It must satisfy various conditions such as having excellent storage stability and not causing dye staining after processing.

On the other hand, it is a technique for improving the image quality of highly sensitive silver halide photographic materials (hereinafter simply referred to as photosensitive materials), such as techniques for improving image quality characteristics such as gradation, graininess, or sharpness. It is a well-known technique to improve image quality by incorporating silver iodide into a silver halide composition, particularly silver halide grains, and utilizing the development-suppressing effect of iodide ions released during development.

For example, silver halide emulsions generally used in silver halide photosensitive materials for black-and-white photography contain silver iodide, and the above-mentioned technique can be used to adjust the image quality. Although it is preferable to increase the viscosity, silver iodide has the disadvantage that it inhibits the sulfur sensitization reaction during chemical ripening or the black-and-white development reaction after exposure.

Furthermore, the above-mentioned panchromatic J-agglomeration sensitizing type sensitizing dyes have a fatal drawback in that the greater the silver iodide content, the greater the desensitization of silver halide inherent sensitivity.

Typical photosensitive materials according to the present invention include, for example, negative photosensitive materials for black and white, photosensitive materials for micronegatives, and negative photosensitive materials for silver salt diffusion transfer, all of which are orthopanchromatic and capable of covering a wide range of light. High sensitivity and uniform tone reproduction are required.

As a conventional technique for such purpose, for example,
26470, or Japanese Patent Publication No. 48-42493, but these methods cannot necessarily be said to be sufficient spectral sensitization methods, and the emergence of photosensitive materials that have high sensitivity over the entire visible light range and a wide exposure latitude has led to the development of spectral sensitization methods. This is the current situation.

[Object of the Invention] The first object of the present invention is to provide a spectrally sensitized silver halide photographic material that exhibits a small decrease in the inherent sensitivity of silver halide and has high sensitivity over the entire visible light range. .

A second object of the present invention is to provide a silver halide photographic material having a wide exposure latitude and excellent tone reproduction.

Further objects of the present invention will become apparent from the description below.

[Structure of the Invention] As a result of intensive studies for the above purpose, the present inventors have found that in a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on a support, the silver halide emulsion layer The silver halide contained in at least two layers of the silver halide layer consists of core/shell type silver halide grains having a higher silver iodide content in the core part than in the shell part, and at least one layer of the silver halide emulsion layer has a silver iodide content higher in the core part than in the shell part. is 0.1 mol% or more and less than 3.0 mol%, and has the following general formula [I], [111
] and [IV] in combination, and at least one of the other layers of the silver halide emulsion layer has a silver iodide content of 3.0 mol %.
consisting of silver halide of 7.0 mol% or less,
It has also been found that this can be achieved by a silver halide photographic material containing a combination of at least one sensitizing dye represented by the following general formulas [II], [Iff] and [IV].

General formula [I] is [conversion a2. Ya2. I8 is displayed. (X+e) Gt m
Represents an anion. 9 represents 0 or 1, and 9 is O when forming an inner salt. ] General formula [1[] [However, 21 and Zz in the formula each represent a sulfur atom or a selenium atom. Yl and Yz each represent a hydrogen atom, a halogen atom or an alkyl group.

R3 and Rt+ are synonymous with R1 and Rz, respectively.

R5- represents an alkyl group, provided that when zI and Zz are each a sulfur atom and Yr and yz are each a hydrogen atom, Rr represents an alkyl group having 2 or more carbon atoms. (Xze) represents an acid anion, I! 1 represents 0 or 1, and when forming an inner salt, the number is 0. ] General formula [11N [However, R6 and R in the formula represent a substituted or unsubstituted alkyl group. Y3 represents a hydrogen atom, an alkyl group or an alkoxy group. z3 represents the atomic group necessary to complete the heterocyclic nucleus. (Xl") represents an acid anion. n represents O or 1, and when forming an inner salt, n is 0.] General formula [IV] R, H.

[During the ceremony, 2pm and z! 5- each represents an atomic group necessary to complete the heterocycle. R8 and R9 each represent a non-modified alkyl group or a substituted alkyl group. (×!
3) represents an acid anion. D represents O or 1, and p is O when forming an inner salt. ] In the above general formulas [I], [II] and [1], Rt
The alkyl groups of SR3, R6, and R7 are preferably carbon! An alkyl group having R number 1 to 5, specifically, for example, methyl group, ethyl group, propyl group, n-butyl group, i
-butyl group and the like.

The substituted alkyl groups of Rt, RZ, R3, Ru, R6, and R7 are preferably substituted alkyl groups having 1 to 5 carbon atoms, such as β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group,
Alkyl groups substituted with sulfo groups such as β-hydroxy-γ-sulfopropyl group, 2-γ-sulfopropoxyethyl group, 2-β-sulfoethoxyethyl group, and salts thereof (e.g., sodium salt, triethylamine salt, etc.) , alkyl groups substituted with carboxy groups such as carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, δ-carboxybutyl group, and salts thereof (e.g., sodium salt, triethylamine salt, etc.), β-hydroxylethyl Examples include an alkyl group substituted with a hydroxy group such as a γ-hydroxypropyl group, and an alkyl group substituted with a carbamoyl group.

In the general formula [], the alkyl group represented by Rr is preferably a linear or branched lower alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl group, ethyl group,
Examples include propyl group and butyl group.

Specific examples of the heterocyclic nucleus formed by the atomic group 73 in general formula [1] include 2-quinoline, 6-
Methyl-2-quinoline, 6-medoxy-2-quinoline,
Quinoline nucleus such as 6-hydroxy-2-quinoline; benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-ethoxybenzothiazole, 6-methylbenzo Thiazole, 6-chlorobenzothiazole, 5-carboxybenzothiazole, 5-7 cetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5. 6-dimethylbenzothiazole, 5-
Acetylaminobenzothiazole, 6-methoxybenzothiazole, 5.6-simethoxybenzothiazole, 5
Benzothiazole nucleus such as 6-dichlorobenzothiazole; naphthothiazole nucleus such as naphtho[1,2-d]thiazole; selenazole, 4-methylselenazole, 4-
Selenazole core such as phenylselenazole, 4,5-dimethylselenazole; benzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole,
Examples include benzoselenazole nuclei such as 5-methylbenzoselenazole, 5-methoxybenzoselenazole, and 5,6-dimethylbenzoselenazole: naphthoselenazole nuclei such as naphthoN, 2-d]selenazole, etc. .

In the general formulas [I], [Ir], [III] and [IV], (Xl), (XzO> (X3Q), and (X
The acid anions respectively represented by o) are, for example, iodo ion, bromide ion, ryo ion, p-
These are acid anions commonly used in cyanine dye salts, such as toluenesulfonate ion, benzenesulfonate ion, sulfate ion, barchlorate ion, and rhodan ion.

In general formula [II], Y and Y1 each represent a hydrogen atom, a halogen atom, or an alkyl group, and among these, preferred are a chlorine atom, a bromine atom, a methyl group, and an ethyl group. Yl and Yz may be the same or different, preferably a chlorine atom or a methyl group.

The halogen atom represented by Y1 and Yl may be a chlorine atom. Further, the alkyl group preferably has 1 to 2 carbon atoms, specifically,
Examples include methyl group and ethyl group.

In the general formula [II], Zt and Zz each represent a sulfur atom or a selenium atom, and may be the same or different, preferably when both ZI and Zz are a sulfur atom or a selenium atom.

In the general formula [11r], Y3 represents a hydrogen atom, an alkyl group, or an alkoxy group, and among these, a hydrogen atom is preferred. The alkyl group represented by Y3 is preferably an alkyl group having 1 to 2 carbon atoms.

In the general formula [IV], Zt and Zr each represent an atomic group necessary to complete a heterocycle, and specific examples of such a heterocycle include a thiazole ring, a benzothiazole ring, and a naphthothiazole ring. , selenazole ring, benzoselenazole ring, naphthoselenazole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, and the like.

These heterocycles can have a substituent, and examples of the substituent include a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom), a hydroxyl group, an alkoxy group (for example, a methoxy group, ethoxy group, apoxy group, butoxy group, etc.), 7mino group (e.g., amino group, methylamino group, dimethylamino group, diethylamino group, etc.), acylamide I (e.g.,
acetamide group, propionamide group, etc.), acyloxy group (e.g., acetoxy group, propionoxy group, etc.), alkoxycarbonyl group (e.g., ethoxycarbonyl group, propoxycarbonyl group, etc.), alkoxycarbonylamino group (e.g., ethoxycarbonylamino group) , proboxycarponylamino L-butoxycarbonylamino group, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, trifluoromethyl group, etc.), aryl groups (e.g., phenyl group, tolyl group, etc.), alkylsulfonyl groups (eg, methylsulfonyl group), and the like.

Further, in the general formula [IV], Rg and R9 represent an unsubstituted alkyl group or a substituted alkyl group, and the unsubstituted alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, Examples include propyl group, n-butyl group, i-butyl group, and n-hexyl group. Examples of the 1m alkyl group represented by R8 and R9 include those similar to the substituted alkyl groups described above for R,, R2, R3, R, R6, and R.

Specific examples of the sensitizing dyes represented by the general formulas CD to CIV'll of the present invention are shown below, but the sensitizing dyes of the present invention are not limited thereto.

Examples of sensitizing dyes represented by general formula [11 (T-4) Hs Specific examples of sensitizing dyes represented by general formula [TI] (ll-1) (II-2) (II-3) (II-4) (II-5) (ll-6) (II-7) (II-8) Specific examples of sensitizing dyes represented by general formula (III) (III-2) (l1l-3) (III-4) ( In-5) (I[l-6) C1-6) Clll-8) Specific examples of sensitizing dyes represented by the general formula (IVI) (IV-1) (IV-2) (IV-3) (IV- 4) (IV-5) (IV-6) (IV-7) (IV-8) (mV-9) (mV-10) (IV-11) (IV-12) (■-13) (mV- 14) (mV-15) ]V-16) (IV-17) (IV-18) (CHs) Goose S Os H (IV-19) (II/-20) (mV-21) (IV-22) (IV-23) (mV-24) (IV-25) (IV-26) (IV-27) (IV-28) (IV-29) (It/-30) (!V-31) (a Muha S Us N!L (fV-32) (IV-33) (■-34) (Ckb) s S Os K (IV-35) (nili2ha8 (JsNa (!V-36) (■-37) (IV-38) C! & (mV-39) Hs (IV-41) ) LOOCC output C mountain C ratio C ru COOH
(IV 42) C2 & (F/ -4
4) C5Hs (fV-46)
C,H.

The general formulas [1], [II] and [
The spectral sensitizing dye represented by [III] can be easily synthesized by a known method.
he Cyanine Dyes and Re1
ated Cow-pounds”Intersc
ience Publisher, New York (
(1964).

Further, the sensitizing dye represented by the general formula [IV] is
Known compounds, such as U.S. Pat. No. 3.149,
No. 105, No. 2,238,231, British Patent No. 74
It can be synthesized according to No. 2.112 or the above-mentioned literature by F. M. Ra5her.

The sensitizing dye represented by the general formula [I] used in the present invention is a thiacarbocyanine having a methyl group at the meso position,
It is characterized by a spectral sensitivity distribution with relatively little green deficiency (all!A photosensitivity defect) and insufficient red photosensitivity.

Therefore, the sensitizing dye represented by the general formula [I] is
The green light sensitivity is further enhanced by the combined use of the green-sensitive monomethine cyanine represented by [IIr] and the blue-sensitive monomethine cyanine represented by the general formula [■]. By using it in an emulsion containing silver halide with a silver iodide content of 0.1 mol% or more and less than 3.0 mol% (hereinafter referred to as the low iodine silver iodobromide emulsion of the present invention), the visible range can be shortened. It is possible to obtain spectral sensitivity characteristics with high sensitivity in the long wavelength region (11 color lights and green light region) and high contrast.

On the other hand, thia and selenacarbocyanine represented by the general formula [1] are symmetrical to the sensitizing dye group of the general formula [1],
In general, although there is a large amount of green deficiency, it is characterized by a spectral sensitivity distribution with strong red light sensitivity of the J-band sensitized type.

Therefore, it is possible to use thia and selenacarbocyanine represented by the general formula [nl] in combination with a green-sensitive monomethine cyanine represented by the general formula [1 [] and a blue-sensitive monomethine cyanine represented by the general formula [IV]. The sensitivity to green light and blue light is enhanced by the addition of at least one of the spectral sensitizing dyes represented by the general formulas [II], [IIr] and [IV], respectively, with a silver iodide content of the present invention. When used in combination in an emulsion consisting of 3.0 mol% or more and 1.0 mol% or less silver halide (hereinafter referred to as the high immersion silver iodobromide emulsion of the present invention), high Spectral sensitivity characteristics with high sensitivity and soft gradation can be obtained.

The above-mentioned silver iodobromide emulsion of the present invention has a low iodine content and a high immersion density.

At least two types of emulsions each containing a multi-H
A silver halide photosensitive material having at least a 2M silver halide emulsion layer containing separately the low iodine content silver iodobromide emulsion and the high immersion content silver iodobromide emulsion of the present invention is a silver halide photosensitive material which is coated and has a silver halide emulsion layer of at least 2M, which separately contains the low iodine content silver iodobromide emulsion and the high iodine content silver iodobromide emulsion of the present invention. There is little desensitization in the area, and the gradation is excellent.

The structure of the coating layer in the present invention is a silver halide emulsion layer containing a low iodide silver iodobromide emulsion according to the present invention and a silver halide emulsion layer containing a high immersion silver iodobromide emulsion according to the present invention. Either of these may be provided close to the support side, but preferably, the layer containing the low iodide silver iodobromide emulsion according to the present invention is provided as the first layer close to the support side, and then the layer containing the low iodide silver iodobromide emulsion according to the present invention is provided adjacent to this. A layer structure in which a layer containing the high immersion silver iodobromide emulsion according to the present invention is provided as the second layer is preferred. However, the present invention is not limited to such a layer configuration, but may be the opposite layer configuration.

The silver halide light-sensitive material of the present invention has, in addition to at least two silver halide emulsion layers separately containing the low-immersion and high-immersion silver iodobromide emulsions, another silver halide emulsion layer. The other silver halide emulsion layer may be a layer containing the low or high immersion silver iodobromide emulsion of the present invention, or may be another emulsion layer.

Note that various layers for photography, such as a subbing layer, an intermediate layer, or a protective layer, may be provided adjacent to these layers.

Furthermore, the at least two types of low iodine and high immersion silver iodobromide emulsions according to the present invention used in the silver halide photographic light-sensitive material of the present invention may be emulsions consisting of monodisperse silver halide silver heptaide grains, or may be composed of monodisperse silver halide silver heptaide grains. Although it may be a dispersible material, a monodisperse material is preferable. In general, emulsions other than the above-mentioned emulsions may also be monodisperse or polydisperse.

Here, "monodisperse silver halide grains" means that when an emulsion is observed using an electron microscope, the shape of each silver halide grain appears uniform and the grain size is defined by the following formula. It has a distribution. That is, when the standard deviation S of the grain size distribution is divided by the average grain size V, the average grain size referred to here is 0.20 or less, and in the case of spherical silver halide grains, the diameter, In the case of particles with a cubic or spherical shape, the average value of the diameter when the projected image is converted into a circular image of the same area. 01, the lower part is defined by the following formula.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis Method JA, S.

T.M., Symposium on Light Microscopy 1955, pp. 94-122 or in chapter 2 of ``Transportation of the Photographic Process'' by Mies and Jace, 3rd edition, published by Macmillan (1966). There is. This particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution will describe this fairly accurately as a diameter or projected area. be able to.

The relationship between grain size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photographic Emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
This can be determined by the method described in the article by Trivelli and Smith, pages 0-338.

In addition, in the present invention, "the shape of the silver halide grains is uniform" means that the value calculated from the lower S/ of the above formula is 0.20 or less, and more specifically, the value of 0.2 to 0.5 μ. Most preferred are low iodide silver iodobromide emulsions having an average grain size and ^-immersion silver iodobromide emulsions having an average grain size of 0.G to 0.9μ.

The silver halide grains of at least two silver halide emulsion layers each composed of a low-immersion silver iodobromide emulsion and a high-immersion silver iodobromide emulsion according to the present invention are formed by combining the monodisperse silver halide grains with the same silver halide emulsion. At least 70 of the total particles in the layer
% or more, and it is particularly preferable that all the grains are monodisperse silver halide grains.

Further, in the present invention, the combination of the sensitizing dyes represented by the general formulas [II, [1] and [IV], respectively, and the sensitizing dyes represented by the general formulas [II], [II[] and [■], respectively) is preferred. Silver halide grains that are effectively spectrally sensitized by a combination of sensitizing dyes are core/shell type silver halide grains that are composed of at least two layers having higher silver iodide content in the core part than in the shell part. It consists of

In the present invention, it is desirable that the silver iodide content in the outermost layer (shell portion) of the silver halide grains having the above composition be as low as possible, and it is particularly preferably close to 0%.

Furthermore, the core portion inside the grain may be formed as two or more layers having different silver iodide contents. Further, the difference in content between the layer with high silver iodide content and the layer with low silver iodide content may have a sharp boundary, or may vary continuously without necessarily having a clear boundary.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures, for example, as described in the 1986 annual conference park summary of the Photographic Society of Japan.

The core/shell type silver halide grains used in the present invention have a core portion made of silver halide containing silver iodide, and a halogen containing a lower content of silver iodide coating the core portion than the content in the core portion. Preferably, the silver halide grains are made of silver halide and have a thickness of 0.001 to 0.1 μm.

In a preferred embodiment of the silver halide grains of the present invention, the average silver iodide content is 0.1 mol% or more and 3
．． Examples include emulsions containing low iodide silver halide of less than 0 mol % and emulsions containing high iodine silver halide of 3.0 mol % or more and 1.0 mol % or less.

The content of silver iodide in each of the core parts is 60% or more of the total, preferably 70% or more, and the content of silver iodide in the shell part is 0.
% or more and 40% or less.

In the silver halide grains of the present invention, the silver halide composition other than the above-mentioned silver iodide is preferably silver bromide. Further, silver chloride may be included as long as the effects of the present invention are not impaired. The silver chloride content in this case is generally less than approximately 1 mol %.

The shape of the silver halide grains according to the present invention may be, for example, hexahedral, octahedral, dodecahedral, plate-like, spherical, etc., or may be a mixture of these various shapes. , octahedral, and tetradecahedral particles are preferred.

At least two types of silver halide emulsions each having a silver iodide content within a specific range according to the present invention can be produced by forming a core portion of polydispersible silver halide grains and coating the core portion with a shell portion. I can do it.

To produce monodisperse silver halide grains of the core portion, grains of a desired size can be obtained by a double jet method while keeping pAg constant. Further, highly monodisperse silver halide grains are disclosed in Japanese Patent Application Laid-Open No. 54-48521.
The method described in the above publication can be applied.

For example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. At this time, by appropriately selecting the time function of addition rate, pH, pAg, degree, etc.
Highly monodisperse silver halide grains can be obtained.

Next, the thickness of the shell portion that covers the core portion must be thick enough not to hide the desirable qualities of the core portion, and conversely, be thick enough to hide the unfavorable qualities of the core portion. That is, the thickness is limited to a narrow range defined by such upper and lower limits. Such a shell portion can be formed by depositing a soluble halogen compound solution and a soluble silver salt solution onto the core portion of monodisperse silver halide grains by a double jet method.

Regarding the method for producing the above-mentioned core/shell type silver halide grains, see 1, for example, West German Patent No. 1,169,290, British Patent No. 1,027,146, and JP-A-57-1.
542324! , and is also described in Japanese Patent Publication No. 51-14H.

In the present invention, general formulas [I] and [If
]', [1] and [IV],
Spectral sensitization is carried out by adding the above-produced monodisperse silver halide grains to a silver halide emulsion containing them. The above-mentioned sensitizing dyes may be added at any time, such as at the start of chemical ripening (also called second ripening) of the silver halide emulsion, during ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. No, but preferably during ripening.

Various methods can be used to add each of the sensitizing dyes represented by the general formulas of the present invention to the photographic emulsion. For example, U.S. Patent No. 3,469,98
7, the sensitizing dye of the present invention may be dissolved in a volatile organic solvent, the M solution may be dispersed in a hydrophilic colloid, and this dispersion may be added to an emulsion. In general, the sensitizing dyes of the present invention may be dissolved individually in the same or different solvents, and these solutions may be mixed before being added to the emulsion; can be added separately to the emulsion.

As the solvent for the sensitizing dye according to the present invention, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone 1 are preferably used.

When the sensitizing dyes according to the present invention represented by the general formulas [I], [II], [II[] and [IV] are added to a silver halide emulsion, the total amount of each added is 1 silver halide. It is preferably 0.05 mmol to 0.7 mmol, more preferably 0.1 mmol to 0.5 mmol per mole. The preferred ratios of the sensitizing dyes according to the present invention are the sensitizing dyes represented by the general formulas CI], [III] and [IV], and the sensitizing dyes represented by the general formula [IV], respectively.
1[], [III] and [IV], respectively, in a weight ratio of i:0.
．． 2 to 0.1 is preferred.

The above-mentioned silver halide emulsion that can be used in the present invention may optionally contain other cyanine, merocyanine,
Sensitization can be achieved by combination with carbocyanine or styryl dye. Dyes that can be used include, for example, U.S. Pat. No. 3,506,443.
No. 3,660,102, No. 3,672,89
No. 8, 7he Theory Of the P ho
tographic processThird
editlon (1966) MeO2C,E,K,
and James T, H, may be used,
The selection can be arbitrarily determined depending on the intended use of the photosensitive material.

The average grain size of each of the low iodide silver iodobromide emulsion and the high immersion silver iodobromide emulsion according to the present invention is selected depending on the intended use of the light-sensitive material. That is, in order to obtain comparatively high-contrast photographic characteristics, the difference in average grain size between the two may be reduced, and in order to obtain relatively soft-contrast photographic characteristics, the difference in average grain size may be increased.

Further, the average grain size of the low iodine silver iodobromide emulsion according to the present invention is preferably 0.1 to 0.6μ, more preferably 0.2μ.
The average grain size of the high immersion silver iodobromide emulsion according to the present invention is 0.5 to 1.2.
μ is preferred, and monodisperse particles in the range of 0.6 to 0.9 μ are more preferred.

Next, as a silver halide emulsion that can be used in the present invention, Teja T. H. James and C. E. K.

The Theory of the
Ph0tO=araoh(c Process'″
3rd edition, published by Macmillan: p, Qraf
lkldes, “Chemie Photoaraphiaue”
It can be prepared by various methods such as the ammonia method, neutral method, acid method, etc., which are described in Prestige, such as Pan1 fvjonte 1, and are commonly used. Further, a single jet method, a double jet method, a controlled jet method, etc. may be used, or two or more types of silver halide emulsions formed separately may be mixed. After forming such silver halide grains, by-produced water-soluble salts (for example, 'f!
When silver bromide was prepared using silver 41 and potassium bromide, potassium nitrate) was washed with water to remove it from the system, followed by heat treatment with a chemical sensitizer, such as sodium thiosulfate, N,
Sensitivity can be increased without coarsening the particles by carrying out in the presence of N,N''-trimethylthiourea, -eumetallic thiocyanate complex, thiosulfate complex, stannous chloride, hexamethylenetetramine, etc. Other chemical sensitizers include, for example, U.S. Pat. Nos. 2,399,083 and 2,597.8.
Gold compounds such as chlorauric acid salts and gold trichloride as shown in the specifications of U.S. Pat. No. 56 and U.S. Pat. No. 2,597,915; , No. 2.566.245, No. 2,566.263,
No. 2,598,019 Salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium as shown in the specifications of U.S. Pat. No. 1,574,944 and U.S. Pat. No. 2,410.689 , No. 3,189,458
Sulfur compounds that react with silver salts to form silver sulfide as described in U.S. Patent No. 2,487.850, U.S. Patent No. 2,518,
No. 698, No. 2,521,925, No. 2,521
, No. 926, No. 2,694,637, No. 2.98
Examples include stannous salts, amines, and other reducing substances as described in No. 3.610 and No. 3,201,254.

The photographic emulsions of the present invention may be used for the purpose of increasing sensitivity, increasing contrast, or accelerating development, such as in U.S. Pat.
, 389; ethers, esters, and amides of polyalkylene oxides described in U.S. Pat. No. 2,708,161; British Patent No. 1,145,188; -109
89, 45-15188, 46-43435, 47-8106, and 47-8106: Other polyalkylene oxide derivatives described in U.S. Pat. Specifications up to No. 3,046,135, Japanese Patent Publication No. 45-9019, No. 47-11
119 @Thioether compounds described in various publications, Japanese Patent Publication No. 4
Thiomorpholines described in U.S. Patent No. 7-28325: Quaternary ammonium compounds described in U.S. Patent No. 3,772,021: Pyrrolidine, etc. described in Japanese Patent Publication No. 45-27037: Publication of Japanese Patent Publication No. 40-23465 Derivatives of urethane or urea described in: Imidazole derivatives described in Japanese Patent Publication No. 47-45541: Japanese Patent Publication No. 45-26471
Polymers described in Japanese Patent Publication No. 45-27670 may also include 3-pyrazolidones described in Japanese Patent Publication No. 45-27670.

Furthermore, various compounds can be added to the photographic emulsion of the photographic light-sensitive material used in the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. Those compounds are 4-hydroxy-
6-thimeru 1.3゜3a, 7-chitrazaindene, 3
-Methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, as well as a large number of compounds such as heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time. Examples of compounds that can be used include T, H, James and C,E.

K. Mees, “The Theory of t
he photo.

-graphlc Process, 3rd edition (1966
Year).

In addition to listing the original documents in Ma (published by JILLAN), U.S. Patent No. 1.758,578@,
No. 110,178, No. 2,131,038, No. 2
, No. 173,628, No. 2,697,040, No. 2,304,962, No. 2,324,123, No. 2,394,198%, No. 2,444,605 ~
No. 2,444,608, No. 2,566.245, No. 2,694.716, No. 2,697,099
No. 2,708,162, No. 2,728,66
3 to No. 2,728,665, No. 2,476.53
No. 6, No. 2,824,001, No. 2,843,4
No. 91, No. 2,886,437, No. 3,052,
544@, same No. 3.137.577, same No. 3,220
, No. 839, No. 3,226,231, No. 3,23
6,652@, same No. 3,251,691, same No. 3.2
No. 52.799, No. 3,287.135, No. 3,
No. 326,681, No. 3,420,668, No. 3
, No. 622, 339, each specification ll.

British Patent No. 893,428, British Patent No. 403,789,
Same No. 1,173,609, Same No. 1,200,188@
Each specification is mentioned.

In the present invention, the photographic emulsion and/or other photographic constituent layers can be hardened.

Examples of hardening agents that can be used include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethyl urea), and 2-hydroxy-4
, 6-dichloro-1°3.5-triazine, and others, U.S. Pat.
3, British Patent No. 974,723, British Patent No. 1,167.
Compounds containing reactive halogens as shown in the specifications of No. 207, divinyl sulfone, 5-7 cetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others U.S. Patent No. 3,635 , No. 718,
No. 3,232,763, No. 3,490,911, No. 3,642,486, British Patent No. 994,86
Compounds with reactive olefins as shown in the specifications of No. 9, N-hydroxymethylphthalimide, and other U.S. Pat.
No. 586,168 as shown in each specification etc.
- Methylol compounds, isocyanates as shown in U.S. Patent No. 3,103,437, etc.; Aziridine compounds such as U.S. Pat. Nos. 2,725,294 and 2.125.295
Acid derivatives as shown in each specification such as No. 3, carbodiimide compounds as shown in U.S. Patent No. 3,100,104, etc., U.S. Patent No. 3,091
, U.S. Patent Nos. 3,321,313 and 3,5.
Isoxazole compounds as shown in the specifications of No. 43,292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or chromium chloride as an inorganic hardening agent. Bread, zirconium sulfate, etc. Also, instead of the above compounds, compounds in the form of precursors, such as alkali metal bisulfphytaldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, etc. may be used. .

If necessary, other known surfactants may be added alone or in combination to the constituent layers of the photosensitive material of the present invention. These may be used as coating aids, but may also be used for other purposes, such as emulsification and dispersion, development acceleration, other photographic property improvements, charge series adjustment, static electricity prevention, and the like.

These surfactants include natural products such as saponin, anionic or nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, and phosphonium or cationic surfactants such as sulfonium, anionic surfactants with acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, 11 esters, phosphoric esters, amino MM, amino sulfones, sulfuric acid or phosphorus of amine alcohols, etc. Includes amphoteric active agents such as acid esters.

Some examples of surfactant compounds that can be used include U.S. Pat. Nos. 2,271,623 and 2,240.
No. 472, No. 2,288,226, No. 2,739
, No. 891, No. 3,068,101, No. 3,15
No. 8,484, No. 3.201.253, No. 3.2
No. 10.191, No. 3,294,540, No. 3,
415,849, WII No. 3,441.413J, WII No. 3,442.654, WII No. 3,475,774,
No. 3,545,574, British Patent No. 1,077.3
No. 17 and No. 1,198,450, as well as Ryohei Oda et al. [Synthesis of surfactants and their applications] (I
III Store, 1964) and A.

J.P., "Surface Active Agents" (Interscience Replication Incorporated, 1958), J.P.

It is described in "Encyclopedia of Active Agents Volume 2" by John Sisley (Chemical Baplish Company, 1964).

The light-sensitive material of the present invention may contain filter dyes or anti-halation and irradiation dyes such as U.S. Pat. No. 2,274,782, U.S. Pat. No. 252,921,
No. 3,177.078 and Special Publication No. 39-2206
It may be used as a backing layer using the dye described in Japanese Patent No. 9, or, if necessary, directly included in the photosensitive material or as an adjacent layer.

Above, typical examples that can be used in the photographic material according to the present invention have been illustrated, but more specifically, "Product Licensing Index J 921.
No.9232. pp. 107-110, Eng-XI, X
VI to XVI, XXI (December 1971) D is described.

Examples of the support include nitrate film, cellulose acetate film, cellulose acetate butyrate film, polystyrene film, polyethylene phthalate film, polycarbonate film, or laminates thereof, glass, and paper.

Furthermore, paper coated or laminated with baryta or α-olefin polymers, especially polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene butylene copolymers, etc., may also be used.

To coat the photographic emulsion of the present invention on these supports,
This can be done using any coating method known in the art, such as a dip method, an air knife method, an extrusion doctor method, a pea coating method, etc.
Particularly preferred is the pea coating method.

The photosensitive material according to the present invention is developed with a common black and white developer. As the developer, silver halide developers such as hydroquinone, 1-phenyl-3-pyrazolidone, and n-methyl-p-7 minophenol are used singly or in combination. In addition, alkaline agents such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metaborate, lower alkanolamines, borax, etc., and preservatives such as sodium sulfite, potassium sulfite, sodium bisulfite, and pyrosulfite. Potassium, as a development fog inhibitor, potassium bromine, moderate potassium, or 5-nitrobenzimidazole, 5-nitropenzoindazole, 6-nitrointindazole, 5-methylbenzotriazole, 5-nitropenzotriazole, 1 -phenyl-5-mercaptotetrazole, etc., and chelating agents such as nitrile triacetic acid, polyphosphoric acid, and ethylenediaminetetraacetic acid.

The pH of the developer is preferably 7 or higher, usually 8 to 12, the processing moisture level is preferably 15°C to 40°C, more preferably 18°C to 30°C, and the processing time is 30 seconds to 30°C. 10 minutes is appropriate.

After the phenomenon, soak in an acidic stop bath! Thereafter, the undeveloped silver may be dissolved and removed by treatment with a fixer or by direct immersion in a fixer. After fixing, it is washed with running water for about 5 minutes and dried.

[Examples] The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A monodisperse silver iodobromide core/shell type emulsion with octahedral crystals and an iodobromide emulsion for comparison were prepared by a double jet method according to a method similar to that described in JP-A-57-154232. Eight types of silver bromide polydisperse twin emulsions were prepared as shown in Table 1 below.

Table 1 Each of the emulsions prepared above was subjected to sensitization using the optimum chemical sensitization method (gold salt and sulfur sensitizer), and then the formulas [I] to [IV] according to the present invention were obtained. The indicated sensitizing dyes were added as shown in Table 2, and after being sufficiently adsorbed, 4-hydroxy-6 was added as a stabilizer to each emulsion.
-Methyl-1゜3.38.7-Titrazaindene suitable m
An appropriate amount of saponin as a coating aid and formalin as a hardening agent were added.

Of the emulsions obtained, a low iodine silver halide emulsion was first coated on a subbed cellulose triacetate film, and then a high immersion silver halide emulsion was coated as a layer on top. and dried to obtain a sample. The amount of silver coated was 20 so/da + 2 (7) for each single layer, and 401 (1/d12 nina 6J) for both layers.This sample was exposed to a photosensitive needle with a light source with a color temperature of 5400 A blue filter, a green filter, and a red filter were respectively attached to the light source using the same method, and light exposure was performed.
Development was carried out at 20° C. for 7 minutes using a developer having the composition shown below, followed by fixation and water washing to obtain a black and white image strip. The sensitivity of each filter was measured at fog+density of 0.2, and is shown in Table 2 as a relative value to a comparative sample.

Composition of developer water 6oo
11 Metol 2g Anhydrous sodium sulfite 100g Hydroquinone 5g Borax (pentahydrate) 1.5g Add water and 1! As is clear from Table 2, Samples 1, 2, 3 and 4 according to the present invention have excellent spectral sensitivity over the entire visible range.

Example-2 Emulsions A, B, and E used in Example-1 and Emulsion C for comparison
A sample was prepared in the same manner as in Example 1 using and H, and was treated in the same manner as in Example 1. The results obtained are shown in Table 3. Note that the sensitivity in the table is a relative value when the sensitivity of each of the blue light, green light, and red light of comparative sample 18 is set as 100, and gamma represents the linear part of the characteristic curve as the exposure range. be.

As is clear from Table 3 below, the samples of the present invention can obtain red light sensitivity without impairing the sensitization of blue light sensitivity (silver halide specific sensitivity part), and have a gamma that is preferable for tone reproduction. It turns out that the value can be obtained.

Example 3 In place of the sensitizing dye represented by the general formula [L] according to the present invention, the following dye [al], which is an orthopan type sensitizing dye, was used for comparison, and the test was carried out in the same manner as in Example 2. As a result, the sensitivity to red light was satisfactory, but the sensitivity to blue light and green light, which are short wavelength regions, was significantly inferior to the sample of the present invention.

Comparative dye [al Example-4 Instead of the sensitizing dye represented by the general formula [IV] according to the present invention, the following dye [al], which is a blue-sensitive sensitizing dye, was used for comparison.
A sample was prepared using B.C. and tested in the same manner as in Example 2. As a result, the sensitivity of the combination according to the present invention to blue light and green light was significantly superior to that of the comparative sample.

Comparative dye [b] (CHI)3SOsH [Effects of the Invention] As is clear from the above examples, the present invention has high sensitivity and wide exposure latitude over the entire visible range, and improves tone reproducibility. It is possible to provide good silver halide photographic materials.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment (
Directions 1. Indication of the case 1982 Patent Application No. 245353 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address 1-26 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 2 name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Benko Layashige 4, Agent 102 Address Matsuoka Kudan Building, 2-2-8 Kudanminami, Chiyoda-ku, Tokyo Phone: 263-9524 Date of dispatch: March 26, 1985 16 Detailed description of the invention in the specification , 49 pages 18-2
0th line r・The Theory of the Pho℃co
arabicProcess Th1rd edi
tion (1966) Mees C,E.

K., and JamesT., Hl-J's description in ``The Theory of the Photographic Process.''

3rd edition (1966) The Mies C.E.C. and The T.H.
0fthe P photoorapHc P r
ocess T hirdition (19
66) Mees C, E, K, andr・T,
In H. James and C. E. Mees, “The
(Theory) of the Photo
hicprocess'' 3rd edition, Macg+1lla
Published by n company: P.

By Grafikldes, “Chemie Ph0t
01) ral) hiQtle ”Pant MOnte
l...'' has been changed to ``...T.H. James (T, H, Jas+es) and C.E.C.
The Theory by C.E. Mees
Of the Photographic Process
theory or the photography
cProcess) 3rd edition, Macmillan
illan) Publishing: B. Gerafkides (P, G
rafkides), Chemie Photographic (
ChemieP photooraphque) Paul Montel (paulMontel>-J).

Margin below Two

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least two silver halide emulsion layers on a support, the silver halide contained in at least two of the silver halide emulsion layers is distributed from the shell portion to the core portion. at least one layer of the silver halide emulsion layer has a silver iodide content of 0.1 mol% or more,
is less than 3.0 mol % silver halide, and contains a combination of at least one sensitizing dye represented by the following general formulas [I], [III] and [IV], and the halogenated At least one of the other layers of the silver emulsion layer is made of silver halide having a silver iodide content of 3.0 mol% or more and 7.0 mol% or less, and has the following general formula [II] or [III
] and [IV] in combination. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ [However, R_1 and R_2 in the formula represent an alkyl group or a substituted alkyl group. (X_1^■) represents an acid anion. Summer represents 0 or 1, and l is 0 when forming an inner salt. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, Z_1 and Z_2 in the formula each represent a sulfur atom or a selenium atom. Y_1 and Y_2 each represent a hydrogen atom, a halogen atom, or an alkyl group. R_
3 and R_4 are synonymous with R_1 and R_2, respectively. R_5 represents an alkyl group, provided that when Z_1 and Z_2 are each a sulfur atom and Y_1 and Y_2 are each a hydrogen atom, R_5 represents an alkyl group having 2 or more carbon atoms. (X_2^■) represents an acid anion. m
represents 0 or 1, and m is 0 when forming an inner salt. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [However, R_6 and R_7 in the formula represent substituted or unsubstituted alkyl groups. Y_3 represents a hydrogen atom, an alkyl group, or an alkoxy group. Z_3 represents the atomic group necessary to complete the heterocyclic nucleus. (X_3^■) represents an acid anion. n represents 0 or 1, and n is 0 when forming an inner salt. ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, Z_4 and Z_5 each represent an atomic group necessary to complete the heterocycle. R_8 and R_9 each represent an unsubstituted alkyl group or a substituted alkyl group. (X_4^■) represents an acid anion. p represents 0 or 1, and p is 0 when forming an inner salt. ]