JPH0844013A - Processing method of imagelike exposure color photographic material - Google Patents

Abstract

PURPOSE: To improve performance in a color developer and to lessen the influence on sensitometry performance in the case of a multilayered color material by processing a photographic material contg. a specific compd. in layers by using a photographic color developer compsn. contg. a dinucleophilic agent. CONSTITUTION: The color photographic material contg. >=1 pieces of the compds. expressed by the formula is processed by using the photographic color developer compsn. contg. the dinucleophilic aGent in the method for processing the material. The compds. expressed by the formula are so selected as to accelerate low-activity development, to suppress high-activity development and to additionally decrease the variations of a sensitometry result under both of a high-activity condition and a low-activity condition. In the formula, T<1> , T<2> are individually detachable timing groups; ETA is a group released as an electron transfer material; R is alkyl, aryl or photographic ballast group substd. with cyclic hydrogen; Z is a group which exists in an arbitrary ring position not adjacent to a quetocarbonyl group and has one of -S-, -O-, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photography and the processing of silver halide color materials.

[0002]

2. Description of the Related Art Our copending patent application 4-05003
No. 79, sensitometry-the result is less scattered,
A method of developing an imagewise exposed silver halide color material is described, which method comprises a black and white silver halide developing agent (in the present description) incorporated in an inert state into said silver halide color material. , An electron transfer agent: referred to as ETA) or a combination thereof.
It promotes development in the low activity state, while inhibiting development in the high activity state, which is caused by changes in process variables such as time, temperature, color developing agent concentration and bromide ion concentration. It includes reducing variations in the LogE curve (characteristic curve). A model example is described in which a black and white silver halide developing agent is present in the developing solution.

This application also states that when a black and white silver halide developing agent is incorporated in a photographic material, it is preferably in an inert state until processing. For example, the developing agent is deactivated by a blocking group, which can be hydrolyzed and removed by immersing the material in a developer (which is usually alkaline).

[0004]

Problems with known hydrolyzable blocked pyrazolidone developing agents (BETA) are as follows.
Even if the compound is unstable, it is only unblocked at the desired pH. If the compounds are stable enough to not disintegrate in the material, they will not be deblocked fast enough (or not at all) to be useful.

[0005]

According to the invention, the general formula:

[0006]

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In the above formula, T ¹ and T ² are individually releasable timing groups, n and m are individually 0 or 1, at least one of n and m is 1, and ETA is , A group released as an electron transfer agent,
x is 0, 1 or 2, R is a substituted or unsubstituted alkyl or aryl, or a photographic ballast group substituted with a ring hydrogen, and R ¹ is a substituted or unsubstituted alkyl. , Z is located at any ring position not adjacent to the ketocarbonyl group and has the formula:

[0008]

[Chemical 6]

A group having one of the following: each R ² is an individually substituted or unsubstituted alkyl, aryl or heterocyclic group, or a carbamoyl, carbonamido, sulfamoyl, sulfonamide, ester or acid group. And R ³ is

[0010]

[Chemical 7]

A substituted or unsubstituted alkyl or aryl, or a photographic ballast group, R ⁴ is a substituted or unsubstituted alkyl or aryl, R ^4
4'is substituted or unsubstituted alkyl, or aryl
Or

[0012]

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Wherein R ⁵ and R ⁶ are each independently hydrogen or substituted or unsubstituted alkyl or aryl, and y is 0, 1, 2 or 3, As described above, the method for processing a color photographic material contained in the layer, wherein the method comprises a dinucleophile (bi
a photographic color developer composition containing a nucleophile) is included to promote low activity development and suppress high activity development under both high activity and low activity conditions. There is provided a method of processing a color photographic material in which the compound of formula (1) is selected so that there is less variability in sensitometry results.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The alkyl group represented by any of R to R ⁶ may be an alkyl group having 1 to 25 carbon atoms, preferably 1 to 6 carbon atoms. Substituents for substituted groups include halogen, alkyl, alkoxy, acyloxy, aroyloxy, keto, ether, ester, sulfonamide,
It may be a sulfamoyl, carbonamido or carbamoyl group. The dinucleophile to be contained in the color developing solution can be, for example, hydroxylamine, hydrogen peroxide, hydrazine, all of which may be substituted or their salts. Good.

Preferred ETA groups have the general formula:

[0016]

[Chemical 9]

In the above formula, each R ⁷ is an alkyl or substituted alkyl group having 1 to 10 carbon atoms, R ⁸ is aryl or substituted aryl, and n is 0, 1, 2, 3 Or 4. Particularly preferred groups for the ETA group have the general formula:

[0018]

[Chemical 10]

In the above formula, R⁹And R^TenAre hydrogen,
An alkyl or alkoxy group having 1 to 3 carbon atoms, or
Substituted alkyl or alkoxy having 1 to 7 carbon atoms
Substituted with groups, eg aryl or ester groups
And R¹¹And R¹²Are each hydrogen or carbon number
1-3 alkyl or hydroxyalkyl groups
R in the above formula⁹And R^TenBoth are hydrogen
R if and¹¹Is acyloxyalkyl or
R is R, except when it is an aroyloxyalkyl group. ⁹Oh
And R^TenAt least one of them is not hydrogen. These E
The TA group belongs to the following type (1).

As is known from patent application 4-0500379, 3 for different types of pyrazolidinones.
A type of behavior is observed. Desensitization with development time is used as an example. For each ETA,
Three broad types of behavior can be observed, which are as follows: Type (1): Reduction of sensitometry spread by suppressing overdevelopment and promoting underdevelopment, Type (2): Dye formation. A moderate reduction in the spread of sensitometry by generally promoting.

Type (3): Reduction of sensitometry spread by generally suppressing dye formation. Therefore, the use of only type (2) ETA is not part of the present invention. Type (1) is the preferred behavior exhibited by the preferred compounds, especially when used alone. Type (2) is another useful and advantageous behaviour, and in some cases is preferred over type (1) where increased contrast or corresponding substitution is desired.

The present invention also provides for the combined use of ETA.
Including. For example, a combination of type (2) and type (3)
Matching is similar or better overall than type (1)
Behavior. Type (1) and Type (3)
The combination of is also the spread of the sensitometry curve
Particularly good control results in good results. Thailand
The ETA group of group (2) is of the formula (4) or (5)
Yes, in the formula, R ⁹, R^TenIs hydrogen or C1-C3
Alkyl and R¹¹And R¹²Is an al having 1 to 3 carbon atoms
Kill or hydroxyalkyl, for example -CH₂OH
Or -C ₃H₇May be

The ETA group of type (3) has the formula (4)
Is of (5), wherein R ⁹~ R¹²Are each hydrogen
Or alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons
Rukoxy, both of which may be substituted, R
⁹~ R¹²With a total carbon number of at least 4
You can The definitions of the above types of ETA are mutually exclusive
It is not recognized as something that cannot be done. Incompatible appropriate settings
Because it is difficult to find righteousness. Three types of examples below
Shown below. Beyond these, those skilled in the art
Which type of specific ETA is
You will be able to decide which belongs to.

Specific examples of the three types of ETA are shown below:

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

Specific examples of BETA compounds used in the present invention have the formula: Unless otherwise noted, these are all types (1).

[0029]

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[0030]

[Chemical 15]

[0031]

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[0032]

[Chemical 17]

[0033]

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The compound of formula (1) may be incorporated into the photographic material by methods known per se. For example, they may be dispersed in high boiling organic solvents often known as "coupler-solvents". Examples of such solvents include triphenyl phosphate and dibutyl phthalate. Usually the coupler is dissolved in the coupler solvent or solvent mixture and then this solution is dispersed in an aqueous gelatin solution. In some cases, a low boiling solvent is used in the coupler-solvent mixture, which is removed after the dispersion is formed.

The present invention is particularly adaptable to the processing of color negative film, but is also adaptable to other processes such as color photographic paper. The material to be processed is
It comprises a support bearing at least one silver halide emulsion layer in combination with a coupler. The coupler is incorporated in the emulsion layer or in a layer adjacent thereto. Preferred color materials contain three dye image-forming units, each containing one or more emulsion layers associated with a coupler, each sensitized to a different region of the spectrum.
Typical color materials contain units that are sensitized to blue, green and red light and are capable of forming yellow, magenta and cyan image dyes, respectively.

Examples of color photographic materials and their processing methods are described in Research Disclosure, Item 308119, 1989 12
Mon, Kenneth Mason Publications, Emsworth, Hants, U
It is described in nitedKingdom. The following examples are included for a better understanding of the present invention. Example 1 Compound 1 in coupler-solvent (1) (diethyllauramide) and solvent (2) (ethyl acetate) in a weight ratio of 1: 2:
3 (compound (1): solvent (1): solvent (2)) was dispersed to obtain a dispersion. This oil layer was then dispersed in gelatin to make 1.0% Compound 1, 4.0% gelatin.

Next, containing a silver halide and a coupler
Coating film obtained by coating Compound 1 on the layer below the coating layer
(Coating) was formed. This coating is shown in Table 1.
Show. Table 1: Coating format for included BETA −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Gelatin (1.0 g / m²) −−−−−−−−−−−−−−−−−−−−−−−−−−−− Coupler-1 (0.6 g / m²) Tabular grain silver bromoiodide emulsion (speed = 400 ASA) (1.0 g / m²) Gelatin (2.7 g / m²) Tetraazaindene (antifoggant) (30 mL / moleAg) −−−−−−−−−−−−−−−−−−−−−−−−−−−− Compound 1 (0.0, 0.05, 0.1 , 0.2, 0.4 g / m²) Gelatin (2.7 g / m²) −−−−−−−−−−−−−−−−−−−−−−−−−−− Transparent support −−−−−−−−−−−−−−−−−− −−−−−−−−−− BETA compound, 0.0, 0.05, 0.1, 0.2, 0.4 g / m²of
Coated in the level range. Released from BETA
ETA is 4'-methoxyphenylpyrazolidinone
is there.Example 2 The coating of Example 1 was treated with hydroxylamine sulfate (HAS) 2
During the following development with a standard C-41 developer containing g / L
For 1, 2.5, 5 and 8 minutes. In Figure 2
Is the sensitometry of the control coating at these four development times.
Shows a reply. Figure 3 shows the same series of development times.
And the effect of BETA coated at the highest level
Are shown with the control plot curve. BETA exists
Then, it can be seen that the spread of sensitometry is reduced.
It This effect is obtained by adding ETA to the developer.
Similar to that obtained, but to a lesser extent. Figure 4
Then, the extent of spread of sensitometry is
Plotted against coating level, but sensitized
The spread of the metric is based on the BETA coating level.
It can be seen that as it increases, it decreases.Example 3 Compound 1 is a diamine contained in the C-41 developer at 2 g / L.
Nucleophile: For the action of hydroxylamine sulfate (HAS)
From ETA: 4'-methoxy-1-phenylpyrazoli
Designed to emit don. Hydroxyla
Min is present as an antioxidant in C-41 developers.
It The action of hydroxylamine on the release of ETA
HAS of 0, 1, 2, 6, 24 and 60 g / L to demonstrate
Several C-41 developers were prepared in the level range. versus
Illuminated coating and highest level of BETA (0.4 g / m²) Paint
The film was treated with these developers to give 0 g / L, 6 g / L and 60
 A comparison of g / L HAS level ranges is shown in Figures 5 and 6.
And 7 respectively. If HAS is not included,
Almost no effect of the BETA being tated
However, it can be seen that the presence of HAS is effective. FIG.
Contains BETA (0.4 g / m²) Contained coating and BETA
For those without, sensitometry showed a decrease in sensitivity.
Plotted against HAS level in image fluid. BETA
For coatings that do not contain,
Cytometry-Slightly reduced sensitivity, but BETA-containing coating
It can be seen that the film has a much lower drop.Example 4 The following multilayer structure was prepared. The number in parentheses is the coverage
(g / m²).  Super-coated gelatin (1.0) --------------------------- UV protective layer ----- −−−−−−−−−−−−−−−−−−−−−−− High-sensitivity blue-sensitive silver halide (0.6) + yellow coupler − (0.18) −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−− Low sensitivity blue sensitive silver halide (0.55) + yellow coupler − (1.0) −−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Scavenger-Intermediate layer −−−−−−−−−−−−−−−−−−−−−−−−−−− --- High-sensitivity green-sensitive silver halide (0.79) + magenta coupler-(0.11) --- --- --- --- --- --- --- --- --- --- ---------- Medium sensitivity green-sensitive silver halide (0.45) + magenta coupler- (0.2) ------------------------- −−−−−−−−−−− Low sensitivity green-sensitive silver halide (0.5) + Magenta coupler − (0.39) −−−−−−−−−−−−−−−−−−−−−− --------------- 1 Scavenger-Intermediate layer ----------------------- High-sensitivity red-sensitive silver halide (1.0) + Cyan coupler- (0.16) ------------------------------------------- Medium sensitivity red-sensitive silver halide (0.5) + Cyan coupler (0.31) ----------------------------------- Low-sensitivity red-sensitive silver halide (0.5) + cyan coupler (0.65 ) −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Anti-halation layer −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−− Film base  The silver halide described above contains an odorant containing an average of 3% iodide.
It is a bromine emulsion. The nature, quantity and position of BETA
Ripples and sensitometry shown in the figure-for results
Their effects are as follows:1. Single BETA in multiple layers (Figures 8 and 9) a) FIG. 8 shows the control in the multilayer antihalation layer 1.
08g / m²In comparison with the inclusion of BETA (compound 8)
Things. The solid line is the control red record, the dotted line
Is a red record with the inclusion of BETA. BE
When TA is included, the spread of sensitometry is small.
It is narrowed down.

B) FIG. 9 shows a control of BETA (compound 1) on both the sensitive and insensitive layers of a multilayer red sensitive pack.
0) is included at 0.33 g / m ² . The solid line is the control red record and the dotted line is the BET.
It is a red color record when A is included. When BETA is included, the spread of sensitometry is appropriately narrowed. 2. Combined BETA in multiple layers (Fig. 10, Fig. 1
1, FIG. 12, FIG. 13) a) FIG. 10 compares a control red recording with the inclusion of BETA (Compound 7) at 0.5 g / m ² in a multilayer antihalation layer. . This compound is a promoter of E
This is an example of BETA that releases TA, so that the dotted curve (BETA) is largely enhanced compared to the solid control line.

B) FIG. 11 compares the control red record with the inclusion of BETA (Compound 9) at 0.5 g / m ² in a multilayer antihalation layer. This compound is an example of BETA that releases inhibitory ETA,
The dotted curve (BETA) is suppressed compared to the control solid line. c) Figure 12 compares the control red record with the inclusion of BETA (Compound 7 and Compound 9) at 0.5 g / m ² each in a multilayer antihalation layer. This compound is an example of a combination of promoting ETA and inhibiting BETA. The dotted curve of the BETA coating shows that it is suppressed at longer development times and accelerated at shorter development times compared to the control solid line.

B) FIG. 13 shows the red recording of the example of FIG.
0.4 g / additional to developer for use in BETA inclusion coatings
This is to be compared with the one obtained by adding L of 4′-methoxy-1-phenyl-3-pyrazolidinone. In this case, it is suppressed to a higher extent than when ETA is not contained in the developing solution, for a longer developing time, and accelerated for a shorter developing time.

[0041]

The color photographic materials of the present invention advantageously have improved performance in color developers, especially in the case of multi-layer color materials, where the effect on sensitometry performance due to variations in processing conditions has previously been found. Fewer. In the present invention, low activity conditions are not only promoted by the ETA-releasing agent used in the present invention, but also high activity conditions are suppressed, so that sensitometry-under both high activity conditions and low activity conditions is performed. There is little variation in the results of. This is
This means that the spread of the characteristic curve is narrowed, as in the attached FIGS.

In particular, it has been found that the presence of ETA emissions reduces the variations caused by variations in development time, development temperature, pH, bromide ion concentration and color developing agent concentration in the color developing solution. Reducing the risk of sensitometry scatter means that the replenishment rate can be further reduced, which results in reduced overflow and effluent. The often required removal of bromide ions from the developing solution may also be dispensed with.

[Brief description of drawings]

FIG. 1 Coating film containing BETA (0.4 g / m ² ) and BET
FIG. 3 is a plot of the decrease in sensitometry-sensitivity versus HAS level in the developer for those without A. FIG.

FIG. 2 shows the sensitometry response of control coatings at four development times.

FIG. 3 shows the effect of BETA coated at the highest level for the same series of development times as in FIG. 2, together with the plot curves of interest.

FIG. 4 shows the extent of sensitometry spread by BETA
Is plotted against the coating level of.

FIG. 5: Control coating and highest level of BETA (0.4 g
/ m < ² >) coatings were treated with a developer at a HAS level of 0 g / L for comparison.

FIG. 6: Control coating and highest level of BETA (0.4 g
/ m < ² >) coatings were treated with a developer at a HAS level of 6 g / L for comparison.

FIG. 7: Control coating and highest level of BETA (0.4 g
/ m ² ) coatings were treated with a developer at a HAS level of 60 g / L for comparison.

FIG. 8: BET in a multi-layer antihalation layer as a control
It is compared with the inclusion of A (Compound 8).

FIG. 9 compares a control with BETA (compound 10) incorporated at 0.33 g / m ² in both the high and low speed layers of a multi-layer red sensitive pack.

FIG. 10 compares the control red record with BETA (Compound 7) incorporated at 0.5 g / m ² in a multilayer antihalation layer.

FIG. 11 compares the control red record with BETA (Compound 9) incorporated at 0.5 g / m ² in a multilayer antihalation layer.

FIG. 12 is a comparison of a control red record with the inclusion of BETA (Compound 7 and Compound 9) at 0.5 g / m ² each in a multilayer antihalation layer.

FIG. 13 compares the red record of the example of FIG. 12 with the addition of 0.4 g / L of additional 4′-methoxy-1-phenyl-3-pyrazolidinone to a developer for use in a BETA containing coating. Is.

Claims (1)

[Claims] 1. A compound of the general formula: In the above formula, T ¹ and T ² are individually releasable timing groups, n and m are individually 0 or 1, at least one of n and m is 1, and ETA is electron transfer Is a group released as an agent, x is 0, 1 or 2, R is a substituted or unsubstituted alkyl or aryl,
Or a photographic ballast group replacing a ring hydrogen, R ¹ is a substituted or unsubstituted alkyl, Z is located at any ring position not adjacent to the ketocarbonyl group, and has the following formula: 2] Each R ² is an individually substituted or unsubstituted alkyl, aryl or heterocyclic group, or a carbamoyl, carbonamido, sulfamoyl, sulfonamide, ester or acid group, R ³ is A substituted or unsubstituted alkyl or aryl, or a photographic ballast group, R ⁴ is a substituted or unsubstituted alkyl or aryl, and R ^{4 ′} is a substituted or unsubstituted alkyl, or an aryl. -Or, or And R ⁵ and R ⁶ are individually hydrogen, or substituted or unsubstituted alkyl or aryl, and y is
A method of processing an imagewise exposure color photographic material comprising one or more of the compounds 0, 1, 2 or 3 in its layer, said method comprising a dinucleophile. Processing the material with a photographic color developer composition for promoting low activity development, inhibiting high activity development, and sensitometry results under both high activity and low activity conditions. (1) so that the variation of
A method for processing an imagewise exposure color photographic material, wherein the above compound is selected.