JPH02287353A - Processing device for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the compact device and to simplify processing operations by replenishing 1st and 2nd color development replenishing liquid parts into a 1st color developing tank of a 1st processing path and replenishing the 1st and 3rd color development replenishing liquid parts into a 2nd color developing tank of a 2nd processing path. CONSTITUTION:The 1st color development replenishing liquid part contg. an alkali agent and a color developing agent preservative is housed into a 1st container 31, the 2nd color development replenishing liquid part contg. a color developing agent for color photosensitive materials for photographing into a 2nd container 32, and the 3rd color development replenishing liquid part contg. a color developing agent for color photosensitive materials for printing into a 3rd container 33. The 1st and 2nd color development replenishing liquid parts are replenished into the 1st color developing tank 12a of the 1st processing path and the 1st and 3rd color development replenishing liquid parts into the 2nd color developing tank 12b of the 2nd processing path, respectively. The common use of the other processing tanks is possible in this way simply by constituting the color developing tanks as separate tanks. The compact processing device is thus obtd. and the processing operations are simplified.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a processing apparatus used for wet processing a silver halide color photographic light-sensitive material.

<Prior Art> Silver halide color photographic materials (hereinafter referred to as color photographic materials) are processed through steps such as color development, desilvering, water washing, and stabilization after exposure. A color developer is used for color development, a bleach solution, a bleach-fix solution, and a fixer solution are used for desilvering treatment, tap water or ion exchange water is used for washing, and a stabilizing solution is used for stabilization treatment. Each treatment liquid is usually 30-40℃
The color photosensitive material is immersed in these processing solutions and processed.

Color photosensitive materials are broadly divided into color photosensitive materials for photography, typified by color negative film, and color photosensitive materials for printing, typified by color vapor, color reversal vapor, and color autopositive vapor.

In general, color photosensitive materials for printing such as color paper use silver chlorobromide, silver chloride, or silver bromide emulsions that do not substantially contain silver iodide and have an average silver iodide content of 1 mol% or less. . On the other hand, silver iodobromide emulsions having an average silver iodide content of 3 mol % or more are used in color photosensitive materials for photography such as color negative films in order to increase sensitivity and improve grain quality.

These color photosensitive materials have traditionally been processed only in large-scale photo labs, but with the recent development of small-scale processing systems called minilabs, they are now being processed at photo shops and other stores. There is.

Another example of small-scale processing is a silver halide photocopier (color copier).

Since these small-scale processing systems are often installed in small stores and the like, it is especially important that the footprint and required work space be small.

For this reason, there is a demand for miniaturization of processing apparatuses such as automatic processors and simplification of processing operations.

In response to such requests, Japanese Patent Application Laid-Open No. 60-129747,
No. 60-129748 and No. 61-134759 disclose that color photosensitive materials for photographing and color photosensitive materials for printing, which were conventionally processed in separate automatic processors, can now be processed using all or part of a processing tank. An integrated automatic processor for mixed processing has been proposed.

In addition, for silver halide photocopiers, a device (color copier AP-5000 manufactured by Fuji Photo Film Co., Ltd.) that mixes color paper, which is a photosensitive material for printing, and color auto-positive vapor in the same processing tank has been put into practical use. has been done.

<Problems to be Solved by the Invention> As mentioned above, processing apparatuses that process different types of color photosensitive materials in the same processing tank have been proposed or put into practical use, but in particular, the sharing of color developing tanks is inherently difficult. , is not preferable in terms of obtaining good photographic properties, and requires complicated processing operations in order to obtain good photographic properties.

For this reason, the current situation is basically to use separate automatic developing machines depending on the type of color photosensitive material.

In particular, since color light-sensitive materials for photography and light-sensitive materials for printing have different halogen compositions in their emulsions as described above, it is often difficult to process them in the same processing tank.

However, for example, silver halide photocopiers, etc.
In cases where the amount of processing of color photosensitive materials for printing is overwhelmingly larger than the amount of processing of color photosensitive materials for photography, providing a separate processing machine is a heavy burden, and some kind of improvement is desired.

Further, in such a case, since the color photosensitive material for photographing is processed in a small amount, there is a problem that the color developing replenisher used therein deteriorates over time due to long-term storage.

The present invention provides a silver halide color that can make the device more compact and simplify the processing work, as well as keep the processing performance of the processing liquid constant, and as a result, can obtain good photographic properties. The object of the present invention is to provide a processing apparatus for photographic materials.

Means for Solving the Problems> In order to achieve the above object, the present invention has the following configuration (1).
has.

(1) It has a first color developing tank containing a color developing solution containing a first color developing agent, and the average silver iodide content of the silver halide emulsion coated on the support is 3 mol% or more. A first method for developing a first silver halide color photographic light-sensitive material of
A silver halide color photographic light-sensitive material having a processing path and a second color developing tank containing a color developing solution containing a second color developing agent, the silver halide emulsion containing substantially no silver iodide. a second processing path for developing the color developing agent, and a first processing path containing an alkaline agent and a color developing agent preservative.
a first container containing a color developer replenisher part containing the first color developer replenisher; a second container containing a second color developer replenisher part containing the first color developer; and a second container containing the second color developer replenisher. a third container storing a third color developer replenisher part containing a third color developer replenisher part; The first and second color developer replenisher parts are replenished, and the second color developer tank of the second processing path is replenished with the first and third color developer replenisher parts from the first and third containers. 1. A processing apparatus for silver halide color photographic light-sensitive materials, characterized in that a color development replenisher part is configured to be replenished.

<Function> According to the present invention, a first silver halide color photographic material (a color photographic material) in which the average silver iodide content of the silver halide emulsion coated on the support is 3 mol% or more. and a second silver halide color photographic light-sensitive material (color light-sensitive material for printing) in which the silver halide emulsion coated on the support does not substantially contain silver iodide. Developing is carried out in the first processing path and the second processing path, respectively.

In this case, color developing tanks containing color developing solutions for color developing the first and second color photosensitive materials are installed separately in the first and second processing paths, and each The color developer tanks are replenished with respective color developer replenishers.

This color developer replenisher is divided into three parts, first, second, and third, and each part is housed in its own container with different components.

That is, the first container contains a first color developing replenisher part containing an alkaline agent and a color developing agent preservative, and the second container contains a first color developing replenisher part containing an alkaline agent and a color developing agent preservative. A third container contains a third color developing replenisher part containing a color developing agent for color photosensitive materials for printing.

The first color developing tank in the first processing path contains first and second color developing replenisher parts, and the second color developing tank in the second processing path contains first and third color developing replenisher parts. The developer replenisher parts are each replenished.

Therefore, the apparatus can be made more compact and the processing work can be simplified, and the resulting images have good photographic properties.

<Example> Examples will be described with reference to the drawings.

FIG. 1 schematically shows the tank arrangement of processing tanks and the color photosensitive material processing path included in the processing apparatus for silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials) of the present invention.

As shown in FIG. 1, in the processing apparatus of the present invention, a first color photosensitive material (photographic color photosensitive material) having an average silver iodide content of 3 mol % or more in a silver halide emulsion coated on a support is used. A first processing path (A) that wet-processes the photosensitive material) after exposure.
and a second processing path in which a second color photosensitive material (photosensitive material for printing) in which the silver halide emulsion coated on the support does not substantially contain silver iodide is wet-processed after exposure.
B) are arranged in parallel.

In FIG. 1, arrows (A) and (B) indicate processing paths through which two types of color photosensitive materials are sequentially conveyed between processing tanks.

Further, as shown in the figure, the processing device includes a first color developing tank 12a containing a color developing solution for color developing the color photosensitive material for imaging, and a color developing solution for color developing the color photosensitive material for printing. The second color development t containing
! 12b, a color developing tank 12a and a color developing tank 12
It is installed separately from and close to b.

A bleach-fix tank 13 containing a bleach-fix solution for bleach-fixing both photographic and printing color photosensitive materials after color development processing is downstream of the color development tanks 12a and 12b.
is installed. Further, in the downstream thereof, washing tanks 14 and 15 containing washing liquid for washing both color photosensitive materials after bleach-fixing processing are installed.

Therefore, the processing path (A) and the processing path (B) for both color photosensitive materials have separate color developing tanks 12a and 12b, and share a bleach-fixing tank and a water washing tank. This also allows the device to be made more compact.

A drying section L6a for drying the color photosensitive material for photographing after the washing process and a drying section 16b for drying the color photosensitive material for printing after the washing process are installed downstream of the washing tank 15.

Normally, the temperature of the drying section 16b is set higher than that of the drying section 16a. This is because it is necessary to produce gloss on the image surface of photosensitive materials for printing.

The processing apparatus of the present invention further includes, as shown in the figure, a first container 31 containing a first color developer replenisher part containing an alkaline agent and a color developer preservative; a second container 32 containing a second color developing replenisher part containing a color developing agent; and a third container 32 containing a third color developing replenisher part containing a color developing agent for color photosensitive materials for printing. A container 33 is installed.

Then, during the color development process of the color photosensitive material for photography, the first and second color development replenisher parts are stored in the first and second containers 3, respectively, in the first color development tank 12a.
It is configured to be replenished from 1.32.

On the other hand, during color development processing of color photosensitive materials for printing, first and third color development replenisher parts are replenished into the second color development tank 12b from the first and third replenishment containers 31 and 33, respectively. is configured to be

In addition, there is an insertion section 2La into which a color photosensitive material for photography is inserted during processing, a recovery section 25a where the color photosensitive material for photography is recovered after processing, an insertion section 21b into which a color photosensitive material for printing is similarly inserted, and a recovery section 25b where it is recovered. is installed.

Furthermore, containers, tanks, and the like are installed for replenishing bleach-fixing solution and washing solution as needed.

Therefore, in the above configuration, the color photosensitive material for photographing is inserted from the insertion section 21a, and the color photosensitive material for photographing is inserted into the first color developing tank 12a, the bleach-fixing tank 13. It is conveyed to washing tanks 14 and 15, and is sequentially subjected to color development, bleach-fixing, and washing in the first processing path (A>. After that, it is dried in the drying section 16a, and then in the first recovery section 25a. It will be collected.

In this case, during the color development process, the first color development tank 1
2a is replenished with the first color developer replenisher parts from the first container 31 and the second color developer replenisher parts from the second container 32.

The amount of replenishment is 100 to 100 liters for the first color developer replenisher part.
OOO+aj/m”, preferably 200-600 m
l/+s”, the second color developer replenisher is 30-300 II
Ii/ff12 preferably 6o~18°Ili/I
m2 in total from 130 to 1300 aIj/I11'', preferably from 260 to 780 ml/m''.

On the other hand, the color photosensitive material for printing is inserted from the insertion section 21b, and is transferred to the second color developer tank 12b, the bleach-fix tank 13.
It is conveyed to washing tanks 14 and 15, and is sequentially subjected to color development, bleach-fixing, and washing in the second processing path (B).
Thereafter, it is dried in the drying section 16b and collected in the collecting section 25b.

In this case, during the color development process, the second color development tank 1
2b is replenished with the first color developer replenisher parts from the first container 31 and the third color developer replenisher parts from the third container 33.

The replenishment amount is 50 to 500 for the first color developer replenisher part.
mg/m”, preferably 75 to 300 mj/n2
The third color developer replenisher is 15 to 150m17m", preferably 20 to 100mj/m", and the total amount is 65 to 650m
rag/m” preferably 95-400 ml/m
”.

The processing device of the present invention is suitable for application to devices that mainly process color photosensitive materials for printing and occasionally process color photosensitive materials for photography, such as silver halide photocopiers (color copiers). preferable.

Originally, color light-sensitive materials for photography and color light-sensitive materials for printing had different halogen compositions in their silver halide emulsions, so it was considered undesirable to process them in the same processing tank in order to obtain good photographic properties. Conventionally, separate processing machines have been used, but the present invention improves this point.

That is, by simply using a separate color developing tank, the other processing tanks can be shared, making it possible to downsize the processing apparatus and simplify processing operations.

Furthermore, it is considered particularly undesirable for the above two types of color photosensitive materials to share a color developing tank because the processing conditions such as development time and temperature, and the processing prescription of the color developer are significantly different.

In the color developing solution, the color developing agents used in both color photosensitive materials are different.

For this reason, in the present invention, each color developing tank is installed in parallel to achieve compactness. In this case, the capacity of the first color developing tank is 1 to 30 i! ,,
The capacity of the second color developing tank is preferably 1 to 15 I2.

Further, in the present invention, a replenishment method is adopted in order to keep the processing performance of the color developer constant.

However, as mentioned above, when the amount of color photosensitive materials for printing is overwhelmingly larger than the amount of color photosensitive materials for photography, the conventional method is to prepare and replenish color developing solutions for each color photosensitive material. If this replenishment method is adopted, deterioration of processing performance will not be a major problem with color developer replenishers for color photosensitive materials for printing, which are frequently used, but deterioration of processing performance will occur with color developer replenishers, which are used infrequently. is remarkable. This is because the color developing agent is oxidized by long-term storage.

For this reason, in the present invention, based on the knowledge that oxidation of a color developing agent is particularly likely to occur in an alkaline solution, a color developing replenisher in which a color developing agent component and an alkaline agent component are separated is used. It is solved by this.

In other words, the color developing agent components for each of the two types of color photosensitive materials and the alkaline component shared by the color developer for these color photosensitive materials are separated into three parts, and the types of color photosensitive materials to be processed are separated. Depending on the situation, two parts are selected and replenished: one containing a color developing agent and one containing an alkaline agent.

By replenishing in this way, the running stability of the color developing solution is improved, and good and stable photographic properties can be obtained.

In the present invention, the ratio of the processing amount of color photosensitive material for printing and color photosensitive material for photography is
) The color light-sensitive material for printing/color light-sensitive material for photographing is preferably applied to a process in which the ratio is 20/1 to 100'/1.

Such a processing amount ratio is, for example, negative film (35 mm
Width x 1m) Color vapor 0.7~3.
5m”.

In terms of the throughput of such color photosensitive materials.

The first . The capacity of the second and third containers is 1 to 50 in order.
ε (preferably 1.5-3°ff), 0.03-11
(preferably o, 05-0.512), 0.3-15β
(preferably about 0.4 to 1042). In addition,
This capacity corresponds to the amount of each part required for processing.

In addition, in the present invention, as mentioned above, when the amount of color photosensitive materials for photography is small, good photographic properties can be obtained without occurrence of desilvering defects or staining even if the bleach-fixing tank and washing tank are shared. can get.

Note that it is preferable that the water washing treatment in the present invention be carried out in a multi-stage countercurrent method in order to improve the treatment efficiency.

The arrangement of the processing apparatus of the present invention is not limited to the embodiment shown in FIG. There is no particular restriction as long as the configuration is arranged in

For example, there are two types of color sensitizers, such as one in which the bleach-fixing process is a two-step bleach-fixing or bleach->bleach-fix process, and one in which the water-washing process is replaced by stabilization or stabilization and water-washing. These treatment steps can be combined depending on the material, and the tank arrangement can be tailored to suit the treatment step.

However, in the present invention, it is particularly preferable to use a shared bleach-fixing tank as shown in FIG. 1 in order to make the apparatus more compact and to simplify processing operations.

In the present invention, all of the processing tanks may be separate tanks for two types of color photosensitive materials, or a shared processing tank may be selected as appropriate.

In addition, when using separate tanks, it is also possible to flow the overflow of one of the processing liquids having the same function into the other processing tank, except for the color developing solution.

Next, the processing steps and the processing liquid used in the present invention will be explained.

The color developing solution used in the development process in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

As the color developing agent, paraphenylenediamine compounds are preferred, and typical examples include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-(β- hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-(β-
methanesulfonamidoethyl)aniline, 3-methyl-
4-amino-N-ethyl-N-(β-methoxyethyl)
Examples include aniline and their sulfates, hydrochlorides, phosphates, p-toluenesulfonates, and the like. Salts of these diamines are generally more stable, and it is preferable to use them in the salt form.

Among these, the color developing agent used in the color developer and its replenisher (the second color developer replenisher part) for photographic color photosensitive materials is preferably one represented by the following formula (I).

Formula (1) (In the above (I), R1 and R4 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2
represents an alkyl group which may have a substituent (hydroxyethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, etc.), and R1 represents an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, propyl, etc.). ) Among them, 3
-Methyl-4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-4-amino-N-
Ethyl-N(β-methoxyethyl)aniline, 3-methyl-4-amino-N, N-diethylaniline, etc. are preferred, especially 3-methyl-4-amino-N-ethyl-N-(
β-hydroxyethyl)aniline is preferred.

Further, the color developing agent used in the color developer and its replenisher (the third color developer replenisher part) for color photosensitive materials for printing is preferably one represented by the following formula (rl).

Formula (II) (In the above formula (n), R and R each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R
6 represents an alkyl group that may have a substituent (methane, sulfonamidoethyl, methanesulfonamidoethyl, ethanesulfonamidoethyl, hydroxyethyl, hydroxypropyl, etc.), and R1 is an alkyl group having 1 to 3 carbon atoms. represents. ) Among them, 3-methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)aniline, 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, etc. are preferred. , especially 3-
Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline is preferred.

The color developing agent is generally used in an amount of 1 g to 1 per color developer 14.
5g, preferably 2g~Log, particularly preferably 3g~
Used in the range of 8g.

In the replenisher, 2 to 20 g/j, preferably 4 to 1
5g/j used.

Further, the color developing agent in the first color developer replenisher part is 10 to 150 g/l, preferably 20 to 100 g/l.
j, while in the second color developer replenisher part 10 to 1
50 g/j, preferably in the range of 15 to 100 g/j.

The color developer and its replenisher (the first color developer replenisher part) contain a preservative.

As such preservatives, substituted hydroxylamines represented by the following formula (llIr) and substituted hydrazines represented by the following formula (IV) are preferred.

Formula (III) RII in the formula R12 represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group R11 and R'' are simultaneously hydrogen atoms Instead, they may be linked together to form a heterocycle with a nitrogen atom.The ring structure of a heterocycle is a 5- to 6-membered ring containing carbon atoms, hydrogen atoms, halogen atoms, and oxygen atoms. atom,
Preferably, R1 and RIt are an alkyl group or an alkenyl group, which is composed of a nitrogen atom, a sulfur atom, etc. and may be saturated or unsaturated, and the number of carbon atoms is preferably 1 to 10, particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by connecting R eyes and R eyes include piperidyl group, pyrrolidyl group, N-
Examples include an alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for the R and R eyes are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Examples of compounds represented by formula (III) are shown below.

Hl-2 III-3 In-8 HOH In-4 Formula (IV) , R34 is a hydroxy group, a hydroxyamino group,
Substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group,
Represents an amino group. The heterocyclic group is a 5- to 6-membered ring, composed of C, Hlo, N, S, halogen atoms, etc., and may be saturated or unsaturated.

Xml is 100-1-8O1- or 1.

Especially when n=o, R14 is an alkyl group, an aryl group,
It represents a group selected from heterocyclic groups, and R33 and R14 may jointly form a heterocyclic group.

In formula (IV), R"R"R" is preferably a hydrogen atom or an alkyl group of C+""C+.
In particular, R31RIt is most preferably a hydrogen atom.

In formula (IV), R14 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group include carboxyl group, sulfo group, nitro group, amino group, and phosphono group. X''' is preferably 100- or -802-, most preferably -00-.

Examples of compounds represented by formula (IV) are shown below.

IV-1 C,H.

/ NH,N \ C,H.

! ■-2 NH,NH(-cub→-SO,H IV-3 N) IJGI + CI (*Chikan H IV-4 IV-5 o4oH / N! (, N \ CIH, OH IV-6 N)1. NHcOcH.

IV-7 NHJHCOOCJs IV-8 IV-14 NHJHCOCONHNH- IV-15 NHtNHCH*C[(zCH*5Oxl(IV-16 IV-9 IV-17 IV-1O NH,N1(CONI(! IV-11 1V -18 Nu, NHCH, C1, C0OH IV-19 IV-12 NH! NHSOs) TV-13 ■ NHINI Guomon.

IV-20 IV-21 TV-22 Among the compounds represented by formula (I[I), 111-
1, m-2, and IH-3 are preferred, and 111-1 is particularly preferred.

Among the compounds represented by formula (IV), I
V-2, IV-12, IV-19, and IV-20 are preferred, and IV-19 is particularly preferred.

Other sugars (D-glucose, D-sorbitol, D-
Galafute, glucosamine, D-mannose, etc.), alkanolamines (triethanolamine, jetanolamine, monoethanolamine, etc.) can also be used.

In the present invention, it is not preferable to use unsubstituted hydroxylamine or hydrazine as a preservative.

The running stability is inferior to the above-mentioned replacement type, and as the amount of preservative increases or decreases, sensitivity and gradation may fluctuate, and fog may occur. Furthermore, the preservative itself is easily oxidized in the air, resulting in poor performance as a preservative.

The preservative is 1 to Log/1. It is preferably used in a range of 2 to 8 g/R1, 2 to 20 g/l in its replenisher, preferably 3 to leg/l.

Also, usually the first color developer replenisher part is 2.5~
It is used at a content of 30 g/l, preferably 4 to 20 g/g.

As a preservative for the color developer and its replenisher (the first, second, and third color developer replenisher parts), sulfite (sodium sulfite, etc.), monobisulfite, etc. may be contained.

In addition, the color developer and its replenisher (the first color developer replenisher part) also contain ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and cyclohexanediaminetetraacetic acid as preservatives and suspending agents. aminopolycarboxylic acids such as ethylenediaminetemethylenephosphonic acid, aminopolyphosphonic acids such as nitrilotrimethylenephosphonic acid, alkylidene diphosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, catechol-3,5 - Various metal chelate forming compounds such as disulfonic acids are used.

Among the above, those with a chelate stability constant of 10 or more with Fe(m), those with a chelate stability constant of 6 or more with Ca(II)Mg(IN) are preferable, and in particular, those with a chelate stability constant of 6 or more with Fe(m), ethylenediaminetetrakismethylenephosphonic acid, l Preferred are -hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, catechol-3,5-disulfonic acid, and the like.

These chelating agents are usually used at a concentration of 0.1 in a color developing solution.
~10g/! , preferably 0.5 to 5 g/j, and 0.15 to 15 g/j for color developer replenisher, preferably 1 to 5 g/j.
Used in the range of 7.5g#.

In addition, in the first color developer replenisher part, 0.2 to 1
8 g/j, preferably in the range of 1.3 to 10 gel.

In addition, the color developer and its replenisher (the first color developer replenisher part) may include benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Amines, color development accelerators such as 3゜6-cythiaoctane-1,8-diol, auxiliary developers such as l-phenyl-3-pyrazolidone, competing compounds for color development reactions such as citradinic acid and hydroquinone, bromides, iodides , antifoggants and development inhibitors such as benzimidazoles and benzothiazoles.

A pH buffer such as a carbonate, a borate, a phosphate, or a diaminostilbene optical brightener may be added depending on the purpose.

Among these, benzyl alcohol has a color developing solution of 5 to 18 mj/j, preferably 8 to 15 mj/I, and a replenisher of 8 to 2 ornl/R%, preferably 10 to 1
It is used in the range of 8mj/j.

In addition, in the first color developer replenisher part, 10 to 2
5ffiIl/i, preferably 12-2oIIIj/e
It is said that

Among bromides, for example, potassium bromide is 0 to 2 g/l, preferably 0.3 to 1.5 g in the color developer, and o to 1 g/l, preferably 0 to 0.7 g in the replenisher. /l range.

In addition, in the first color developer replenisher part, O-1,
5g/j, preferably O~1.0g#.

The pH of the color developer is usually set in the range of 9 to 12, but is often in the range of 9.5 to 1O15.

In this case, an alkaline agent to adjust the pH or the first
The alkaline agents to be contained in the color developer replenisher include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, tripotassium phosphate, and triphosphate.
Preferred are sodium, potassium borate, sodium borate, potassium hydrogen carbonate, sodium hydrogen carbonate, dipotassium phosphate, disodium phosphate, and the like.

The alkaline agent is usually 10 to 50 g/l in color developer.
, preferably 15 to 45 g/l, and 15 to 45 g/l with its replenisher
60 get, preferably in the range of 20 to 50 gel.

In addition, in the first color developer replenisher part, 20 to 70
g/1. Preferably it is 25 to 60 g/l.

In the present invention, the temperature of the color development treatment is set in the range of 25 to 45°C, preferably 30 to 40°C. The processing time can be set arbitrarily depending on the type of photosensitive material, but for color photosensitive materials for printing, the processing time is set in the range of 30 seconds to 4 minutes, and for processing aimed at speeding up, it is set in the range of 30 seconds to 1 minute and 40 seconds. , 1 to 4 minutes for color photosensitive materials for photography, and 1 to 2 minutes for processing aimed at speeding up processing.
Can be set to seconds.

Preferred processing chemicals and their contents as essential components contained in the first, second, and third color development replenishers used in the present invention are shown below.

(1) First color development replenisher parts ■ Alkaline agent Usually, at least one kind is selected from the above compound group and used in combination in the above amount.

■Preservative (2) Second color developing replenisher part ■Color developing agent Usually, at least one kind is selected from the above compound group and used in combination in the above amount.

Furthermore, sulfite (addition amount 1 to 5 g/j) is mentioned as a substance that is preferably used in combination, although it is not an essential component.

In addition to this essential ingredient, 0 to 1% potassium bromide is added as an antifoggant. It is preferable to add og/l.

(3) Third Color Development Replenisher Part - Color Developing Agent In the present invention, a bleach-fix solution is used in the bleach-fix process that is preferably applied after the color development process.

As a bleaching agent used in bleach-fix solutions.

For example, iron (III) cobalt (m) chromium (I)
V) Polyvalent metal compounds such as copper (II), peracids, quinones, nitro compounds, etc. can be mentioned, but the most preferred bleaching agent is an organic acid complex salt of iron (III). Specifically, iron (
Complex salts with m) are preferred; these complex salts are Research Disclosure No.

They can be used in various combinations as described in No. 24023 (April 1984).

The amount of the above bleach used in the bleach-fix solution is 0 per lβ
．． 05 to 0.5 mol, preferably 0.1 to 0.4
It is a mole.

It is preferable to use a bleach accelerator in the bleach-fix solution for speeding up the bleaching process. Preferred bleach accelerators include US Pat. No. 3,893,858 and German Patent No. 1,290,8.
No. 12, JP-A No. 53-95630, Research Discology 'l'-No. 17129 (July 1978)
Examples include compounds having a mercapto group or disulfide bond as described in Japanese Patent Publication No. 53-11854, and compounds described in US Pat. No. 4,552.834. These bleach accelerators are bleach-fix solution 1
It is added at a rate of 0.001 to 0.05 mol per °C.

As a fixing agent, thiosulfate, thioether, thiourea,
Examples include iodides, but thiosulfates are most commonly used, with ammonium thiosulfate being particularly preferred. The amount of the fixing agent used is in the range of 0.3 to 3 mol, preferably 0.5 to 2 mol, per bleach-fix solution IJ2.

Further, as a preservative for thiosulfate, sulfite, bisulfite, carbonyl bisulfite adduct, etc. are used.

The pH of the bleach-fix solution can be set within the range of 3 to 9, but is generally preferably 4 to 8. In addition, especially in processing aimed at speeding up, it is preferable to set the pH to a range of 4 to 6.

The bleach-fixing process is carried out at a temperature of 25 to 45°C, preferably 30 to 40°C, and if speed is required, it is generally preferable to set the temperature to a higher temperature. In the case of materials, the time is 20 seconds to 3 minutes, but in processing that requires rapid processing, it can be set to 20 seconds to 1 minute. 1 to 5 for color photosensitive materials for photography
1 minute, but it can also be set to 1 to 3 minutes in rapid processing.

In the present invention, the replenishment amount of the bleach-fixing solution is 20 to 300II11 per color photosensitive material for printing.
100N1200 for color photosensitive material LAD for photography
It is set within the range of +aj. However, in the present invention, it is preferable that the amount of replenishment is smaller; specifically, it is less than 200 m1 for 1 m'' of color photosensitive material for printing, and 800 mj for 1 m'' of color photosensitive material for photography.
The following are preferred.

In the present invention, after the bleach-fixing process, a washing process and/or a stabilizing process are performed.

It is preferable to use deionized water as described in Japanese Patent Application No. 131632/1988 as the washing liquid or stabilizing liquid in the washing process and stabilization process. First, thiabendazoles, benzotriazoles, chlorinated incyanurates, and the like can be added as fungicides or fungicides. Additionally, water softeners such as ethylenediaminetetraacetic acid, optical brighteners, and the like can also be added.

In addition to the above, an image stabilizer such as formalin or ammonium salt is added to the stabilizing solution.

In addition, the washing liquid and the stabilizing liquid contain a surfactant, especially a nonionic surfactant [for example, (n) CIOH*l-0(-CH, CHlo +H).

(n)C-H+eOO+ CH*CH-0+ H2S (n)C,H+-004GHzCHtO+H etc.] is preferably used.

This improves washing efficiency.

It is preferable that the water washing or stabilization treatment process be configured with a plurality of tanks, and use a multistage countercurrent system in which the last tank is replenished as described above. The number of tanks is usually 2 to 6, preferably 2 to 4.

The pH of the washing solution and stabilizing solution is generally in the range of 5 to 9.
Preferably it is 6-8. The processing time in the washing tank or stabilization tank can be set arbitrarily depending on the purpose, but generally it is
The range is from 0 seconds to 5 minutes, and if speeding up is required, it is set in the range from 30 seconds to 1 minute and 30 seconds. Also, the processing temperature is 2
The temperature is 0 to 40°C, but in rapid processing, it is set to around 35°C in order to promote cleaning.

In the present invention, the replenishment amount of the washing tank or stabilizing tank is 100 to 500 rai per 1 m" of color photosensitive material for printing.
200-12 per color photosensitive material III+2 for 1 photography
It is set in the range of 00mj, but it can also be set to 400a+j or less per 1m'' of color photosensitive material for printing, or 800m1 or less per 11II2 of color photosensitive material for photography.

Next, the color photosensitive material to be processed in the present invention will be explained.

The silver halide emulsion of the color light-sensitive material processed by the method of the present invention contains at least one of silver chloride, silver bromide, and silver iodide, but in the case of a color light-sensitive material for printing, it contains substantially iodine. Silver chlorobromide containing no silver is preferred.Substantially free of silver iodide means that the content of silver iodide is 1 mol% or less based on the total amount of silver halide, preferably 0. 3 mol% or less, more preferably 0
．． It should contain no more than 1 mol % of silver iodide, most preferably no silver iodide.

The emulsion of the color photosensitive material for printing preferably used in the present invention is a silver chlorobromide emulsion having a silver bromide content of 10 mol % or more. In particular, in order to obtain an emulsion having sufficient sensitivity without increasing fog, the silver bromide content is preferably 20 mol % or more. However, if rapid processing with shortened development time, etc. is required, the silver bromide content is 10%.
Silver chlorobromide emulsions with a silver bromide content of 3 mol % or less are preferred, and silver chlorobromide emulsions with a silver bromide content of 1 mol % or less are particularly preferred, and silver bromide emulsions with a silver bromide content of 1 mol % or less are preferred. More preferred are emulsions containing no silver chloride.

Reducing the content of silver bromide not only improves the development speed (but also reduces the amount of bromide ions eluted into the developer when developing a photosensitive material containing silver bromide, making it possible to develop with a smaller amount of replenisher. Can maintain activity.

Specific examples of such color photosensitive materials for printing include color vapor, color reversal vapor, color autopositive vapor, and the like.

In addition, in color photographic materials, silver iodobromide or silver iodochlorobromide emulsions containing 30 mol% or less of silver iodide are used, and in particular silver iodide containing 3 mol% to 25 mol% of silver iodide is used. A silver iodobromide emulsion containing the following is preferred. Among these, the preferred silver iodide content for the present invention is from 3 mol% to 11 mol%, most preferably from 3 mol% to 8.0 mol%.

Specific examples of such color photographic materials include color negative films.

Silver halide grains in photographic emulsions may be so-called regieler grains having regular crystals such as cubic, octahedral, dodecahedral, and polydodecahedral, or may have irregular crystal shapes such as spherical. It may be one with crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less or large grains with a projected area diameter of up to about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method.
(RD) No. 17643 (December 1798),
pp. 22-23, “r. Emulsion p.
187) 6 (November 1979), 648.
You can follow the method described on page.

The photographic emulsion used in the present invention is based on "Physics and Chemistry of Photography" by Glafkide, published by Ballmontel (P.
des, Chimie et PhysiquePh
otographique Paul Montel,
1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F. Uffin, Photo
graphic Emulsion Chemistry
(Focal Press, 19 [i6), Zelikman et al. [Production and Coating of Photographic Emulsions], Focal Press Publishing (V, L., Zelikman et al, Ma
King and Coating Photograp
hic Emulsion, FocalPress
, 1964).

It is preferable to use a monodisperse emulsion in the present invention.

As a monodisperse emulsion, silver halide grains with an average grain diameter of more than about 0.1 micron, and a small number of silver halide grains (both about 95
Emulsions in which the weight percent is within ±40% of the average grain diameter are typical. The average grain diameter is from about 0.25 to 2 microns, and at least about 95% by weight or quantity of silver halide grains are comprised of an average grain diameter of ±20 microns.
% can be used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutoff.

Photographic 5science and
Engineering), Volume 14, 248-257
Page (1970); U.S. Pat. No. 4,434,226;
British Patent No. 4.414.310, British Patent No. 4,430,048, British Patent No. 4,439,520 and British Patent No. 2゜11
It can be easily prepared by the method described in No. 2.157. When using tabular grains, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat.
It is described in detail in No. 434.226.

The crystal structure may be --like, or the inside and outside may have different compositions. A typical example of a heterogeneous composition is a core-shell type or double structure type particle in which the interior and surface layers of the particle have different halogen compositions. In such particles, the core shape and the overall shape with the shell may be the same or different.

Specifically, some particles have a cubic core and a shell with a cubic shape, while others have an octahedral shape.

Some are the opposite. Further, instead of having a simple double structure, a triple structure or a more multilayer structure, or a core-shell double structure grain having a thin layer of silver halide having a different composition on its surface may be used.

The color photosensitive material processed by the method of the present invention has a uniform halogen composition within the grains.
Emulsions consisting of grains having some structure are preferably used. In silver chlorobromide emulsions such as those used in color vapors, grains having a halogen composition with a lower silver bromide content on the grain surface than on the grain interior are more preferably used. A typical example is a core-shell emulsion in which the core contains a higher content of silver bromide than the shell. The difference in silver bromide content between the core and shell is 3 mol%.
It is preferably 95 mol% or less, and the silver ratio (mole ratio) between the core and the shell is 5:95 to 95:5, more preferably 7:93 to
90:10 is preferred.

In addition, in a silver iodobromide emulsion such as a color negative film, the core part has a higher silver iodide content than the shell part, and the silver iodide content is 10 to 45 mol%, and even 15 to 45 mol%.
40 mol% is preferred. The shell portion preferably contains silver iodide in an amount of 5 mol % or less, particularly 2 mol % or less.

The silver content ratio between the core and the shell is preferably 15:85 to 85:15, more preferably 15:85 to 75:25.

Such emulsion grains are described in British Patent No. 1,027.146, US Pat. No. 3,505,068, US Pat.
No. 877 and Japanese Patent Application No. 58-248469.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are
It is a pigment belonging to cyanine pigments, merocyanine pigments, and complex merocyanine pigments.

As the sensitizing dye used in the present invention, RESEARC
HDISCLOSURE Volume 176, Item 76
431V, page P, 23 (December 1978 issue).

Here, the sensitizing dye can be used in any step of the manufacturing process of the photographic emulsion, or can be present in any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

In particular, U.S. Pat.
No. 25,666 discloses that by adding a spectral sensitizing dye to the emulsion after the formation of stable nuclei for silver halide grain formation, the photographic sensitivity is increased and the adsorption of the spectral sensitizing dye by the silver halide grains is enhanced. It has been disclosed that there are advantages.

The silver halide photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or stabilizing photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3n, 7) tetraazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

Regarding these, please refer to Research Disclosure (R
D) No. 17643 and No.

18716, and the locations are listed in the table below.

l Chemical sensitizer 2 Sensitivity increasing agent 3. Spectral sensitizer.

Super sensitizer 4 Brightener 5 Anti-capri agent, stabilizer dye image stabilizer hardener binder plasticizer, lubricant coating aid, surfactant RD 17643 23 pages 23-24 pages 24 pages 24-25 Page 25 Page 26 Page 26 Page 27 Page 26-27 RD 18716 Page 648 Right column Same as above Page 648 Right column ~ Page 649 Right column Page 649 Right column Left to right column Page 651 Left column Same as above 650 Page Right column Same as above Processed by the present invention The silver halide color light-sensitive material used can contain various color couplers. For example, Research Disclosure, December 1978, 1
7643■-ri section and November 1979, 1871
Typical examples include the cyan, magenta and yellow dye-forming couplers described in the patent issued by No. 7, No. 7, No. These couplers are preferably made diffusion resistant by introducing a ballast group or by multimerizing dimers or more, and may be 4-equivalent couplers or 2-equivalent couplers. Couplers that improve graininess and DIR couplers that release development inhibitors and the like upon coupling reaction and produce edge effects or multilayer effects can also be used.

Furthermore, in order to increase sensitivity, a group having a development accelerating effect or a group having a fogging effect on silver halide is released during the coupling reaction, for example, in JP-A-57-1.
No. 50845, No. 59-50439, No. 59-157
No. 638, No. 59-170840 and patent application No. 1983-
Compounds described in No. 146097 and the like can also be used.

In addition, as a color coupler, it is easy to obtain the effects of the compound of the hydrophobic invention, which has a low usage ratio of 4-equivalent couplers.
Specifically, the proportion of 4-equivalent couplers among all the couplers contained in the light-sensitive material is preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 30 mol% or less.

The yellow coupler is preferably an α-pivaloyl or α-benzoylacetanilide coupler that leaves at an oxygen atom or a nitrogen atom. Particularly preferable examples of these two-equivalent couplers include U.S. Pat.
408゜194, same No. 3.447.928, same No. 3
933.501 and US Pat. No. 4,022,620, etc., or US Pat. No. 3.973.968 and US Pat.
, No. 023, Japanese Patent Publication No. 10739/1982, Japanese Patent Application Publication No. 1987-
132926, West German Application No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2.329.587
Examples include the nitrogen atom separation type yellow couplers described in No. 2,433.812 and the like.

Magenta couplers include 5-pyrazolone couplers, pyrazolo[5,1-c][1,2,4] triazoles described in U.S. Pat. No. 3,725,067, or European Patent No. 119,860. pyrazolo [5
, lb] El, 2,4] triazole, etc. can be used. Also preferred is a magenta coupler made into two equivalents by a leaving group bonded to the coupling active position via a nitrogen atom or a sulfur atom.

As the cyan coupler, a coupler that is robust against humidity and temperature is preferably used, and typical examples include the phenolic coupler described in U.S. Pat. No. 3,772,002; Gansho 58
2,5-diacylaminophenol couplers described in US Pat. No. 42671 and JP-A-58-133293, etc.; Examples include phenolic couplers having an acylamino group at the 5-position; and naphthol couplers described in Japanese Patent Application No. 59-93605.

In order to correct unnecessary sub-absorption existing on the short wavelength side of the main absorption of the coloring dye, a yellow or magenta colored coupler may be used in combination. These couplers are
It is usually used by emulsifying and dispersing it in an aqueous medium using a high boiling point organic solvent such as phthalic esters or phosphoric esters having 16 to 32 carbon atoms and, if necessary, an organic solvent such as ethyl acetate. Standard usage amounts of color couplers are preferably o, oi to 0.5 mole for yellow couplers, 0.003 to 0.3 mole for magenta couplers, and 0.003 to 0.3 moles for cyan couplers per mole of photosensitive silver halide. It is 0.002 to 0.3 mole.

Examples of the support used in the present invention include flexible supports such as plastic film, paper, and cloth, and rigid supports such as glass, ceramic, and metal. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer, etc.).

The present invention is suitable for application to small-sized automatic processors in minilabs, silver halide photocopiers, and the like.

It is preferable to use it for processing a combination of color paper and color negative film, or color auto-positive paper and color negative film.

<Effects of the Invention> According to the present invention, it is possible to make the apparatus more compact and to simplify the processing work.

In addition, the color development replenisher has good stability over time, and as a result, running stability is good, and good and stable photographic properties can be obtained even after long-term running.

In order to confirm the above effect, the present inventor To this end, we conducted various experiments. An example is shown below.

Experimental Example 1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material (color negative film) consisting of each layer having the composition shown below was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in g/ml of silver for silver halide and colloidal silver, and the amount expressed in g/m2 for couplers, additives and gelatin. The sensitizing dye is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.2 gelatin
1.3 Coupler C-10,06 Ultraviolet absorber tJV-10,1 Same as above UV-20,2 Dispersion oil 0il-10,01 Same as above 0il-20,01 2nd layer (intermediate layer) Fine grain silver bromide (average grain Diameter 0.07 Gelatin Cobra-C-2 Dispersion oil 0il-1 3rd layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, ratio 2.5, average grain size 0. 3 AgI type) Silver gelatin sensitizing dye Technique Sensitizing dye ■ Sensitizing dye ■ Coupler C-3 Coupler C-4 Coupler C-8 Coupler C-2 Dispersion oil Of f-1 Same as above 0i1-3 Diameter/Thickness μ, Internal High 0.4 0.6 1, OX 10-'3.0XlO-'lXl0-'' 0.06 0.06 0.04 0.03 0.03 0.012 μ) 0.15 1.0 0.02 0.1 4th layer (second red emulsion store) Silver iodobromide emulsion (silver iodide 5 mol%, diameter/thickness ratio 4.0
, average particle size 0.7μ, internal height AgI type)
Silver 0.7 sensitizing dyestuff ix to-
' Sensitizing dye II 3X 10-' Sensitizing dye In lXl0-' Coupler C-30,24 Coupler C-40,24 Coupler C-80,04 Coupler C-20,04 Dispersion oil 0il-10,15 Same as above 0iL- 30,02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, diameter/thickness ratio 1.
3. Average particle size 0.8μ, internal height AgI type)
silver 1.0 gelatin
1°0 sensitizing dye I lx
10-' Sensitizing dye If 3X
10-' Sensitizing dye III lXl
0-'Coupler C-60,05 Coupler C-70,1 Dispersion oil Oi l -10,01 Same as above Oi 1-2 0.05 6th layer (intermediate layer) Gelatin 1.0 Compound Cpd
-A 0.03 dispersed oil i 1
-1 0.05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, diameter/thickness ratio 2.5
, average particle size 0.3μ, internal height AgI type)
Silver 0.3 sensitizing dye IV
5X10-'sensitizing dye Vl
O,3X 10-' sensitizing dye V
2X 10-'gelatin 1.
0 Coupler C-90,2 Coupler C-50,03 Coupler C-10,03 Compound Cpd-CO,012 Dispersed oil i l -10,5 8th layer (second edge-sensitive emulsion layer) Silver iodobromide emulsion ( Silver iodide 4 mol%, diameter/thickness ratio 4.0
, average particle size 0.6 μ, internal high AgI type)
Silver 0.4 sensitizing dye■5X1. O-
' Sensitizing dye V 2X 10-' Sensitizing dye VI 0.3XIO-' Coupler C
-90,25 Coupler C-10,03 Coupler C-1o 01015 Coupler C-50,01 Compound Cp d -CO,012 Dispersion i 1-1 0.2 9th layer (
Third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, diameter/thickness ratio 1.2
, average particle size 1.0μ, internal height AgI type)
silver 0.85 gelatin
1.0 Sensitizing dye ■ 3.5
X to-'sensitizing dye Vllll'
1.4XIO'' coupler c-t a
o, ot coupler C-120,03 Coupler C-90,20 Coupler C-10゜02 Coupler C-150,02 Dispersed oil Oil -10,20 Same as above 0il-20,05 10th layer (yellow filter layer) Gelatin 1.2 Yellow Colloidal Silver 0.08 Compound Cpd-B
O,1 dispersion oil Oi 1-1
0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, diameter/thickness ratio 1.5, average grain size 0.5μ, internal high AgI type)
Silver 0.4 Gelatin 1.
0 sensitizing dye IX 2 10 mol% silver, diameter/thickness ratio 4.
5. Average particle size 1.3μ, internal height AgI type)
silver 0.4 gelatin
0,6 sensitizing dye IX
IX 10'' coupler C-140,25 Dispersion oil 0il-10,07 13th layer (first protective layer) Gelatin 0.8 Ultraviolet absorber UV-10,1 Same as above UV-20,2 Dispersion oil 0il-10 ,01 Dispersion oil 0il-20,01 14th layer (2nd protection m> Fine grain silver bromide (average particle size 0-0'ju l 0.5 Gelatin 0.45 Polymethyl methacrylate particles (diameter 1, 5μ) 0.2 Hardener H-10,4 n-butyl p-hydroxybenzoate 0.012 Formaldehyde scavenger 5-10.5 Formaldehyde scavenger 5-20.5 In addition to the above components, each layer contains surfactant. The agent was added as a coating aid.

In the above photosensitive material, the total thickness of the photographic layer coated on the support is 17.5μ, and the 50% swelling rate T1/2 is 6 seconds when immersed in the color developer of this experimental example (38°C). Met.

Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below.

UV-1 UV-2 tricresyl phosphate dibutyl phthalate N-3 Bis(2-ethylhexyl) phthalate C) Im mol. wt.

about 20,000 C-t.

C-11 pd-A pd-B pac-c Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye IV Sensitizing dye V Sensitizing dye ■ Js Sensitizing dye vr Sensitizing dye ■ Sensitizing dye ■ ■ (2) On the other hand, a color paper for printing having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(Preparation of coating liquid for the first layer) Yellow couplers (ExY-1) and (ExY-2)
10.2g, 9.1g and color image stabilizer (Cpd-
1) Add and dissolve 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling point solvent (Solv-1) to 4.4 g, and dissolve this solution into a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. It was emulsified and dispersed in 185cc. This emulsified dispersion and emulsions EMI and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-oxy-3,5
-dichloro-8-triazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m''). Silver halide emulsions represent the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Tie) and a bluish dye. ] th layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM 1 ) spectrally sensitized with a sensitizing dye (ExS-1) ...0.13 Spectrally sensitized with a sensitizing dye (ExS-1) Sensitized monodisperse silver chlorobromide emulsion (EM2) ...0.13 Gelatin ...1.86 Yellow coupler (Ex Y -1) = -0,44 Yellow coupler (ExY-2) -0 ,39 color image stabilizer (Cpd-1)...0.19 solvent (So
1 v −1) =・0.35 5th layer (
Color mixing prevention layer) Gelatin...0.99 Color mixing prevention agent (Cpd-3)...0.08 Fifth M
(Green Sensitivity H) Monodisperse silver chlorobromide emulsion (EM3) spectrally sensitized with sensitizing dyes (Exs-2, 3)...0.05 Spectral sensitization with sensitizing dyes (Exs-2, 3) Sensitized monodisperse silver chlorobromide emulsion (EM4) Gelatin magenta coupler (ExM-1) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-6) Solvent ( Solv-2) Solvent (Solv-3) ...0.11 ...1.80 ...0.39 ...0.20 ...0.02 ...0.03 ...0 .12...0.25 Fourth layer (ultraviolet absorption layer) Gelatin...1.60 Ultraviolet absorber (Cpd-7/Cpd-8/Cpd-9=
3 / 2 / 6: Weight ratio)...0.70 Color mixture prevention agent (Cpd-10)...0.05 Solvent (Solv-4)...0.27 Fifth layer (red sensitive layer) Increase Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with a sensitizing dye (ExS-4, 5) ...0.07 Monodisperse salt spectrally sensitized with a sensitizing dye (ExS-4, 5) Silver bromide emulsion (EM6)...0.16 Gelatin cyanogen (ExC-1) Color image stabilizer (Cpd-8/Cpd-9/Cpd-12 = 3/4/2: weight ratio) Dispersion Polymer (Cpd-11) ...0.92 ...0.32 ...0.17 ...0.28 Solvent (Sol v-2) = -0,20
Sixth layer (ultraviolet absorption layer) Gelatin...0.54 ultraviolet absorber (Cp d -7/Cp d -9/Cpd
-12 = 115/3: weight ratio)...0.21 Solvent (So 1 v-2) -0,08 Seventh layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) ...-0.17 Liquid paraffin ...0.03 In addition, at this time, the irradiation prevention dye is (Cpd-1
3, cpci-14) was used.

Furthermore, each layer contains Alkanol B (Dupont), sodium alkylbenzene sulfonate, succinate ester, and MageF as an emulsifying dispersant and coating aid.
acxF-120 (manufactured by Dainippon Ink Co., Ltd.) was used.
As a stabilizer for silver halide, (Cpd-14,15
) was used.

Details of the emulsion used are as follows.

Emulsion name Shape Particle size Br content Coefficient of variation (μ)
(mo1%) 1.0 80 0.0g0.75
80 0.0?0.5
83 0.090.4 83'
0.100.5 73
0.090.4 73 0.10
Cube Cube Cube Cube Cube Cube MI M2 M3 M4 EMS M6 The structural formulas of the compounds used are as follows.

ExY-1 ExY-2 ExY-1 xS-4 xS-5 cpcl-1 pd-2 y no repair xC-1 xS-1 xS-2 xS-3 cpcl-3 pd-4 pd-5 Js pd-6 Cp d -7 cpct-s cpct-9 cpa-10 cpa-11 cpa-15 death Open cpa-16 cpa-12 olv-1 hmm Bu blood le centre Ta Re to olv-2 to licresyl phosphate olv-3 trioctyl phosphate olv-4 to Li nonyl phosphate to cpa-13 cpa-14 Double-sided polyethylene Mine paper support On top of the, Autopositive color with the layer structure shown below I made a vapor.

(Layer structure) The composition of each layer is shown below. The numbers represent the amount of coating per m2.

For silver halide emulsions and colloidal silver, the coating amount is expressed in grams of silver.
The amount of the spectral sensitizing dye added per mole of silver halide is expressed in moles.

Support polyethylene laminate paper [E1 [side polyethylene contains white pigment (TiOi) and bluish dye (ulmarine blue]] E1 layer Silver halide emulsion 0.26 Spectral sensitizing dye (ExSS-1) 1. OX 10-' spectral sensitizing dye (ExSS-2) 6.1 x 1
0-' Gelatin 1.11 Cyan coupler (ExCC-1) 0.21
Cyan coupler (ExCC-2) 0.2
6 UV absorber (ExUV-110, 17 solvent (ExS
-1) 0.23 development regulator (
ExGC-1) 0.02 stabilizer (E
xA-1) Nucleating accelerator (εxZS-1) Nucleating agent (ExZK-1) E2 layer gelatin color mixing inhibitor (ExKB-1) Solvent (ExS-1) Solvent (ExS-2) E3M Silver halide Emulsion spectral sensitizing dye (ExSS-3) Gelatin magenta coupler (ExMC-1) Color image stabilizer (ExSA-1) Solvent (ExS-3) Development regulator (ExGC-1) Stabilizer (ExA-1) Nucleation Accelerator (ExZS-1) Nucleating agent (ExZ to -1) 0.006 3, OX 10-4 8, OX 10-' 1.41 0.09 0.10 0.10 0.23 3, OX to -' l, 05 0.16 0.20 0.25 0.02 0.00G 2.7X 10-' 1.4X 10-' E4 layer gelatin color mixing inhibitor (ExKB-1) Solvent (ExS-1) Solvent (ExS-2) No. E5! Colloidal silver gelatin color mixing inhibitor (ExKB-1) Solvent (ExS-1) Solvent (ExS-2) Same as 66th layer and E4 layer 0.47 0.03 0.03 0.03 0.09 0.49 0 .03 0.03 0.03 E7 layer silver halide emulsion spectral sensitizing dye (ExSS-3) Gelatin yellow coupler (ExYC-1) Solvent (ExS-2) Solvent (ExS-4) Development regulator (ExGC- 1) Stabilizer (εxA-1) Nucleation accelerator (ExZS-11 Nucleation agent (ExZK-1) E8th layer gelatin ultraviolet absorber (ExUV-2) Solvent (ExS-4) 0.40 4.2X 10 -' 2.17 0.51 0.20 0.20 0.06 0.001 s, ox to-' 1.2X 10"' 0.54 0.21 0.08 Structural formula of compound used in layer B9 is as follows.

gelatin 1.28 (ExCC-1) cyan coupler Po Li Vinyl alcohol acrylic Lyle modified copolymer (denaturation degree 17%) 0.17 liquid paraff I hmm 0.03 Po Li Mail Ta nine Methyl lylate (ExCC-2) cyan coupler centre x particles (Average particle size 2,8 0.05 B1 layer gelatin 8.70 (ExMC-1) magenta coupler No. 82N Same as layer B9 In addition to the above composition, each layer contains centre chin hardener 1 and a surfactant were added.

(ExYC-1) Yellow coupler (ExSS-3) Spectral sensitizing dye (ExSS-4) Spectral sensitizing dye (ExSS-1) Spectral sensitizing dye (ExS-1) Solvent (ExSS-2) Spectral sensitizing dye ( ExS-2) Solvent (ExS-3) Solvent (ExUV-2) Ultraviolet absorber Above (1): (2): 2 of (3): 9:
si compound (weight ratio) (ExSA-1) 1:1 mixture of color image stabilizer (volume ratio) (ExS-4) Solvent 0=P-1-0-Cv H+5(iso) ) s, (
ExLtV-1) Ultraviolet absorber (ExKB-1) Color mixing inhibitor (ExGC-1) Development regulator n 5:8:9 mixture (weight ratio) of (1): (2): (3) (ExA- 1) Stabilizer 4-hydroxy-5,6-drimethylene-1,3,3a
, 7-tetrazaindene (ExZS-1) nucleating agent 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) nucleating agent 6-ni Toxythiocarponylamino-2-methyl-1-
Propargyl quinolinium trifluoromethanesulfonate (ExGK-1) Gelatin hardener Preparation of l-oxy-3,5-dichloro-8-triazine sodium salt emulsion An aqueous solution of potassium bromide and silver nitrate was added at 0.3 molar concentration per mole of Ag.
75 g of 3.4-dimethyl-1,3-thiazoline-2-thione was added to an aqueous gelatin solution with vigorous stirring.
It took about 20 minutes to add them at the same time at ℃, and the average particle size was about 0.
A monodisperse silver bromide emulsion of 404 octahedrons was obtained. A chemical sensitization treatment was carried out by adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating it at 75° C. for 80 minutes.

Using the thus obtained silver bromide grains as cores, they are further grown in the same precipitation environment as the first time, and the final average grain size is about 0.
A monodisperse core/shell silver bromide emulsion with seven hedrons was obtained.

The coefficient of variation in particle size was approximately 10%.

To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 B of chloroauric acid (tetrahydrate) per mole of silver, and the
Chemical sensitization treatment was performed by heating for a minute to obtain an internal latent image type halogenated emulsion.

35ff1 color negative film produced as above
The color paper was cut into 82.5 mm width, and the autopositive paper was cut into A4 lengthwise width.

After exposing these color negative films, color paper, and auto-positive color paper, respectively,
The following treatments were performed using the automatic processor shown in FIG.

The color development replenisher had the following composition.

(1) First color developer replenisher Partslow Sorvit 0.20 g Sodium naphthalene sulfonate/formalin condensate 0.20 g Ethylenediaminetetrakis methylene phosphonic acid 1.5 g Diethylene glycol L6. Qm! Benzyl alcohol 18.0 ml Potassium bromide benzotriazole 0.004 g Sodium sulfite 3.2 g N,N-bis[carboxymethyl)hydrazine 8. OgD-glucose 2.4g triethanolamine 8.0g potassium carbonate
25.0 g Fluorescent brightener (diaminostilbene type) 1.2 g Add water to 900 ml (2) Second color developer replenisher parts (for negatives) 3-methyl-4-
Amino-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 5.5g Sodium sulfite 0.3g Potassium bromide
Add 1.0 g water
100 ml (3) Third color developer replenisher part (for paper) 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 8.5 g Sodium sulfite 0. Add 3g water
100 tag car paper and volumetric color development 135 seconds 38°C 5j 300ml/m" Dark fixing water washing (1) Water washing (2) Drying 40 seconds 40 seconds 40 seconds 30 seconds 33°C 33°C 33°C 80°C j 30hj/m" 320+nj/replenishes the washing water by refilling the washing bath (1) and
The overflow liquid from step 2) was introduced into the washing bath (1) (a so-called countercurrent replenishment method was adopted).

The composition of each treatment liquid was as follows.

1111j Mother l Night water added D-sorbitol diethylene glycol benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite D-glucose triethanolamine 0.15 g 12.0 ml 13.5 ml O, 80 g 0.003 g 2.4 g 2 .0 g 6゜Og p) + (25℃) l Uni 11 (both mother liquor and replenisher) Ethylenediaminetetraacetic acid, disodium, dihydrate ethylenediaminetetraacetic acid, Fe (IIIr), ammonium, dihydrate ammonium thiosulfate ( 700g/1) Sodium p-1-luenesulfinate Sodium bisulfite 5-mercapto-1,3,4-triazole Ammonium nitrate Add water and pH (25°C) 1O150 4,0 70,0 20,0 20,0 0 ,5 10,0 6,20 Potassium carbonate 30.0 g 'LLi (both mother liquor and replenisher) Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion. Water was passed through a mixed bed column filled with exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3I1 g/j or less.

To this water 11 was added 0.3 g of polyoxyethylene p-monononylphenyl ether (average degree of polymerization 10).

Color development of Kergaflum 3 minutes 15 seconds 38℃ j 0ml Bleach-fixing Washing with water (1) Washing with water (2) Drying 33℃ 33℃ 33℃ 60℃ j i 0mff1 0mj $35mm film D-Sorvit Sodium naphthalene sulfonate/formalin condensate Ethylenediamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-bis(carboxymethyl)hydrazine D-Glucose triethanolamine 3-Methyl-4-amino- N-ethyl-N-(β-hydroxyethyl)-aniline sulfate potassium carbonate mother liquor 0.15 g 0.15 g 1.5 g 12.0 al 13.5 ml 1.70 g 0.003 g 2.4 g 6゜Og 2.0 g 6, Og 46.0 g 30.0 g Fluorescent brightener (diaminostilbene type) 1.0 g Add water 100θ III pH
(25℃)
10.50 Temperature "L Constant" L Travel Color Vapor and Auto-Positive Color Vapor and Auto-Positive Color Vapor. The ratio is expressed as an area (m”) ratio, (autopositive color paper)/
(Color paper) / (Color negative film) = 20 /
It was 10/1.

In this manner, three or four rounds of running processing were performed in a color developing tank for color vapor for 20 days. At this time, there were 1.7 rounds of running in the color developing tank for color negatives.

For auto-positive color paper and color negative film, changes in photographic properties at the start of the run and at the end of the above-mentioned run were investigated by processing each wedge-exposed light-sensitive material. Photographic properties are defined as maximum density (I), fog density (D,, n), and sensitivity, and these changes are shown in Table 1 as the difference between the start and end times.

Table 1 M M M From Table 1, it can be seen that there is little change in the photographic properties of auto-positive color vapor, color paper, and color negative film.

Furthermore, no desilvering failure occurred.

In addition, the preservative N, N-bis(
When the same mole of hydroxylamine was used instead of carboxymethyl)hydrazine and the same treatment was carried out, the change in photographic properties was found to be about twice as large (as compared to the results in Table 1), which was unfavorable.

Furthermore, the processing apparatus of the present invention can be made more compact, such as by being able to share the processing tank except for the color developing tank. Further, it is possible to simplify the work in preparing the processing liquid and the like.

D, □ 0.02 0.03 0.01Q, 02 0
．． 02 0.01 0.03 0°02 0.02 D-+-0,010,010,01 0,010,000,01 0,020,020,0! Sensitivity 0.020.010.02 0.020.01 Q
, (110,020,010,00

[Brief explanation of drawings]

FIG. 1 is a plan view schematically showing the tank arrangement in the processing apparatus of the present invention. Explanation of symbols 12a...First color developing tank 12b...Second color developing tank 31...First container 32...Second container 33...Third container

Claims (1)

[Claims] (1) It has a first color developing tank containing a color developing solution containing a first color developing agent, and the average silver iodide content of the silver halide emulsion coated on the support is 3 mol% or more. A first method for developing a first silver halide color photographic light-sensitive material of
A silver halide color photographic light-sensitive material having a processing path and a second color developing tank containing a color developing solution containing a second color developing agent, the silver halide emulsion containing substantially no silver iodide. a second processing path for developing the color developing agent, and a first processing path containing an alkaline agent and a color developing agent preservative.
a first container containing a color developer replenisher part containing the first color developer replenisher; a second container containing a second color developer replenisher part containing the first color developer; and a second container containing the second color developer replenisher. a third container storing a third color developer replenisher part containing a third color developer replenisher part; The first and second color developer replenisher parts are replenished, and the second color developer tank of the second processing path is supplied with the first and third color developer replenishers from the first and third containers. A processing apparatus for silver halide color photographic materials, characterized in that the replenisher parts are configured to be replenished.