JPS6029746A - Process for forming direct posi-color picture image - Google Patents

Abstract

PURPOSE:To obtain satisfactory color balance in color development by using a specified compd. as a cyan coupler and applying general exposure in the presence of a specified phenol deriv. after executing image exposure but prior to color development. CONSTITUTION:Image exposure is executed on a silver halide color sensitizer for direct positive comprising silver halide emulsion layer formed on a base and contg. silver halide particles for forming internal latent image which are not treated with a coupler, and contg. also a cyan coupler in order to obtain direct posi-color picture image, then applying general exposure to the sensitive material prior to or during color development in the presence of a phenidon deriv. expressed by the formula ( I ) (wherein R1 is H, alkyl, aryl; R2-5 are each H, alkyl, aryl, or OH) to obtain a direct posi-picture image. A compd. expressed by the formula (II) is also used as cyan coupler. In the formula (II), R6 is alkyl, aryl, cycloalkyl, or heterocyclic group. R7 is alkyl, or aryl; R8 is H, halogen, alkyl or alkoxy; J is an imino group; n is zero or 1; Z1 is H or an eliminative group by the reaction with an oxidized body of an aromatic primary amine type color developing primary agent). By this process, satisfactory color balance is obtd. in both high density part and low density part in a short developing time. Moreover, stable picture image is obtd. even if variation of illuminance due to fog is happened.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to an image forming method for a direct positive silver halide color photographic light-sensitive material, and more specifically, it relates to a method for forming an image on a direct positive silver halide color photographic light-sensitive material. Internally activated silver halide color photographic material C from which images can be obtained
The present invention relates to an image forming method.

It is well known that it is generally possible to form V-contact positive images using silver halide photosensitive materials without requiring a middle n processing step or a negative photographic image.

The sixth method used to form a positive image using a conventionally known direct positive type halogenated Tsukuda photographic material is as follows:
Considering practical usefulness, except for special cases, it can be divided into two main types.

One type uses a silver halide emulsion that has been coupled in advance and creates a positive image after development by destroying the capri nuclei (latent image) in the exposed area using the reversal phenomenon of the solarized area or the Burschel effect. Another type uses an internal latent image type silver halide photographic emulsion whose surface is uncoupled, and after imagewise exposure, after capri processing with a capping agent or light, and/or A positive image is obtained by developing the surface of silver halide with a surface developer while undergoing processing.

[Here, the above-mentioned internal latent image type silver halide photographic emulsion refers to silver halide grains that mainly have photosensitive nuclei inside the grains, and when exposed to light. A silver oxide photographic emulsion.

This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques are known in this technical field. For example, U.S. Pat. No. 2,592.250;
Same No. 2,466,957.

. Same No. 2,497,875, Same No. 2,588,98
No. 2, No. 3.761.266, No. 3,761.2
No. 76, No. 3.796.577 and British Patent No. 1
, No. 151,363, the main ones are those described in the respective specifications.

By using these known methods, silver halide photographic materials with relatively high sensitivity can be produced as direct photosensitive materials.

Furthermore, although it cannot be said that a clear explanation has been given regarding the details of the structure of the direct positive image, for example, ``The Theory of the Orientation'' by Mies and James, Graph Ink Lu Process J (The T
, heory of the Photographic
[Process) @ 3rd edition] The process of forming a positive image can be understood to some extent by the ``desensitization effect by the internal neck image'' as discussed on page 61.

In other words, due to the surface desensitization effect caused by the so-called internal latent image that resides inside the silver halide grains due to the first imagewise exposure, the surface of the unexposed silver halide grains is selectively affected in the subsequent complete lightless process. For books on which fog nuclei are generated and then or simultaneously developed by normal surface development to form a positive photographic image in the unexposed areas) - However, + lead included. There are two methods to form a photosensitive layer, which is usually called a photoreactive layer, in which the entire surface of the photosensitive layer is exposed uniformly to couple silver halide on the surface, and a method called a chemical capri, which is a method of coupling silver halide on the surface. A method of coupling the surface of silver halide using a chemical is known.

Among the above methods, the chemical capri method uses a high pH of 12 or more.
Because of the harsh conditions in which the effect of the capri agent can only be obtained in the following conditions, the capri agent is likely to deteriorate due to air oxidation, which has the disadvantage that the capri effect is significantly reduced.

On the other hand, in the case of the Capri method, the conditions are not as severe as those mentioned above, so it is convenient in practice, but in order to serve the purpose of six purposes in a wide range of photographic fields, it requires some technical improvements. Problems remain. That is, the photofogging method is based on the formation of capri nuclei by photodecomposition of silver halide, and the appropriate exposure intensity varies depending on the characteristics.

In the light power purification method, for example, 1% Kosho 45-12709
The publication describes a method of uniformly exposing the entire surface to light of low intensity. It has been reported that this produces a different image.

Further, as a result of studies conducted by the present inventors, in order to obtain a relatively good positive image, it is necessary to perform capri exposure at a relatively low illuminance in a limited range, and even lower illuminance is necessary. Even with a sufficient amount of exposure, a sufficient maximum image density cannot be obtained, and at higher illuminances, the maximum density decreases in proportion to the given illuminance, and the minimum density also increases, so to speak, the illuminance at the time of optical fog increases. It turns out that there is a phenomenon called failure.

Therefore, as a result of further research, the present inventors found that when a positive silver halide photographic light-sensitive material is directly exposed to light over its entire surface in the presence of a phenidone derivative and subjected to color development processing, it becomes stable against illuminance fluctuations during optical power pre-printing. We found that it is possible to obtain images with (Special Application No. 57-2250) However,
This method has made several technical advances in that it is possible to obtain images that are stable against fluctuations in illuminance during optical pre-printing, and it is also possible to shorten the development time. It was found that there is a tendency for the pressure to be high contrast. For example, when this method is applied to a multilayer color photographic material composed of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers to form a positive color image, yellow, magenta,
Among the cyan and positive images, the contrast of the cyan positive image is particularly remarkable, and as a result, in the high density areas of the positive color image, it is difficult to reproduce images with good color balance. On the other hand, in low-density areas, non-uniformity occurs in the sensitometric characteristics between each layer, which is particularly noticeable in cyan-positive images, where the contrast in low-density areas is markedly increased, and the color of color images becomes uneven. This had the disadvantage of deteriorating reproducibility.

■ Purpose of the Invention The present inventors have completed the present invention as a result of extensive research in order to solve these drawbacks. That is, the object of the present invention is to use a direct positive color photographic light-sensitive material containing a cyan coupler to produce good results in both high-density and low-density areas in a short development time by color development treatment accompanied by photofogging light. The object of the present invention is to provide a method for forming a direct positive color image that provides color balance.

A second object of the present invention is to provide a method for directly forming a positive color image, which can obtain a stable image even with variations in illuminance during optical power pre-printing.

The above object of the present invention is to form a direct positive color image on a support having a silver halide emulsion layer containing internal latent image type silver halide grains and a cyan coupler whose grain surfaces are not fogged in advance. After imagewise exposure of a silver halide color photographic light-sensitive material and prior to color development or during a color development process, direct exposure is applied to the entire surface in the presence of a phenidone anticonductor represented by the following general formula (I). The image forming method for obtaining a positive image is achieved by a direct positive color image forming method using a compound represented by the following general formula (n) as the cyan coupler.

General formula (I) R11 ■ 1 (In the formula, each represents a hydrogen atom, an alkyl group, or an aryl group, and R1 & Ra l R4 and R1 each represent a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group.) 2゜(In the formula, R6 represents an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group. R represents an alkyl group or an a+7-al group. R8 represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group. J represents an imino group, and n represents 0 or 1. 2. represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ) ■Specific Structure of the Invention The direct positive silver halide color photographic light-sensitive material used in the present invention contains a phenidone visiting conductor represented by the general formula (IJ) after imagewise exposure, prior to color development, or during the color development process. The entire surface is exposed in the presence of .

In the general formula tI) of the present invention, the alkyl group represented by R is preferably an alkyl group having 1 to 4 carbon atoms.

This alkyl group may have a substituent.

Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, and an amino group.

The aryl group represented by B can be, for example, a phenyl group, and this aryl group can have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkylamino group, an alkoxy group, and an acylamino group.

Moreover, in the above general formula (I), 几! e Ra R
The alkyl group represented by 4 and 几 can preferably be an alkyl group having 1 to 4 carbon atoms, and this alkyl group can have a substituent. Examples of the substituent include the substituents listed above. Also"
The aryl group represented by tpJpB and R is,
For example, phenyl group can be mentioned.

This aryl group can have a substituent, and examples of the substituent include the substituent of the above-mentioned aryl group in B1.

Next, the compounds represented by the above general formula (I) used in the present invention are specifically illustrated below, but the present invention is not limited to these compounds.

[Exemplary compounds] For example, 1-phenyl-3-pyrazolidone.

]-p-) Zyl-3-pyrazolidone, 5-7 ether-3
-pyrazolidone, 5-methyl-3-pyrazo'))"y,
1-p-chlorophenyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-m-)dyl-3-pyrazolidone, ]-phenyl-5-methyl-3
-pyrazolidone, 1-p-tolyl-5-phenyl-3-
Pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, ]-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-cyjf-3
-pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-m-p-aminophenyl-
4-Methyl-4-propyl-3-pyrazolidone, 1-0
-chlorophenyl-4-methyl-4-ethyl-3-virasoliton, 1-(p-β-hydroxyethylphenyl)
-4,4-dimethyl-3-pyrazolidone.

1-p-hydroxyphenyl-4,4-dimethyl-3-
Pyrazolidone, 1-p-)lylu-4,4-dimethyl-3
-pyrazolidone, 1-(7-hydroxy-2-naphthyl)-4-methyl-4-n-propyl-3-pyrazolidone, -1-p-diphenyl-4,4-dimethyl-3-pyrazolidone, 1-(p -β-hydroxyethylphenyl)
-3-pyrazolidone, 1-0-)dyl-3-pyrazolidone, 1-0-tolyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
4-Hydroxy-4-methyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyA/-1-
Phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1,-pheny/l/-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-'e
:5zolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc.

In the present invention, the compound represented by the general formula (1) may be directly incorporated into a positive silver halide photographic material (hereinafter referred to as the "photosensitive material of the present invention"), or may be added to a pre-bath. It may be contained in the color developing solution, and its form does not matter. If it is added to the photosensitive material of the present invention, it may cause problems such as the influence on the storage stability of the photosensitive material of the present invention, so it is preferably added to the s'r++1 bath or color developer.

It is preferable to add it during one color development.

In order to incorporate the compound represented by the general formula (2) into the light-sensitive material of the present invention, various methods known in the art can be employed.

The amount added is 0.05 per mole of silver halide.
f~50t, preferably 0.1f~10#. or,
When the compound of general formula (I) is added to the bath or color developing solution for impregnating the light-sensitive material of the present invention, the amount added is 10 mt/1 to 10:.t/, preferably 20 mt/1 to 10:.t/.
WLt/l~3t,/l.

The direct printing silver halide color photographic light-sensitive material of the present invention has a silver halide emulsion layer containing a cyan coupler on a support. In the present invention, the following general formula (company)
A cyan coupler shown in is used.

General formula (II) H (wherein 6 is an alkyl group, an aryl group, or a cycloalkyl group.

or represents a heterocyclic group, J represents an imino group, and n is 0
Or represents 1. R7 represents an alkyl group or an aryl group. R8 represents a hydrogen atom, )\rogen atom, an alkyl group or an alkoxy group. 2. represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ) Examples of the alkyl group represented by R6 in the general formula (n) include methyl group, ethyl group, butyl group, and pentadecyl group. This alkyl group may have a substituent, and examples of the substituent include 1, a hydrogen atom, a hydroxyl group,
Cyan group, nitro group, alkoxy group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, aminosulfonamide group, acylamino group, carbamoyl group , a sulfonyl group, a sulfinyl group, a sulfooxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonyl group, and the like. Examples of the aryl group represented by 几 include phenyl group, naphthyl group, etc. Among these, phenyl group is preferable.

This aryl group may have one or more substituents. Examples of this substituent include, in addition to an alkyl group, a substituent for an alkyl group represented by the above-mentioned R.

Examples of the cycloalkyl group represented by R6 include Example L, cyclopropyl group, and cyclohexyl group. Examples of the heterocyclic group represented by R6 include a pyridyl group and a furan group. This heterocyclic group can have a substituent. Examples of substituents include:

In addition to the alkyl group, substituents for the alkyl group represented by R6 above can be mentioned.

Preferred groups represented by R6 include fN, a phenyl group without water exchange, a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfamoyl group, and an irisulfasoyl group. , an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a phenyl group having a cyan group as a substituent. The phenyl group may have two or more of these substituents, and in this case, the substituents may be the same or different.

The alkyl group represented by B is linear or branched, and includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a nonyl group, and a tridecyl group. Further, the aryl group is, for example, a phenyl group or a naphthyl group. These groups represented by σ)n may have a single or multiple waste water r.
For example, a typical substituent introduced into a phenyl group is a norogen atom (e.g. fluorine, chlorine, bromine, etc.)
, alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkyl sulfonamide group (e.g. methyl group) sulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl, l), arylsulfamoyl group ( (e.g. evaphenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g. evamethyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. evaphenylsulfamoyl group, etc.),
For example, phenyloxycarbonyl group), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group.

Sulfo group, aryloxy group, alkoxy group.

Examples include a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonyl group, and the like. Two or more of these substituents may be introduced into the phenyl group. In this case, the substituents may be the same or different. As the halogen atom represented by R,
Examples include fluorine atom, chlorine atom, bromine atom, etc.
Examples of the alkyl group represented by 8 include methyl group, ethyl group, propyl group, and dodecyl group.

Further, examples of the alkoxy group represented by Re include methoxy group, ethoxy group, propyloxy group, butoxy group, and the like.

Among the cyan couplers represented by the general formula (II) in the present invention, suitable cyan couplers in which n is 0 are as follows:
This is a compound represented by the following general formula (Ill).

In the general formula (1), R- represents a phenyl group.

This phenyl group may have a single or multiple substituents (typical substituents to be introduced).
10 gene atoms (for example, fluorine, chlorine, bromine, etc.), alkyl groups (for example, methyl group, ethyl group, globyl group, pudelle group, octyisododecyl group, etc.), hydroxyl group, cyano group.

Nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group) ), alkylsulfamoyl groups (e.g., butylsulfamoyl group), arylsulfamoyl groups (e.g., t-haphenylsulfamoyl group, etc.), arylsulfamoyl groups (e.g.,
), 7'-oxycarbonyl group (eg, methyloxycarbonyl group, etc.), and -yloxycarbonyl group (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by Ro include:

Phenyl group or halogen atom (preferably fluorine,
chlorine, bromine), alkylsulfonamide group (preferably 0-methylsulfonamide group% p-octylsulfonamide group, 0-dotecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group)
, alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group), alkyl group (preferably methyl group, trifluoromethyl group), alkoxy group (preferably methoxy group) , ethoxy group) is a phenyl group having one or more cyano groups as substituents.

TLIo is an alkyl group or an aryl group.

The alkyl group or aryl group may have a single or multiple substituents, and typical examples of the substituent include halogen radicals, chlorine, bromine, etc.) hydroxyl group, carboxyl group, Alkyl group! For example, methyl group, ethyl group, propyl group, butyl group, octyl group,
dodecyl group, etc.), aralgyl group, cyan group, nitro group,
Alkoxy groups (e.g. methoxy group, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenyl A/suA/
honamide group, naphthylsulfonamide group, etc.) alkylsulfamoyl group (e.g., ehaphthylsulfamoyl group, etc.)
, arylsulfamoyl group (e.g. evaphenylsulfur II-I/14, etc.), alkyloxycarbonyl group (
For example, methyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, etc.)
, an aminosulfonamide group (e.g. dimethylaminosulfonamide group, etc.), an alkylsulfonyl group, an alkylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, and a sulfinyl%tx. can. Three or more of these fit methyl groups may be substituted.

Preferred groups represented by RIf are an alkyl group when 1=00 and an aryl group when 7=1 or more. R
, J is a more preferable group represented by no=0
When 0, it is an alkyl group with ~22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group), and when it is 1-1 or more, it is a phenyl group or an alkyl group ( (preferably t-butyl group, t-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group) ),
It is a phenyl group having one or more substituents of an aminosulfonamide group (preferably a dimethylaminosulfonamide group) or an alkyloxycarbonyl group (preferably a methyloxycarbonyl group or a butyloxycarbonyl group).

R+ represents an alkylene group. It represents a linear or branched alkylene group having 1 to 20 carbon atoms, typically 1 to 12 carbon atoms.

1 (+2 represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine or iodine). Preferably it is a hydrogen atom.

l is 0 or a positive integer, preferably 0 or l.

X is -O-, -CO-1coo, oco, bOtN
Rx-%-N to Nn1W, s o- or -s□
, -represents a divalent group. Here, RIx and FLX represent an alkylene group. X is preferably -Q+, -5-
1-8O-1-8O3- represents a hydrogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the general formulas 0 and (Ill), the groups obtained by the reaction with the oxidized product of the aromatic primary amine thread color developing agent represented by Zl and Z, [, are well known to those skilled in the art, and the groups obtained from the coupler in a coating layer or other layer containing a coupler in a silver halide color photographic light-sensitive material by modifying the reactivity of the coupler or separating it from the coupler.

It works advantageously by fulfilling functions such as development inhibition, bleaching inhibition, and color correction.

A typical example is a halogen atom.

Examples include an alkoxy group, an aryloxy group, an arylazo group, a thioether group, a carbamoyloxy group, an acyloxy group, an imide group, a sulfonamide group, a thiocyano group, or a heterocyclic group (eg, oxasilyl, diazolyl, triazolyl, tetrazolyl, etc.). ZI or Z
! Particularly preferred is a hydrogen atom or a salt atom.

Typical specific examples of the cyan coupler represented by the formula (Company) where n is O are listed below, but the invention is not limited to these.

The following margins (I-2) (I-3) (I-6) (I-8) (I-13) (I-17) (I-18) (I-19) (I-20) (I- 21) (I-23) (I-24) (I-25) (I-26) (I-27) (I-29) (I-31) (I-33) (i-34) -35) F (I-37) (I-38) H (I-39) 01 (Also, in the general formula (It) of the present invention, n is 1 and J has an imino group. Examples are shown below, but the present invention is not limited thereto.

(1-40) (I-41) (I-42) (I-43) (I-44) (I-45) (I-46) (I-47) H (I-49) (I-50) (I-51) (I-52) 04H.

(I-53) (I-54) (I-55) (I-56) (I-57) (I-58) ( (I-60) O.A.T. (I-61) (I-62) (I-65) (I-66) (I-67) C4H.

(I-68) (I-69) (I-70) (I-71) (I-72) (I-73) (1-74) (i-75) The present invention represented by the formula [■] The cyan coupler concerned is
The methods used in conventional cyan dye-forming techniques are similarly applicable and a silver halide emulsion layer containing a cyan coupler according to the invention is coated onto a support to form a photographic element. The photographic element may be a single color element or a multicolor element. In the case of multicolor elements, the cyan coupler according to the invention is usually contained in a red-sensitive silver halide emulsion layer, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. You can let me. Each structural unit forming the dye 1iij image in the present invention is a single-pore agent layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

In order to incorporate the cyan coupler according to the present invention into an emulsion,
A conventionally known method may be followed. For example, high-boiling organic solvents such as phthalates (such as dibutyl phthalate), phosphoric esters (such as tricresyl phosphate), or N,N-dialkyl-substituted amides (such as N,N-diethyllaurinamide), and butyl acetate. Or, after dissolving the cyan coupler according to the present invention in a low boiling point organic solvent such as butyl bupionate, or in a mixture of these solvents as necessary, a surfactant mixed with an aqueous gelatin solution containing
Next, after emulsifying and dispersing using a high-speed rotary mixer, a colloid mill, or an ultrasonic dispersion machine, the silver halide emulsion used in the present invention can be prepared by adding silver halide to the cyanide according to the present invention. When a coupler is added to a silver halide emulsion, it is usually about 0.05 molar per mole of silver halide.
It is added in an amount of 0.1 to 1 mole, preferably 0.1 to 1 mole.

The direct positive silver halide photosensitive material of the present invention comprises:
After imagewise exposure to form a direct positive color image, a full exposure is provided prior to or during the color development process.

In the present invention, "to give full-face exposure prior to color development" means, for example, to perform full-face exposure after imagewise exposure in a processing bath (pre-bath) for processing prior to color development. The treatment bath may contain reducing substances, alkaline agents, inhibitors, desensitizers, etc., if necessary. On the other hand, "giving the entire surface exposure during the color development process" literally means that the entire surface is exposed to light at any time during the color development process, but it is better to expose the entire surface at an early stage of development to shorten the development time. In this case, it is advantageous to start exposure after the developer has sufficiently penetrated the emulsion layer.

In the present invention, the illuminance of the entire surface exposure, that is, the illuminance of the optical power pre-printing is preferably an illuminance that does not cause illuminance failure during the optical power pre-printing, and although it varies depending on the photosensitive material of the present invention, it is generally 0.01 to 20.
Light of 0.00 lux, preferably 0.05 to 30 lux, more preferably 0.1 to 5 lux can be used. This adjustment of the light power pre-illuminance may be carried out by changing the luminous intensity of the light source, by attenuating the light using various filters, by using the distance between the light-sensitive material of the present invention and the light source, the angle between the light-sensitive material and the light source, etc. be able to. In addition, in order to shorten the optical power pre-exposure time, it is also possible to adopt a method in which a weak light is used for coupling at the beginning of the one-light coupler exposure, and then a stronger light is used for coupling.

In the present invention, as a light source for photofogging, it is sufficient to use at least one light source within the wavelength range to which the photographic light-sensitive material is sensitive;
It is desirable to use at least one light source with a wide spectral distribution over the range of 00 nm to 700 nm, and a fluorescent lamp with high color rendering properties as described in JP-A-56-17350 can also be used. . Also, two or more types of light sources with different emission distributions and color temperatures may be used in combination,
Various types of filters such as color temperature conversion filters may be used.

The color developing solution used in the present invention is a color developing solution that does not substantially contain a silver halide solvent, and examples of developers that can be used in the color developing solution include common color developing agents. It will be done. Preferred color developing agents are aromatic primary amine color developing agents, typical examples of which include p-phenylenediamines and p-aminophenols. For example, aminephenol, N-methyl-aminophenol, N.

N-diethyl-p-phenylenediamine, 4-amino-
3-Methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-amino-3-methyl-N-
Ethyl-N-(β-hydroxyethyl)aniline, 4-
Amino-3-methyl-N, N-diethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N
-β-methoxyethyl-p-7 22-diamine and the like. These developers may be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution.

The amount of these aromatic primary amine color developing agents used varies depending on the type of light-sensitive material, but it is easy to determine experimentally and is generally 0.0 per ton of developer.
It may be used in a range of 0.002 to 0.7 mol.

Further, the color developer may contain specific antifoggants and development inhibitors, or these developer additives may be optionally incorporated into the constituent layers of the photographic material. Typically useful anti-capri agents include tetrazaindenes, benzotriazoles, benzimidazoles, benzothiazoles, benzoxazoles,
Included are heterocyclic thiones, aromatic and aliphatic mercapto compounds such as 1-phenyl-5-mercaptotetrazole.

In the present invention, in particular, when a tetrazaindene is contained in a color developing solution, the tetrazaindene acts with the compound represented by the general formula (I) to reduce the illuminance at the time of optical power generation. This has the effect of reducing fluctuations in image density with respect to fluctuations. The effect is synergistic. Preferred tetrazaindenes are represented by the following general formula nV).

General formula ('lT1 In general formula (5), R13 and R14 are each a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a group of nonmetallic atoms necessary for bonding with each other to form a 5- or 6-membered ring, R15 is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms; Represents an alkyl group or an aryl group.

Specific examples of tetrazaindenes that can be effectively used in the present invention include 4-hydroxy-1,3°3a,7-
Tetrazaindene, i-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 4-methyl-6hydroxy-1.3.3a, 7-tetrazaindene, 4
-Hydroxy-6butyru-1.3.3a, 7-tetrazaindene, 4-human dayxy-5.6-dimethyl-1.
3.3a, 7-tetrazaindene, 2-ethyl-4-
Hydroxy-6-broby-1.3.3a.

7-thitrazaindene, 2-allyl-4-hydroxy-1,3,3a, 7-tetrazaindene, 4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene, 2-propyl -4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene, 2-mercaptomethyl-4-hydroxy-6-methyl-1,3,
3a, 7-tetrazaindene, 4-hydroxy-5
, 6-)rimethylene-1,3,3a, 7-tetrazaindene, and the like. These tetrazaindenes are 1
It is possible to use one species or a combination of two or more kinds, and the amount added to the color developing solution is preferably 1 amy/L to 5 t7t. Furthermore, various commonly added components may be added to the color developer. For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali gold hethiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners and developers. Examples include accelerators. The pH value of the color developing solution is usually 7 or higher and 69, most commonly about 9 to about 14.5, more preferably 10 to 14.

The various additives that are added to these color developing solutions as necessary include, for example, alkali metal or ammonium water to maintain the pH at a constant value, carbonates, phosphates, pH adjustment or Buffers (for example, weak acids and weak bases such as acetic acid and boric acid, and their salts), development accelerators such as pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate, polyethylene glycol condensates, phenyl cellosolve, phenyl calpitol, Examples include alkyl cellosolve, phenyl calpitol, dialkyl formamide, alkyl phosphates and their derivatives, nonionic compounds such as polythioethers, sulfide esters, polymer compounds, organic amines such as pyridine and ethanolamine, and benzyl alcohol.

The working temperature of the color developing solution used in the present invention is usually 20
℃~70℃, preferably 30℃~45℃.

Additives to the color developer used in the present invention include, in addition to the above, anti-stain agents, anti-streak agents, interlayer effect promoters, preservatives (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide adducts, etc.). In addition, chelating agents include phosphates such as polyphosphates, aminopolycarboxylic acids such as nitrilotriacetic acid and 1-3-diamine-2-propatoltetraacetic acid, oxycarboxylic acids such as citric acid and gluconic acid, and l-hydroxycarboxylic acids such as citric acid and gluconic acid. Ethylidene, 1.1-
There are diphosphonic and others. It is also possible to use lithium sulfate together with a chelating agent, and these chelating agents may be combined.

Various methods can be used to transport the photosensitive material during processing, and various types of processing equipment can be used accordingly. For example, there are various types such as a hanger set, a cine type, and a roller conveyance type.

Furthermore, conventionally, when processing an exposed photosensitive material with an automatic processor, a method has been used in which the material is processed while replenishing a processing solution depending on the photosensitive material to be processed. When using a liquid replenishment solution kit, each part of the kit may be replenished separately. In addition, methods have been developed to reuse processing solutions and to recover chemicals that are important in terms of pollution or resources, such as developing agents and heavy metals.
Some processing equipment has these devices built into it,
These may be used as appropriate.

The direct positive silver halide color photographic light-sensitive material of the present invention has a silver halide emulsion layer containing a cyan coupler as an essential component, but usually the cyan, magenta and yellow couplers are red-sensitive and green. It applies to multicolor photographic elements containing light-sensitive and blue-sensitive silver halide emulsion layers, respectively.

When the direct positive silver halide color photographic light-sensitive material of the present invention is comprised of a multicolor element, the layers necessary for the photographic element, including the layers of the above-mentioned image forming units, may vary as known in the art. can be arranged in this order. A typical multicolor photographic element comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having a cyan dye-forming coupler (at least one of the cyan dye-forming couplers).
A magenta dye image consisting of at least one green-sensitive direct positive silver halide emulsion layer having at least one magenta dye-forming coupler (a cyan coupler according to the invention of formula (IF)) The image-forming unit comprises a yellow dye image-forming unit supported on a support, comprising at least one blue-sensitive direct positive silver halide emulsion layer having at least one yellow dye-forming coupler.

Photographic elements can have additional layers, such as non-light sensitive layers such as filter layers, interlayers, protective layers, antihalation layers, subbing layers, and the like.

As the yellow dye-forming turnip 2- used in the present invention, a compound represented by the following general formula (1) is preferable.

General formula ■] R1, -C-CH-C-N) I -R1゜If l n Y O In the formula, R□6 is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.) or Aryl M (e.g. Ld, phenyl group, p-methoxy7-dyl, etc.), Bit represents an aryl group, and Y represents a hydrogen atom or a group that is eliminated during the color development reaction process. .

Furthermore, particularly preferred yellow couplers for forming the dye image according to the present invention are compounds represented by the following general formula [V'].

General formula [V'] In the formula, R1□ represents a halogen atom, an alkoxy group or an aryloxy group, and RI8, RlG and R, Ill
are a hydrogen atom, /'10 atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a carbonyl group, a sulfonyl group, a carboxyl group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, and a sulfone group, respectively. It represents an amide group, an acylamido group, a ureido group or an amino group, and Y has the above-mentioned meaning.

These include, for example, U.S. Patent No. 2,778,658, U.S. Patent No. 2.875,057, U.S. Pat.
Same No. 3.253.924, No. 3,265,506, No. 3.277.155, No. 3,341,331
No. 3,369,895, No. 3,384,65
No. 7, No. 3,408,194, No. 3,415,6
No. 52, No. 3,447,928, No. 3,551,
No. 155, No. 3.582, 322, No. 3.725
, No. 072, No. 3.894,875, etc.,
German Patent Publication No. 1.547.868, German Patent Publication No. 2.05
No. 7,941, No. 2.162,899, No. 2.1
No. 63.812, No. 2,213,461, No. 2.
No. 219,917, No. 2,261,361, No. 2
, 263,875, JP 49-13,576, JP 48-29,432, JP 48-66.834,
No. 49-10,736, No. 49-122,335,
No. 50-28,834 and No. 50-132,92
It is described in Publication No. 6, etc.

As the magenta dye image-forming coupler, a coupler represented by the following general formula can be preferably used.

General formula (capital) (In the formula, Ar represents an aryl group, R21 represents a hydrogen atom, a halogen atom, an alkyl atom, or an alkoxy group, and R represents an alkyl group, an amide group, an imido group, an N-
It represents an alkylcarbamoyl group, an N-alkylsulfamoyl group, an alkoxycarbonyl group, an acyloxy group, a sulfonamide group, or a urethane group. Y is the same as in general formula (■), and W is -NH-, -NH
It represents CO- (the N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-. ) These include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
Same No. 3.127.269, No. 3,311,476, No. 3,152,896, No. 3.419,391
No. 3,519,429, No. 3,555,31
No. 8, No. 3,684,514, No. 3,888,6
No. 80, No. 3,907,571, No. 3,928,
No. 044, No. 3,930,861, No. 3,930
, No. 866, specifications such as No. 3,933,500, JP-A No. 49-29.639, No. 49-111,631, No. 49-129,538, No. 50-13,044. , No. 52-58,922, No. 55-62,454,
Publications No. 55-118,034 and No. 56-38,043, British Patent No. 1.247.493. Specifications of Belgian Patent No. 769,116, Belgian Patent No. 792,525, and West German Patent No. 2,156,111, Japanese Patent Publication No. 46-6
It is described in Publication No. 0,479 and the like. Next, specific representative examples of yellow and magenta dye-forming couplers preferably used in the present invention will be listed, but the invention is not limited thereto.

Yellow coupler (y-i) α-benzoyl-2-chloro-5-[α-(todecyloxycarbonyl)-ethoxycarbonyltoacetanilide.

(Y-2) α-benzoyl-2-chloro-5-[γ-(2°4-di-7-amylfenogysi)-butylamidocouacetanilide.

(Y-3) α-pivalyl α-(4-(4-benzyloxyphenylsulfonyl)-phenoxif-2-chloro-5-[γ
-(2,4-di-t-amylphenoxy)-butyramide]acetanilide.

(Y-4) α-(2-Me)xybenzoyl)-α-(4-acetoxyphenoxy)-4-chloro-2-(4-1-octylphenoxy)-acetanilide.

(Y-5) α-pivalyl α-(3,3-dipropyl-2,4-dioxy-acetidin-1-yl)-2-chloro-5-
(α-(dotecyloxycarbonyl)-ethoxycarbonyltoacetanilide.

(Y-6) α-pivalyl α-succinimide 2-kuroke-5-
Cr-(2,4-di-t-amylphenococo)butyramide]acetanilide.

(Y-7) α-pivalyl α-(3-tetradecyl-1-succinimide) acetanilide (Y-8) α-pivalyl α-phthalimide)'-2-Jo.

-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-9) α-2-furyl-α-phthalimido-2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)butyl agdo]acetanilide.

(y-io) α-3-[α-(2,4-di-t-amylphenoxy)
butylamide]-benzoyl-α-succinimide 2
-Methoxyacetanilide.

(Y-11) α-phthalimide-α-piparyl-2-methoxy4-
((N-Methyl-N-octadecyl)-sulfamoyl]-7toanilide (Y-12)
-((N-methyl-N-octadecyl)sulfamoyl]-acetanilide.

(Y-13) α-cyclobutyryl-α-(3-methyl-3-ethyl-
1-succinimide)-2-chloro-5-((2,5-
di-t-amylphenoxy)acetamide]acetanilide.

(Y-14) α-(2,6-di-oxo-3-n-propyl-piperidin-1-yl)-α-pivalyl-2-chloro5-[
γ-(2,4-di-t-amylphenoxy)butylcarbamoyl]acetanilide.

(Y-15) α-(1-benzyl-2,4-dioxo-imidasolidin-3-yl)-α-bivalyl-2-chloro4-5-[γ
-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-16) α-(1-Benzyl-2-phenyl-3,5-dioxo-1,2,4-)riazin-4-yl)-α-pivalyl-2-chloro5-[γ-(2, 4-di-t-amylphenoxy)butyramidocouacetanilide.

(Y-17) α-(3,3-dimethyl-1-succinimide)-α-
biparyl-2-chloro-5-[α-(2,4-di-t-
amylphenoxy)butyramide]-7toanilide (Y-18) α-(3-(p-chlorophenyl)-4,4-dimethyl-2,5-dioxo-1-imidazolyl]-α-bivalyl-2-chloro -5-(r-(2,4-di-t-amylphenoxy)-butyramidocouacetanilide.

(Y-19) α-pivalyl α-(2,5-dioxo-1,3,4=
triazin-1-yl)-2-methoxy-5-[α-(
2,4-di-t-amylphenoxy)-butyramide toacetanilide.

(Y-20) α-(5-pe/Gi-2,4-dioxo-3-oxasoyl)-α-Vivali-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)-butyramide toacetanilide.

(Y-21) α-(5,5-dimethyl-2,4-dioxo-3-oxazoyl)-α-pivalyl-2-chloro5-[α-(
2,4-di-t-amylphenoxy)-butyramide toacetanilide.

(Y-22) α-(3,5-dioxy-4-oxazinyl)-α-pivalyl-2-chloro0-5-[r-(2,4-di-t-amylphenoxy)-pterazed]-acetanilide.

(Y-23) α-[4,5-dichloro-3(2H)-pyridazone-2
-yl2α-benzoyl-2-chloro-5-[α-(
dotecyloxycarbonyl)-ethoxycarbonyl]-
Acetanilide.

(Y-24) α-(1-phenyl-tetrazol-5-oxy)-α
- pivalru2-chlororu5-[γ-(2,4-di-t
-amylphenoxy)-butyramide toacetanilide.

Magenta coupler (M-1) 1-(2,4,6-)dichlorophenyl)-3-(2-
10Rho 5-octadecylcarbamoyl-anilino)-
5-Pyrazolone.

(M-2) 1-(2,4,6-)dichlorophenyl)-3-(2
-Chloro-5-tetradecanamide-anilino)-5-
Pyrazolone.

(M-3) 1-(2,4,6-)dichlorophenyl) -3-[2
-Chloro-5-γ-(2,4-di-t-amylphenoxy)-butylcarbamoyltuanilino-5-pyrazolone.

(M-4) 1-(2,4,6-)dichlorophenyl)-4-diphenylmethyl-3-[2-chloro-5-(γ-octadecynylsuccinimide)-propylsulfamoyltuanilino-5 -Pyrazolone.

(M-5) 1-[γ-(3-pentadecylphenoxy)-butyramide]-phenyl-3-anilino-4-(1-phenyl-tetrazol-5-thio)-5-pyzolone.

(M-6) 1-(2,4,6-trichlorophenyl)-3-(2
-Chlogastric-5-octadecylsuccinimide)-anilino-5-pyrazolone.

(M-7) 1-(2,4,6-trichlorophenyl)-3-(2-
> Rolow 5-octadecenylsuccinimide)-anilino-5-pyrazolone.

(M-8) 1-(2,4,6-)dichlorophenyl)-3-[2-
Chloro-5(N-phenyl-N-octylcarbamoyl)]-]anilino-5-pyrazolone (M-9) 1-(2,4,6-)lichlorenyl)-3-[2
-Chloμm5-(2,4-di-carboxy-5-phenylcarbamoyl)-benzylamidetuanilino-5-
Pyrazolone.

(M-10) 1-(2,4,6-)dichlorophenyl)-3-(4-
Tetradecylthiomethylsuccinimide)-7nilino-5-pyrazolone.

(M-11) 1-(2,4,6-dolychloroenyl)-3-(2-
/rollo5-(3-pentadecylphenyl)phenylcarbonylamide]-7nilino5-pyrazolo-n.

(M-12) 1-(2,4,6-)dichlorophenyl)-3-(2
-Chloro-5-(2-(3-t-butyl-4-hydroxyphenoxy)-tetradecanamidetoanilino)-
5-Pyrazolone.

(M-13) 1-(2,6-dichloro-4-methoxyphenyl)-
3-(2-Methyl-5-tetradecanamido)-anilino-5-pyrazolone.

(M-14) 4.4'-(2-chloro)benzyldenbis[1-(2
,4,6-trichlorophenyl)-3-(2-chloro-
5-dodecylsuccinimide)-anilino-5-pyrazolone].

(M-15) 4.4'-methylenebis(1-(2,4,6-)lichlorenyl)-3-(2-/coro-5-1"fcenylsuccinimide)-anilino-5-pyrazolone)] c(M
-16) 1-(2,4,6-)dichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone.

(M-17) 3-ethoxy-1-4-[:α-(3-pentadecylphenoxy)butyramide] phenyl-5-pyrazolone.

(M-18) 1-(2,4,6-trichlorophenyl)-3-[2-
Chloro-5-(α-(3-t-butyl-4-hydroxy)-phenyl)-tetradecanamidotuanilino-5
-Pyrazolone.

These yellow dye-forming couplers and magenta dye-forming grays are directly contained in the positive silver halide emulsion layer in an amount of about 0.05 to 2 moles per mole of silver halide.

The halogenated silver emulsion used in the halogenated color photographic light-sensitive material of the present invention mainly forms latent images inside the silver halide grains without coupling the grain surfaces in advance.
It is an emulsion having silver halide grains with most of the photosensitive nuclei inside the grains, and contains any silver halide such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloride iodine. Silver bromide and the like are included.

In the internal latent image type silver halide grains of the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

The meaning that the grain surfaces are not prefogged means that the emulsion used in the present invention is coated asq on a transparent film support.
When a test piece coated to give Ag/υ is developed with the following surface developer A at 20°C for 10 minutes without exposure, the density obtained should not exceed 0.6, preferably 0.4. say.

[Surface developer A]

Further, the silver halide emulsion of the present invention provides sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation.

[Internal developer B]

To be more specific, a portion of the test piece was
When exposed to a light intensity scale for a defined time up to 2 seconds and developed in the internal developer B at 20°C for 4 minutes, another part of the specimen exposed under the same conditions was exposed to the surface developer B. It exhibits a maximum density that is at least 5 times, preferably at least 10 times, that obtained when developed at 20 DEG C. for 4 minutes at A.

Specifically, for example, converged tetragonal silver halide emulsions described in U.S. Pat. No. 2,592,250, U.S. Pat. No. 3.761,266, U.S. Pat.
Core/shell type silver halide emulsions doped with internal chemical sensitizing nuclei or polyvalent metal ions described in the specifications of JP-A-50-8524, JP-A-50-38525, and JP-A-53- Laminated silver norogenide emulsions described in each publication of No. 2408, and other JP-A-52-156614
Examples thereof include emulsions described in Japanese Patent Publication No. 55-127549.

The silver halide emulsion of the present invention can be optically sensitized using commonly used sensitizing dyes.

Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, see Research Disclosure 2- (Ra5
each Disclosure) Nu 1516
2 can be referred to.

The silver halide emulsion of the present invention uses commonly used stabilizers, such as compounds having an azaindene ring and a complex compound having a mercapto ring, in order to suppress the surface sensitivity as low as possible, provide a lower minimum density, and provide more stable properties. cyclic compounds (typically each 4-hydroxy-
Examples include 6-methyl-1,3,3a, 7-chitrazaindene and 1-phenyl-5-mercaptotetrazole.

) can be included.

In addition, the silver halide emulsion of the present invention may contain antifoggants or stabilizers such as mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, zinc compounds, and the like.

Various photographic additives may optionally be added to the silver halide emulsion of the present invention. Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid. Some fine particulate polymeric substances obtained by emulsion polymerization, such as copolymers with copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride bar-7 argyl ester copolymers, etc., are suitable. Examples of the auxiliary agent include saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizer,
surfactant, ultraviolet absorber, pH adjuster, antioxidant,
It is optional to use antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development rate regulators, matting agents, and the like.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to obtain an internal latent image type silver halide photographic light-sensitive material.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylateryl, and benzophenone compounds to prevent browning of dye images caused by short-wavelength actinic rays.
It is advantageous to use 0, 326, 327, and 328 (all Ciba Geigy H) alone or in combination.

Any support can be used for the photosensitive material of the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, cellulose acetate film, and baryta film, which are subbed-treated as necessary. Includes paper, polyethylene laminate paper, etc.

In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion of the present invention depending on the purpose.

Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders may be included depending on the purpose. In addition to gelatin, suitable binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 19 ~
Cellulose derivatives such as cellulose acetate hydrolyzed to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers, polyvinyl The emulsion layer contains alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, and polyethyleneamine. Or intermediate layer, protective layer,
It can be added to the photosensitive material constituent layers such as a filter layer and a backing layer depending on the purpose, and the hydrophilic binder can also contain a suitable plasticizer, lubricant, etc. depending on the purpose.

Further, the constituent layers of the photosensitive material of the present invention can be hardened with any suitable hardening agent. Examples of these hardening agents include chromium salts, zirconium salts, formaldehyde and formaldehyde-based hardeners such as mucohalogen acids, halotriazine-based hardeners, polyepoxy compounds, ethyleneimine-based hardeners, vinyl sulfone-based hardeners, and acryloyl-based hardeners. It will be done.

In addition, the photosensitive material of the present invention can be coated with a large number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a preservation layer, a subbing layer, a backing layer, and an antihalation layer on a support. is possible.

(2) Specific Examples of the Present Invention The present invention will be explained in more detail with reference to the following Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Sample 1 Ni-Xe was prepared by sequentially applying the following layers to a resin-coated paper support from the support side.

Layer 1: cyan image-forming red-sensitive silver halide emulsion layer.

An internal latent image type silver chloroiodobromide emulsion was prepared by a conversion method according to the method described in Example 1 of US Pat. No. 2,592,250. As the cyan image-forming couplers, six types of cyan couplers (1) to (2) of the present invention and four types of cyan couplers (1) to (X) outside the present invention described below were used.

(I) (n) (III) (IV) (V) H (Vl) (■) (■) (IX) 0.157 each of the cyan couplers from (I) above
In addition, 100 g of 2.5-di-tert-octylnohedoquinone, 200 g of dibutyl 7 thale, and 50 g of ethyl acetate were mixed and dissolved, and the mixture was added to a gelatin solution containing sodium dodecylbenzenesulfonate and dispersed. The solution was added to the emulsion which had been spectrally sensitized with the dye and the amount of silver was 400W.
/m'' and coupler amount s 20 my/m'.

Layer 2...Protective layer The amount of gelatin should be 200/- It was applied to. In addition, there is a hardening agent in layer l. Bisvinylsulfonyl methyl ether Contains saponin as a coating aid I forced it.

Samples α) to ■ were subjected to wedge exposure using a xenon lamp, and the following [Processing 1] was performed. ) - Bleach-fixing (1 minute 30 seconds) - Washing with water (1 minute)
30 seconds) - Stable (45 seconds) - Rinse (3 seconds) The processing temperature was 38° C. in each step, and the composition of each processing solution was as shown below.

[Color developer composition]

It consists of an aqueous solution of chemicals with the following types and concentrations (g/L):

[Bleach-fix solution composition]

It is composed of an aqueous solution of chemicals with the following types and concentrations <g'yt>.

[Stable liquid composition]

The exposure conditions for optical fog were as follows: a daylight color fluorescent lamp (Ra: 77) was used as the light source, and the illuminance was set to 1 lux on the photosensitive surface using a neutral density filter.

Light power pre-exposure was carried out for 10 seconds after immersing the sample in the developer for 10 seconds, taking it out of the developer and positioning it horizontally so that the light hit the photosensitive surface vertically, and then immersing it in the developer again after exposure.

Also, for samples (I) to ■, color developer 1 of [treatment 1]
[Processing 1] except that cI-phenyl-4,4-dimethyl-3-pyrazolidone was added to Color Developer 1 at 9150 μm, and the color development times were 1 minute 40 seconds and 1 minute 20 seconds, respectively.
The same [Processing 2] and [Processing 3] were performed.

Table 1 shows the minimum cyan density, γ (gamma), and maximum cyan density of each sample obtained by performing the above-mentioned [Processing 1] and [Processing 2].

Note that the γ (gamma) value is the minimum concentration factor 〇 on the characteristic curve,
The leg γ (gamma) on the characteristic curve is expressed as the tangent value of the inclination angle of the straight line connecting the two points 0.05 and minimum density +0.30.

As is clear from the results in Margin Table 1 below, samples (I) of the present invention ~
Regarding η, even when treated for a short time using a phenidone derivative, a good cyan image was obtained with almost no decrease in γ (gamma) of the cyan legs. On the other hand, in the samples (■) to (X) containing cyan couplers other than those of the present invention, when a positive image is directly formed by processing for a short time in the presence of a phenidone derivative, γ (gamma) increases and the contrast is high. A great image was obtained.

Example 2 [Treatment 2] was performed using samples I, II, ■, and ■ of the present invention in Example 1 and samples ■, ■, ■, and X outside the present invention, and the The illuminance was adjusted to 0.3.0 at the photosensitive surface using a neutral density filter.
, 5.1.0.1.5.2.0 lux was changed, but the same process as in Example 1 was performed. Table 2 shows the minimum density and maximum density of the cyan image of each sample obtained by performing the above processing.

Table-2 (Part 2) From the results of Table-2, samples LII, IV, and ■
The samples also exhibited the same stability against changes in illuminance during optical fog as samples (2), (2), (2), and (X) other than the present invention using conventional cyan couplers.

Example 3 Samples M through 3 were prepared by sequentially coating the following layers on a resin-coated paper support from the support side.

Layer 1: Cyan-forming red-sensitive silver halide emulsion layer An internal latent image type silver halide emulsion was prepared according to the method described in JP-A-55-127549.

That is, to 220 - of a 1 molar aqueous solution of potassium chloride containing 10 g of gelatin, 200 - of a 1 molar aqueous solution of silver nitrate was added at 60°C.
was added immediately. After 10 minutes of physical heat formation, a mixed solution of 200 mm of a 1 molar aqueous solution of potassium bromide and 50 mm of a 0.1 molar aqueous solution of potassium iodide was added. In order to cover the obtained converged silver chloroiodobromide grains with a silver chloride shell, 150 d of a 1 molar aqueous solution of silver nitrate was added over 5 minutes, and after physical heat formation for 20 minutes, the grains were washed with water.

(XI) (X[I) (X[ll) C section H3 (XV) (XVI) OUT (xyIll) Add 0.138 mol of each of the above M-shoulder cyan couplers and add 2.5-ditert. - Octylnohydroquinone 2g 1 Diptylintalate 50g 1 Ethyl acetate 14
0 g was mixed and dissolved, added to a gelatin solution containing sodium isopropylnaphthalene sulfonate, and emulsified and dispersed.

The dispersion was then added to the emulsion previously spectrally sensitized with dye and 4-hydroxy-6-methyl-1,3,3a,7-titrazymedene I.
g, 2,5-dihydroxy-4sec-octadecyl-
1 g of potassium benzenesulfonate, 7 JDi, and bis(vinylsulfoni)methyl)ether were added as a hardening agent, and coating was carried out so that the amount of silver was 400 μ/nl and the amount of coupler was 460 MfAI.

Layer 2...Intermediate layer 5 g of gray colloidal silver and 10 2,5-di-tert-octylhydroquinone dispersed in diptyl 7 talate
100tnt of 2.5% gelatin solution containing 400 kg/lr of colloidal silver? It was applied so that

Layer 3: Magenta-forming green-sensitive halogen ratio silver emulsion layer 1-(2,4,6-)chlorophenyl)-3-(2-chloro-5-octa) as magenta coupler Decylsuccinimide anilino)-5-pyrazolone 40g,
2.5-tert-octylhydroquinone 1g1
75 g of dioctyl phthalate and 30 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium inpropylnaphthalene sulfonate for emulsification and dispersion. The dispersion was then added to the emulsion previously spectrally sensitized with the dye and 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene Ig, 4-(6 )-potassium octadecylbenzenesulfonate Igt-added L,
Bis(vinylsulfonylmethyl)ether was added as a hardening agent, and the amount of silver was 400 mW/n? , turnip 2 - amount 400
■It was applied so that it became /-.

Layer 4...Yellow filter 1 layer Yellow colloidal silver 200 Q /l
r? It was applied so that

Layer 5...Yellow-forming blue-sensitive silver halide emulsion layer α-(4-(1-benzyl-
2-phenyl-3,5-dioxy-1,2,4-triaziridinyl)]-]α-bivalyl-2-chloro-5-γ
-(2,4-di-tert-amylphenoxy)butyramide]acetanilide 80g 12.5-di-tert
-octylhydroquinone 1g1 diptylphthalate)
80 g and 200 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate to emulsify and disperse. The dispersion was then added to the emulsion, and 4-hydroxy-6-methyl-1,3,3a,
7-chitrazaindene Ig, 2,5-dihydroxy-4
Potassium sec-octadecyl-benzenesulfonate I
In addition, bis(vinylsulfonylmethyl)ether was added as a hardening agent, and coating was carried out so that the amount of silver was 400 W/m' and the amount of coupler was 530 W/m'.

Layer 6... Protective layer gelatin amount is 200119/lr? It was applied so that it became Vc.

Note that Layer 1, Layer 2, Layer 3, Layer 4, Layer 5, and Layer 6 contained saponin as a coating aid.

For the prepared sample M-shoulder, 1-phenyl-4-methyl-4-human tetraxymethyl- was used in place of 1-phenyl-4,4-dimethyl-3-pyrazolidone used in [Treatment 2] of Example 1. [Treatment-3] was carried out in the same manner as [Treatment 2] except that 3-py2zolidone was used.

The minimum density, γ (gamma), and maximum density of each dye image of yellow (T), magenta M, and cyan (Q) of the sample obtained by the above processing were measured.These results are shown in Table 3. .

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Claims (1)

[Scope of Claims] A direct positive image forming apparatus for forming a direct positive color image having a silver halide emulsion layer containing internal latent image type silver halide grains and a cyan coupler on a support whose grain surfaces are not fogged in advance. After imagewise exposure of a silver halide color photographic light-sensitive material, prior to color development or during the color development process, direct positive exposure is applied in the presence of a phenidone derivative represented by the following general formula (I). A direct positive color image forming method, wherein the cyan coupler is represented by the following general formula (n).几. (In the formula, R1 represents a hydrogen atom, an alkyl group, or an aryl group, and "!y "m #Ra and hiR@ each represent a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group.) General formula (n ) H 2゜ (in the formula, % R6 represents an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group. R represents an alkyl group or an aryl group. R1 represents a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. J4-l represents an imino group, n represents 0 or 1. 2. represents a group that can be separated by reaction with a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent. ]