JPH02157751A - Method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow processing with stable photographic performance in spite of continuous processing with an increase number of processing sheets of internal latent image type direct positive and negative type photosensitive materials by designing the ratio of the sensitivity of the photosensitive layers of the internal latent image type direct positive silver halide photographic sensitive material and negative type silver halide photographic sensitive material within the range of specific values. CONSTITUTION:At least the internal latent image type direct positive silver halide photographic sensitive material and negative type silver halide photographic sensitive material contain one layer each of a blue photosensitive layer, green photosensitive layer and red photosensitive in case of subjecting there materials to a development processing in the same development processing bath. The ratio SB/SG of the sensitivity of the blue photosensitive layer to the sensitivity of the green photosensitive layer is designed to be within the range of 0.3<=SB/SB<=3.0 and the ratio SR/SG of the sensitivity of the red photosensitive layer to the sensitivity of the blue photosensitive layer within the range of 0.2<=SR/SG<=2.0. The always stable photographic performance is obtd. in this way by subjecting the internal latent image type direct positive photosensitive material and negative type photosensitive material in the developing soln. bath common to these materials.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to processing internal latent images using a common developer for direct positive silver halide photographic materials (hereinafter referred to as internal temperature type direct positive light-sensitive materials). The present invention relates to a development processing method.

[Background of the invention]

Conventionally known methods for obtaining direct positive images are mainly divided into two types. One type uses a silver halide emulsion that has fog in advance, and uses solarization or the Burschel effect to destroy the fog and latent image in the exposed area, thereby obtaining a positive image after development. It is something. Another type is
Using an internal latent image type silver halide emulsion that does not cause fog (generally surface fog) until image exposure, fogging treatment (nucleation treatment) is performed after image exposure, and then surface development is performed, or after image exposure A positive image can be obtained by performing surface development while performing fogging treatment.

The above fogging treatment may be performed by exposing the entire surface to light, chemically using a fogging agent, using a strong developer, or by heat treatment. The internal latent image type silver halide emulsion is a silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide crystal grains and forms a latent image inside the grains upon exposure. .

Of the above two methods for forming a positive image, the latter type of method has -
Highly sensitive to aggregation, suitable for applications requiring high sensitivity.

Various techniques are known in this technical field. For example, U.S. Patent Nos. 2,592.250, 2,466.957, 2,497.875, and 2
, No. 588,982, No. 3,761,266, No. 3,
The methods described in No. 761,276, No. 3,796.577 and British Patent No. 1.151.363 are known.

Regarding the formation mechanism of positive images, for example, Photographic Science and Engineering (Ph.D.
otographic 5science and en
gineering), Vol. 20, p. 158 (1976), it is considered as follows. Photoelectrons generated within the silver halide crystal grains by imagewise exposure are selectively captured inside the grains, forming an internal latent image.

This internal latent image acts as an effective trapping center for electrons in the conductive band, so in exposed particles, electrons injected during the subsequent fog development process are captured internally and strengthen the latent image. become. In this case, the latent image is all internal and is not developed. - For particles that have not undergone imagewise exposure, at least some of the injected electrons are captured on the particle surface and the particle is developed by surface development.

By the way, when processing internal temperature type direct positive photosensitive materials in a photo processing laboratory, a dedicated processing line for internal temperature type direct positive photosensitive materials is set up separately from the conventional processing line for negative type photosensitive materials. It is common for there to be.

For example, a processing line for negative-tone photosensitive materials has three types of equipment installed separately: an automatic developing machine for negative film, an automatic developing machine for negative paper, and an automatic printing device. The processing line for transparent materials consists of two types of equipment: a dedicated automatic printing device and a dedicated automatic developing machine.

Generally, a certain amount of work space is required around each of these devices, and additional space is required around each of these devices for adjusting the refill cock, correcting evaporation, replacing tank liquid, and refilling. must be ensured.

Therefore, if the above-mentioned equipment is placed separately, it is necessary to ensure that the work space around each equipment does not overlap, which may hinder work in a narrow space such as a small-scale color photo lab. Simplifying processing methods and downsizing automatic processors are important issues.

On the other hand, in recent years, demand for internal temperature type direct positive photosensitive materials has been increasing in the market, and processing lines for internal temperature type direct positive photosensitive materials have become extremely important. but,
Most color photo processing laboratories do not have a dedicated processing line for internally heated direct positive materials due to problems such as work space, cost, and personnel.

In view of this background, there has recently been a strong desire for a method in which an internal temperature type direct positive light-sensitive material and a negative tone sensitive material can be developed in the same development bath.

A developing solution that commonly processes two different types of photosensitive materials requires maintenance and management of the activity of the solution more than other aerosols, making it difficult to maintain stable photographic performance and reducing density due to continuous processing. , problems such as increased fog, and variations in gradation occur.

Conventionally, various techniques have been known for directly and stably processing internal temperature of positive and negative sensitive materials using a common processing solution. For example, No. 62-139548 attempts to standardize the Br' concentration in the developing solution by defining it within a certain range. Further, in Jikai No. 63-92949, an attempt is made to achieve commonality by adding a hydroxylamine derivative to the developing solution.

Although these technologies have made it possible to process stably to some extent, they are still not sufficient. In particular, when continuous processing is performed with a large increase in the number of sheets to be processed, there is a problem that gradation fluctuations occur and the gradation balance is disrupted, and a more stable common processing is desired.

As a result of intensive studies on the stable common processing of internal temperature direct positive photosensitive materials and negative photosensitive materials, the inventors of the present invention discovered that internal temperature direct positive photosensitive materials and negatives can be processed continuously by increasing the number of processed sheets of the internal temperature direct positive photosensitive materials. but,
We have found that processing with very stable photographic performance is possible. Furthermore, surprisingly, it has been found that common processing in which both photosensitive materials are sequentially processed at a certain rate can provide processing with more stable photographic performance than sequential processing of each photosensitive material alone.

[Purpose of the invention]

The first object of the present invention is to process a silver halide photographic material in which stable photographic performance can always be obtained by developing an internal temperature type direct positive-sensitive material and a negative-tone sensitive material in a common developer solution. Our goal is to provide the following.

A second object of the present invention is to provide a processing method that requires less work space and installation area by developing an internal temperature type direct positive light-sensitive material and a negative type light-sensitive material in a common developer solution.

Other purposes will become clear in the following specification.

[Structure of the invention]

The above objects of the present invention are (1) Processing of silver halide photographic materials in which internal latent image type direct positive silver halide photographic materials and negative working silver halide photographic materials are developed in the same development bath; In the method, the internal latent image type direct positive silver halide photographic light-sensitive material and the negative-working silver halide photographic light-sensitive material are developed in the same development bath. The internal latent image type direct positive silver halide photographic light-sensitive material and the negative 2-type silver halide photographic light-sensitive material each contain at least one blue light-sensitive layer, one green light-sensitive layer, and one red light-sensitive layer, and the green light-sensitive layer The ratio of the sensitivity of the blue-sensitive layer to the sensitivity of the layer (SB
/SG) is 0.3≦SB/SG≦3.0, and the ratio of the sensitivity of the red photosensitive layer to the sensitivity of the green photosensitive layer (expressed as SB/SG) is 0.2≦SR /SG≦2.
0, and (2) at least one of an internal latent image type direct positive silver halide photographic material and a negative silver halide photographic material. is characterized by containing at least one compound represented by -1 below.

This was achieved by the method for processing silver halide photographic materials described in (1).

General Formula CM-1) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of the color-forming herbal medicine, and R represents a hydrogen atom or a substituent.

Furthermore, (3) the ratio of the number of processed sheets of the internal latent image type direct positive silver halide photographic light-sensitive material (P) and the negative-tone silver halide photographic light-sensitive material (N) is 20/80≦P/N≦80/20. This was achieved by the method for processing a silver halide photographic material described in (1) and (2) above, which is characterized in that it falls within the range of (1) and (2) above.

Next, the magenta coupler represented by the formula CM-1] will be explained.

In general formula CM-1), the substituent represented by R is not particularly limited, but typically includes multiple groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfonyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio polygroups, spiro compound residues, bridged hydrocarbon compound residues etc. can also be mentioned.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc. Niacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc.; Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; examples of the heterocyclic group include preferably 5- to 7-membered ones, specifically 2-furyl, 2-thienyl, and 2- Pyrimidinyl group, 2-benzothiazolyl group; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3
．． 4.5.6-tetrahydrobilanyl-2-oxy group,
l-phenyltetrazole-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy- 1,3,5-1 lyazole-6 monothio group, etc.; siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group , 7-thalimide group, glutarimide group, etc.; spiro compound residues include spiro [3,3]hebutan-1-yl; and bridged hydrocarbon compound residues include bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
Examples include 1,71 decane-1-yl, 7,7-dimethyl-bicyclo[2,2,11 heptan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
Carboxyl, is a chlorine atom.

Further, examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituent that the ring may have include those described above for R; Things can be mentioned.

More specifically, what is represented by the general formula (M-1) is, for example, the following formula (M-n:I ~ (M-■)
Represented by

(R1' is the same as the above R, Z' is the same as the above Z, and R2' and R, / represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group). However, preferably a halogen atom, especially N-N-Nti General formula (M-V) General formula CM-Vl) General formula [M-■] In the above-mentioned formula (M-n) to [M-■], R
l'= R* and X have the same meanings as R and X above.

Also, among the formulas (M-I), those represented by the following formulas [M-■] are preferred.

- Formula [M-■] In the formula, Rr, X and zl have the same meanings as R, X and 2 in the general formula CM-1).

Among the magenta couplers represented by the above formulas (M-11) to [M-■], a magenta coupler represented by the general formula (M-11) is particularly preferred. In addition, when used for positive image formation, -Math CM-1)~
Regarding the substituents on the heterocycle in [M-■],
-Formula CM-I), R is also -Formula (M-1)
In 1) to [M-■], it is preferable that R satisfies the following condition 1, more preferably the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following condition 1.2 is satisfied.
and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2 Only one hydrogen atom is bonded to the carbon atom, or there is no bond at all.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R that satisfy the above conditions are those represented by the following formula (M-11).

General formula (M-111) usRro-C- In the formula, Rh, Rro and R11 each have the same meaning as R above.

Also, the above R,,R,. and two of R1, for example R9 and R1°, may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle),
Furthermore, R1 may be bonded to the linear ring to constitute a bridged hydrocarbon compound residue.

-Among the formulas (M-X), (i) is preferable.
When at least two of R* to R0 are alkyl groups,
(ti) One of R1-R11, for example, R1, is a hydrogen atom, and the other two, R1 and R5°, combine to form a cycloalkyl together with the root carbon atom.

Furthermore, it is preferable among (i) that two of R9 to R1+ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, substituents which the ring formed by Z in the formula CM-I) and the ring formed by zl in the formula [M-■] may have, and the substituents of the formula CM-I [) to (M
-R1-R6 in VI) are as follows-Math CM-
Those represented by X) are preferred.

General formula CM-X) -R'-8O, -R1 In the formula, R'li represents a fullkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the alkylene group is straight chain or branched.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

Moreover, when used for forming a negative image, - Formula (M-1) ~ [M
Regarding the substituent on the heterocycle in -■], R in -formula CM-1) is also -formula CM-IF)~
In [M-■], it is preferable that R1 satisfies the following condition 1, and more preferably the case that the following conditions 1 and 2 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: At least two hydrogen atoms are bonded to the carbon atom.

The most preferred substituents R and R6 that satisfy the above conditions are those represented by the following formula (Mn).

General formula (M-n) Rlz-〇　H* In the formula, R1 has the same meaning as R above.

Preferred as R12 is a hydrogen atom or an alkyl group.

Below, the compound represented by the general formula CM-1) (M-4
) (M-5) Hs Hs (M-6) (M-7) (M-8) CM-9) (M-10) (M-15) (M-16) (M-17) C1aH3? (M-11) CM-13) CH.

Hs (M-23) (M-24) (M-31) (M-34) (M-35) (M-27) (M-30) (M-40) C@nts C, H, @ CH.

CH.

(M-41) (M-42) (M-44) (M-49) (M-51) (M-52) tisNl-1>S,L;,,l-1,.

(M-46) (M-47) (M-54) (M-56) CM-57) (M-58) (M-61) (M-68) (M-69) C,,H,.

(M-63) (M-64) (M-66) CM-67) (M-73) -Q u-U -Q Q□0 In addition to the above representative examples, Among the compounds described on pages 66 to 122 of the specification, Nos. 1 to 4, 6, 8 to 17, and 19 to 24.
26~43°45~59.61~104.106~12
Compounds represented by 1.123 to 162.164 to 223 can be mentioned.

In addition, the coupler is described in the Journal of the Chemical Industry.
Society ((Journal of the Che
micalSociety), Perk
in) I (1977), 2047-2052,
U.S. Patent No. 3,725.067, JP 59-9943
No. 7, No. 58-42045, No. 59-162548, No. 59-171956, No. 60-33552, No. 60-43659, No. 60-172982, and No. 6
It can be synthesized by referring to No. 0-190779 and the like.

The above couplers usually contain IX 10 per mole of silver halide.
-3 mol to 1 mol, preferably I x 10-" mol to
It can be used in the range of s x io-' moles.

The above couplers can also be used in combination with other types of magenta couplers.

In the present invention, the internal temperature type direct positive light-sensitive material and the negative light-sensitive material are:
Each contains at least one blue photosensitive layer, one green photosensitive layer, and one red photosensitive layer, and the ratio of the sensitivity of the blue photosensitive layer to the sensitivity of the green photosensitive layer (SIl/S) is 0.3≦Ss/
Sa≦3.0, and the ratio of the sensitivity of the red photosensitive layer to the sensitivity of the green photosensitive layer (Ss+/Sc) is 0.2≦
It is designed within the range of SR/SG≦2.0. More preferably, (Ss/Si)' is 0.5≦Ss/S*≦2.
0, and (Ss/Sa) is 0.2≦St/Sc≦1.
It is 2.

Here, the sensitivity (Sa) of the green photosensitive layer, the sensitivity (Sa) of the blue photosensitive layer, and the sensitivity (Sl) of the red photosensitive layer are defined as follows. That is, the internal temperature direct positive photosensitive material and the negative photosensitive material are used as a photosensitive layer (color temperature of light source: 2854'K).

When wedge exposure was performed using a tungsten lamp (light source: tungsten lamp), development was performed in the same development bath as defined in the present invention, and sensitometry was performed on the resulting image.
1/2X of the image corresponding to the green photosensitive layer (Dmax+
Let Sc be the reciprocal of the exposure amount that gives the density (Dmin).

(Here, Dmax and Dmin indicate the maximum density value and minimum density value of the image when measured at a wavelength corresponding to the main tL length of spectral absorption of the image). In addition, the reciprocal of the exposure amount that gives a density of 1/2X (Dmax + Dmin) of the image corresponding to the blue photosensitive layer is 5ll (here, Dmax
and Dmin indicate the maximum density value and minimum density value of the image when measured at a wavelength corresponding to the dominant wavelength of spectral absorption of the image). 1/2X of the image corresponding to the red photosensitive layer (
The reciprocal of the exposure amount that gives the density of Dmax+Dhoin) is s
m (here, Dmax and D+oin indicate the maximum density value and minimum density value of the image when measured at a wavelength corresponding to the dominant wavelength of spectral absorption of the image).

The sensitivity of the internal temperature type direct positive photosensitive material was obtained under the same developing conditions as the present invention, and the sensitivity of the negative tone sensitive material was obtained under the same developing conditions as the present invention. It is something that was given.

In the present invention, negative photosensitive material means color photographic paper, color negative film, color reversal film, and color reversal paper.

The processing step used in the present invention is preferably a color development process as a development step.

In particular, as a color development process, it is preferable to perform a color development process, a bleaching process, a fixing process, and a water washing alternative stabilizing process, but instead of the process using a bleaching solution and the process using a stabilizing solution. Then, using l-bath bleach-fix solution,
A bleach-fix treatment step may also be performed.

In addition, in combination with these treatment steps, a pre-hardening treatment step,
A neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the sensitive material and the development process is performed using an activator solution.

Representative examples of these processes are shown below.

In these treatments, as a final step (final bath), any one of (1) water washing treatment step, (2) water washing alternative stabilization treatment step, or (2) water washing treatment step and stabilization treatment step is performed.

In the processing steps of the present invention, the developing tank is substantially common, and the processing tanks can be made into a unit and connected as needed.

As for the structure of the processing tank in the processing method of the present invention, a processing tank including known processing steps may be used.

*→(Final bath (A)) *→(Final bath (B)) *-(Fixing (A))-(Final bath (A)) *-(Fixing (B)
)) - (Final bath (B)) (7) [Color development] - [Bleaching]
- [Fixing] - [Final bath] (8) [Color development] → [Bleach-fixing] - [Final bath] (9) [Color development] - [Neutralization] - [Bleach] - [Fixing] - [Final bath] ] (10) [: Color development] →
[Neutralization] → [Bleach-fixing] → [Final bath] (IIX color development) → [Neutralization] → [Color development] → [Neutralization] → [Washing] → [
Bleaching] - * * - [Fixing] - [Water washing] → [Postdural] → [Final bath] (12) (Color development] → (Black and white development (B)) → (
Neutralization (B)) - (Water washing (B)) - * * → [Color development] →
[Bleaching] - [Fixing] → [Final bath] Above processing steps (1) ~
(12) In the middle, the steps enclosed in [ ] represent common processing steps, while the steps enclosed in () are separate processing steps,
A represents an internal temperature type direct positive material, and B represents a negative temperature sensitive material.

In the present invention, the term "substantially common processing tank" usually means one tank, but also includes a countercurrent system (cascade system) partitioned into two or three tanks. The countercurrent method includes a countercurrent method in which the moving direction of the photosensitive material to be processed is parallel in plan view, and a parallel overflow method in which the moving direction is perpendicular to the direction of movement of the photosensitive material to be processed. Also 2
It also includes processing tanks in which tanks are connected by piping or holes.

Details of these are described in JP-A No. 60-280207.

The color developing solution used in the present invention means a surface developing solution that does not substantially contain a silver halide solvent,
The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, aminophenol type and p-
Contains phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, p-1 luenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can.

These compounds are generally about 0.0% in color developer lQ.
Concentrations from 1 g to about 200 g, more preferably from about 1 g to 50 g.
Use at a concentration of g.

Further, the processing temperature with the color developing solution is preferably i0°C to 65°C, more preferably 25°C to 45°C.

Examples of the aminophenol developer include 0-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-oxytoluene, 2-oxy-3-amino-1,4- Dimethyl-benzene and the like are included.

A particularly useful aromatic primary amine color developer is N-N'
-Dialkyl-p-7 It is a unilene diamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N/-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N-N'-dimethyl-p-phenylenediamine hydrochloride, 2-Amino-8-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β -Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-(Z-methoxyethyl)-
Examples include N-ethyl-3-methylaniline-p-+-luenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

For example, a method of incorporating a color developing agent in the form of a metal salt as described in US Pat.
2.559 and Research Disclosure (Re
search Disclosure) 1976 N0
．． 15159, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429
A method of incorporating the color developing agent as a dye precursor as shown in US Pat. No. 3,342,597, etc. can be used. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Furthermore, various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, etc. can be contained.

Further, as a development regulator, for example, citradinic acid or the like may be contained. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethyl formaldehyde or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more, preferably about 9-13.

The color developing solution used in the present invention may optionally contain tetronic acid, tetronimide, and 2 as antioxidants.
- Anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
Organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid)
or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2゜3-tricarboxylic acid, polyphosphoric acid such as tribolyphosphoric acid or hexamethanoic acid. , polyhydroxy compounds, and the like.

In the present invention, the bleaching process refers to a process of bleaching the developed silver image after the color development process with an oxidizing agent (bleaching agent).

As the bleaching agent, metal complex salts of organic acids are preferably used.
For example, polycarboxylic acids, aminopolycarboxylic acids, or organic acids such as sulfuric acid and citric acid, which are coordinated with metal ions such as iron, cobalt, and copper, are used. Among the above organic acids, the most preferred organic acids include polycaribonic acid and aminopolycarboxylic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following. That is, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, and the like.

These bleaches contain 5 to 450 g/Q, more preferably 2
Use in amounts of 0 to 250 g, l.

In addition to the bleaching agent mentioned above, it is preferable to add a halide such as ammonium bromide to the bleaching solution. As the above-mentioned halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used. Can be done.

In the present invention, the fixing process refers to a process of desilvering and fixing using a fixing solution containing a silver halide fixing agent. Silver halide fixing agents used in the fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as thiosulfates, thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5 g IQ or more, within a range that can be dissolved, but generally 70 g to 250 g IQ.

In the present invention, it is preferable that the bleaching process and the fixing process are performed in one process using a bleach-fix solution,
The metal complex salt of an organic acid as a bleaching agent used in the bleach-fix solution coordinates a metal ion such as iron, cobalt, or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid.
It is something. As the organic acid used to form such a metal complex salt of an organic acid, the same organic acid as a bleaching solution can be used.

As the silver halide fixing agent contained in the bleach-fix solution, there is used a compound which reacts with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processing.

After the treatment with a treatment liquid having fixing ability, a normal water washing treatment may be performed, but particularly in the present invention, it is preferable to apply a stabilizing treatment liquid without substantially including a water washing step.

In the present invention, a stabilization treatment that does not substantially include a water washing step refers to a stabilization treatment that is an alternative to water washing using a single tank or multiple tank countercurrent method immediately after treatment with a treatment liquid having fixing ability. It may also include processing steps other than general washing, such as rinsing, auxiliary washing, and known washing promotion baths.

In the stabilization treatment step of the present invention, the method of bringing the stabilizing solution into contact with the silver halide photosensitive material is preferably by immersing the silver halide photographic material in a bath like a general processing solution, but using a sponge bath. , both sides of the emulsion surface and the transport leader of the silver halide photographic light-sensitive material using synthetic fiber cloth, etc.
It may be applied to the conveyor belt, or it may be sprayed onto the conveyor belt. In the following, the case where a stabilizing column using the immersion method is used will be mainly explained.

The stabilizing liquid preferably contains a chelating agent having a xylate stability constant of 6 or more with respect to iron ions.

Examples of xylate agents having a xylate stability constant of 6 or more for iron ions include organic cariponic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, and the like. Note that the above-mentioned iron ion means ferric ion (Fe'').

Specific examples of chelating agents having a chelate stability constant of 6 or more with ferric ions include diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and the like.

The amount of the above chelating agent used is o, oi per 112 of the stabilizing liquid.
~50g 1, preferably 0.05~20g.

Furthermore, preferred compounds to be added to the stabilizing solution include:
Examples include anti-spill agents, water-soluble metal salts, ammonium compounds, and the like. The above anti-piping agents include hydroxybenzoic acid compounds, phenol compounds, inthiazole compounds,
Pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, inoxazole compounds, propatoolamine compounds, sulfamide compounds, amino acid compounds, and Penz Examples include triazole compounds.

Furthermore, as metal salts, Ba, Ca, Ce, Co, I
n, La, Mn.

Metal salts of Ni, Pb, Sn, Zn, Ti, Mg, AQ, Sr, and as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. Can be supplied. The usage amount is 1 per stabilizing liquid Iff.
x10-' to iX10-' mol, preferably 4xlO-4 to 2xlO-! mol, more preferably in the range of 8 x 10-' to ix io-'' moles.

In addition to the above compounds, the stabilizing liquid also contains optical brighteners, organic sulfur compound neonium salts, hardeners, quaternary salts, water droplet prevention agents such as polyethylene oxide derivatives, siloxane derivatives, etc.
Sulfuric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide,
Various types of agents for improving and expanding processing effects, such as pH adjusters such as sodium acetate and potassium citrate, organic solvents such as methanothyl, ethanol, and dimethyl sulfate 7 oxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone adjusting agents. Adding additives is optional.

The above compounds and other additives can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives may be added to the stabilizing liquid supplied to the stabilization tank and then stabilized. There are various methods, such as using it as a supply solution for the stabilizing solution, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the silver halide photographic light-sensitive material to be processed. It may be added by such an addition method.

When using the multi-tank countercurrent method, the method of supplying the stabilizing liquid in the stabilization treatment process is to supply it to the rear bath and to over 70-min from the front bath.
It is preferable to let

The preferred pH value of the treated solution in the stable column is p) 14 to 8.

Further, the DH can be adjusted using the above-mentioned pH adjusting agent.

The treatment temperature during the stabilization treatment is, for example, 20°C to 50°C.
℃, preferably in the range of 25°C to 40°C. In addition, from the viewpoint of rapid processing, a short treatment time is preferable, but it is usually 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes. It is preferable that the post-stage treatment time is long.

d storehouse.

In the present invention, washing with water may not be necessary before and after the stabilization treatment, but the surface may be cleaned by rinsing with a small amount of water in a short period of time or with a sponge, stabilizing the image, and improving the surface properties of the silver halide photographic light-sensitive material. It is optional to provide a treatment tank for adjustment. Examples of the agent for stabilizing the image and adjusting the surface properties of the silver halide photographic light-sensitive material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts.

In the present invention, it is optional to provide additional processing steps in addition to the above processing steps. Furthermore, silver may be recovered by a known method not only from the above-mentioned stabilizing solution but also from a processing solution containing a soluble silver complex such as a fixing solution or a bleach-fixing solution.

In addition, if the above-mentioned stabilization treatment is performed, the washing process is virtually unnecessary, so there is no need for piping equipment for washing.
This has the advantage that the device itself can be easily installed at any location.

In addition to these treatments, there are methods in which the developer produced by color development is subjected to halogenation bleaching and then color development is performed again, various intensification treatments (amplification treatments) described in JP-A-58-154839, etc. It may be processed using a developing method that increases the amount of dye produced.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or contacting a carrier impregnated with the processing solution, can be used. A web method using viscous development processing, a method using viscous development processing, etc. may also be used.

When the image forming layer of the light-sensitive material of the present invention is an internal latent image type silver halide emulsion layer and a positive image is directly formed using this layer, the main process is to form an internal latent image type silver halide emulsion layer that has not been fogged in advance. It is common to carry out surface development of a silver photographic material after image exposure and after subjecting it to a fogging treatment, or while carrying out a fogging treatment. The fogging treatment can be carried out by uniformly exposing the entire surface to light or by using a fogging agent. In this case, the entire surface uniform exposure is preferably carried out by immersing or moistening the image-exposed internal latent image type silver halide photographic material in a developer or other aqueous solution, and then uniformly exposing the entire surface. . The light source used here may be any light within the wavelength range to which the internal latent image type silver halide photographic light-sensitive material is sensitive.
Further, high-intensity light such as flash light may be irradiated for a short time, or weak light may be irradiated for a long time.

The time for uniform exposure over the entire surface can be varied over a wide range depending on the internal latent image type silver halide photographic light-sensitive material, the processing conditions, and the type of light source used so as to ultimately obtain the best positive image. Further, a wide variety of compounds can be used as the above-mentioned fogging agent, and it is sufficient that the fogging agent is present during the development process, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer, or during development. It may be contained in a liquid or a processing liquid prior to development processing, but it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (particularly preferably in a silver halide emulsion layer). The amount used can be varied widely depending on the purpose, and the preferred additive is 1-1% per mole of silver halide when added to a silver halide emulsion layer.
500sg, particularly preferably 10-1000mg. Further, when added to a processing solution such as a developer, a preferable additive is 0.01 to 5 g/a1, particularly preferably 0.08 to 5 g/a1.
It is 0.15g/12. Such fogging agents include, for example, U.S. Pat.
82, or the hydrazide or hydrazone compounds described in U.S. Pat. No. 3,227.522, and U.S. Pat. .494,
Heterocyclic quaternary nitrogen compounds described in US Pat. No. 3,734.738 and US Pat. No. 3,759.901, as well as US Pat.
, 030,925. Further, these fogging agents can also be used in combination. For example, Research Disclosure + - (Research Disclosure
) No. 15162 describes the use in combination with a non-adsorption type fogging agent, which can also be applied to the present invention.

The internal latent image type silver halide emulsion used in the present invention is an emulsion having decagenide grains that mainly form a latent image inside the silver halide grains and having most of the photosensitive nuclei inside the grains. , any silver genide such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. In particular, silver chloride, silver chlorobromide, silver chloroiodobromide, and silver iodochloride are preferred from the viewpoint of grains with a high development speed.

It is preferable that the internal latent image type silver halide grains used in the present invention have their surfaces not chemically sensitized, or even if they are sensitized, the sensitization is only slight.

Specifically, for example, the compound silver halogen emulsion described in US Pat. No. 2,592,250, US Pat. No. 3,761,266, US Pat.
, 246, a core/shell type silver halide emulsion doped with internal chemical sensitizing nuclei or polyvalent metal ions, JP-A-50-8524, JP-A-50-3852.
No. 5, the laminated type silver 10-genide emulsion described in No. 53-2408, and other frameworks Sho 52-156614
Examples include emulsions described in Japanese Patent Application No. 54-35361.

Hereinafter, unless otherwise specified, the silver halide emulsion of the present invention will collectively refer to an internal temperature type direct positive silver halide emulsion and a negative type silver halide emulsion.

The silver halide grains used in the silver halide emulsion of 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 produced. The method for producing the seed particles and the method for growing them may be the same or different.

In the silver halide emulsion of the present invention, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pLl)Ag in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in an appropriate reducing atmosphere, a reduction sensitizing liquid can be applied to the interior of the particles and/or the surface of the particles.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left in them.

When removing the salts, please refer to Research Disclosure.
It can be carried out based on the method described in No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. It may be.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. It may also have a crystalline form.

In these particles, any ratio of the (100) plane to the (111) plane 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 average grain size (grain size: defined below) of the silver halide grains of the present invention is preferably 5 μl or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less, preferably 0.15 or less.In the case of spherical silver halide, the grain size is the diameter of the silver halide other than spherical. In the case of particles, the shape indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination of several types.

Further, a mixture of a multidistribution emulsion and a monodistribution emulsion may be used.

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

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. 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. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Silver halide emulsion is applied during chemical ripening, at the end of chemical ripening, and/or after chemical ripening for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. By now, compounds known in the photographic industry as antifoggants or stabilizers can be added.

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

The photographic emulsion layer and other hydrophilic colloid layers of the photosensitive material using the silver halide emulsion of the present invention (hereinafter referred to as the photosensitive material of the present invention) crosslink binder (or protective colloid) molecules to increase film strength. Hardening can be achieved by using one or more hardening agents. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an 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 may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developing agent (e.g., p-)unilene diamine derivative, aminophenol derivative, etc.) during color development processing. Dye-forming couplers are used that form dyes. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced to form one molecule of dye, and 2-equivalent, in which only 2 molecules of silver ion need to be reduced. Either is fine. Dye-forming couplers include developers with oxidized developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers. Compounds that release photographically useful fragments such as These dye-forming couplers may be used in combination with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. In place of the DIR coupler, or in combination with the coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

Although a coupling reaction is carried out with an oxidized product of an aromatic primary amine developing agent, a colorless coupler that does not form a dye can also be used in combination with a dye-forming coupler.

The support used in the photosensitive material of the present invention includes a flexible reflective support such as paper laminated with an α-olefin polymer (for example, polyethylene, bo-Vt-robylene, ethylene/butene copolymer), synthetic paper, etc. Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, glass, Includes metals, ceramics, etc.

The photosensitive material of 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 lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X
Light emitted from a phosphor excited by rays, gamma rays, a-rays, etc. [Example] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are limited thereby. It's not a thing.

A monodisperse silver bromide emulsion was prepared as follows.

An aqueous solution containing ossein gelatin was controlled at 70°C, and while stirring vigorously, an aqueous silver nitrate solution and an aqueous potassium bromide solution were simultaneously added to the solution using the Chondrold double jet method to obtain particles with an average particle size of 0.15 μm and 0.5 μm. 26μra,
Three octahedral emulsions of 0.40 μm were obtained. The difference in particle size was determined by changing the addition time of the silver nitrate aqueous solution and the potassium bromide aqueous solution.

To the above three emulsions, 5 mg of sodium thiosulfate and 5 mg of chloroauric acid tetrahydrate per mole of silver were added and chemically ripened at 75°C for 80 minutes to obtain three types of silver bromide core emulsions. .

Each of the three types of core emulsions obtained in this way was further grown by adding a silver nitrate aqueous solution and a potassium bromide aqueous solution, and from the core emulsion with an average grain size of 0.15 μm, the core emulsion with an average grain size of 0.27 μm11 with an average grain size of 0.26 μm. An octahedral monodisperse core/shell type silver bromide emulsion was obtained from the emulsion with a core emulsion of 0.45 μm and an average grain size of 0.70 μm from the core emulsion of 0.140 μm. After washing and desalting, each of these emulsions contained 1.3 m/mole of silver.
Chemical sensitization was carried out at 60° C. for 70 minutes by adding sodium thiosulfate and chloroauric acid tetrahydrate (3 g), and three types of internal latent image type silver halide emulsions (0, 27, um (A), 0. 45μ
m (B), 0.70 μm (C)) were obtained.

Using these emulsions, form the following layer structure on a paper support laminated on both sides with polyethylene (the first layer is on the paper support side).
Internal temperature type direct positive sensitive material (sample No.

101) was created.

The numbers in each layer indicate the coating amount (mg/dm").
The amount of emulsion applied is expressed as the amount applied in terms of silver, and the spectral sensitizing dye is expressed as the amount added (mol/m2) per unit surface area of the silver halide emulsion grains contained in the corresponding layer. Further, the amount of the fogging agent added per mole Ag of the silver halide emulsion contained in the corresponding layer (mol 1 mol Ag) is indicated.

7th layer (protective layer) Gelatin 12.3 (mg/dm2
) 6th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (So-3) 5th layer (blue photosensitive layer) Emulsion (C) Spectral sensitizing dye (Z -1,) 5.4 1.0 2.8 1.2 4.0 6, OX 10-'(mol/m'') Fogging agent (N-1) 5.5X 10-' (mol 1 mol Ag) gelatin
13.5 yellow coupler (Y
C-1) 8.4 Image stabilizer (A O-3'
) 3.0 solvent (So-1)
5.2 4th layer (yellow filter layer) Gelatin 4.2 Yellow colloidal silver l, 0 Ultraviolet absorber (U V
-1) 0.5 Ultraviolet absorber (UV-2) 1.4 Color mixing inhibitor (AS-1) 0.4 Solvent (So-3) 0.8 Third layer (red photosensitive layer) Emulsion (A ) 2.5 spectral sensitizing dye (Z-3) 1.54X 10-'(Mo4/m") spectral sensitizing dye (
Z-4) 0.46x 10-' (mol/m Recovering agent (N-1) 5.5X 10 (mol/+l Ag) Gelatin
13.8 cyan coupler (CC-
1), 1.8 cyan coupler (CC-1)
1.7 Image stabilizer (A O-3)
2.0 Solvent (So-1) 3.3 2nd layer (color mixing prevention layer) Gelatin 7.5 Color mixing prevention agent (A S-1”) 0.55 Solvent (S
o-2) 0.72 1st layer (green photosensitive layer) Emulsion CB) 3.0 Spectral sensitizing dye (Z-2) 3, OX 10-' (mol/m2) Fogging agent (N-1) 5. 5X 10-' (mol 1 mol Ag) gelatin
13.0 magenta coupler (M
C-1) 3.3 Image stabilizer (AO-1)
2.0 solvent (So-4)
3.15 In addition, 5A-1, 5A-
2 and HA-1 as a hardening agent.

C-1 S-1 Q So-1 So-2 AO-1 O-3 O-4 cc-i SA-2 Next, inner layer type direct positive sensitive materials (sample Nos. IQ2 to No.

106) was created as follows. That is, sample no. Sample No. 101 was used except that the emulsions of the fifth layer (blue photosensitive layer), third layer (red photosensitive layer), and first layer (green photosensitive layer) were changed as shown in Table 1. It was created in the same way as lOl.

Next, an inner layer type direct positive light-sensitive material (sample No. 201) was prepared as follows. That is, sample no. 1st of lOl
Sample No. except that the magenta coupler in the layer (green photosensitive layer) was changed to (M-3). l Created exactly the same as the old one.

Next, an inner layer type direct positive light-sensitive material (sample No. 301) was prepared as follows. That is, sample no. 101 5th layer (blue photosensitive layer), 3rd layer (red photosensitive layer), 1st layer (
A sample No. 101 was prepared in exactly the same manner as sample No. 101 except that the fogging agent added to the green photosensitive layer was not added.

Creation of negative photosensitive material A monodisperse silver chlorobromide emulsion was prepared as follows.

An aqueous solution containing ossein gelatin was controlled at 60°C, and while stirring vigorously, an aqueous silver nitrate solution and an aqueous halide solution consisting of sodium chloride and potassium bromide were simultaneously added to the solution using the Chondrold double jet method. .25μfil, 0142μm.

Three cubic emulsions of 0.60 p weight were obtained.

The above three emulsions were chemically sensitized by a conventional method using a combination of chloroauric acid (5XIOi 1 mol AgX) and sodium thiosulfate (2rag 1 mol AgX), and the three types of silver chlorobromide emulsions were made to a thickness of 0.25 μm ( a ), 0.42 p m (b
), 0.60 μm (c) was obtained.

Using these emulsions, a negative photosensitive material (Sample No. 11) having the following layer structure (first layer on the paper support side) was prepared on a paper support laminated on both sides with polyethylene.

The numbers in each layer indicate the coating amount (mg/dm2).

The amount of emulsion applied is shown in terms of the amount applied in terms of silver, and the spectral sensitizing dye is shown in the amount (mol/power) added per surface area of each silver halide emulsion grain contained in the corresponding layer.

7th layer (protective layer) Gelatin 9.2 6th layer (ultraviolet absorption layer) Gelatin 10.0 Ultraviolet absorber (UV-1) 1.7 Ultraviolet absorber (
UV-2) 4.7 Solvent (So-3)
2.0 Fifth layer (red photosensitive layer) Emulsion (a) 2.5 Spectral sensitizing dye (Z-5) 2, OX 10-' (mol/m2) Gelatin 14.0 Cyan coupler (CC-1) 4 .5 Image stabilizer (A
O-3) 2.5 solvent (SO-4'
) 4th layer (intermediate layer) 3rd gelatin layer (green photosensitive layer) Emulsion (b) Spectral sensitizing dye (Z-6) 4.2 5.0 3.0 3, OX to 'C mol/m2) Gelatin 12.5 Magenta coupler (MC-1) 4.2 Image stabilizer (A
O-1') 2.5 solvent (So-4)
4.0 Second layer (intermediate layer) Gelatin 7.0 First layer (blue-sensitive layer) Emulsion (c) 3.7 Spectral sensitizing dye (Z-7) 6, Ox 10-' (mol/m lyselatin 12 .0 Yellow coupler (YC-1) 8.0 Image stabilizer (A
O-3”) 2.9 Solvent (So-1)
5.0 In addition, S as a coating aid
Coating was carried out using A-1, 5A-2 and HA-1 as a hardening agent.

Next, negative-tone sensitive materials (Samples No. 12 to No. 16) were prepared as follows. That is, sample No. 11
layer (blue photosensitive layer), third layer (green photosensitive layer) and fifth layer (
Samples No. 1 and 1 were prepared in the same manner except that the emulsion of the red photosensitive layer was changed as shown in Table 2 below.

Next, a negative type photosensitive material (sample No. 21) was prepared as follows. That is, it was prepared exactly the same as Sample No. 11 except that the magenta coupler in the third layer (green photosensitive layer) of Sample No. 11 was changed to (M-4).

The internal latent type direct positive light-sensitive material and the negative produced as described above were wedge-exposed with a light-sensitive needle (light source color temperature: 2854@K, light source tungsten lamp), and the processing steps (1, 2, 3 and 4), and sensitometry was performed on the obtained image.

S a / S o of each sample from the sensitometric value
, S*/SC were calculated and the results are shown in Table 3.

Next, the sample was cut to a width of 82 mm, and sample No. 101 to
For 106.20L 301, a color reversal film was photographed with an ASA 100 camera, and a positive obtained by color development was used to give a uniform image exposure using an auto color printer: Sample No., 11 to 16. For No. 21, a color negative film was photographed with an ASA 100 camera, and the negative obtained by color development was used to expose the image for position using an auto color printer. With the combination of samples shown in Table 4, the following The treatment was carried out under the following treatment conditions (Experiment Nos. 1 to 22).

Processing conditions Processing process Processing temperature Processing time 1, Color development (Note-1) 38℃ 2 minutes 2, Bleach fixing 35℃ 1 minute 3, Stabilization treatment
30°c 1 minute 30 seconds 4, dry
80°C for 1 minute (Note-1) Fog exposure was applied during color development only when processing sample No. 301. The fog exposure was performed at 1 lux for 10 seconds 8 seconds after the sample entered the color developer.

A processing solution having the following composition was used.

The processing solution includes: Processing solution composition (color developer) Benzyl alcohol Ce2(SO+)s Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate 4-Hydroxy-6-methyl-1,3,3a,7-titrazaindene Hydroxyamine sulfate diethylenetriaminepentaacetic acid optical brightener (4,4'-diaminostilbendisulfonic acid derivative) Potassium hydroxide N-ethyl-N-(β-hydroxyethyl) paraphenylenediamine diethylene glycol 5m12 0.015g mQ 2.5g 0.8g 0.2g 25.0g 0.1g 5.0g g 1.0g 2.0g 4.2g 5m12 Add water to make a total volume of 14, and adjust the pH to 10.20 with potassium hydroxide and sulfuric acid.

(Color developer replenisher) Benzyl alcohol C3z(SO*)i Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate 4-Hydroxy-6-methyl-1,3,3a,7-titrazaindene hydroxyamine sulfate Diethylenetriamine Acetic acid optical brightener (4,4'-diaminostilbendisulfonic acid derivative) Potassium hydroxide N-ethyl-N-(β-hydroxyethyl) phenylenediamine diethylene glycol rum or 9m12 0.019g 10m+2 3.1g 0.2g 0 .1g 31.3g 0.13g 6.3g 2.5g 1.25g 2.5g 5.3g 9m12 Add water to bring the total volume to 1α, and adjust the pH to 10.60 with potassium hydroxide or sulfuric acid.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 Gourd Q Ammonium sulfite (4
0% solution) Adjust the pH to 7.1 with 27.5v2 potassium carbonate or glacial acetic acid and add water to bring the total volume to IQ.

(Bleach-fix replenisher) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 70g Ethylenediaminetetraacetic acid 3.5g Ammonium thiosulfate (70% solution) 120m! Ammonium sulfite (40% solution) 50ffi + 2 Adjust pH to 6.7 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1.

(Stabilizing solution and stable replenishing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol logl-hydroxyethylidene-1,1 diphosphonic acid 2.5 g Bismuth chloride 0.2 g Magnesium chloride 0. 1g ammonium hydroxide (28% aqueous solution) 2.0g sodium nitrilotriacetate 1.0g water was added to bring the total amount to 1Q,
Adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

Color developing replenisher is replenished to 4.0 m4 color developing bath per 1 m' of light-sensitive material, and bleach-fixing replenisher is replenished to 1 m' of light-sensitive material.
2 per 4.0 m4 bleach-fix bath. Further, the stable replenisher is replenished at 4.0 mQ per m 2 of photosensitive material.

The stabilizing liquid is used in a two-tank countercurrent system, and is replenished into the final tank.

Processing is continued until the total amount of color developer replenisher becomes twice the amount of the color developer tank (hereinafter referred to as 2 rounds), and then continues until the total amount becomes 4 times the amount of color developer replenisher (hereinafter referred to as 4 rounds). ) Continuous processing is performed.

In addition, in experiments No. 005 to 18, the internal temperature was measured directly on the positive sensitive material 3.
ml and 3m of negative sensitive material! Experiment No.

In Nos. 19 to 22, treatments were performed alternately on the following areas.

Experiment No. Internal temperature type direct positive sensitive material Negative sensitive material 19
1.8ta” 4.8m”20
4.8m” 1.2m”21
1.0m” 5.0m”22
5.0m"1.0m" In order to see how much the photographic performance of the sample used in the continuous processing of each experiment changes during the continuous processing of the experiment, the sample was measured with a sensitometer (color of light source). Wedge exposure was performed at a temperature of 22854' using a light source (tungsten lamp), and the treatments were performed at the start of the process, at the end of the second round, and at the end of the fourth round, respectively.

Sensitometry was performed on the obtained images of each sample, and the tone balance γ of the magenta image (M) was determined.

/γ was calculated.

Table 4 shows the values of γ and /γ.

Note that the gradation (γl) is the density of the characteristic curve (9,5+D m
1n) and (1,5+ D win), and the gradation (γ,) is the density (0,3+ D win) of the characteristic curve.
This is the slope of the straight line connecting the points D m1n) and (0,8+D m1n).

The values of data, sensitivity, gradation (γ1, γ,) and Dmin are P
D A-65 concentration meter (manufactured by Konica Corporation) was used.
It was measured using

Table-4 As is clear from the results in Table-4, the sensitivity ratio is 0.3≦S
An internal temperature type direct positive photosensitive material and a negative photosensitive material having a/Sa≦3.0.0.2≦Se/S,≦2.0 were developed in the same processing bath. Experiment Nos. 14 to 22 are
Even at the end of the 2nd and 4th rounds, in which continuous processing was greatly increased, fluctuations in gradation balance were extremely small and stable processing was possible. Even more surprisingly, compared to independently and continuously processing the internal temperature type direct positive sensitive material and the negative sensitive material (Experiment No.
1-4) Stable processing.

〔Effect of the invention〕

According to the present invention, a method for processing a silver halide photographic material having stable photographic properties with little variation in gradation balance even during continuous processing has been obtained.

Such effects of the present invention were remarkable when an internal temperature type direct positive light-sensitive material and a negative tone sensitive material were simultaneously combined and continuously processed.

Claims (3)

[Claims] (1) In a method for processing silver halide photographic materials, in which an internal latent image type direct positive silver halide photographic material and a negative type silver halide photographic material are developed in the same development bath. , the internal latent image type direct positive silver halide photographic light-sensitive material and the negative-working silver halide photographic light-sensitive material each contain at least one blue light-sensitive layer, one green light-sensitive layer and one red light-sensitive layer; The ratio of the sensitivity of the blue photosensitive layer to the sensitivity (expressed as SB/SG) is 0.3≦S
B/SG≦3.0, and the ratio of the sensitivity of the red photosensitive layer to the sensitivity of the green photosensitive layer (expressed as SR/SG) is 0.
．． A method for processing a silver halide photographic material, characterized in that it is designed within the range of 2≦SR/SG≦2.0. (2) At least one of the internal latent image type direct positive silver halide photographic material and the negative silver halide photographic material contains at least one compound represented by the following general formula [M-1]. Claim (1) characterized in that it contains
A method for processing the silver halide photographic material described above. General formula [M-1] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of the color developer, and R represents a hydrogen atom or a substituent. ] (3) Internal latent image type direct positive silver halide photographic material (
Claims (1) and (2) characterized in that the ratio of the number of processed sheets of negative-working silver halide photographic material (N) to P) is in the range of 20/80≦P/N≦80/20. ) Processing method for a silver halide photographic light-sensitive material.