JPS61123832A - 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 contg. a silver iodide - bromide (AgX) having a high and a low iodine concns. and coloring matters of a sensitizer having a specific combination respectively and also having a monodispersibility. CONSTITUTION:The titled material is prepared by forming on a substrate at least two silver halide emulsion layers dispersing silver halide particles having the monodispersibility. One of the prescribed layers contains the AgX having 0.1-3.0mol% a low silver iodide concn. and also a combination of the prescribed coloring matters shown by formulas I, II, and IV wherein R1, R2, R6-R4 are each an alkyl group, Y3 is a hydrogen atom or an alkyl group, Z3-Z5 are an atom capable of forming a heterocyclic ring, X<->1, X<->3 and X<->4 are each an acid anion, (l), (n), (p) are each 0 or 1. Another one of the prescribed layers contains the AgX having 3.0-7.0mol% a high silver iodide 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, an alkyl group, R3-R5 are each an alkyl group, (m) is 0 or 1, and also the 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 DH, etc.)
It is also greatly affected by various photographic additives, including stabilizers, that coexist in the emulsion.

In general, when the amount of a sensitizing dye added to an emulsion increases, the sensitivity of the spectral sensitized part increases, but the blue light sensitivity region inherent to silver halide usually becomes desensitized, especially in panchromatic and J- Aggregation-sensitized type dyes have great desensitization properties. Desensitization of the inherent sensitivity of silver halide by such a sensitizing dye leads to a decrease in white light sensitivity for use in 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 A number of techniques have been developed for spectrally sensitizing silver halide emulsions so that they can be properly sensitized to red light. In addition to increasing spectral sensitivity, it is necessary that the spectral sensitization wavelength range is appropriate, and in addition, it must not be reactive with other types of additives, and it must not deteriorate photographic properties.
It must satisfy various conditions such as having excellent storage stability and not causing dye staining after processing.

On the other hand, it is one of the techniques for improving the image quality of highly sensitive silver halide photographic materials (hereinafter simply referred to as photosensitive materials), such as improving the image quality characteristics such as 1iII property, 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 reduce this, it has the disadvantage that silver iodide acts to suppress the sulfur sensitization reaction during chemical ripening or the black-and-white development reaction after photography.

Furthermore, the aforementioned 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 have a high intensity in the entire visible light range. Sensitivity and uniform tone reproduction are required.

As a conventional technique for such purpose, for example,
Although many methods are known, such as 26470 or Japanese Patent Publication No. 48-42493, they are not necessarily sufficient spectral sensitization methods, and the emergence of a photosensitive material with jI sensitivity over the entire visible light range and a wide exposure latitude is awaited. 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. be.

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 will become apparent from the description below.

C 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 emulsion layer is substantially monodisperse silver halide grains having a particle size distribution represented by the following formula [A], and at least one of the silver halide emulsion layers is Silver iodide content is 0.1 mol% or more, 3
．． It consists of less than 0 mol % of silver halide and contains a combination of at least one sensitizing dye represented by the following general formulas [I], [III] and [IV], and contains a small amount of other layers. (Both layers have 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], [III] and [rV].

Formula [A] S/r≦0.20 [Here, S and 〒 represent the standard deviation and 7 the average grain size, respectively, in the grain size distribution of silver halide grains, which is expressed by the following formula. l [However, rl represents the particle size of the first particle, and nl represents the number of the first particle. (XIe) represents an acid anion.

When 1 represents O or 1 and forms an inner salt! is 0
It is. ] General formula [II] [However, 21 and zl in the formula each represent a sulfur atom or a selenium atom, Yl and Yl each represent a hydrogen atom, a halogen atom, or an alkyl group.

R3 and R are synonymous with R1 and R2, respectively. R represents an alkyl group, provided that when zl and zl are each a sulfur atom and Yl and Yl are each a hydrogen atom, RC; represents an alkyl group having 21X carbon atoms. (X2e) represents an acid anion. ■ represents 0 or 1, and when forming an inner salt, the symbol is O. ] General formula [I[] [wherein R6 and R7 represent an alkyl group or a substituted alkyl group]. Y3 represents a hydrogen atom, an alkyl group or an alkoxy group. z3 represents an atomic group necessary to complete the heterocyclic nucleus. (X3e) represents an acid anion. n is O
or 1, and when forming an inner salt, n is O. general formula [rV] [wherein 2+ and 2. each represents an atomic group necessary to complete a heterocycle, and R8 and R9 each represent an alkyl group or a substituted alkyl group.

(X4e) represents an acid anion, p represents 0 or 1, and p is O when forming an inner salt. ] In the above general formulas [I], [II] and [I[I], R,, R
The alkyl group of 3, R6 and R7 is preferably an alkyl group having 1 to 5 carbon atoms, and specifically includes, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, rhohexyl group, etc. R+, R2, R
The IF-substituted alkyl group of 3, R4, R(,, R7 is preferably a substituted alkyl group having 1 to 5 carbon atoms, and specifically, β-sulfoethyl group, γ-sulfopropyl group, T-
Alkyl groups substituted with sulfo groups such as sulfobutyl group, δ-sulfobutyl group, β-hydroxy-γ-sulfopropyl group, 2-γ-sulfopropoxyethyl group, 2-β-sulfoethyl group, and salts thereof (e.g. , sodium salt, triethylamine salt, etc.), carboxymethyl group,
β-carboxyethyl group, γ-carboxypropyl group,
With a carboxy group such as δ-carboxybutyl group, r! Monosubstituted alkyl groups and their salts (e.g., sodium salts, triethylamine salts, etc.), β- and droxyethyl groups, γ-
Examples thereof include an alkyl group substituted with a hydroxy group such as a hydroxybuvir group, an alkyl group substituted with a carbamoyl group, and the like.

In the general formula [I[], the alkyl group represented by R5 is preferably carbon f! ! 1 to 5 linear or branched lower alkyl groups, specific examples of which include methyl, ethyl, propyl, butyl, and the like.

Specific examples of the heterocyclic nucleus formed by the atomic group 73 in general formula [II1] include 2-quinoline, 6-
Methyl-2-quinoline, 6-medoxy-2-quinoline,
Quinoline cough, such as 6-hydroxy-2-quinoline, benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-
Methoxybenzothiazole, 5-ethoxybenzothiazole, 6-methylbenzothiazole, 6-chlorobenzothiazole, 5-carboxybenzothiazole, 5-acetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-
Trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5.6-dimethylbenzothiazole, 5
-acetylaminobenzothiazole, 6-methoxybenzothiazole, 5.6-simethoxybenzothiazole,
5゜Dichloropenzotisol nucleus such as 6-cyclopenzotisol, naphthothiazole nucleus such as naphtho[1,2-dlthiazole, selenazole, 4-methylselenazole, 4-7I-nylselenazole, 4゜Selenazole core such as 5-dimethylselenazole, benzoselenazole, 5-
Benzoselenazole cores such as chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, naphtho[1,2-d] Examples include naphthoselenazole cores such as selenazole.

In the general formulas [I], [I[], [IIrJ and [IV], r (X, ○), (X20), (X, ○) and
Acid anions represented by O) are used in common cyanine dye salts, such as iodo ion, bromide ion, chloro ion, p-toluenesulfonate ion, benzenesulfonate ion, sulfate ion, barchlorate ion, Odan ion, etc. It is an acid anion.

In the general formula [I[], Y1 and Yl each represent a hydrogen atom, a halogen atom, or an alkyl group, and among these, preferred are a halogen atom such as a chlorine atom or a bromine atom, and an alkyl group such as a methyl group or an ethyl group. It is the basis. Yl and Yl may each be the same or different, preferably a chlorine atom or a methyl group at the same time.

Examples of the halogen atom represented by Y1 and Yl include a chlorine atom and a bromine atom. Also,
The alkyl group preferably has 1 to 2 carbon atoms, and specific examples include a methyl group and an ethyl group.

In the general formula [1[], 71 and z2 each represent a sulfur atom or a selenium atom, and may be the same or different. Preferably, both zl and z2 represent a sulfur atom or a selenium atom. This is the case.

In the general formula [IIr], 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], z4 and z5 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, benzoxacyl 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, propoxy group, butoxy group, etc.), 7mino group (e.g., amino group, methylamino group, dimethylamim L diethylamino group, etc.), acylamide group (e.g., acetamide group, propionamide group, etc.), acyloxy group ( for example,
acetoxy group, propionoxy group, etc.), alkoxycarbonyl group (e.g., ethoxycarbonyl group, propoxycarbonyl group, etc.), alkoxycarbonylamino group (
For example, ethoxyl propoxycarbonylamino group, butoxycarbonylamino group, etc.), alkyl group (e.g. methyl group, ethyl group, propyl group, trifluoromethyl group, etc.), aryl group (e.g. phenyl group, tolyl group, etc.) ), an alkylsulfonyl group (for example, a methylsulfonyl group), and the like.

Moreover, in general formula [IV], R2 and R? represents 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, ethyl group, propyl group, n-butyl group, or 1-butyl group. , n-hexyl group and the like. Examples of the substituted alkyl groups represented by R2 and R9 include those similar to the substituted alkyl groups described above for R,, R2, R,, R4, Rc and R7.

Specific examples of the sensitizing dyes represented by formulas (1) to [■] 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 (1) (I-3) (, l-5) Specific examples of sensitizing dyes represented by general formula [■] (II-1) (It-2) (It-3 ) (■-4) (U-5) (II-6) (n-7) (II-8) Specific examples of sensitizing dyes represented by general formula (III) Cm-1) (In-2) ( ■-3 (ffl-5) (III-6) Cm-7) (III-8) Specific examples of sensitizing dyes represented by the general formula [■] (IV-1) (IV-2) (IV- 3) (IV-4) (8l-5) (IV-6) (fl/-7) (IV-8') (IV-9) (IV-10) (IV-11) (IV-12) (CH2)icOOH(CHs)xokl(IV-13
) (IV-14) (IV-15) (■-16) (■-17) (IV-18) (IV-1c+) (IV-20) (It/-21) (IV-22) (■- 23) (IV-24) (IV-25) (CH2)s S Os Na (IV-26) (IV-27) (IV-28) (IV-29) (IV-30J (IV-31) (, Ckix)sis(J3f'Ja (■-32) (mV-33) (CHz)ssOsH (IV-34) (Ckb) s S 03 )i (IV-35) (IV-36) (IV-37) ( IV-38) C!H1l Honey (IV-39) CHl (IV-40) C!I(s (IV-41) (IV-44) CtJmu (■-45) CHtCHtOCOC) b (■-46)
. 81 Mu (IV-47) 02 City The spectral sensitizing dyes represented by the general formulas [I], [II] and [III] used in the present invention can be easily synthesized by known methods,
For example, “The Cyan” by F. M. Hamer.
ine Dyes and Re1ated Co
w -pounds”Interscience Pu
Blisher, New York (1964).

Further, the sensitizing dye represented by the general formula [rV] is a known compound, for example, US Pat. No. 3.149,1
No. 05, No. 2,238,231, British Patent No. 742
．． No. 112, or the above-mentioned literature by F. M. HaIler.

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 has relatively few green defects (defects in green light sensitivity), and has a spectral sensitivity distribution with insufficient red light sensitivity.

Therefore, the sensitizing dye represented by the general formula [I] is converted into a sensitizing dye represented by the general formula (
M] and the green-sensitive monomethine cyanine represented by the general formula [
By using it in combination with blue-sensitive monomethine cyanine represented by
These sensitizing dyes are applied to an emulsion of the present invention consisting of monodisperse silver halide having a silver iodide content of 0.1 mol% or more and less than 3.0 mol% (hereinafter referred to as the low iodine iodine emulsion of the present invention). silver bromide emulsion).
It is possible to obtain high sensitivity in the blue light and green light regions) and high contrast spectral sensitivity characteristics.

On the other hand, the thia and selena carbocyanines represented by the general formula [II] are symmetrical to the sensitizing dye group of the general formula [I],
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, by using thia and selenacarbocyanine represented by general formula [II] in combination with green-sensitive monomethine cyanine represented by general formula [I] and blue-sensitive monomethine cyanine represented by general formula [rV], The sensitivity of green light and blue light is enhanced, and these general formulas [
At least 111 of each of the spectral sensitizing dyes represented by [1r], [III] and [IV], respectively, of the present invention have a monodisperse silver iodide content of 3.0 mol% or more and 7°0 mol%.
When used in combination in an emulsion consisting of the following silver halides (J: J, referred to as a high iodine silver iodobromide emulsion developed by Sewage Invention), high sensitivity and soft gradation can be obtained over the entire visible range. It is possible to obtain spectral sensitivity characteristics with characteristics.

At least two types of emulsions containing the above-mentioned low iodine and high iodine silver iodobromide emulsions of the present invention are separately coated in multilayers on a support without being mixed with each other. A silver halide photosensitive material having at least two silver halide emulsion layers each separately containing a low iodine content silver iodobromide emulsion and a high iodine content silver iodobromide emulsion according to the invention has desensitization in the blue light region, which is the objective of the present invention. There are few and the gradation is excellent.

The composition 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 iodide silver iodobromide emulsion according to the present invention. Any of the layers 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 adjacent to this is provided as the first layer close to the support side. A layer structure in which a layer containing the high iodine silver iodobromide emulsion according to the present invention is provided as the second layer is preferable. but,
The present invention is not limited to such a layer structure, but may be the opposite layer structure.

The silver halide light-sensitive material of the present invention has, in addition to at least two silver halide emulsion layers containing the low-iodium and high-iodium silver iodobromide emulsions separately, another silver halide emulsion layer. This other silver halide emulsion layer may be a layer containing the low or high iodo 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, at least two kinds of low iodine and high iodine silver iodobromide emulsions according to the present invention used in the silver halide photographic light-sensitive material of the present invention are each composed of monodisperse silver halide grains. Although the emulsion is required to be an emulsion, other emulsions may be monodisperse or polydisperse.

Here, "monodisperse silver halide grains" means that when the emulsion is observed using an electron microscope, the shape of each silver halide grain appears uniform and the grain size distribution is defined by the following formula. It has the following. That is, when the standard deviation S of the grain size distribution is divided by the average grain size, the average grain size referred to here is 0.20 or less, and in the case of spherical silver halide grains, the diameter, In addition, in the case of particles with shapes other than cubic or spherical, the average value of the diameter when the projected image is converted into a circular image of the same area, and the individual particle size is 1, and the number is 01. , then 〒 is defined by the following formula.

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

T.M., Symposium on Light Microscope and - 1955, pp. 94-122 or in chapter 2 of ``Theory of the Photographic Process'' by Mies and Gies, 3rd edition, Macmillan Publishing Co., Ltd. (1966). It is being done. 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.
0-338 True This can be determined using the method described in the Trivelli and Smith paper.

In addition, in the present invention, “the shape of the silver halide grains is uniform”
J refers to a low iodine silver iodobromide emulsion whose value calculated from S/r in the above formula is 0.20 or less, and more specifically has an average grain size of 0.2 to 0.5μ. Most preferred is a high iodide silver iodobromide emulsion having an average grain size of from 0.6 to 0.9 .mu.m.

The silver halide grains of at least 2M silver halide emulsion layers respectively constituted by low and high iodide silver iodobromide emulsions according to the present invention are formed by dispersing the monodisperse silver halide grains in the same silver halide emulsion layer. at least 10 of the total particles in
% or more, and it is particularly preferable that all the grains are monodisperse silver halide grains.

Further, in the present invention, the general formula [II, [II1
and silver halide grains that are effectively spectrally sensitized by a combination of sensitizing dyes represented by [rV] and sensitizing dyes represented by general formulas [II, [III] and [rV], respectively. contains at least two types of silver iodide having different silver iodide contents in separate layers.

Preferred embodiments of the silver halide grains of the present invention include an average silver iodide content of 0.1 mol% or more and 3.
．． Examples include emulsions containing low iodide silver halide of less than 0 mol % and emulsions containing high iodide silver halide of 3.0 mol % or more and 7.0 mol % or less.

Silver halide grains in the present invention preferably contain silver bromide as a silver halide composition other than the above-mentioned silver iodide, but may contain silver chloride 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.

To produce the substantially monodisperse silver halide grains of the present invention, grains of a desired size can be obtained by a double jet method while keeping 9AQ constant. In addition, highly monodisperse silver halide grains are disclosed in Japanese Patent Application Laid-Open No. 54-48
The method described in No. 521 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, the addition rate, 1)
H,EIAIII! Highly monodisperse silver halide grains can be obtained by appropriately selecting the degree and the like.

In the present invention, the general formula [II, [],
Spectral sensitization is carried out by adding the sensitizing dyes represented by [1] and [IV] to the silver halide emulsion containing monodisperse silver halide grains produced as described above. 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
As described in No. 7, the sensitizing dye of the present invention may be dissolved in a volatile organic solvent, the solution may be dispersed in a hydrophilic colloid, and this dispersion may be added to an emulsion. Additionally, the sensitizing dyes of the present invention may be dissolved individually in the same or a different solvent, and the solutions may be mixed before being added to the emulsion, or these solutions may be mixed separately. can be added to the emulsion.

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

General formula [r], []r], [rIiJ and h[IV]t'
The amount of each of the sensitizing dyes according to the present invention added to a silver halide emulsion is preferably from 0.05 mmol to 0.7 mmol, more preferably from 0.05 mmol to 0.7 mmol per mol of silver halide in total. 1 mmol to 0.5
Millimoles. The preferred usage ratios of the sensitizing dyes according to the present invention are the sensitizing dyes represented by the general formulas [I], [IIN and [IV], respectively, and the general formula [
The weight ratio between the sensitizing dyes represented by [n], [I[] and [rV], respectively, is 1:0.2 to 0.
7 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. 3.1360.102, No. 3,672.8
No. 98, The Theory of the Ph.
otographlcProcessThlrd
edition (1966) Mees C,E,
Those described in J. K. and James T. H. D may be used, and the selection thereof 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 normal iodide silver iodobromide emulsion according to the present invention is selected depending on the intended use of the light-sensitive material. That is, relatively li! In order to obtain sharp photographic characteristics, it is sufficient to reduce the difference in average grain size between the two, and to obtain comparatively soft photographic characteristics, it is necessary to increase the difference in average grain size.

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.
Monodisperse grains in the range of ~0.5μ, on the other hand, the average grain size of the normal 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.

Silver halide emulsions that can be used in the present invention include T, H, James and C, E, K.

“The theory of
the P photo -graphlCProc
ess” 3rd edition, published by Macrillan = p, Q
Written by raNkldes, ” Chemie Photograph+ue
It can be prepared by various methods such as the commonly used ammonia method, neutral method, acidic method, etc. Also, it can be prepared by the single jet method or double jet method. , control 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, nitrile
When silver bromide was made using silver 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, N,
The sensitivity can be increased without coarsening the particles by carrying out the reaction in the presence of N-trimethylthiourea, -valent gold thiocyanate complex, thiosulfate complex, stannous chloride, hexamethylenetetramine, etc. These methods are described in the above book. Other chemical sensitizers include, for example, U.S. Pat.
No. 2,597,915. Gold compounds such as gold chloride m salts and gold trichloride as shown in the specifications of US Patent No. 2,597,915,
No. 448,060, No. 2,540,086, No. 2
．． Platinum as shown in the specifications of No. 566.245, No. 2,568,263, and No. 2,598,079;
Salts of noble metals such as palladium, iridium, rhodium, ruthenium, U.S. Patent Nos. 1,574,944, 2,410,689, 3,189,458
Sulfur compounds that react with silver salts to form silver sulfide as described in U.S. Pat. No. 3,501,313, etc., U.S. Pat.
No. 98, 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. 1,145,186; -109
No. 89, No. 45-15188, No. 46-43435J
! , No. 47-8106, and No. 47-8106. Other polyalkylene oxide derivatives described in U.S. Pat. No. 3.046.132 to U.S. Pat. No. 3,046.135
Specifications up to No. 45-9019, 47-1
Thioether compounds described in Japanese Patent Publication No. 1119, thiomorpholines described in Japanese Patent Publication No. 47-28325: Quaternary ammonium compounds described in U.S. Patent No. 3,772,021: Pyrrolidine, etc.: Urethane or urea derivatives described in Japanese Patent Publication No. 40-23465: Imidazole derivatives described in Japanese Patent Publication No. 47-45541: Japanese Patent Publication No. 45-2647
Polymers described in Japanese Patent Publication No. 1, 3-pyrazolidones described in Japanese Patent Publication No. 45-27670, and the like may be included.

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 capri 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 are T, HlJalleS and C,E.

K. Mees 1. ”The Theory
of the photo.

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

In addition to the original documents listed in Maca+1Ilan, U.S. Patent Nos. 1,758,576 and 2,
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. 2,444,805 ~
Same No. 2,444,808, Same No. 2,566.245, Same No. 2,694.716, Same No. 2,697,09
No. 9, No. 2,708,162, No. 2,728,
663 to 2,728,665, 2,478.
No. 536, No. 2,824,001, No. 2,843
．． No. 491, No. 2,886,437%, No. 3,05
No. 2,544, No. 3.137.577, No. 3,2
No. 20,839, No. 3,226,231, No. 3,
No. 236,652, No. 3,251,691, No. 3
, 252.799, 3,287.135, 3,326,681, 3,420,668, 3,622,339, British Patent No. 893,
428@, No. 403,789, No. 1.173,6
No. 09 and No. 1,200.188%.

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

Examples of hardening agents used include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl urea), and 2-hydroxy-4
, 6-dichloro-1°3.5-triazine, and others U.S. Pat. No. 3,288.715, U.S. Pat. No. 2,732,30
3, British Patent No. 974,723, British Patent No. 1,167.
Compounds having reactive halogens as shown in No. 207 specifications A11, etc., divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5
-1 riazine, etc. U.S. Patent No. 3,635,718
No. 3,232,763M, No. 3,490,91
No. 1, No. 3,842,486, British Patent No. 994,
Compounds with reactive olefins such as those shown in No. 869 fm8, N-hydroxymethylphthalimide, and other U.S. Patent No. 2.732.316,
N-methylol compounds as shown in U.S. Patent No. 2,588,168, U.S. Pat. No. 3,103.
Isocyanates such as those shown in U.S. Pat. No. 3,017,280, U.S. Pat. [3,611
Aziridine compounds as shown in the specifications of U.S. Patent No. 2,725,294, U.S. Patent No. 2,125.
No. 295, etc. Mei IB! As shown in l! derivatives, carbodiimide compounds as shown in US Pat. No. 3,100,704, epoxy compounds as shown in US Pat. No. 3,091,537, etc.; Inoxazole compounds as shown in U.S. Patent Nos. 3,321,313 and 3,543,292, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, dichloro Dioxane derivatives such as dioxane,
Or another inorganic W! Membrane agents include chrome light pan, zirconium sulfate, etc. Moreover, instead of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, and primary aliphatic ditroalcohols may be used.

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, enhancement of image formation, other improvements in photographic properties, charge series adjustment, and prevention of static electricity.

These surfactants include natural products such as saponin, alkylene oxide type, glycerin type, glycidol type, etc.
ionic or nonionic surfactants, high t & furkyl amines, quaternary ammonium moieties, pyridine and other complex top layers, cationic surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids, phosphoric acids, sulfates, phosphate esters These include anionic surfactants having acidic groups, such as amino surfactants, aminosulfonic acids, and amphoteric surfactants such as ram or phosphoric acid esters of amine alcohols.

Some examples of surfactant compounds that can be used include U.S. Pat. Nos. 2,271,623 and 2,240.
472F4, No. 2,288,226, No. 2,73
No. 9,891, No. 3,068.101, No. 3,1
No. 58,484, No. 3,2'01.253, No. 3
, 210.191, 3,294,540, 3,415,649, 3,441,413, 3,442.654, 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.'s "Synthesis of Surfactants and Their Applications" (
Shin Shoten, 1964) and A.

W. Berry, Surface Active Agents (Inter Science Replication, Inc., 1958), J.P.

``Encyclopedia of Active Agents Volume 2'' by 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,
Same 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 light-sensitive material according to the present invention have been illustrated.
o, 9232. '107-110 pages, Eng-X1lr,
XVI-X■, XXm (December 1971).

Examples of the support include nitrate film, cellulose acedate 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 coating methods well known in the art. For example, the depth method, air knife method, extrusion doctor method, bead 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-aminophenol 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 binitrate, Potassium pyrosulfite, as a development fog inhibitor, potassium bromine, potassium immersion, or 5-nitrobenzimidazole, 5-nitropenzoindazole, 6-nitroitindazole, 5-methylbenzotriazole, 5-nitropenzo Chelating agents such as triazole and 1-phenyl-5-mercaptotetrazole include nitrile triacetic acid, polyphosphoric acid, and ethylenediaminetetraacetic acid.

l)H of the developer is 7 or more, usually 8 to 12, and the processing II temperature is preferably 15 to 40 °C, more preferably 18 to 30 °C, and the opening during processing is 3
0 seconds to 10 minutes is appropriate.

After development, the undeveloped silver may be dissolved and removed by immersion in an acidic stop bath and then treatment with a fixer, or by immersing directly 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 emulsion with octahedral crystals and a silver iodobromide polyamide emulsion for comparison were prepared by a double jet method according to a method similar to that described in JP-A-57-154232. There are 8 types of dispersed twin emulsion W4 as shown in Table 1 below.
Manufactured by Y4.

The following is Table 1 in the margin.Each emulsion prepared as described above was subjected to a sensitization method using an optimal chemical sensitizer (gold salt and sulfur sensitizer), and then the general formulas [I] to [IV ] j! s
After adding the dyes as shown in Table 2 and allowing them to be sufficiently adsorbed, 4-hydroxy- as a stabilizer was added to each emulsion.
An appropriate amount of 6-methyl-1°3.3a, 7-chitrazaindene, saponin as a coating aid, and formalin as a hardening agent were added.

Of the emulsions obtained, the low iodine emulsion was first coated on a subbed cellulose triacetate film base, and then the high immersion emulsion was coated on top of it in a layered layer and dried to obtain a sample. The amount of silver coated was 20 Il for each single layer.
Both sides were coated uniformly at 1 g/dI2 so that the amount was 40 mg/6 m2. This sample was measured using a sensitometer with a light source with a color temperature of 5400°, and each light source was equipped with a blue filter, a green filter, and a red filter. !
The exposure was set to 11.

Next, development was carried out at 20° C. for 7 minutes using a developer having the composition shown below, followed by fixing and washing with water to obtain a black and white image strip. The sensitivity of each filter was measured at a fog density of 0.2, and is shown in Table 2 as a relative value with respect to a comparative sample.

Composition of developer water 6oo
cl, p Metol 2 Anhydrous sodium sulfite 1001J Hydroquinone 5g Borax (pentahydrate) 1.5g Add water and 1! As is clear from Table 2 in the margin below, Samples n1.2.3 and 4 according to the present invention have excellent spectral sensitivity over the entire visible range.

Example 2 Samples were prepared in the same manner as in Example 1 using emulsions A and F used in Example 1 and comparative emulsions C and H, and were processed in the same manner as in Example 1. The results obtained are shown in Table 3. The sensitivities in the table are relative values when the blue light sensitivity of Comparative Sample 18 is taken as 100. As is clear from Table 3, the samples of the present invention have blue light sensitivity (silver halide specific sensitivity part It can be seen that sensitivity to red light can be obtained without impairing the sensitization properties of ), and gamma values preferable for tone reproduction can be obtained.

Example 3 In place of the sensitizing dye represented by the general formula [I] according to the present invention, the following dye [a], which is an orthopan type sensitizing dye, was used for comparison, but in the same manner as in Example 2. As a result of the test, 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 samples of the present invention.

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

Comparative dye [b] (CH!)I 5OIIH [Effects of the invention] As is clear from the above examples, the present invention has high sensitivity over the entire visible range, a wide exposure latitude, and excellent tone reproduction. It is possible to provide a silver halide photographic material with good properties.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment (
Method) % formula % 1. Indication of the case Patent Application No. 245352 of 1982 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 Name
(127> Representative Director of Roku Konishi Photo Industry Co., Ltd.
Coeducational level 4, agent 102 Address Matsuoka Kudan Building, 2-2-8 Kudanminami, Chiyoda-ku, Tokyo Igi! 1263-9524 Shipping date 1985 0
March 26th 6, Subject of correction [IBmm's ``Improper explanation of g 101ゝ\1, Akira 1
In the Detailed Description of the Invention column, page 48, lines 13-15, "...the Theory of the Ph0
tO1llral) hlcProcess Th1r
d edition (196B) Mess C0E.

K, and JataesT, H, - J's description of the theory of the photographic process.

3rd edition (1966) Mies C.E.K. and G.E.
dition (196B) Mees C, E, K
, andJamesT, H,...J.

2. Mei am page 49 lines 12-16 “...T.

H. Jai+es and C. E. Mees, “Th
e(Theory) of the Photo
raphlc Process” 3rd edition, Macmil
Published by P. Grafikldes, “Ch.
elif3 P photographique″Pan
1 Montel ・J’s description was changed to “…T.H.

)-1, Jales) and C.E.K. Mies (C.

E., K. Mees), The Theory of the Photographic Process (The Theory of the Photographic Process)
y Ofthe Photographic Pr
ocess) 3rd edition, Macmillan (Maca+1lla
n) Corporate use: B. Gerafkides (P, Grafk)
ides), Chemie Photography (Chem
ie photograph) Ball O-F:
>Chill (Paul Montel)-J.

Margin below

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:
Substantially monodisperse silver halide grains having a grain size distribution represented by the following formula [A], wherein at least one of the silver halide emulsion layers has a silver iodide content of 0.1 mol% or more, It consists of less than 3.0 mol % of silver halide and contains a combination of at least one sensitizing dye represented by the following general formulas [I], [III] and [IV], and other layers at least one layer has a silver iodide content of 3.0 mol%
consisting of silver halide of 7.0 mol% or less,
A silver halide photographic material comprising a combination of at least one sensitizing dye represented by the following general formulas [II], [III] and [IV]. Formula [A] S/@r@≦0.20 [Here, S and @r@ represent the standard deviation and @r@ the average grain size in the grain size distribution of silver halide grains, respectively, It is shown by the following formula. ] S=√[(Σ(@r@−ri)＾2ni)/(Σni)
]@r@=(Σniri)/Σni [However, ri represents the particle size of the i-th particle, and ni represents the i
represents the number of particles. ] General formula [ I ] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_1 and R_2 represent an alkyl group or a substituted alkyl group. (X_1^■) represents an acid anion. l represents 0 or 1, and when forming an inner salt, l is 0
It is. ] 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_4 and R_2, respectively. R_5 represents an alkyl group, provided that Z_1 and Z_2
are each a sulfur atom, and when 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 when forming an inner salt, m is 0
It is. ] General formula [III] [In the formula, R_6 and R_7 represent an alkyl group or a substituted alkyl group. 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 when forming an inner salt, n
is 0. ] General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [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 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. ]