JPS62191847A - Silver halide photographic sensitive material improved in green spectral sensitivity and color stains - Google Patents

Abstract

PURPOSE:To enhance spectral sensitivity in the green light region by incorporating substantially monodispersed silver halide grains sensitized with at least one combination of 2 types of sensitizing dyes specified in structure in at least one emulsion layer. CONSTITUTION:The monodispersed silver halide grains are sensitized with at least one combination of at least one of the sensitizing dyes represented by formulae I and II and at least one of the sensitizing dyes represented by formula III. In these formulae, R1 is H or alkyl; each is H, alkyl, or the like; Z is a nonmetallic atomic group necessary to form an oxazolidine ring or the like; X1<-> is an anion; m is 1 or 2; each of W1 and W3 is a group having a Hammett constant sigmap of >=-0.01; each of W2 and W4 is a group having that of >=0.24; X2<-> is an anion; and n is 1 or 2, thus permitting the obtained photosensitive material to have low fog density, high green spectral sensitivity having the maximum spectral sensitivity in the green light region, especially near 550nm, and relieved dye stains after processing.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is applicable as a photographic material in the field of photographic technology, and more specifically, the present invention can be used as a photographic material in the field of photographic technology. This invention relates to a photographic material using a monodisperse silver halide emulsion that has an increased spectral sensitivity in the spectral sensitivity range.

[Background of the Invention] In recent years, demands on silver halide photosensitive materials for photography (hereinafter referred to as photosensitive materials) have become increasingly strict, such as graininess,
There is a strong demand for the development of photosensitive materials with excellent image properties such as sharpness, gradation, and even color reproducibility.

That is, in a color photosensitive material with excellent color reproducibility, it is desired that the green light sensitivity has a maximum around 550 nl, and in an X-ray photosensitive material that is rapidly processed, a high green sensitivity matching the bright line emission of 545 nm is desired. It is desired that the density of residual color stains after processing derived from sensitizing dyes be low.

To meet these demands, a silver halide emulsion with a low fog density and high sensitivity is required.

One method for achieving the above-mentioned photographic performance such as high sensitivity and low fog density is sensitization using sulfur sensitization, selenium sensitization, gold sensitization, reduction sensitization, etc., either alone or in combination. A means to improve the single-child efficiency using monodisperse silver halide grains has been considered.

On the other hand, as is well known, the wavelength range of silver halide's inherent sensitivity is limited to the near-external to blue light range, so effective spectral sensitization technology is essential to achieve high sensitivity in the visible light range. be. It is well known that dyes such as cyanine or merocyanine are used alone as a means of spectral sensitization, and it is also well known that multiple dyes can be used in combination to superadditively sensitize any wavelength range. . Regarding sensitization in the green light range using a dye in combination, for example, the combination technology of oxacarbocyanine and penzimidasooxacarbocyanine or oxathiacarbocyanine is disclosed in JP-A-52-23931, JP-A-57-14834, and JP-B-Sho 55. Publications No. -14411 and No. 56-27864,
U.S. Patent No. 3.580.724, U.S. Patent No. 3.840.3
No. 73, each town Jll of Sayama Patent No. 2.127.671
Then, the technology of coarsely combining oxacarbocyanine and benzimidazocarbocyanine was published
No. 6, JP-A No. 50-87636, JP-A No. 54-80118
No. 59-116646, No. 59-11664
7 publications, U.S. Patent No. 2,688,545, U.S. Patent No. 3,397,060, U.S. Patent No. 3,663,210, U.S. Patent No. 3,814, fs09@, British Patent No. 1,231, 0
No. 79 and No. 1,542.062. The combination of these dyes has little interaction with photographic additives and is evaluated as a technology that provides 14 speed and low fog density.

However, the application of these existing techniques to monodisperse silver halide grains does not necessarily result in significant increases in color sensitization by 4 degrees, and new problems arise such as instability of emulsion photographic properties during production. I end up.

One example of a technology that solved these problems is JP-A-59-
Although Japanese Patent No. 140443 is disclosed, it is insufficient to achieve various photographic performances currently required such as higher sensitivity, lower fog density, and lower dye staining.

[Objective of the Invention] An object of the present invention is to provide a photosensitive material having a low fog density and a high green spectral sensitivity having a maximum spectral sensitivity in the green light region, particularly around 550 nll; another object is to An object of the present invention is to provide a light-sensitive material that is spectrally sensitized to green light and has reduced dye staining after processing.

[Structure of the Invention] As a result of repeated studies by the present inventors, the above object was achieved in a silver halide photographic light-sensitive material having at least 1ffi of silver halide emulsion layer on a support. Both layers contain substantially monodisperse silver halide grains, and the silver halide grains are
At least one sensitizing dye represented by the following general formula [A] and the general formula [Ibl, and the following general formula [
At least IFl! of the sensitizing dye represented by []! The present inventors have discovered that the present invention can be achieved by a silver halide photographic material characterized by being color sensitized using a combination of the following.

General formula [111 General formula [Ibl [wherein, R1 represents a hydrogen atom or an alkyl group, R2
and R3 each represent an alkyl group. (2) 1 represents a halogen atom, a hydroxyl group, an alkoxy group, or an aryl group, and V2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, or a halogen atom. Z is an oxazolidine ring, a 2 (3H)-oxazole ring, a 2 (3H)-benzoxazole ring,
2 (3 days) naphtho[2,3-111A xazole ring, 2
(IH) naphtho[1,2-dl ogisazole ring, or 2
(IH) Does not represent a nonmetallic atomic group necessary to form a naphtho[2,1-d]oxazole ring.

×1 represents an anion, and l represents an integer of 1 or 2. However, when m represents 1, R2 or R3 does not represent a group that forms an inner salt. ] General formula [11 [In the formula, R4, R5, R6 and R7 do not each represent an alkyl group or an alkenyl group. Wl and W3 each represent a group whose Hammett σ p value is more positive than −0,01, and W2 and W4 each represent a group whose Hammett σ p value is more positive than −0,01.
．． Represents an electron-withdrawing group that is more positive than 24. X2e
represents an anion, and n represents an integer of 1 or 2. However, when n represents 1, R') or R5 does not represent a group capable of forming an inner salt. That is, the present invention provides substantially monodisperse silver halide grains comprising at least one sensitizing dye represented by the general formula [Ial or [Ibl] and at least one sensitizing dye represented by the general formula [11]. This method is characterized by spectral sensitization through a specific combination of 2 and 4. This makes it possible to obtain a photosensitive material with high sensitivity, low capri density, and low color staining after processing.

The present invention will be further explained below.

The alkyl group represented by R in the general formulas [Ial and [Ibl] is preferably a lower alkyl group, such as methyl, ethyl, 10-biru, etc. Examples of the alkyl groups represented by R2 and R3 include methyl, ethyl, sulfoethyl, carboxypropyl, butyl, sulfobutyl, and at least one of them is a sulfo-substituted alkyl group, such as sulfoethyl, sulfobutyl, sulfobutyl. It is preferable that it is a group such as.

■For the halogen atoms represented by 1 and V2, for example, J? There are A, bromine, iodine, and fluorine. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy, and examples of aryl groups include phenyl and tolyl. The alkyl group preferably includes lower alkyl groups, such as methyl, ethyl, propyl, and the like.

The oxazolidine ring and 2(3H)-oxazole ring formed by Z can have a substituent at the 4th or 5th position,
For example, 4,4-dimethyloxazolidine, 4-methyl-
2(3)-1) ochrysyl, 4-phenyl-2(3H
)oxazole, 5-methyl-2(3H)oxazole, 5-phenyl-2(3day)oxazole, 4.5-dimethyl-2(3H)oxazole, 4.5-diphenyl-2(3H)oxazole, etc. Examples include rings. Preferably, Z forms 2(3H)-
The benzoxazole ring has a halogen atom at the 5th or 6th position,
Groups such as alkyl groups, alkoxy groups, and aryl groups can be substituted, and specifically, 5-chloro-2(3H)benzoxazole, 6-chloro-2(3)-1>benzoxazole, 5-chloro-2(3H)benzoxazole, Mediru 2 (31-()benzoxazole, 5-methoxy-2(3H) benzoxazole, 5-phenyl-2(31-1) benzoxazole, 5-chloro-6-chloro-2(3H) benzoxazole, 5 , 6-dimedoxy2(3H)benzoxazole, 5,6-dichloro-2(3H)benzoxazole, 6-medoxy2<38)benzoxazole, 6
-Hydroxy-2(31-4)benzoxazole, 5
．． 6-Simethoxy 2(3H)benzoxazole, 6
- Represents a benzoxazole ring such as -phenyl-2(3H)benzoxazole.

Examples of the anion represented by ×1° include chloride, bromide, iodide, thiocyanate, sulfate, methylsulfate, ethylsulfate, verchlorate,
There are p-toluenesulfothyi 1 and the like.

Next 1; In the general formula [n], the alkyl groups represented by R4, R5, R6 and R7 are, for example, methyl, ethyl, sulfoethyl, carboxypropyl,
Carboxymethyl, sulfopropyl, sulfobutyl, butyl, pentyl, sulfopropyloxyethoxyethyl, carbamoylethyl, methoxycarbonylpropyl,
There are groups such as hydroxyethyl, 2.2.3.3-tetrafluoropropyl, perfluoroethyl, hydroxyethoxyethyl, methoxyethyl, and 2-phenylethyl, and the alkenyl group includes an allyl group.

At least one of R4 and R5 is preferably an alkyl group substituted with an acidic group, and examples of 5W1 and W2 include groups such as carboxymethyl, carboxyethyl, sulfoethyl, sulfopropyl, sulfobutyl group, sulfopropyloxyethoxyethyl, etc. Specific examples of groups whose Hammett σρ values are more positive than 10 and 01 are hydrogen atoms, acyloxy groups, alkoxycarbonyluloxycarbonyl groups, halogen atoms, carbonyl groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, and cyanogen atoms. group, trifluoromethyl group, and the like.

The acyloxy groups represented by Wl and W2 include, for example, acetoxy, propionoxy, etc., the alkoxycarbonyl includes, for example, ethoxycarbonyl, propoxycarbonyl, etc., and the halogen atoms include, for example, chlorine, bromine, iodine, Examples include fluorine, and carbonyl groups include acetyl, propionyl,
There are groups such as benzoyl, sulfonyl groups include, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, etc., and carbamoyl groups include, for example, carbamoyl, N-methylcarbamoyl, etc.
Examples of sulfamoyl groups include sulfamoyl, N
Examples include groups such as -methylsulfamoyl, morpholinosulfonyl, and piperidinosulfonyl.

W3 and W now represent respectively]~σρ value is 0
．． A specific example of a group more positive than 24 is a cyano group (σp
= 0.56), t-lifluoromethyl group (σp=
0.54'), an alkoxycarbonyl group, an aryloxycarbonyl oxide group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a perfluorohydrocarbon group, and the like.

W3 and W4 are not represented respectively, and the alkoxycarbonyl group is, for example, methoxycarbonyl (σp=0.
Examples of aryloxycarbonyl groups include phenoxycarbonyl (σp=0.44), and carbonyl groups include acetyl (σp=0.44).
50), propionyl (σll=0.48),
Isobutyroyl (σp = 0.4'7) Benzoyl (σ
p=0.43), and examples of the sulfoxide group include methyl sulfoxide (σp-0.49).
), examples of sulfonyl groups include methylsulfonyl (σ p = 0.72), difluoromethylsulfonyl (σ p = 0.86), trifluoromethylsulfonyl (σ O- 0,93), fluorosulfonyl ( There are groups such as σl) = 0.91), and examples of carbamoyl groups include carbamoyl (σp = 0.3G
), examples of sulfamoyl groups include groups such as sulfamoyl (σp=0.57), examples of perfluorohydrocarbon groups include perfluorobutyl groups (
σp=0.52), perfluorophenyl (σp
- 0'. 41) and the like.

The value of 1-σρ used in the above general formula [I] is H
This is the substituent constant determined from the effect of the 1stie group on the hydrolysis of benzoate esters by Allllett et al., Journal of Organic Chemistry Vol. 23, 42G-427 (1958), Experimental Chemistry Lecture Vol. 14 (Marukubi Publishing). , Physical Organic Chemistry (Mc Gray-HillBo
OK Publishing) (1940), "Structure-Activity Relationship of Drugs" (Nankodo), p. 96 (1979), etc.

Preferably W3J and J. Examples of the substituents represented by and W4 include a cyano group, a carbamoyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a trifluoromethyl group, an acetyl group, a methylsulfonyl group, a trifluoromethylsulfonyl group, a sulfamoyl group, and a perfluorophenyl group. Among them, a cyamic carbamoyl group, a trifluoromethylsulfonyl group, and a fluorosulfonyl group are particularly preferred.

Furthermore, the anions represented by x20 include, for example, chloride, bromide, iodide, thiocyanate, sulfur-1,
Represents an anion such as methylsulfate, ethylsulfur-1., perchloride, p-toluenesulfonate, etc.

Next, the general formulas [Ia] and [Ibl] used in the present invention are
Specific representative examples of the sensitizing dyes represented by and [II] are listed below, but the sensitizing dyes used in the present invention are not limited to these.

The following margins (general formula [1 ml and (exemplary compound of Ibl)] [1 ml
-11 [1m-2] [1m-31 [1a-4] [1a-7] Ha-8] [1m-9] [1a-10] [1a-11] [fa-12] [1a-13] [1a-16] [1a-17] CH.

[Ib-1] [Ib-21 [Ib-31 [Ib-4] [Ib-5] [Ib-6] [Ib-7] [Ib-81 [Ib-91 [Ib-10] [Ib-11] [Ib-14] [Ib-15] [Ib-16] [Ib-17] Sith mercenary (Exemplary compounds of general formula [11]) [11-11 100NH.

[1-2] [11-3] C2Hs　　　　　　　　C2Hs[11-4] S　O2N　Ht [11-5] [11-61 CH.

[11-71 n-al COOCtHs [1-101 -CH,CH,0(CH,),SO,Na[1-12] 19O,NHC [1-131 [n-141 [11-151 [■-161 [[-17] [11-18] [11-19] [11-20] zero -COOC2H.

[1-211 [11-221 [1-23] [I[-24] [1-27] [11-281 Margin below Sensitization represented by the general formulas [Ial, [Ib] and [II] of the present invention Dyes are described, for example, in U.S. Patent No. 2,072.9.
No. 08, No. 3,711,288, British Patent No. 841
, No. 119, No. 955,961, and Soviet Patent No. 244.120, Special Publication No. 38-78
No. 28, No. 43-14497, No. 44-16589 @
, No. 45-27676, Japanese Unexamined Patent Publication No. 59-81338, F. M. Harma Mei, Shinin-Dice & Related Compounds (published by 1'l & Interscience Publishers), etc. Selected from the known ones listed.

Incidentally, sensitizing dyes not described in the above patent specification e1 can also be easily synthesized by those skilled in the art according to the synthesis method described above.

In the light-sensitive material of the present invention, the silver halide grains according to the present invention contained in at least one silver halide emulsion layer provided on the support are represented by the above general formulas [Ial, ] The spectral sensitizing effect etc. can be obtained by sensitizing the sensitizing dyes according to the present invention represented by the combination, but especially when the general formula [Ial and the general formula [II] are used in combination In addition, a remarkable improvement in photographic properties can be obtained. According to the present invention, the coefficient of variation of the grain size distribution of the substantially monodisperse silver halide grains contained in the silver halide emulsion layer is 20% or less, and more preferably, the coefficient of variation is 15%. Indicates the following values.

This coefficient of variation is It is defined as a measure of monodispersity.

The above particle diameter 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 [Theory of the Photographic Process], co-authored by Mies and James.

It is described in Chapter 2 of the 3rd edition, published by Macmillan (1966). The particle size can be measured using the projected area or approximate diameter of the particle.

If the particles are of substantially uniform shape, the particle size distribution can be expressed fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in [Pursensi 1 - Empirical relationship between metric distribution and grain size distribution] DePhotographic Journal, Vol. LXXIX.

This can be determined by the method described in the article by Trivelli and Smith (1949), pp. 330-338.

Substantially monodisperse silver halide grains according to the present invention include:
They may be used alone, or two or more types of monodisperse silver halide grains having different average particle diameters may be arbitrarily mixed and used.

In the present invention, halogenated compounds that can be effectively spectrally sensitized by the sensitizing dyes represented by the general formulas [Ial, [■b] and [II] (hereinafter referred to as sensitizing dyes according to the present invention) Silver grains have a grain structure composed of 2M1 or more groups having different silver iodide contents, and are hereinafter referred to as core/shell type. ) is preferred. It is preferable that the average silver iodide content in the outermost layer of the two or more layers is lower than the average silver iodide content in the inner layers. The effect of the present invention is that silver halide containing silver halide grains having a grain structure in which the silver iodide content in the outermost layer (referred to as Scherch) is lower than that in the inside than in the outermost surface layer (referred to as Scherch) as described above. The effect is even more pronounced when an emulsion is used.

The core/shell type silver halide grains preferably used in the present invention have an inner layer (
The silver iodide content of the core may be 6 to 40 mol %, preferably 8 to 30 mol %, more preferably 10 mol %.
~20Tnyl%.

The silver iodide content of the outermost layer is 0.5 to 6 mol%, preferably 0.5 to 40 mol%.

The shell portion of the core/shell type silver halide grains accounts for 10 to 80%, preferably 15 to 70%, and more preferably 20 to 60%.

Further, the proportion occupied by the core portion is desirably 10 to 80% of the entire particle, and particularly preferably 20 to 50%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. Also preferably used is one having an intermediate layer between the core and the shell having a silver iodide content between the core and the shell.

The volume of the platform intermediate layer made of the core/shell type silver halide grains having the intermediate shell is preferably 5 to 60%, more preferably 20 to 55%, of the entire grain.

The difference in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core is preferably 3 mol % or more, and the difference in silver iodide content between the shell and the core is preferably 6 mol % or more.

In the present invention, the average silver iodide content of the core/shell type silver halide grains is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

The core/shell type emulsion of the present invention is disclosed in JP-A-59-1775.
No. 35, No. 60-138538, No. 59-52238
No. 60-143331, No. 60-35726, No. 60-258536, and the like.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A-60-138538, the center of the grains must have a halogen composition region different from that of the core. is possible.

In such a case, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, or silver chloride, but if the silver iodide content is Silver iodobromide or silver bromide of 10 mol % or less is preferred.

The proportion of the seed emulsion in the total silver halide is preferably 50% or less, particularly preferably 10% or less.

The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or using X-ray diffraction.

The core/shell type silver halide grains of the present invention are cubic,
It may be a normal crystal such as a tetradecahedron or an octahedron, it may be composed of twin crystals, or a mixture thereof, but a normal crystal is preferable.

In the present invention, for example, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or one salt thereof, a rhodium salt or a lead salt thereof, etc. may be allowed to coexist in the manufacturing process of the silver halide grains according to the present invention. good.

In the present invention, spectral sensitization is carried out by adding the sensitizing dye according to the present invention to a silver halide emulsion containing monodisperse silver halide grains produced as described above. The above-mentioned sensitizing dye may be added at any stage, such as at the start of chemical ripening (also called second ripening) of the silver halide emulsion, during ripening, after the completion of ripening, or at an appropriate h period prior to emulsion coating. do not have.

In addition, various conventionally proposed methods can be applied to add the sensitizing dyes represented by the general formulas of the present invention to the silver halide emulsion. For example, JP-A-50-808
No. 26, protonation dissolution method described in No. 50-80827, JP-A No. 49-44895, JP-A No. 50-1
The method of dispersing and adding with a surfactant described in No. 1419, US Pat. No. 3,676,147, US Pat.
．． No. 469.987, No. 4,247,627, No. 5
No. 3-102733, No. 53-137131, No. 58
The method of adding the compound by dispersing it in a hydrophilic substrate as described in the specification of No. 105141, the method of adding it as a solid solution of the compound described in the specification of East German Patent No. 143.324, etc. can be applied.

Also, East German Patent No. 21,802, Special Publication No. 50-406
59, JP-A-59-148053, etc., water-soluble solvents that dissolve the dye, such as water, methanol, ethanol, propyl alcohol, ahitone, fluorinated alcohol, and dimethylformamide. The dye may be dissolved in at least one solvent and added to the emulsion. Furthermore, the sensitizing dyes of the present invention can be individually dissolved in the same or different solvents, and the solutions can be mixed or added separately before being added to the emulsion.

When the sensitizing dye according to the present invention is added to a silver halide emulsion, the amount of O added is 1X10- per mol of silver halide.
5 moles to 2.5X 10-2 moles, preferably 1.
OX i Q-4 mol to 1. OX 10' moles. The preferred ratio of the sensitizing dyes according to the present invention is in the range of 1 to 9:9 to 1 according to the general formulas [I] and [], respectively.

The sensitizing dye according to the present invention can also be used (If) with other sensitizing dyes or supersensitizers.

[Examples] Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A. Preparation of silver halide emulsion First, silver halide seed particles and gelatin aqueous solution were put into a reaction pot, and while controlling the 11A (l and pH) in the reaction pot, ammoniacal nitrate M was added. A silver aqueous solution, a potassium iodobromide aqueous solution (1), and a potassium iodobromide aqueous solution (2-1) or a potassium bromide aqueous solution (2-2), which has a lower potassium iodide content than solution (1), are used for particle growth. Add in proportion to the increase in surface area of the solution (
Solution (, 2-1') or solution (2-2) for 1)
The addition ratio was increased and the addition was continued. In some cases, the addition ratio of solution (2-1) or solution (2-2) to solution (1) was increased in two stages. Then,
Add Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and magnesium sulfate aqueous solution, perform precipitation desalting, add geratin, and prepare an emulsion of I) AO 7.8, pH 6.0. Furthermore,
Add sodium thiosulfate, chloroauric acid and ammonium rhodanate, perform chemical ripening, add 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 6-nitropenzimidazole, and then Gelatin was added to form 1 q of core/shell type silver iodobromide emulsion.

Here, solution (1) and solution (2-1) or solution (2-
By changing the addition ratio of 2), the silver iodide mol% can be changed, and by changing the addition m of ammoniacal silver nitrate and potassium halide, the grain size can be changed. (1) and solution (2-1)
Alternatively, by changing the particle diameter when changing the addition ratio of solution (2-2), the outermost shell thickness and middle shell thickness are changed, and furthermore, by changing the pAg during the reaction, the crystal habit is changed, Core/shell type silver iodobromide emulsion samples EM-1 and EM-2 as shown in Table 1 were prepared.

Each of the emulsion samples shown in the following table was found to be a monodisperse emulsion with an average grain size of 1 and a coefficient of variation of grain size distribution shown in the table by electron microscopy. The addition port in the halogenated photographic light-sensitive material is expressed per 1f unless otherwise specified. Silver halide and colloidal silver are shown as fusuma tubes on the fruit.

Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triahityl cellulose film support from the support side.

Sample-1 (comparison) 1st layer; antihalation layer (HC-1>gelatin layer containing black colloidal silver.

21st ffi+intermediate ([,L,) 2.5-di-t-octyl hydroxide A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1) Emulsion (EM-1> ・-・-1! Coating: L +, 8Q
/v' Sensitizing dye■... 6X10-5 moles per mole of silver Sensitizing dye IV...... per mole of silver 1. OX 10' Morcian coupler (C-1)...0.06 per mole of silver
Molar colored cyan coupler (CC-1) 0.003 mol DIR compound per 811 mol DIR compound <D-1) 0.0015 mol DIR compound (D-2) per 1 mol silver ... 0.002 mol per mol of silver No. 4; Highly sensitive red-sensitive silver halide emulsion layer (R 1-1
) Emulsion (EM-2)... Silver coating l1ff! 1.3
Sensitizing dye ■・・・・・・3×10−5 mol per mole of silver Sensitizing dye■・・・・・・1. OXl Q-5 Morcian coupler (C-1)...0.02 per mole of silver
Mol colored cyan coupler (CC-1>...Silver 1
0.0015 mol per mole DIR compound (D-2)...0.001 mol per mol of silver 5th layer: Intermediate layer (1,L,) Same as the 2nd layer, gelatin layer.

6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-EM-1... Coated silver Wi 1. Sa /
12 Sensitizing dye... Added to each sample as shown in Table 1.

Magenta coupler (M-1)...0.050 mol per mol of silver Colored magenta coupler (CM-1)...0.009 mol per mol of silver DIR compound ( D-1)... 0.0010 mol per mol of silver DIR compound (D-3)... 0.0030 mol per mol of silver 7th layer: High sensitivity green Sensitive silver halide emulsion layer (GH-1) Emulsion-EM-2...Coated silver lit 1.4a
/f Sensitizing dye... The same sensitizing dye used in the 6th layer is used for each sample, and the amount added is 0.6 times that of the 6th layer magenta coupler (M-1)...・0.020 mol of colored magenta coupler (CM-1>...0.002 mol of DIR compound (D-3) per 1 mol of silver per 1 mol of silver... Silver 1 0.0010 mole to mole 8th layer: Yellow filter single layer (YC-1) Gelatin layer comprising yellow colloidal silver and an emulsified dispersion of 2.5-di[-octylhydroquinone.

9th layer: Low sensitivity blue-sensitive silver halide emulsion layer (BL-1) Emulsion (EM-1) --- Silver cloth ia o,
9g/f Sensitizing dye V...1.3X per mole of silver 1Q-5 mole Yellow coupler (Y-1)...0.2 per mole of silver
9 mol 10th layer; high sensitivity blue sensitive emulsion layer (BH-1) emulsion (EM
-2)... Silver coating amount 0.5g/i' sensitizing dye V
...... 1 mole of silver. Ox 1Q-5 mol Yellow coupler (Y-1)...0.08 per mol of silver
Mol DIR compound (D-2)... 0.0015 mol to 111 mol 11th! First protection PIJ (Pro-1) Silver iodobromide (A (111 mol% average particle size 0.07 μi) Silver coating f2t O, 50/m' Gelatin containing ultraviolet absorbers UV-1, LIV-2 layer.

12th layer; 2nd protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (H8-1) In addition to the above composition, each layer also contains piratin Hardening agent (H-
1) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye ■: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropylanine hydroxide) Sensitizing dye ■: Anhydro 9-ethyl-3,3'-di(
Anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo-5'- Margin below methoxythiacyanine C-I CC-1 -I M-1 V-1 C→t'b(L) υV-2 MS-1 Margin below Sample prepared in this way) INo, 1 to 8 are white The samples exposed by a wedge of light and those exposed by spectrophotography with a built-in prism were subjected to the following development process.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 1) Drying for 30 seconds The composition of the processing solution used in each processing step is It is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniso,n.1iI
! I acid salt 4.7
50 Anhydrous Sodium Sulfite 4.259 Hydroxylamine 1y2 Sulfur M Salt 2. OQ anhydrous potassium carbonate 37.5 g Sodium bromide 1.30 Nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.59 Potassium hydroxide 1.0 g Add water to make 12.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100. (1
Ethylenediaminetetravinegar W2 Ammonium salt 10.0 (Ammonium monobromide 150.00 Wood vinegar M1
o, o B Add water to make 1y, and use ammonia water to pH = 6.
Adjust to 0.

[Fixer]

Ammonium diosulfate 175.0g Anhydrous 5AM sodium 8.5゜ Sodium metasulfite 2.3g Add water to make 12,
Adjust DI-1 to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 me
Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 m [Add water to make 11.

The density of the sample processed after wedge exposure was measured using green light, and magenta image sensitometry was performed. The sensitivity was determined by the reciprocal of the exposure distance giving an optical density of fog + 0.1, and the relative values are shown in Table 1. On the other hand, the wavelengths at which the maximum sensitivity was obtained were determined from the samples exposed to light using a light camera and are listed in Table 1.

Margin 1 below L I= I! l + 1r: J-j, car missing m * 6 color system 1 Shimotsu I Ni Hosu.

[■-11 [■-2] Example-2 shown below 60°C, pAo = 8, I) While controlling I-1 = 2.0, an average particle size of 0.3 μm was produced using the double jet method.
A monodisperse cubic emulsion of silver iodobromide emulsion containing 2.0 mol % of silver iodide was obtained.

Of this emulsion, about 8 mol % of the total silver halide used for growth was used as a seed crystal to grow as follows.

That is, the seed crystals were dissolved in 8.5 mL of a solution containing protected gelatin and optionally ammonia kept at 40°C, and the flH was adjusted with roughly glacial acetic acid.

Using this solution as a mother liquid, a 3.2N aqueous ammoniacal silver ion solution and an aqueous halide solution were added by a double jet method in a flow pattern as shown in FIG. 3, followed by stirring and U-coupling.

Next, I) keeping Ag constant at 9.0 and changing the pH from 9 to 8 in proportion to the addition of ammoniacal silver ions;
A shell of pure silver bromide was formed. 3 minutes at the end of grain growth1) A And so.

After removing excess water-soluble salts from the emulsion obtained in the above manner by coagulation-sedimentation method, ammonium thiocyanate chloroauric acid and Hypo were added, followed by chemical ripening.
Sensitizing dyes were added as shown in the table. and the usual stabilizers,
An emulsion was prepared by adding a hardener and a coating aid.

Each of the emulsions thus obtained was coated on the following supports to obtain samples. That is, a copolymer aqueous dispersion obtained by diluting a copolymer consisting of three monomers of 50 wt% glycidyl methacrylate, 10 wt% methyl acrylate, and 4 Qwt% butyl methacrylate to a concentration of iowt% was subbed. This emulsion was uniformly coated on both sides of a polyethylene terephthalate film base coated as a liquid and dried to obtain a sensitometric sample.

This sample has a silver content of 25 mQ/100c on one side.
It was applied evenly so that it was 1 m1.

The sensitometry of each of these samples was performed as follows: sensitization (exposure) to light and X! ! Two methods were used: sensitization in combination with irradiation. In other words, the exposure color temperature is t! This was done by exposing through an optical wedge for 1150 seconds using a light source of 15400@. Exposure m is 3.2 C, M, S.

Met.

In xIi sensitometry, each sample is sandwiched between two fluorescent screens and passed through an aluminum wedge at a tube voltage of 100 kVP.
XS was irradiated for 1/20 second at a tube current of 1001 A. The fluorescent intensifying screen used at this time was Sakura Hi-Ortho Screen KS manufactured by Konishiroku Photography 5A.

These samples were processed for 90 seconds with XD-90 developing solution using a Konishi Roku Photo Industry Q Light sensitivity is fog ← XWA at density 1o
The sensitivity was expressed as relative sensitivity, taking the concentration as 1.0.

Moreover, the evaluation of residual color was expressed as follows.

1: Not at all 2: Slightly present, but no problem 3: Clearly present Next, use this sample to test the Macbeth transmission densitometer TD-50
Green transmission density was measured using 4A with a Status AA filter.

The results above are as follows: According to the present invention, there is little fogging and residual color, and the spectral sensitivity λmax is 550 nm.
Yes, and X is used in conjunction with four earth intensifying screens.
The odor C according to the line photographic sensitivity phase is particularly important for XI! It is clear that the iI sensitivity is high.

Applicant: Roku Konishi Photo Industry Co., Ltd. Procedural amendment date (method) % formula % 2. Name of the invention Silver halide photographic light-sensitive material with improved green spectral sensitivity and color staining 3. Person making the amendment Relationship with the case Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127> Roku Konishi Photo Industry Co., Ltd. Representative Director Kan
) 1 move 4, agent 〒102

Claims (1)

[Scope of Claims] 1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is substantially monodisperse. The silver halide grains have the following general formula [I a] and general formula [I b]
At least one kind selected from the sensitizing dyes represented by;
A silver halide photographic light-sensitive material characterized in that it is color sensitized using a combination of at least one sensitizing dye represented by the following general formula [II]. General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents a hydrogen atom or an alkyl group, and R
^2 and R^3 each represent an alkyl group. V^
1 represents a halogen atom, a hydroxyl group, an alkoxy group, or an aryl group, and V^2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, or a halogen atom. Z is an oxazolidine ring, 2(3
H)-oxazole ring, 2(3H)-benzoxazole ring, 2(3H) naphtho[2,3-d]oxazole ring, 2(1H) naphtho[1,2-d]oxazole ring, or 2(1H) Represents a group of nonmetallic atoms necessary to form a naphtho[2,1-d]oxazole ring. X_1^■ represents an anion, and m represents an integer of 1 or 2. However, when m represents 1, R^2 or R^3
represents a group capable of forming an inner salt. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, R^4, R^5, R^6 and R^7 each represent an alkyl group or an alkenyl group. W^1 and W^3 each represent a group whose Hammett σp value is more positive than -0.01, and W^2 and W^4 each represent an electron-withdrawing group whose Hammett σp value is more positive than 0.24. represents. X_2^■ represents an anion, n represents an integer of 1 or 2, however, when n represents 1, R^4 or R
^5 represents a group capable of forming an inner salt. ]