JPS62178250A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent color forming fogging and color clouding in the stage of color forming development by incorporating a specific compd. into >=1 layers of photographic constituting layers and executing a color forming development stage in the presence of the specific compd. CONSTITUTION:The compd. expressed by the formula I is incorporated into at least one layer of the photographic constituting layers and the color development stage is executed in the presence of at least one compd. selected from the compds. expressed by the formula II-formula V. In the formula I, R1, R2: an alkyl group, n: 1-20 integer, k: 1 or 2, A: CO-X-R3, etc., X: -O- or NR4-, R4: H, alkyl group, etc. B: an alkyl group, etc. In the formula II, R5: a halogen atom, alkyl group, etc., n1: 0-4 integer, in the formula III, R6, R7: H, R8: a halogen atom, alkyl group, etc., n2: 0-4 integer. In the formula IV, X: H, etc., R9: an aryl group, R10-R13: an alkyl group, etc. In the formula V, Y: S, O.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials.
More specifically, the present invention relates to a silver halide photographic light-sensitive material that has improved developability, excellent photographic performance such as sensitivity and maximum density, and less color fog.

[Background of the Invention] In general, silver halide color photographic light-sensitive materials consist of three types of silver halide color photographs that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is coated.

For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes.

Furthermore, for example, in light-sensitive materials for color photographic paper, the layers are generally coated in the order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer from the exposed side, and each layer has a special coating, similar to the light-sensitive material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with a dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5
- Pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyanoacetyl magenta couplers and acylacetamide or benzoylmethane yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. The present invention relates to a silver halide photographic material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, various measures have been taken to speed up color development. As one method, it is known to use a development accelerator when developing an exposed silver halide color photographic light-sensitive material using an aromatic primary amine color developing agent. Among such development accelerators, compounds with relatively high activity often have the disadvantage of forming fog. However, among these compounds, certain black-and-white developing agents exhibiting superadditivity in color development can provide a development accelerating effect with relatively low fog generation compared to other development accelerators. Examples of such black and white developing agents include British Patent 811,1
1-phenyl-3-pyrazolidone described in No. 85, N-methyl-p-aminophenol described in U.S. Pat. No. 2,417,514, N5NS described in JP-A-50-15554.
Examples include N', N'-tetramethyl-p-phenylenediamine. Regarding the mechanism of superadditive development in color development, see G. F. Van Veele.
Journal of the Photographic Science, No. 20, p. 94 (1972). There are two ways to obtain the effect of promoting color development using such a black and white developing agent as an auxiliary developer: one is to include it in advance in a silver halide color photographic light-sensitive material, and the other is to include it in a color developer. There is.

Among these, 1-aryl-3-pyrazolidones are particularly preferably used when the black-and-white developing agent is included in a silver halide photographic material to promote color development. For example, JP-A-56-89739 discloses that a silver halide color photographic light-sensitive material having silver halide emulsion layers having silver halide grain size ratios different by 50% or more on a support has 1-aryl-3- The addition of pyrazolidones is disclosed. However, the silver halide color photographic light-sensitive material containing 1-aryl-3-pyrazolidone disclosed in this publication is used for intensification treatment in the presence of an intensifier such as a cobalt complex salt. Therefore, when processed for ordinary color development, its development promotion effect is extremely insufficient, especially when ordinary color development is carried out using a silver halide emulsion with a large average grain size. It was found that almost no effect of promoting color development could be obtained.

Furthermore, JP-A-56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and further describes a method for adding a 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic material.
No. 57-144547, No. 58-50532, No. 5B
-50533, 58-50534, 58-50
No. 535 and No. 58-50532 disclose that 1-aryl-3-pyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short development time. .

However, although each of the techniques described in these publications may be satisfactory in terms of simply obtaining the effect of accelerating development, it is not necessarily satisfactory when photographic performance such as sensitivity, gradation, and maximum density are taken into consideration comprehensively. It is hard to say that it was.

Furthermore, when color development is performed using such a development acceleration technique, there is another problem in that color fogging and color turbidity are likely to occur.

Conventionally, it has been well known that certain hydroquinone derivatives are used to prevent color fogging and color turbidity. However, when these hydroquinone derivatives are added in order to prevent color development, although it is effective against color fog, it has an effect on photographic performance such as a decrease in sensitivity and maximum density.

Furthermore, when color development is carried out in the presence of the above-mentioned publication, the effect is particularly small, and it is currently desired to reduce color fog and improve color turbidity in rapid development processing.

[Objective of the Invention] The object of the present invention is to provide a rapid color development process that has good photographic performance such as sensitivity and maximum density, has significantly less color fog and color turbidity during color development, and accelerates color development. It is an object of the present invention to provide a method for processing silver halide photosensitive materials suitable for. Furthermore, the purpose of the pond will become clear from the description below.

[Structure of the Invention] The above object of the present invention is to provide a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer J5 containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and A method for processing a silver halide photographic material, which comprises the steps of substituting exposure and color development of a silver halide photographic material having a photographic constituent layer composed of a non-light-sensitive layer, wherein at least one of the photographic constituent layers is contains a compound represented by the following general formula [I], and the color developing step is a compound selected from the following general formulas [I[], [III], [IV] and [VI]. This is achieved by a method for processing a silver halide photographic material, which is characterized in that it is carried out in the presence of at least one.

General formula [I] [wherein R1 and R2 each represent an alkyl group having 1 to 5 carbon atoms, n represents an integer of 1 to 20, and k is 1
or 2. A represents a hydrogen atom, R3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and R4 represents a hydrogen atom, an alkyl group, or an aryl group. ) , -0Y (where Y is R3
Represents Masoichi〇-R3, where R3 has the same meaning as above. ), R3, R3 has the same meaning as above, R6 is a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, alkenyl group or aryl group. ) or cyan group.

B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group or the like, and R1, R2, nl and A each have the same meanings as above. ). J represents an alkyl group, R1 and R2a and/or R3
and R4 combine with each other and together with the nitrogen atom, it has the same meaning as gold fertilizer. )
represents. ] A nitrogen heterocycle may be formed. R5 is a halogen atom,
represents an alkyl group or an alkoxy group, nl is 0 to 4
represents an integer. When nl is an integer of 2 to 4, R5 may be the same or different. ) General formula [I[1] OH In the formula, R6 and R7 each represent a hydrogen atom or an alkyl group, and R6 and R7 may be bonded to each other to form a nitrogen-containing heterocycle. R8 represents a halogen atom, an alkyl group or an alkoxy group, and R2 represents an integer of O to 4. When R2 is an integer of 2 to 4, R8 may be the same or different. ) 几9 (In the formula, X represents a hydrogen atom or a hydrolyzable group, R9 represents an aryl group, R'10 sR+1, R
+2 and R13 each represent a hydrogen atom, an alkyl group or an aryl group, ) General formula [V] (wherein A and B each represent a secondary amine group bonded to the carbon atom of the mother nucleus through a nitrogen atom, , Y represents a sulfur atom or an oxygen atom.) [Specific structure of the invention] In the general formula [D], the alkyl group having 1 to 5 carbon atoms represented by R1 and R2 includes, for example, a methyl group, an ethyl group, Examples include n-propyl group, i-propyl group, n-butyl group, S-butyl group, n-pentyl group, and neopentyl group. n represents an integer of 1 to 20, preferably an integer of 2 to 15; k represents 1 or 2;

I A Bar C-X -R3 (where X is 10- or -
represents N-, R3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group;
4 represents a hydrogen atom, an alkyl group or an aryl group.

), -0Y (where, Y represents R3 or -C, -Ra, R3 represents the same as above ○ -C-R3, R3 has the same meaning as above.), ○R3, and R3 has the same meaning as above. , R6 is a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, alkenyl group or aryl group. ) or a cyano group.

B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a group represented by -C-CVtR2←A)k (
Here, R+, R2, n, and A each have the same meanings as above. ), an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group represented by R3, an alkyl group, an aryl group represented by R4, an alkyl group, an aryl group represented by R5, an alkyl group represented by R6,
The cycloalkyl group, alkenyl group, aryl group, and the alkyl group, alkenyl group, cycloalkyl group, aryl group, and heterocyclic group represented by B include those each having a substituent. , for example, a halogen atom, a cycloalkyl group, an alkenyl group,
Examples include aryl groups, alkoxy groups, aryloxy groups, acyl groups, heterocyclic groups, cyan groups, etc. Substituents for the above alkenyl groups, cycloalkyl groups, aryl groups, and heterocyclic groups include, for example, halogen atoms, alkyl groups, etc. , cycloalkyl group, alkenyl group, aryl group, alkoxy group,
Examples include an aryloxy group, an acyl group, a heterocyclic group, and a cyano group.

Examples of the alkyl group represented by R3, R4, R5, R6 and B include methyl group, ethyl group, n-propyl group, n-butyl group, S-bugyl group, rhohexyl group, 2
-ethyl-hexyl group, n-dodecyl group, n-hexadecyl group, benzyl group, etc., R3, R4, Rs
, Rs and B include, for example, a furyl group, and examples of the cycloalkyl group represented by R3, R6 and B include cyclo,
Examples of the aryl group represented by R3, R, R5, R6 and B include a hexyl group, and a phenyl group and a naphthyl group.

The compound represented by the general formula [1,] is preferably a compound represented by the following general formula [I-1] or a precursor thereof.

General formula [I-1] [wherein R+, R2, Ra, X and n are represented by general formula [I-1]
It has the same meaning as R1, R2, R3, XJ5 and n in [I].

Hereinafter, specific examples of the compound represented by the general formula [I] used in the present invention will be shown, but the present invention is not limited thereto.

Margin below H(1) H(2) To I(3) 1″13 H(4) H(5) H(6) H H(8) H(9) '-7zl'ls CM
Col1(10) H(11) H(12) H(14) II(15) 1((1G) Regarding the compound represented by the general formula [I],
Basically, the compounds described in JP-A-58-24141 are included, and the synthesis methods described therein can be referred to.

The compound represented by the general formula [I] according to the present invention can be used in the photographic constituent layers of a silver halide photographic light-sensitive material, that is, each silver halide emulsion layer containing a yellow, magenta or cyan coupler, and a non-photosensitive layer. (For example, the middle class,
It can be contained in any layer selected from sublayers, filter layers, etc.), and the amount added is not particularly limited, but
Preferably 1 X 10-6 to I X 10-2 mol/
It is 12. The compounds represented by the general formula [I] according to the present invention may be used alone or in combination of two or more.

In the general formula [I[], the alkyl group represented by R1, R2, R3, and R4 may be linear or branched, and is preferably an alkyl group having 1 to 4 carbon atoms, and this alkyl group is a substituent. Substituents include, for example, hydroxy groups, alkoxy groups (e.g. methoxy groups, ethoxy groups, etc.), sulfonamide groups (e.g. alkylsulfonamide groups such as methanesulfonamide groups,
Examples include arylsulfonamide groups such as benzenesulfonamide groups), tetraaryl groups (eg, phenyl groups), and the like. Examples of the alkyl group represented by R1, R2, R3 and R4 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 5et-butyl group, hydroxymethyl group, β-hydroxy Methyl group, β
-methoxyethyl group, methanesulfonamidoethyl group, etc. The nitrogen-containing heterocyclic nucleus formed by R1 and R2 and/or R3 and R4 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, etc. I can do it.

Examples of the halogen atom represented by R5 in general formula [I] include a bromine atom and a chlorine atom, examples of an alkyl group include a methyl group and an ethyl group, and examples of an alkoxy group include a methoxy group. , ethoxy group, etc. The alkyl group and alkoxy group represented by R5 include those having a substituent.

Specific examples of the compound represented by the general formula [II] used in the present invention are shown below, but the present invention is not limited thereto.

Below margin 11-1 n-21
1-3ll-4 ()83 CR3 and-13 These compounds, except for some, are known (for example, described in JP-A-50-15554, JP-A-58-120248, etc.). ), can be easily synthesized by those skilled in the art. The synthesis of these compounds is described, for example, in [Bent, Deslotsch, Fassett, James, Laby, Sterner, Pittam, Peaceberger; Journal of the American Chemical Society, (Be
nt, Dessloch.

Fassett, Jan+es, Ruby, 5
terner, Vittum.

Weissberqer: J, Am, Che
n+, Soc, )] Ldan, 3100 (19
51) and [Bent, Brown, Gressmanes, Harnisch; Photo Science Engineering, Bent
, Brovn.

Glesmaness, Harnish; ph
ot, SCi.

Ena, ]) 8. 125 (1964) etc.

In the general formula [I [[], the alkyl group represented by R6 and R7 may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, and these alkyl groups have a substituent. Examples of substituents include hydroxy groups, alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), sulfonamide groups (e.g., alkylsulfonamide groups such as methanesulfonamide groups, and arylsulfonamide groups such as benzenesulfonamide groups). ) etc. Examples of the alkyl group represented by R6 and R7 include methyl group, ethyl group, butyl group, hexyl group, hydroxymethyl group, β-hydroxyethyl group, methoxymethyl group, β-methanesulfonamidoethyl group, etc. . The nitrogen-containing heterocyclic nucleus formed by R6 and R7 may contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atom represented by R8 include a bromine atom and a chlorine atom, examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxy group include a methoxy group and an ethoxy group. It will be done.

The alkyl group and alkoxy group represented by R8 include those having a substituent.

When n2 is 2 to 4, R8 may be the same or different.

Specific examples of the compound represented by the general formula [■] used in the present invention are shown below, but the present invention is not limited thereto.

Below is the margin, lll-1m-2 M-3, [-4 11[-511-6 m-71-8 DI -1111[-12 H ]I[-15m-16 A17 II-18 These compounds are, for example U.S. Patent No. 2.286.678, U.S. Patent No. 2.483.374, U.S. Patent No. 2.776, 313
No. 3, No. 060.225, British Patent No. 928.6
Specification No. 71, Berichte der Deutschen Chemischen Gesellschaft, Volume 16, Page 724 (Ber
ichte der Deutschen Chemi
schen Ge5ellschaft) Same magazine tube 34
Volume 2, 125 pages, Chemisier Berichte Volume 92, No. 3
, 223 pages (Chemische Berichte
), Photographic Science and Engineering Vol. 12, p. 41 (Photoarap
hicScience and Il:nginee
ring) and Journal of the Chemical Society Vol. 1947, p. 182 (Journal
of the Chemical 5ociet
It can be synthesized according to the method described in y) etc.

In the general formula [rV], X represents a hydrogen atom or a hydrolyzable group, and the hydrolyzable group represented by X is preferably an acetyl group. X is preferably a hydrogen atom.

Examples of the aryl group represented by R9 in the general formula [IV] include phenyl group and naphthyl group, with phenyl group being preferred. This aryl group includes those having substituents, such as alkyl groups (
For example, methyl group, ethyl group, propyl group, etc.), halogen atom (chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, etc.), sulfonyl group, amide group (methylamide group, ethylamide group, etc.), etc. be able to.

Rhos Rt+ , R+2 and R of general formula [IV]
The alkyl group represented by +3 preferably includes an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.). This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amino group, and an acyloxy group. Further, examples of the aryl group of RlolRll, RI2 and R+3 include a phenyl group and a naphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group, ethyl group,
(propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy groups (methoxy group, ethoxy group, etc.), and hydroxyl groups.

Typical specific examples of the compound represented by the general formula [IV] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

Below margin CR3CH3 γ-19$7-20 1f-21Iv-22 y-23'rv''-24 Hs ff-2511r-26 ff-2711-28 Eng γ-29W-30 111r-31B'-32 Eng 1- 33[-34 1γ-35γ-36 w-37W-38 R3 t if-45Ir-46 Compounds represented by the general formula [IV] are commercially available, but US Pat. No. 2.688.024 , same 2
, 704,762, JP-A-56-64339, and JP-A-57-211147.

In the general formula [V], the secondary amino group bonded to the carbon atom of the mother nucleus represented by A and B through the nitrogen atom can contain various aliphatic or aromatic components, and A and B are the same as each other. may be different.

The above A and B are specifically -NH-R+4 and -N
Each can be expressed as H−Rts, where R++
and R15 are each an aliphatic group or an aromatic group, and R++ and R15 are preferably electron-donating groups.

Specific examples of the groups represented by R+4 and R15 include alkyl groups, alkenyl groups, and aryl groups, and these alkyl groups, alkenyl groups, and aryl groups also include those having substituents.

Examples of these substituents include alkoxy groups (eg, methoxy group, ethoxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.), and the like. R1, 1 and 1 (15 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a me-1-xymethyl group, a β-me1-xyethyl group, a β-ethyl-1-xyethyl group, a methylthioethyl group,
Examples include ethyldiomedyl group, allyl group, phenyl group, methoxyphenyl group, ethoxyphenyl group, methylthiophenyl group, and ethylthiophenyl group.

Specific examples of compounds represented by the general formula [VJ used in the present invention are shown below, but the present invention is not limited thereto.

V-12,5-bis(methylamine)-1゜3.4-deadiazole■-22-methylamino-5-ethylamino-1,3,
4-thiadiazole V-32,5-bis(ethylamino)-1°3.4-thiadiazole V-42,5-bis(n-butylamino)-1,3,4
-deadiazole v-52-allylamino-5-methylamino-1,3,
4-Thiadiazole V-62-(2-ethoxyethylamino)-5-methylamino-1,3,4- Thiadiazole V-72,5-bis(phenylamino)-1,3,4-
Thiadiazole V-82,5-bis(2-methoxyethylamino)-1
,3,4-thiadiazole V-92-(2-ethoxyethylamino)-5-(2-
methoxyethylamino) -1,3,4-thiadiazole V-102,5-bis(2-ethoxyethylamino)-
1,3,4-thiadiazole V-112-(2-methoxyethylamino)-5-phenylamino-1,3,4-thiadiazole V-122-(1)-methoxyphenylamino)-5-
(2-Methoxyethylamino)-1,3,4-thiadiazole V-132-(3-methylthiopropylamino')-5
-(2-Methoxyethylamino)-1,3,4-thiadiazole V-142,5-bis(butylamino)-1゜3.4-
Oxadiazole V-152,5-bis(ethylamino)-1゜3.4-
Oxadiazole An example of a method for producing a diazole compound represented by the above general formula [VJ] is described in Japanese Patent Application Laid-Open No. 53-61334 [B.C., Guha, Journal of the American Chemical Society, (P.C.

Guha, Journal of Ameri
can Chemical Society, ) ]
45, p, 1036 (1928), and [
Journal of Mechanism, Physical Chemistry, Jo
Urnal or Medical Chemistry
stry, vol, )] 15, No, 3. o,
315 (1972), etc.

In the present invention, general formulas [111, [III], [I
Color development is carried out in the presence of a compound represented by V] or [Vl, but the presence here means that it is present at the time of color development, and the compound is contained in the silver halide color light-sensitive material in advance. Alternatively, it may be included in the color developing solution in advance. Furthermore, it may be included in advance in both the silver halide photosensitive material and the color developing solution.

The general formula [I], [II[], [TV] or [VJ
When adding a compound represented by the formula to a silver halide color light-sensitive material, the amount added varies widely depending on the halogen composition of the silver halide emulsion, the amount of silver, etc.
The amount is approximately o,ooi mole to 1 mole per mole, preferably 0.002 mole to 0.02 mole. In addition, when there are two or more photosensitive silver halide emulsion layers, it is generally contained within the range of 2 X 10-5 mol to 2 X 10-3 mol, preferably 5 X 10-5 mol to 5 X 10-3 mol, per 112. be able to.

The compound represented by the general formula [n], [III], [■ or [VJ] can be used in any layer constituting a silver halide color photographic light-sensitive material such as each light-sensitive emulsion layer, subbing layer, intermediate layer, protective layer, etc. It may be added to the undercoat layer, the lowest layer in contact with the undercoat layer (R is also the layer closest to the support side), or the lowest layer of each light-sensitive emulsion layer (the emulsion layer closest to the support side). ) is preferably added.

In order to add the compound represented by the general formula [I[], [III], [IV] or [V] of the present invention to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, the photographic constituent layer is directly dispersed in the forming hydrophilic colloid solution, or
Alternatively, it may be added to the hydrophilic colloid solution after being dissolved in one or a mixture of two or more suitable solvents such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, ethyl acetate, etc. . For example, after dissolving in one or a mixed solvent of two or more high boiling point organic solvents such as dibutyl phthalate, dioctyl phthalate, dimethyl phthalate, tri-cresyl phosphate, trioctyl phosphate, etc., it is added to a hydrophilic colloid solution. It may be emulsified and dispersed. Furthermore, when this compound is added to the photosensitive silver halide emulsion layer, this compound can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution.

The general formula of the present invention [■, [III], [IV] or [
The timing of adding the compound represented by V] to the coating solution is as follows:
This compound may be added to the photosensitive silver halide emulsion layer at any time after the preparation of the photosensitive silver halide emulsion. When the photosensitive silver halide emulsion is a surface latent image type emulsion that mainly forms a latent image on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. Further, when the photosensitive silver halide emulsion is an internal latent image type emulsion that mainly forms latent images inside the grains, it may be carried out at any time after the silver halide emulsion has been prepared and optically sensitized. Further, general formula [I], [III], [IV] or [
The compound represented by V] may be added to the non-photosensitive emulsion layer at any time before coating this emulsion layer, but it is preferably added immediately before coating.

Furthermore, the general formulas [I[], [1[[] used in the present invention
, [■] or [V] is added to the color developer in an amount equal to 1! of the color developer. ;1-500II1g per liter, more preferably 10-30
It is in the range of 0 mg.

In order to add the compound represented by the general formula [I], [11, [IV] or [V] used in the present invention to the color developing solution, for example, methanol, ethanol, isopropanol, acetone, dimethylformamide, etc. It may be added to the color developer after being dissolved in one or a mixture of two or more suitable solvents.

The silver halide photographic light-sensitive material used in the present invention can be applied to any type of photographic light-sensitive material, such as color negative and positive films, and color photographic paper, but is especially suitable for direct viewing. The effects of the method of the present invention are effectively exhibited when used as color photographic paper.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers, and a non-light-sensitive layer are usually used. Although it has a structure in which layers are laminated on a support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and the purpose of use.

The specific structure of the silver halide photographic light-sensitive material used in the present invention includes a subbing layer, a yellow dye image-forming layer, an intermediate layer, a magenta dye image-forming layer, and an intermediate layer formed on the support in order from the support side. , cyan dye image forming layer, intermediate layer,
Preferably, it is arranged with a protective layer.

The silver halide emulsion used in the present invention includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Although silver chlorobromide emulsions can be used, silver chlorobromide emulsions are preferred.

The silver halide grains used in the present invention may be obtained by any of the acid method, neutral method, and ammonia method.

The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
It may be produced by controlling H and pAa and adding them sequentially or simultaneously. After growth, a conversion method may be used to change the silver halide composition of the grains.

When producing the silver halide emulsion used in the present invention, by using a silver halide solvent as necessary, the grain size, grain shape, grain size distribution of silver halide grains,
The growth rate of particles can be controlled.

The silver halide grains used in the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron salt or complex salt in the process of forming and/or growing the grain. Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be added to the inside of the particles and/or on the surface of the particles. I can do it.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure 1764.
This can be done based on the method described in No. 3.

The silver halide grains used in the present invention may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The silver halide grains used in the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, [1
, 0, 0] plane and the [1, 1, 1] plane, any ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion used in the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion used in the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion used in the present invention may be used during chemical ripening and/or to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. At the end of ripening and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the binder (or protective colloid) for the silver halide emulsion used in the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as cellulose derivatives, single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material used in the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Filmed. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material used in the present invention.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer is added to the photographic emulsion layer and other hydrophilic colloids 1 of the photosensitive material using the silver halide emulsion used in the present invention for the purpose of improving dimensional stability. It can be included.

In the emulsion layer of the silver halide photographic light-sensitive material used in the present invention, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine rust conductor) in the color development process. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in the blue light-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), magenta dye-forming couplers include azole couplers, 5-pyrazolone couplers, open-chain acylacetonitrile couplers, and cyan dyes. Forming couplers include naphthol couplers,
and phenol couplers.

Among the yellow couplers, those represented by the general formula [A] are preferred.

General formula (A) In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction.

R1 is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially t-butyl group), and R2 is an aryl group (preferably phenyl group)
The alkyl group and aryl group represented by R1 and R2 include those having substituents, and the aryl group of R2 is preferably substituted with a halogen atom, an alkyl group, etc. X is the following general formula (8) or (C
) are preferable, and among general formula (B), groups represented by general formula (B') are particularly preferable.

General Formula (B) In the formula, Zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (C) -O-R++ In the formula, Ra1 represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula (B') the law of nature Represents a group of nonmetallic atoms consisting of:

A preferred yellow coupler according to the present invention in the general formula (A) is represented by the following formula -82 (A').

General Formula (A') In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable.

R15, Rls, and R17 are a water atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, and an acylamido group, respectively. , represents a ureido group or an amino group, R+s and R+s are each a hydrogen atom, and R17 is preferably an alkoxycarbonyl or an alkylsulfonamide group. ·Also,
X represents a group having the same meaning as that represented by the above general formula (Δ), preferably the above general formula (B) or (C), or more preferably the above general formula (B') among (B).
Examples include groups represented by:

Specific examples of yellow couplers preferably used in the present invention are not shown below, but the present invention is not limited thereto.

Below margin (y-i) (Y-2) (Y-3) Connected H3 (Y-7) 1”/ (Y-8) (Y-9) (Y-10) (Y-11)
(CH20C2H6 (Y-12) t Y-13) Y-14) Description of yellow-forming couplers that can be used = No. 1031, No. 47-26133, No. 48-94432, No. 5G-87650, No. 51-
No. 3631, No. 52-1152194, No. 54-994
No. 33, No. 54-133329, No. 56-30127
No. 2,875,057, U.S. Patent No. 3,253.
No. 924, No. 3,265,506, No. 3,408,1
No. 94, No. 3,551,155, No. 3,551.15
No. 6, No. 3,664,841, No. 3,725,07
No. 2, @3, No. 730.722, No. 3,891,44
No. 5, No. 3.900.483, No. 3,929,48
No. 4, No. 3.933.500, No. 3,973,968
No. 3,990,896, No. 4,012,259, No. 4,022.620, No. 4,029,508, No. 4.057.432, No. 4.106,942
No. 4,133,958, No. 4,269,93
No. 6, No. 4,286,053, No. 4,304,845
No. 4,314,023, No. 4,336,327, No. 4,356,258, No. 4.3861155,
Those described in No. 4,401,752 and the like can be used.

In the silver halide photographic light-sensitive material used in the present invention, the magenta dye image-forming coupler has the following general formula [
Couplers represented by [a] and [aI] can be preferably used.

General formula [a] Ar [wherein, Ar represents an aryl group, Rt + represents a hydrogen atom or a substituent, R2L2 represents a substituent, Y represents a hydrogen atom or a reaction with an oxidized product of a color developing agent W is -NH-1-Nl-IC
It represents O- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONI-1-, and ■ is an integer of 1 or 2. ] Below is a specific example of the blank [a] m-40,/-t General formula [aI] In the magenta coupler represented by the general formula [aI], Zt is a nonmetal necessary to form a nitrogen-containing heterocycle. represents an atomic group, and the Z
The ring formed by N 2 may have an M substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Further, R2 represents a hydrogen atom or a substituent.

Examples of the substituent represented by R1 include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, and a carbamoyl group. group, sulfamoyl u1 cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, Amim L acylamino group, sulfonamide group, Examples thereof include an imide group, a ureido group, a sulfamoylami LL alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

The following margin m-8 CsHo(t) 2H5 Used in the present invention - General formula [a ] and [a
The magenta couplers represented by I] are disclosed in, for example, U.S. Pat. No. 2.600.788, U.S. Pat.
Same No. 3,311.476, Same No. 3,152,896, Same No. 3,419,391, Same No. 3,519,429
No. 3,555,318, No. 3.684.51
No. 4, No. 3,888,680, No. 3,907,5
No. 71, No. 3,928,044, No. 3.930.
No. 861, No. 3.930.866, No. 3.933
．． Specifications such as No. 500, JP-A No. 49-29639, No. 49-111631, No. 49-129538, No. 50-13041, No. 52-58922, No. 55-
No. 62454, No. 55-118034, No. 56-36
No. 043, No. 57-35858, No. 60-23855
British Patent No. 1,247,493, Belgian Patent No. 769.116, Belgian Patent No. 792,525, and West German Patent No. 2,156,111
-60479, JP-A-59-125732, JP-A No. 59
No.-228252, No. 59-162548, No. 59
-171956, 60-33552, 60-4
No. 3659, West German Patent No. 1,070,030, and US Patent No. 3,725,067.

As the cyan image forming coupler used in the present invention, couplers represented by the following general formulas [E] and [F] can be preferably used.

General Formula [E] In the formula, R+ε represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2E represents an alkyl group or a phenyl group. R3ε represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

z1ε represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

2F In the formula, Rqy+ represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R
5p represents an alkyl group (eg, methyl group, ethyl group, etc.). R6Fi represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

Z2F represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Typical examples of cyan image forming couplers used in the present invention are described below, but the present invention is not limited thereto.

Margin below (n) CI2H25SO2NH Couplers represented by the general formulas [E] and [F] of the present invention are, for example, JP-A-59-146050, JP-A-60
-117249 and No. 59-31953.

Examples of the cyan coupler used in the Ikemi invention include U.S. Pat. Nos. 2,306,410 and 2
, 356,475, 2.362.598, 2,367, 531, 2,369,929, 2,423,730, 2,474,293 ,
2.476,008, 2.498.466, 2,545,687, 2.728.660
No. 2.772.162, No. 2.895.82
No. 6, No. 2.976.146, No. 3,002.8
No. 36, No. 3,419,390, No. 3,446.
Ei No. 22, Ei No. 3,476.563, Ei No. 3,73
7,316, 3,758,308, 3,8
39,044, British Patent No. 478,991, British Patent No. 9
No. 45,542, No. 1, No. 084.480, No. 1,
The specifications of No. 377.233, No. 1,388,024, and No. 1.543.040, as well as JP-A-47-
No. 37425, No. 50-10135, No. 50-252
No. 28, No. 50-112038, No. 50-1174
No. 22, No. 50-130441, No. 51-6551
No. 51-37647, No. 51-52828, No. 51-108841, No. 53-109630, No. 5
No. 4-48237, No. 54-66129, No. 54-1
It is published in publications such as No. 31931 and No. 55-32071.

Two or more of the above yellow, magenta and cyan couplers may be contained in the same blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, respectively. Also, the same coupler may be included in two or more different layers having the same color sensitivity.

These yellow, magenta and cyan couplers are generally present in an amount of 2X10-3 mole to 1 mole, preferably 1X10-2 mole to 8X10' per mole of silver in the emulsion layer.
Used in the molar range.

The method of adding yellow coupler, magenta coupler, and cyan coupler to the silver halide emulsion layer is as follows:
For example, various methods such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method can be used, and these methods can be appropriately selected depending on the chemical structure of the coupler and the like. The oil-in-water emulsion dispersion method can be applied to a method of dispersing hydrophobic additives such as couplers, and is usually used in a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary, a low-boiling point and/or water-soluble loading solvent. After emulsifying and dispersing the halogen in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, the halogen It may be added to the silver oxide emulsion layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

Examples of high-boiling organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoates, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent. A high boiling point organic solvent with a dielectric constant of 6.0 or less is preferably used.

There are various types of high boiling point organic solvents with a dielectric constant of 6.0 or less that are preferably used, such as phthalate esters,
These include esters such as phosphoric acid esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably the dielectric constant is 6.
Vapor pressure at 100℃ is 0.5 m when the temperature is 0 or less and 1.9 or more.
Rinse with a high boiling point organic solvent below mHg. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture is 6.
It is sufficient if it is 0 or less. Note that the dielectric constant in the present invention is 30
It shows the dielectric constant at °C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [VI].

General Formula [VI] In the formula, R33 and R34 each represent a narkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R33 and R34 is 9 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, the alkyl group represented by RJ3 and R3+ in the general formula [Vl] is a linear or branched one, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group. group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group,
Such as octadecyl group. The aryl group represented by R wing and R34 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. , an alkenyl group, an alkoxycarbonyl group, etc., and examples of substituents for the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. These n t(p R
Two or more of these may be introduced into the alkyl group, alkenyl group or aryl group.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [Vl].

General formula [■] (2) In the formula, Ras, Ras and R37 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms represented by R35, Rss and R37 is 24 to 54.

The alkyl group represented by Ras, Rss and R37 in the general formula [■] is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Aryl groups include phenyl group, naphthyl group, etc. Alkenyl groups include hexenyl group, heptenyl group, octadecenyl group, etc. These are the basics.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably Rss, R36 and R37 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3
．． 5.5-trimethylhexyl group, 0-nonyl group, 0-
Decyl group, 5ec-decyl group, 5ec-dodecyl group, [
-octyl group and the like.

Specific examples of preferred high boiling point organic solvents are shown below.

Below is a blank illustrative organic solvent C2Hs 5-12 Cz)Isl 0C*H+*(n) U C+oHt+(n) -2O The above yk electric rate of 6.0 or less and a high boiling point ta solvent is 10 to 10% for the coupler. It is preferably used in a proportion of 200 fl 5%, more preferably 20 to 150 fl 5%.

Between the emulsion layers of the color photographic light-sensitive material used in the present invention (
(between the same color-sensitive layers and/or between different color-sensitive layers), to prevent color turbidity, deterioration of sharpness, and noticeable graininess caused by the movement of the oxidized form of the developing agent or the electron transfer agent. A color antifoggant is used for this purpose. The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

The silver halide color photographic light-sensitive material used in the present invention contains dye image stabilizers (for example, phenolic compounds, bisphenol compounds, hydroxychroman compounds, bispirochroman compounds, hydantoin compounds, dialkoxybenzene compounds, etc.). ) may be included.

Hydrophilic colloid layers such as protective layers and intermediate layers of the photosensitive material used in the present invention absorb ultraviolet rays to prevent fogging due to discharge caused by charging of the photosensitive material with flJm, etc., and to prevent image deterioration due to UV light. It may also contain an agent.

The color light-sensitive material using the silver halide emulsion used in the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer, if necessary. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion used in the present invention reduces the gloss of the photosensitive material, increases the addability, A matting agent can be added to prevent sticking.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion used in the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the light-sensitive material using the silver halide emulsion used in the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support where the emulsion is not layered with Vi, or in the antistatic layer on the side of the support where the emulsion layer is laminated with respect to the emulsion layer and/or the support. It may also be used as a protective colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion used in the present invention has the following properties: improves coating properties, prevents static electricity, improves slipperiness, emulsification dispersion, prevents adhesion, and (promotes development). Various surfactants are used for the purpose of improving photographic properties (such as hardening, sensitization, etc.).

The light-sensitive material using the silver halide emulsion used in the present invention has a photographic emulsion layer, and the other layers are made of baryta paper, paper laminated with α-olefin polymer, etc., a flexible reflective support such as synthetic paper, cellulose acetate, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, boreethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material used in the present invention can be used directly or (adhesiveness, antistatic property,
1) to improve dimensional stability, wear resistance, hardness, antihalation properties, friction properties, and/or other properties.
Alternatively, it may be applied through two or more undercoat layers.

When coating a photographic light-sensitive material using the silver halide emulsion used in the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The photosensitive material used in the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the photosensitive material is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, X-rays, and gamma rays. Any known light source can be used, such as light emitted from a phosphor excited by alpha rays or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material used in the present invention can form an image by color development as known in the art.

The color developing agent used in the color developing solution in the method for processing silver halide color photographic materials of the present invention is preferably an aromatic primary amine compound, particularly one based on p-phenylenediamine, such as N, N- Diethyl-p-phenylenediamine hydrochloride, N-ethy p-phenylenediamine hydrochloride, N+N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N -Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N-(2-methoxyethyl) −
N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)-
Examples include 3-methyl-4-aminoaniline. These color developing agents may be used alone or in combination of two or more.

The color developing solution of the present invention includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium bicarbonate, and tribasic sodium phosphate; development inhibitors such as sodium bromide and potassium bromide; Methanol, ethanol, acetone, butanol, benzyl alcohol, phenoxybutanol, diethylene glycol,
Various solvents such as ethylene glycol and N,N-dimethylformamide, preservatives such as hydroxylamine and sodium sulfite, development control agents such as citradinic acid, polyethylene glycol, and polyvinylpyrrolidone, and water-soluble compounds such as diaminostilbene compounds. Various known additives such as a fluorescent brightener, a heavy metal ion masking agent such as ethylenediaminetetraacetic acid and alkyliminodiacetic acid, and a development accelerator can be included as necessary.

In the present invention, the imagewise exposed silver halide color photographic material is color developed with the color developing solution of the present invention to form a dye image and a silver image. Thereafter, in order to leave only the dye image, a negative-positive method can be used in which the silver salt is oxidized to silver salt in a bleaching bath, and then the remaining silver halide and other silver salts are dissolved and removed in a fixing bath.

The bleaching and fixing treatments performed to leave a dye image may be performed in separate steps, but from the standpoint of rapid processing, it is preferable to perform the bleaching treatment and the fixing treatment at the same time.

When performing individual bleaching treatments, the bleaching agent is iron (■
), compounds of other valent metals such as cobalt (■), chromium (Vl), copper (n), peracids, quinones, nitroso compounds, etc. can be used.

Specifically, ferricyanide, dichromate, iron (I
II) or organic acid salts of cobalt (III), such as aminopolycarboxylic acid salts such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1゜3-diamino-2-propatoltetraacetic acid, or organic acid salts such as citric acid, tartaric acid, malic acid, etc. Complex salts of similar acids: persulfates, permanganates; nitrosophenols, etc. can be used.

Examples of fixing agents include thiosulfates (e.g., ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, etc.), thiocyanates (e.g., ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, etc.), 3.6 -Thioether compounds such as 1,8-octanediol can be mentioned.

From the viewpoint of rapid processing, the processing temperature of the various processing steps of color development, bleach-fixing, washing with water, stabilization, and drying 1 (1) of the silver halide color photographic light-sensitive material used in the present invention is 30°C or higher from the viewpoint of rapid processing. Preferably, it is carried out in

[Specific effects of the present invention] When the present invention is applied to a method for processing photosensitive materials for printing, rapid color development can be achieved, color fogging and color turbidity, which are problems at this time, are prevented, and the material has excellent suitability for rapid processing. A method for processing a silver halide photographic material for printing can be provided.

[Specific Examples of the Invention] The present invention will be described in detail with reference to specific examples below, but the present invention is not limited thereto.

The following margins [Example 1] A silver halide photosensitive material was prepared by sequentially coating the following eight layers on a copolyethylene-coated paper support.

Note that the amounts added below are per 112 unless otherwise specified.

Layer-1...Compound represented by general formulas [II], [1], [IV] and [V]* 0.03g gelatin
1.0gM-2...gelatin
2.0g blue-sensitive silver chlorobromide emulsion
0.39 (converted to silver amount) Yellow coupler (Y-2) 0.8 (1 high boiling point organic solvent dioctyl phthalate* 0.3 (1 layer-3...
Gelatin 1.5g High-boiling organic solvent dinonyl phthalate layer-4 Gelatin 1.5g Green-sensitive silver chlorobromide emulsion 0.4g (converted to silver amount) Magenta coupler (m-4) o, 4g dioctyl phthalate *0.25111 (high boiling point solvent) Layer-5... Gelatin 1.5g UV absorber LIV-1 umbrella 0.5g UV-2 umbrella
0.2g dinonyl phthalate umbrella* 0.3 (1 (high boiling point solvent) Layer-6...Gelatin 1.2g red-sensitive silver chlorobromide emulsion 0.25!II (converted to silver amount) Cyan coupler (C -11') 0.5Q high-boiling solvent dioctyl-phthalate 0.2 (] Layer-7... Gelatin 1.0g Ultraviolet absorber LI V -1$ 0.2 (1UV-
2 Ne 0.1g High boiling point organic solvent dinonyl rifthalate umbrella* 0.2g Layer-8...
Gelatin 1.0g Car Dioctyl phthalate (Example high boiling point organic solvent 5-2) *Rate Dinonyl phthalate (Example high boiling point organic solvent $-6) The following are general formulas [n], [III], [TV] and [V ] Table 1 shows the types of compounds represented by formula [I], the types of compounds represented by general formula [I], and the added layers.

Furthermore, the amount of the compound represented by the general formula [I] and the comparative compound As-1 is 0.02 per 1f when added to layers 2, 4 and 6! ; l, o and osg when added to layers 3 and 5.

Comparative compounds AS-1 and tJV-1 and UV-2 are shown below.

Below are the blanks: Ultraviolet absorber (IJV-1) Ultraviolet absorber (LJV-2) Comparative compound (As-1) H After photo-exposure using green light, the following treatments were performed.

Standard treatment process (processing temperature and processing time) [1 color development, 38°C, 1 minute 30 seconds.

2 minutes and 30 seconds.

3 minutes 30 seconds [2] Bleach constant @ 33℃ 1 minute [3] Washing treatment 25-30℃ 3 minutes [4] Drying 75-8
0° C. for about 2 minutes. However, the following color developing solution [A] which does not contain the compounds of general formulas [I[1 to [V]] according to the present invention was used.

Processing solution composition (color developer [A1 composition) Benzyl alcohol 151g Ethylene glycol 15i12 Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.29 potassium carbonate
30.0 (1-hydroxylamine sulfate
3.01;1 polyphosphoric acid (TPPS)
2.503-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4=-diaminostilbenzsulfonic acid derivative) i, Add 2.0 g of og potassium hydroxide water to bring the total mass to 12, and adjust to p) -110,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 (1 ethylenediaminetetraacetic acid 39 Ammonium thiosulfate (10% solution) ioo, g
Ammonium sulfite (40% solution) 27.5d Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total m to 11L.

Color turbidity was evaluated as follows. Magenta density (D') of a sample processed by removing cyan coupler and yellow coupler from sample No. 18 as a comparative sample for color turbidity 1
．． □XL and R- at 0 were measured using an optical densitometer (Model PD-65, manufactured by Konishiroku Photo Industry Co., Ltd.). Next, samples N001 to 21 are processed to obtain D″=1 for each sample.
．． The OR and R8 at 0 were measured and used as the value of color turbidity as shown below.

△oR=c%-oR<color turbidity due to cyan coloring) ΔD”
=D"-Di (color turbidity due to yellow color development) Furthermore, in order to evaluate the color developability, white exposure was performed instead of the green exposure, and the maximum of cyan, magenta, and yellow of each sample was processed at each time. The density ([)max) was measured with an optical densitometer.

The results obtained are shown in Table-2.

Margin below Next, the results shown in Table 2 will be explained.

In this Example-1, development accelerators which are compounds represented by the general formulas [I] to [VI according to the present invention are used only in the photosensitive material, and further, development accelerators which are compounds represented by the general formulas [I] according to the present invention are used. These are the results of an investigation using a compound (the comparative compound is AS-1).

Comparative sample 20, which does not contain the compounds of general formula [I] and general formulas [I[] to [VI], has insufficient rapid development processing and extremely large color turbidity. In addition, comparative sample 16 using only the compound of general formula [I] without using general formulas [I[] to [VI], and a comparison sample 16 using only the compound of general formula [I] and the comparative compound of general formula [I] Comparative sample 17 and comparative sample 1 using only the comparative compound of general formula [I]
In each of No. 8, the effect of preventing color turbidity can be obtained, but the rapid development process remains unsatisfactory. On the other hand, general formula [I] ~
[When the compound of VI was used, the rapid development process was satisfactory in all samples, but in sample 19 using the comparative compound of general formula [I], the improvement effect on preventing color turbidity was not sufficient. That is, even if the compounds of general formulas [11 to [VI] are not used, they have the effect of preventing color turbidity, but when the compounds of general formulas [I] to [VI are used, the comparative compounds have no effect of preventing color turbidity. It turns out that it has little effect.

On the other hand, in samples 1 to 15 in which the compound of general formula [I] and the compounds of general formulas [ff] to [VI according to the present invention were used together, the maximum density at a development time of 1 minute and 30 seconds was cyan, Both magenta and yellow are almost the same as the maximum density at a development time of 3 minutes and 30 seconds for comparative sample No. 16.17°18.20 that does not contain a development accelerator, and at a development time of 1 minute and 30 seconds.
From 0 seconds to 3 minutes and 30 seconds, it is stable with almost no change,
It can be seen that brown turbidity is well prevented. Furthermore, from Samples 9, 10 and 11, the general formula according to the present invention [
It can be seen that the compound of [I] may be used in combination with the comparative compound.

[Example-2] The following color developer [B] was prepared using the photosensitive material samples Nos. 16 and 18 used in Example-1.

[0], [D] and [E] were prepared and treated in the same manner as in Example-1 using this color developing solution, and each of the obtained samples was evaluated. Evaluation samples 1 to 8 were used, respectively.

Color development processing solution [B]... 100 m/12 ll-1 in color development processing solution [A']
Color development processing solution [C]... Added ■-15 to color development processing solution [A'] at 100 m/min.
Q Added color development processing solution [D]... a9a physical solution for color development [A']] 2 IV-4 1ffi
100 + 11 (] added per color developing solution [E]... V-3 per 11 i 00 to color developing solution [A']
However, here, the color developer [A'] is the color developer [A'] added with mQ.
A] excluding benzyl alcohol.

Table 3 shows the results of color turbidity at a development time of 1 minute and 30 seconds.

Table 3 shows that even when the development accelerator represented by the general formulas [1] to [V] of the present invention is added to the developer, the compound represented by the general formula [I] of the present invention does not differ from Example-1. It turns out that it is equally effective.

Table 3 In addition, examples of color developability when development accelerators of general formulas [n] to [V] are added to the developer are also shown.
The same results as in Example 1 were obtained.

[Example-3] ゛ Using the photosensitive materials Nos. 7, 8, 16, 18, and 19 used in Example-1, the color turbidity and the maximum at a developing time of 1 minute and 30 seconds were determined in the same manner as in Example-1. The density and color fog (Dmin) were evaluated. Evaluation sample No.0 for each
．． It was set as 9 to 13.

However, the processing steps were the same as in Example-1 except that the color developer (F) shown below was used.

The results are shown in Table 4.

From Table 4, evaluation sample No. 13 has a high maximum density but has a lot of color turbidity. Evaluation samples No. 11 and 12 had good color turbidity, but the maximum density was insufficient.

In contrast, it can be seen that evaluation sample No. 9°10 of the present invention has little color turbidity and sufficient maximum density. However, although the objective of the present invention was achieved in evaluation sample No. 10, the color fog was slightly higher than in No. 19.

Color developer [F] Composition Ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride
0.2Q potassium carbonate
so g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.503-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfur M salt 8g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1. OQ potassium hydroxide 2.0g Water was added to bring the total m to 12, and the pl was adjusted to 111.0.

[Example 4] In the above Example-3, the 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfur M salt in the color developer [F] was 3-methyl-4-amino-N-ethyl-N-hydroxyethyl-aniline sulfate, 3-methyl-4-amino-N instead
-ethyl-N=(2-methoxyethyl)-aniline-p
Color developing solutions [G] and [H] were prepared with the same composition except that -toluenesulfonate was used in equimolar amounts.

Example except that the above color developing solutions [G] and [H] were used.
When tested in the same manner as in Example 3, almost the same results as in Example 3 were obtained.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment 1 set) % formula % 2. Name of the invention Processing method for silver halide photographic light-sensitive materials 3. Relationship with the person making the amendment Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Benko 4, Agent 102 Address: 1-1 Kudankita 4-chome, Chiyoda-ku, Tokyo” (Delivery date) April 22, 1985 6, Engraving of the entire text of the specification subject to amendment (no change in content) procedure? rll official book (spontaneous) December 24, 1986

Claims (1)

[Scope of Claims] A silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and a non-photosensitive layer are formed on a support. In a method for processing a silver halide photographic material, which includes a step of imagewise exposing a silver halide photographic material having a photographic constituent layer and a step of color development, at least one of the photographic constituent layers has the following general formula [ Contains the compound represented by I],
In addition, the color development step is performed using the following general formulas [II] and [III].
], [IV] and [V]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.
represents 1 or 2. A has ▲mathematical formulas, chemical formulas, tables, etc.▼(Here, X is -O-
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R_3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group;
4 represents a hydrogen atom, an alkyl group or an aryl group. ), -OY (Here, Y represents R_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_3 has the same meaning as above.)
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_4
has the same meaning as above, R_5 represents a hydrogen atom, an alkyl group, an aryl group, or ▲a numerical formula, a chemical formula, a table, etc.▼, and R_3 has the same meaning as above. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(
Here, 1 represents 0 or 1, R_3 has the same meaning as above, and R_6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. ) or a cyano group. B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a group represented by ▲ which has a numerical formula, chemical formula, table, etc. (where R_1, R_2, n, k and A each have the same meanings as above) ). ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. may form a nitrogen-containing heterocycle together. R_5 represents a halogen atom, an alkyl group, or an alkoxy group, and n_1 is 0 to 4.
represents an integer. If n_1 is an integer from 2 to 4, R_5
may be the same or different. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. Good. R_8 represents a halogen atom, an alkyl group, or an alkoxy group, and n_2 represents an integer of 0 to 4. When n_2 is an integer of 2 to 4,
R_8 may be the same or different. ) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a hydrogen atom or a hydrolyzable group, R_9 represents an aryl group, R_1_0, R_1_
1, R_1_2 and R_1_3 are each a hydrogen atom,
Represents an alkyl group or an aryl group. ) General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. (represents an atom)