JPH03107144A - Black and white image forming method - Google Patents

Abstract

PURPOSE:To form images having a less difference in neutrality by a change in an observing light source, the low min. density and an excellent image preservable property by processing a prescribed photographic sensitive material by using a specified color developing soln. and a fixer. CONSTITUTION:The silver halide photographic sensitive material which contains at least one layer of the silver halide emulsion layers having the same color sensitivity in all the emulsion layers and contains at least one kind of cyan couplers, magenta couplers and yellow couplers from the same emulsion layers into another emulsion layers having the same color sensitivity is constituted by processing the material with a color developer contg. an arom. primary amine developing agent, then processing the same with the fixer which has no bleaching power. The form of the constitution is such that the coupler groups of the three colors are constituted of the groups to attain the value within 0.02 in the apparent sensitivity difference (logarithm) at 0.2 density point of the three colors when the photosensitive material formed by mixing and dispersing the above-mentioned coupler groups and adding the mixture into the single emulsion layer is formed on a reflecting base and is subjected to sensimetry in a fixing processing stage after development processing and the reflection densities of the three colors are measured and are so regulated that the middle density part attains an equal gamma balance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method that provides an excellent neutral black and white dye image. The present invention relates to a method for forming a black and white image which has little difference in neutrality due to color and has excellent whiteness and image storage stability.

[Background of the invention]

In conventional black-and-white photographic systems, a latent image is produced in a silver halide photographic light-sensitive material by light, and this is developed using a common black-and-white developing agent (such as metol, phenidone, pyrogallol, hydroquinone, etc., which are well known in the art). The metallic silver produced in the exposed area by developing with a developer containing 2 is used as an image. The oxidized developing agent is then promptly removed from the system. If the oxidized developing agent can be used as a substantially black dye image, further improvements in density and sensitivity can be expected.

West German Patent No. 1,158.836 and others describe a method of producing a black color image by condensation of this oxidation product with an active methylene compound using a 4-aminopyrazolinobenzimidazole developing agent. .

However, it is practically difficult to obtain a substantially neutral black dye image of sufficient density by this method.

Also, for example, British Patent No. 1,210.417, US Patent No. 3
No. 615509 describes a method by Devkasler. This involves developing a silver halide emulsion using a developing agent having a p-aminophenol developing agent part and a coupler part consisting of phenol, etc. in the same molecule to produce a polymerized dye in the exposed area, which is then exposed to an alkaline bath. Alternatively, the dye is chelated by copper chelate bath treatment to obtain a substantially black dye image with sufficiently high density.

However, since this method uses a so-called developer coupler, it naturally involves external processing, which leaves problems with the stability of the processing bath, processing problems due to the use of copper chelate, and image stability. There is.

Furthermore, in U.S. Pat. No. 3,674,490, silver images obtained by current black-and-white photographic processing are oxidized using hydrogen peroxide as a reaction catalyst, and aromatic hydroxyamino compounds are oxidized in the silver image area. A method for forming a quinone-based black pigment by force/twisting is described. However, this method requires a large number of processing baths and it is difficult to obtain a sufficient concentration under normal conditions.

West German Patents No. 492,518 and West German Patent No. 537,923, etc., include methods commonly used in color photography at present.
A method of forming a black dye image by mixing couplers such as yellow, magenta, and cyan and performing color development is described. However, in this method, coupling speeds between these three color couplers and color developing agents such as para-phenylene diamine color developing agents and p-amine phenol color developing agents are different, and this method cannot be applied over the entire density range. Therefore, it is difficult to obtain a neutral black image, and it is even more difficult to obtain a method for forming a black and white image that combines low minimum density and image storage stability. That is, there is a problem in that certain couplers become more discolored due to storage and the neutral gray balance is disrupted.

[Purpose of the invention]

The present invention has been made to solve the above-mentioned problems, and the first object of the present invention is to have small differences in neutrality due to changes in observation light source, low minimum density, and excellent image storage stability. An object of the present invention is to provide a method for forming a black and white image.

A second object of the present invention is to provide a method for forming a black and white image in which a black and white positive image can be obtained by direct photography or copying using the same equipment as for color photographic materials.

A third object of the present invention is to provide a method for forming a black and white image in which the neutral gray balance does not collapse even when a developed image is stored for a long period of time.

A fourth object of the present invention is to provide a method for forming a black-and-white image by which a black-and-white negative image can be obtained using the same equipment as for color photographic materials.

A fifth object of the present invention is to provide a method for forming a black and white image in which negative and positive black and white images can be obtained using the same equipment.

[Structure of the invention]

The above object of the present invention is to combine at least one silver halide emulsion layer in which all emulsion layers have the same color sensitivity, at least one cyan coupler, magenta coupler, and yellow coupler in the same emulsion layer or having the same color sensitivity. A silver halide photographic light-sensitive material containing in another emulsion layer having the following characteristics is processed with a color developer containing an aromatic primary amine developer, and then processed with a fixer having no bleaching ability. This was achieved by a method of forming black and white images.

Note that the following embodiments are preferable in that the effects of the present invention can be more fully exhibited.

(2) A photosensitive material in which the three color couplers are mixed and dispersed and added to a single emulsion layer is formed on a reflective support and processed with a developer containing an aromatic primary amine developer. After that, in the bleach-fixing process, sensitometry was performed to measure the red reflection density, green reflection density, and blue reflection density, and the compounding ratio of couplers was adjusted so that the gamma balance in the mid-density area was equal. 1. The black-and-white image according to claim 1, wherein the black-and-white image is constituted by a group of couplers such that the apparent sensitivity difference expressed in logarithm at a density point of 0.2 among the three colors is within 0.02. How to form.

(3) The cyan coupler and the magenta coupler are cyan couplers represented by the following general formula [I] and/or general formula (I[), and magenta couplers represented by the following general formula [■], respectively. [I] 2° In the formula, R1 represents an alkyl group or an aryl group.

R8 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R1 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Further, R1 may cooperate with R to form a ring.

Zl represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine developer.

General formula (n) z In the formula, R4 represents a ballast group, and R1 represents an alkyl group. Z represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine developer.

General formula (I[I) R' In the formula, R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R'' represents an alkyl group, an aryl group, a heterocyclic group, a substituted oxy group, or an amino group. represents.

(4) The aromatic primary amine developer has the following general formula [I
4. The image forming method according to claim 3, wherein the compound is a compound represented by V].

General formula (IM) 1 In the formula, Rs is a β-methanesulfonamidoethyl group or β
- represents a hydroxyethyl group; R4 represents a hydrogen atom or a methyl group;

(5) The image forming method according to claim 1, wherein the silver halide emulsion is an internal latent image type direct positive emulsion.

(6) The image forming method according to claim 4, wherein the silver halide emulsion layer and/or the adjacent layer contains 10 to 80+og/@'' of the following compound A.

Compound A (7) The image forming method according to claim 1, wherein the silver halide emulsion is a negative emulsion.

(8) The image forming method according to claim 1, wherein a black-and-white negative image can be obtained by using a negative emulsion, and a black-and-white positive image can be obtained by using a positive emulsion, using the same liquid solution.

The present invention will be explained in detail below.

In the present invention, it has been found that even better black and white image formation can be achieved if, after color development, a fixing process used in black and white photography is performed instead of a bleach fixing process normally used in color processing. That is, the residual silver image further improves the neutrality of the image. That is, when attempting to construct a black-and-white image using only a coupler coloring dye, the hue will vary slightly depending on the viewing light source, but it has been found that this can be resolved by adding a silver image.

In addition, it was found that the addition of a silver image significantly reduces the loss of neutrality in terms of image storage stability.

In the cyan coupler represented by the general formula [I],
The alkyl group represented by RI has 1 to 32 carbon atoms.
These are preferably linear or branched, and include those having substituents.

The aryl group represented by R1 is preferably a phenyl group, including those having substituents.

The alkyl group represented by R3 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and include those having substituents.

The cycloalkyl group represented by R2 has 3 to 1 carbon atoms.
2 is preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by R8 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R2 is preferably a 5- to 7-membered one, may have a substituent, and may be fused.

R1 is a hydrogen atom, a halogen atom, an alkyl group or let
7 Le:! It represents an xy group, and the alkyl group and the alkoxy group include those having a substituent, but R1 is preferably a hydrogen atom.

Further, the ring formed jointly by R1 and R3 is preferably a 5- to 6-membered ring, and examples include the oxidized product of the aromatic primary amine developer represented by zl in the general formula [I]. Groups that can be separated by the reaction include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups,
Examples include an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, and an alkoxy group.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula (, I-A).

General formula CI-A) Z.

In the formula, Rol represents a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom.

Rc and t have the same meanings as R□ in the general formula (I).

Zo represents a halogen atom, an aryloxy group, or an alkoxy group, including those having a substituent.

Cyan coupler represented by the following general formula: Specific examples of the above-mentioned cyan coupler include Japanese Patent Application No. Sho 61-21853, pages 26 to 35, Japanese Patent Application No. Sho 60-225155, page 7, bottom left column to the lower right column on page 1O, the upper left column on page 6 to the lower right column on page 8 of JP-A-60-222853, and the lower left column on page 6 to the upper left column on page 9 of JP-A-59-185335. It includes the 2,5-diacylamino cyan couplers described in the column 1, and can be synthesized according to the methods described in these specifications and publications.

The cyan dye type coupler of the present invention represented by the above general formula (1) usually has IX 10- per mole of silver halide.
'~1 mol, preferably I X 10-'' mol-8XI
It can be used within the range of 0 moles.

In the general formula Cff), the ballast group represented by R2 is of a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing into the multilayer from the layer to which it is applied. It is an organic group having

The preferred ballast group is the following general formula % -CH-0-Ar 1 R@R6 represents an alkyl group having 1 to 12 carbon atoms, and Ar
represents an aryl group such as a phenyl group, and this aryl group may have a substituent.

The alkyl group represented by R may be linear or branched.

Groups that can be separated by reaction with the oxidized product of the aromatic primary amine developer represented by z2 include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, and sulfonylamino groups. ,
Examples include an alkoxycarbonyloxy group and an imide group, but preferably a halogen atom, an aryloxy group, and an alkoxy group. Typical specific examples of the cyan coupler represented by the general formula [I[] are shown below.

Specific examples of cyan couplers that can be used in the present invention, including these, include JP-B No. 49-11572, JP-A No. 61-3142, JP-A No. 61-9652, JP-A No. 61-9.
No. 653, No. 61-39045, No. 61-50136
No. 61-99141, No. 61-105545, etc.

The cyan coupler represented by the general formula (n) of the present invention usually has a molecular weight of 2×10 −3 to 8 X per mole of silver halide.
It can be used in an amount of 10-1 mol, preferably in the range of 1X10-'' to 10-1 mol.

In the present invention, 5-pyrazolones in which the 3-position of the pyrazolone ring is substituted with an acylamino group are used.

General formula CIII) 1 In the formula, R1 is a hydrogen atom, a chain or cyclic alkyl group (for example, methyl, ethyl, isopropyl, t-butyl, t-octyl, allyl, cyclohexyl, norborni, etc.) or a substituted chain Or a cyclic alkyl group (
Examples of substituents include those selected from halogen atoms, nitro, cyanoaryl, alkoxy, aryloxycarboxy, alkoxycarbonylsulfamoyl, carbamoyl, acyl, aminoureido, heterocycle, arylsulfonyloxy and oxo groups, such as β -cyanoethyl, β-chloroethyl, benzyl, nitrobenzyl, dichlorobenzyl, γ-(2,4-di[-pentylphenoxy)-propyl, β-phenoxyethyl, etc.).

Furthermore, R1 is an aryl group (e.g. phenyl, σ- or β-
naphthyl group, etc.) or an aryl group having one or more substituents (for example, alkyl, alkoxy, aryloxy, halogen atom, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkyl sulfonamide, arylsulfonamide, cyano, and nitro group). In particular, a phenyl group in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. (e.g. If2.4.6-dolychlorophenyl group, 2.6
-dichloro-4-methoxyphenyl, etc.) are useful. R' can also be a heterocyclic group (a nitrogen atom as a heteroatom,
5- to 6-membered heterocycles and fused heterocycles containing oxygen atoms, sulfur atoms, etc., such as pyrrolyl, pyridylquinolyl, furyl,
benzothiazolyl, oxasilyl, imidazolyl, naphthoxasilyl, etc.) or a heterocyclic group which is further substituted with the substituents listed for the aryl group above.

R2 represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group, each having the same meaning as R1 described above.

R2 can also be a substituted oxy group (e.g. methoxy, ethoxy, phenoxy, tolyloxy group, etc.) or an amino group (
For example, each substituted or unsubstituted N-alkylamino,
Cycloalkylamino, N,N-dialkylamino, N
-alkyl-N-arylamino, N-arylamino group, etc.).

Next, specific examples of 3-acylamino-5-pyrazolones (hereinafter referred to as pyrazolones of the present invention) used in the present invention are shown below, but the pyrazolones of the present invention are not limited thereto.

([1-1) Cu (III-2) Cu Cm-3) (III-4) (I[-5) (III-6) (III-7) ooii (II[-8) (III-9) (ll-10) (ll-11) +J (II[-12) (I[l-13) C2 (m-14) u (ll-15) (I[l-16) (m-17) This invention As the yellow dye-forming coupler used in , compounds represented by the following general formula CV) are preferred.

General formula (j) In the formula, R11 represents an alkyl group (e.g., methyl, tyl, propyl, butyl group, etc.) or an aryl group (e.g., phenyl, p-methoxyphenyl, etc.), and R12
represents an aryl group, and Y represents a hydrogen atom or a group that is eliminated during the color development reaction.

Further, particularly preferred yellow couplers for forming the dye image according to the present invention are compounds represented by the following general formula CV').

General formula [V'] In the formula, R+3 represents a halogen atom, an alkoxy group, or an aryl group, and R8, R1, and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, It represents an aryloxy group, a carbonyl group, a sulfonyl group, a carboxyl group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, a sulfonamide group, an acylamido group, a ureido group, or an amino group, and Y has the above-mentioned meaning.

These include, for example, U.S. Pat. No. 2,778.658;
875°057, 2,908,573, 3,2
27.155, 3,227゜550, 3,25
No. 3,924, No. 3,265,506, No. 3,277
No. 155, No. 3,341.331, No. 3,369.
No. 895, No. 3,384゜657, No. 3,408.1
No. 94, No. 3,415.652, No. 3,447°92
No. 8, No. 3,551,155, No. 3,582,322
No. 3,725°072, No. 3,894.875, West German Patent Publication No. 1,547.868, No. 2,057,
No. 941, No. 2,162.899, No. 2,163,8
No. 12, No. 2,213.461, No. 2,219.91
No. 7, No. 2,261,361, No. 2,263.875
No. 49-13576, Japanese Patent Publication No. 48-2943
No. 2, No. 48-63834, No. 49-10736,
No. 49-122335, No. 50-28834, No. 5
No. 0-132926.

Next, specific representative examples of yellow couplers preferably used in the present invention will be listed, but the invention is not limited thereto.

(Y-1) a-benzoyl-2-chloro-5-(a-(Fdecyloxycarbonyl)ethoxycarbonyl]acetanilide (Y-2) α-benzoyl-2-chloro-5-[γ-(2,4 -amylphenoxy)butyramide]acetanilide (Y-3) a-fluoro-a-pivalyl-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butyramide]
Acetanilide (Y-4') α-pivalyl-σ-stearoyloxy-4-sulfamoylacetanilide F (Y-5) σ-Viva I)) Re α-(4-(4-benzyloxyphenylsulfonyl)phenoxy) -2-chloro-5-
(γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide (Y-6) α-(2-methoxybenzoyl)-σ~(4-acetoxyphenoxy)-4-chloro-2-(4- t-Octylphenoxy)acetanilide (Y-7) a-Bivalyl σ-(3,3-dipropyl-2,4-dioxoacetidin-1-yl)-2-chloro-5-[α
-(dodecyloxycarbonyl)ethoxycarbonylcetanilide (Y-8) α-hyhalyl α-succinimide-2-chloro-5 [
γ-2.4-di-t-amylphenoxy]butyramide]acetanilide (y-9) α-hyhalyl α-(3-tetradecyl-1-succinimide)acetanilide (y-10) a-C4-F decyloxybenzoyl)-α- (3methoxy-l-succinimide)-3,5-dicarboxyacetanilide dipotassium salt (Y-11) α-vivalyl α-7thalimide 2-chloro-5-(
γ-(2,4-di-amylphenoxy)butyramide]
Acetanilide (y-12) a-2-furyl-σ-7talimito 2-chloro5-
(γ-(2.4-di-t-amylphenoxy)butyramide]acetanilide (Y-13) α-3-[α-(2.4-di-t-amylphenoxy)
Butylamide] benzoyl α-succinimide 2-
Methoxyacetanilide (Y-14) σ-phthalimide α-bivalyl 2-methoxy-4-
((N-methyl-N-octadecyl)sulfamoyl]
Acetanilide (y-15) α-acetyl-σ-succinimide 2-methoxy-4
-((N-methyl-N-octadecyl)sulfamoyl]acetanilide (Y-i6) α-cyclobutyryl-α-(3-methyl-3-ethyl-
1-succinimide)-2-chloro-5- ( (2.
5-di-t-amylphenoxy)acetamide]acetanili(Y-17) α-(3-octadecyl-l-succinimide)-α-
Propenoylacetanilide (Y-18) α-(2,6-di-oxo-3-n-propyl-piperidin-1-yl)-α-biparyl-2-chloro5-[
γ-(2.

4-di-t-amylphenoxy)butylcarbamoylacetanilide (Y-19) α-(l-benzyl-2,4-dioxo-imidazolidin-3-yl)-a-pivalyl-2-chloro-5-[γ
-(2.

4-di-t-amylphenoxy)butyramide]acetanilide (Y-20) α-(l-benzyl-2-phenyl-3,5-dioxo-l.

2,4-1-Ryazin-4-yl)-σ-bivalyl-2-chloro5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide (y-21) α-(3,3-dimethyl -1-succinimide)-α-
Hibivalyl-2-chloro-5-α-(2,4-di-t-
amylphenoxy)butyramide]acetanilide (Y
-22) α-[3-p-chlorophenyl”)-4,4-dimethyl-2゜5-dioxo-1-imidazolyl)-a-bivalyl-2-chloro-5-[γ-(2,4-di- t-Amylphenoxy)butyramide]acetanilide (y-23) α-Bivalyl a-(2,5-dioxo-1,3,4
-) riazin-1-yl)-2-me)xy-5-(a
-(2,4-di-amylphenoxy)butyramide]acetanilide (y -24) α-(5-benzyl-2,4-dioxo-3-oxazoyl)-a-valyl-2-chloro-5-[γ- (2,
4-Diamylphenoxy)butyramide]acetanilide (Y-25) α-(5,5-dimethyl-2,4-dioxo-3-oxacyyl)-σ-bivalyl-2-chloro5-[α-(
2,4-di-t-amylphenoxy)butyramide]acetanilide (Y-26) α-(3,5-dioxo-4-oxazinyl> -, -
Valilu 2-chloro-5-[γ-(2,4-di-t-
amylphenoxy)butyramide]acetanilide(y
-27) a-Vivalyl α-(2,4-dioxo-5-methyl-
3-thiazolyl)-2-chloro-5-[γ-(2,4-
di-t-amylphenoxy)butyramide]acetanilide (Y-28) a -(3(2ti)-pyridazon-2-yl]-σ-
Vivalylu 2-chloro-5-[γ-(2,4-di-7-
amylphenoxy)butyramide]acetanilide (Y-29) α-[4,5-dichloro-3(2H)-pyridazone-2
-yl)-a-benzoyl-2-chloro-5-[α-(
dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (Y-30) α-(l-phenyltetrazol-5-oxy)=,-
Valilu 2-chloro-5-[γ-(2,4-di-t-
amylphenoxy)butyramide]acetanilide (Y
-31) 4.4'-di(acetoacetamino)-3,3-dimethyldiphenylmethane (Y -32) p,p'-di(acetoacetamino)diphenylmethane Next, the aroma represented by the above general formula [IV] Typical specific examples of group primary amine developers are shown below.

(■-1) (IV-2) (IV-3) In the present invention, these developers can be used alone or in combination depending on the case.

The silver halide emulsion according to the present invention may be an internal latent image type direct positive emulsion or a normal negative emulsion, but is not limited thereto.

Tenon color emulsions that produce internal latent images directly are used for direct photography such as facial photographs. In the facial photography market, there is as much demand for black and white images as there is for color images; however, because ordinary silver images are currently used, it is not possible to use the same equipment or processing solution as for color images. On the other hand, according to the present invention, the above object can be achieved.

Methods used to create a positive image using a positive light-sensitive material directly using internal temperature can be mainly divided into two types, excluding special methods, in consideration of practical usefulness.

One type uses a silver halide emulsion that has been fogged in advance and obtains a positive image after development by destroying fog nuclei (latent images) in exposed areas by utilizing solarization, the Burschel effect, or the like.

Another type is to obtain a positive image by using a silver halide emulsion for an unfogged internal latent image and subjecting it to image exposure and then subjecting it to fogging treatment, or then surface development while carrying out fogging treatment.

The above-mentioned internal latent image type silver halide emulsion refers to a silver halide photographic emulsion which has photosensitive nuclei mainly inside the silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method is more sensitive than the former type - for boat fishing and is suitable for applications requiring high sensitivity, and it is with this latter type that the present invention relates.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250;
, 466.957, 2,497.875, 2,
No. 588.982, No. 3,761.266, No. 3,7
The main methods are those described in No. 61.276, No. 3,796.577, British Patent No. 1,151.363, etc., and when these methods are used, relatively high costs are achieved as a direct positive type. It is possible to make high-speed photographic materials.

Although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory of the Seven Autographic Processes'' by Mies and James ( The Theory
of the Photographic Process
ss) 3rd edition, p. 161, the process by which a positive image is formed can be understood to some extent by the ``desensitizing effect of an internal latent image.''

In other words, fog nuclei are selectively generated only on the surfaces of unexposed silver halide grains due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide grains by the first image exposure, and then It is believed that a photographic image is formed in the unexposed areas by normal development.

As a means for selectively generating fog nuclei as described above,
Two known methods are known: "chemical fogging," which uses chemicals such as fogging agents, and "optical fogging," which involves exposing the entire surface to light.

In internal latent image type direct positive emulsions, in order to maintain a low minimum density and improve whiteness, the above compound A may be used in addition to the commonly used color mixing inhibitor 2,5-di-t-octylhydroquinone. good. However, the present inventors have found that using an excessive amount of this compound is unfavorable from the viewpoint of image storage stability.

That is, it was discovered that the color balance is greatly disrupted and the neutrality is significantly deteriorated due to storage, leading to the present invention. That is, the amount added is 1O~80mg/m
'' is preferable; below this range, the whiteness will not be sufficient, and above this range, the bright and dark fading of the coloring dye will be significant.

In the present invention, negative emulsions refer to emulsions for color photographic paper, color negative films, color reversal films, color reversal papers, and the like.

In the present invention, an internal temperature type direct positive light-sensitive material and a negative tone light-sensitive material can be developed using a common processing solution. In other words, when the internal temperature type direct positive photosensitive material is carried into the processing tank,
If the internal temperature type direct positive photosensitive material is of the type that directly forms a positive surface image due to light fog, the entire surface is exposed to light, and when the negative tone sensitive material is carried into the processing tank, the entire surface is exposed to light. It is possible to use an automatic developing machine that can control the exposure of the entire surface so as to avoid exposure. If the internal temperature type direct positive photosensitive material is of the type that directly forms a positive image in the presence of a fogging agent, it is not necessary to expose the entire surface to light even when the direct positive photosensitive material is carried into the processing tank. do not have.

According to the present invention, positive and negative black and white images can be obtained using the same processor.

In the present invention, bleach-fixing treatment may be performed after the usual color processing, that is, color development, but even better results can be obtained by performing the fixing treatment used in ordinary black-and-white photography after color development. That is, the residual silver image further improves the neutrality of the image. Normally, when trying to construct a black and white image using only a color-forming coupler, the appearance becomes somewhat distorted depending on the viewing light source, but it has been found that this problem can be resolved by adding a silver image to this. It was also found that with regard to image storage stability, the addition of a silver image significantly reduces the loss of neutrality.

Supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper: transparent supports with a reflective layer or a reflector; glass plates: cellulose acetate, cellulose snitrate, polyethylene Examples include polyester films such as terephthalate; polyamide films; polycarbonate films; polystyrene films. These supports are appropriately selected depending on the purpose of use of the silver halide photographic material of the present invention.

Various coating methods such as dipping coating, F-doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and non-photosensitive layer used in the present invention.

The silver halide used in the silver halide emulsion according to the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Includes anything that These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of (100) planes to (111) planes can be used. Furthermore, even though the crystal structure of these silver halide grains is uniform from the inside to the outside,
The inside and outside may have a different layered structure. Further, these silver halides may be of a type that forms a latent image primarily on the surface, or may be of a type that forms a latent image inside the grain.

Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. Manufactured silver halide grains are also applicable.

The silver halide emulsion according to the present invention contains a sulfur sensitizer, such as arylthiocarbamide, thiourea, cystine, etc.
active or inactive selenium sensitizers and reduction sensitizers,
Noble metal sensitizers such as stannous salts, polyamines, etc., such as gold sensitizers, specifically potassium aurithiocyanate,
Potassium chloroaurate, 2-oresulfobenzothiazole methyl chloride, etc., or sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chloroparadate, and sodium chloroparadate. alone,
Alternatively, chemical sensitization can be achieved by using appropriate combinations. Further, the silver halide emulsion according to the present invention can contain various known photographic additives. For example, “Research Disclosure J December 1976, No. 1
7643.

There are various possible layer configurations for the light-sensitive material of the present invention, but all the couplers may be contained in a single emulsion layer, or they may be present separately in multiple emulsion layers having the same color sensitivity. You can. Since all the emulsions have the same color sensitivity, black and white images can be formed over the entire sensitive wavelength range.

The emulsion used in the present invention can be spectral sensitized by using various spectral sensitizing dyes alone or in combination depending on the purpose. For example, by using a panchromatic sensitizing dye and an ortho sensitizing dye together before and after the chemical sensitization, or by using a regular sensitizing dye in combination, it is possible to provide a spectral sensitivity depending on the application.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 710, No. 2,454.620, and the like.

The silver halide emulsion layer and non-photosensitive layer of the silver halide photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, color stain inhibitors, optical brighteners, antistatic agents, hardeners, plasticizers, wetting agents, ultraviolet absorbers, and the like described in Research Disclosure No. 17643 can be used as appropriate.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of internal temperature type direct positive emulsion A) A conversion type core emulsion was prepared as follows (emulsion-1)
. A 2 molar aqueous solution of silver nitrate (175■β) and a 2.1 molar aqueous solution of potassium chloride (175 Q) were simultaneously added over a period of 10 minutes to a solution containing 10 g of gelatin while controlling the temperature at 60°C, and physical ripening was performed for 10 minutes. Thereafter, 200 mff of a 2 molar potassium bromide aqueous solution was added, and physical ripening was further performed for 10 minutes. Next, after washing with water to remove water-soluble halides, 10g of gelatin was added and water was added to make a total volume of 500+
affi.

A silver chlorobromide emulsion with an average grain size of 0.3 μm was obtained (compositional analysis revealed that the silver bromide content was 96 mol %).

Core emulsion (emulsion-1) A silver chloride shell was precipitated by simultaneously adding 100 m<+ of a 2 molar aqueous solution of silver nitrate and 100 mff of a 2.1 molar aqueous solution of potassium chloride at 60°C at 60°C to 500 mff, and then washed with water. . A core/shell emulsion was obtained having an average grain size of 0.35 μI and a silver chloride shell content of 36 mol % based on the total amount of silver halide.

For emulsion A prepared as above, the following sensitizing dye GD
-1 and RD-1 were sequentially added to perform spectral sensitization, and emulsion A
-1.

RD-1 RD-1 Next, Y of the formulation shown in Table 1.

M.

03 color couplers and 2.5-di-t-octylhydroquinone 0.
5g.

Compound A 1.25g, dibutyl phthalate 30mff
was added to 30 mQ of ethyl acetate and dissolved at 60°C.

This solution was mixed with a 10% aqueous solution of alkanol xC (sodium alkylnaphthalene sulfonate, manufactured by DuPont).
It was mixed with mQ and 700 ml of a 5% gelatin aqueous solution and emulsified using an ultrasonic homogenizer to obtain respective dispersions.

Next, the emulsion A-1 and the coupler dispersion were mixed and additives were added to prepare a coating solution for a photosensitive emulsion layer.

Separately, a coating solution containing the ultraviolet absorber UV-1 for the first protective layer and a coating solution mainly consisting of gelatin for the second protective layer were prepared, and both sides of a base paper with a basis weight of 160 g/m'' were coated with polyethylene resin. Simultaneous coating, drying, and incubation were performed on the coated support to obtain samples 1 to 4 as shown in Table 1 with the following layer configurations.

(Layer structure) The amount added indicates the amount added per 1+a''.

Layer 1: Photosensitive emulsion layer With sensitizing dyes GD-1 and RD-1 Spectrally sensitized emulsion A-1 (Converted to silver) coupler 2.5-di-t-octylhide Compound A gelatin Layer 2: First protective layer Ultraviolet absorber (UV-1) gelatin Layer 3: Second protective layer gelatin In addition, coating aid and 2 and hardener H-1 were used.

-1 and surfactant S-1, S- 1.0g Shown in Table 1 Rokinone 12+og 0mg 2.5g 0.5g 1.5g 2.0g C2H.

■ NaO, S-CHCOOCH, CHC, H.

CHICOOCHzCHC<It C,H.

NaO, 5-CHCOOCH, (CF, CF-2H-1Na) Using the samples obtained above and shown in Table 1, samples were prepared by exposing them to light through a wedge for sensitometric performance evaluation.

Each sample was developed under the following processing conditions.

Treatment process (1) Temperature Time (1)
Immersion (color developer) 38°0 8 seconds [2] Fog exposure -1/Rex [3] Color developer [4] Bleach [5] Stabilization Asahi [6] Drying processing solution composition is as follows [Color developer] Benzyl alcohol cerium sulfate 10 seconds at 38°C 2 minutes at 35°C 60 seconds at 25-30°C 1 minute and 30 seconds at 75-80°C for 1 minute.

15 ■a 0.015g ethylene glycol potassium sulfite potassium bromide sodium chloride potassium carbonate T-4 hydroxylamine sulfate diethylenetriaminepentaacetic acid sodium Developing agent (IV-1) Developing agent (IV-2) Optical brightener (4,4'-diamino pendisulfonic acid derivative) potassium hydroxide diethylene glycol Add water and make the total amount IQ, Ru.

[Bleach-fix solution]

Ferric ammonium diethylenetriaminepentaacetate 1.0 g 2.0 g 15 mQ Adjust to pH 10,15 2 g O,6X 10-"mol 0.9X 10-"mol Stil 8 Food Q 2.5g 0.6g 0.2g 25. 0 g 0.1 g 5.0 g 0 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% solution) 180 m (1 Ammonium sulfite (40% solution) 27, 5 mf
f3-mercapto-1,2,4-triazole 0
．． Add 15 g of water to bring the total volume to 1Q, and adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid] 0-Phenylphenol 0.3g Potassium sulfite (50% solution) 12 Iris a ethylene glycol 10 gl-Hydroxyethylidene-1,1-diphosphonic acid 2.5g Bismuth chloride 0.2g Zinc sulfate heptahydrate 0 .7g ammonium hydroxide (28% aqueous solution) 2.0g polyvinylpyrrolidone (K-17) 0.2g optical brightener (4,
4'-Diaminostilbendisulfonic acid derivative) 2g Add water to bring the total amount to 1Q, and adjust the pH to 7.5 with ammonium hydroxide or sulfuric acid.

Processing step (2) Processing step (2) was performed under exactly the same processing conditions as processing step (1), except that the bleach-fix solution in processing step (1) was changed to a fixer with the following composition. .

[Fixer] Ammonium thiosulfate 90 g Ammonium sulfite 12.4 g Sodium metabisulfite 4 g Add water and adjust the total amount to IQ
and adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.

Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration.

The treated samples were stored for one week under irradiation with a xenon lamp, and changes in yellow, magenta and cyan dye concentrations were measured using a spectral reflection densitometer PDA-65 (manufactured by Konica).

The results are shown in Table 1.

Regarding the obtained image, the apparent sensitivity difference at a density point of 0.2 was evaluated using a mid-density gamma balance due to the green radiant density and a mid-density gamma due to the blue reflection density.

In addition, facial photographs were taken directly using the photosensitive material, and neutrality in highlighted areas was evaluated through practical skill.

At the same time, image storage stability was also evaluated based on light storage stability and dark storage stability.

<Light storage stability> Using a xenon fetometer, the dye image was exposed to light at 45,000 lux for 150 hours, and then the residual density at an initial density of 1.0 was measured.

<Dark storage stability> After storage for 2 weeks at 77°C in the dark, the initial concentration was 1.0.Comparative coupler MC-1 Ca Comparative coupler MC-2 Q Ca Comparative coupler MC~3 As shown in Table I As compared to bleach-fixing, fixing improves black background under fluorescent lighting, etc.
There is little difference in neutrality due to differences in observation light sources,
It is also found that the image storage property is excellent.

Example 2 Samples 5 to 16 were prepared in the same manner as in Example 1 by changing the composition of cyan coupler and magenta coupler as shown in Table 2.
was created and subjected to the same process as the geographical step (2) of Example 1 together with the sample created in Example 1, and the rality of the highlighted area was evaluated by sensitometry and direct photography. Furthermore, image storage stability was evaluated from light storage stability and dark storage stability. Comparison coupler CC-1 CQ Comparison coupler CC-2 Cα As is clear from Table 2, according to the present invention, the highlight part neutrality is good, It can also be seen that image formation with good image storage stability can be obtained.

Example 3 Samples 17 to 24 were prepared in the same manner as in Example 1, except that Compound A in Sample 4 was changed. Furthermore, sample 4 is prepared as follows.
A sample was prepared in which the coating amount ratio of the coupler was the same as that of the sample, only the Y coupler was dispersed in a separate layer, and another Y coupler layer was provided using the same emulsion as that used for the MC coupler layer.
It was designated as sample 25.

(Layer structure of sample 25) Addition amount is per 1m'' shows.

Layer 1: Y coupler layer With sensitizing dyes GD-1 and RD-1 Spectrally sensitized emulsion A-1 (Converted to silver) Y coupler (Y-19) 2.5-di-t-octylhydroquinone 0.36g 0.45g 0.45mg Zelagoon Layer 2 layer M coupler layer With sensitizing dyes GD-1 and RD-1 Spectrally sensitized emulsion A-1 (Converted to silver) M coupler (III-1) C coupler (n-20) C coupler (I-2) Compound A gelatin Layer 32 layer 4 is 0.64g 0.27g 0.12g 0.24g 0B 1.6g Layer 21 layer 3 and layer 3 of Example 1, respectively. 1.0g The same.

The same treatment as in treatment step (2) of Example 1 was performed, and the sensitometry and light resistance of the Y coupler were evaluated.

The test conditions were the same as in Example 2.

As seen in Table 3, the coating amount of compound A was foam/l.
If it is less than 112, the minimum density increases significantly and is not preferable for white backgrounds. Moreover, if it exceeds 80 mg/m2, the light resistance of the Y coupler will be poor and the neutral balance will be disrupted during image storage.

On the other hand, it can be seen that when the Y coupler is formed in a separate layer, the Y light resistance is further improved.

Example 4 The same spectral sensitizing dye as in Example 1 was used, the emulsion was changed directly to a positive emulsion, and a silver chlorobromide negative emulsion containing 80 mol% silver bromide was used, except that Compound A was not used. A sample was prepared in the same manner as in Example 1. Next, processing was carried out in the same manner as in Example 1 except that fog exposure was not performed, and the same evaluation as in Example 1 was performed, and the same results were obtained.

Example 5 Next, sample 4 of Example 1 was processed by changing only the developing agent in the color developer of Example 1 (the number of moles added was the same),
Sensitometry was performed.

Table 4 shows the types of developing agents and the minimum and maximum concentrations determined by sensitometry.

This comparative developer DC-1 N.H.

C-2 As shown in Table 4, according to the present invention, the minimum concentration is low;
It can be seen that images with high maximum density and excellent neutrality are formed.

Claims (8)

[Claims] (1) At least one silver halide emulsion layer in which all emulsion layers have the same color sensitivity and at least one cyan coupler, magenta coupler, and yellow coupler are placed in the same emulsion layer or in another layer having the same color sensitivity. Formation of a black and white image characterized in that a silver halide photographic light-sensitive material contained in an emulsion layer is processed with a color developer containing an aromatic primary amine developer and then processed with a fixer having no bleaching ability. Method. (2) A photosensitive material in which the three color couplers are mixed and dispersed and added to a single emulsion layer is formed on a reflective support and processed with a developer containing an aromatic primary amine developer. After that, in the bleach-fixing process, sensitometry was performed to measure the red reflection density, green reflection density, and blue reflection density, and the compounding ratio of couplers was adjusted so that the gamma balance in the mid-density area was equal. 2. The black-and-white image according to claim 1, wherein the black-and-white image is composed of a group of couplers such that the apparent sensitivity difference expressed in logarithm at a density point of 0.2 among the three colors is within 0.02. How to form. (3) The cyan coupler and the magenta coupler are a cyan coupler represented by the following general formula [I] and/or a general formula [II], and a magenta coupler represented by the following general formula [III], respectively. Image forming method. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an alkyl group or an aryl group. R
_2 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. R_3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. Moreover, R_3 may form a ring together with R_1. Z_1 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine developer. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_4 represents a palust group, and R_5 represents an alkyl group. Z_2 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine developer. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc.
Represents a heterocyclic group, substituted oxy group or amino group. ] (4) The aromatic primary amine developer has the following general formula [I
4. The image forming method according to claim 3, which is a compound represented by V]. General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. . ] (5) The image forming method according to claim 1, wherein the silver halide emulsion is an internal latent image type direct positive emulsion. (6) The image forming method according to claim 4, wherein the silver halide emulsion layer and/or the adjacent layer contains 10 to 80 mg/m^2 of the following compound A. Compound A ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (7) The image forming method according to claim 1, wherein the silver halide emulsion is a negative emulsion. (8) The image forming method according to claim 1, wherein a black and white negative image using a negative emulsion and a black and white positive image using a positive emulsion can be obtained with the same processing solution.