JP2670890B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it is rapid and suitable for processing stability, and has excellent gray balance and high color image stability. The present invention relates to a method for processing a light-sensitive material capable of providing an image having properties.

(Prior Art) Processing of a silver halide color photographic light-sensitive material basically involves three steps of development (in the case of a color reversal material, there is black and white first development before color development), desilvering and washing with water. Become. Desilvering consists of a bleaching and fixing step or a single-bath bleach-fixing step combining these steps. In addition to this, additional treatment steps such as stabilization treatment, pre-bath treatment before each step, and termination treatment are used. In color development, the exposed silver halide is reduced by a color developing agent to produce silver and halide ions. Simultaneously, the oxidized color developing agent reacts with the coupler to form a dye. Therefore, when a large amount of silver halide photographic material is continuously processed by an automatic developing machine or the like, halogen ions are accumulated in the developing solution. In recent years, low replenishment has been actively promoted for the purpose of resource saving and low pollution.
However, simply reducing the replenishment rate of the developing solution causes a problem that the developing activity is lowered due to the accumulation of the eluate of the light-sensitive material, particularly iodide ion and bromine ion which are strong development inhibitors, and the rapidity is impaired. As one of the means for solving the problem, there is a method of increasing the pH of the developing solution and the processing temperature. However, in these methods, other serious problems occur in that the photographic performance fluctuates greatly during continuous processing and the stability of the developing solution deteriorates.

On the other hand, for the purpose of reducing the accumulation of iodide ions and bromine ions which are strong development inhibitors, and aiming at speeding up, JP-A-58-95345, 59-232342, 61-70552, WO
No. 87-04534 discloses a method using a silver halide light-sensitive material having a high silver chloride content, which is considered to be an effective means for enabling rapid processing even with a low replenishment of a developing solution.

Also, a method of rapidly processing such a silver halide photosensitive material having a high silver chloride content in a color developing solution substantially free of benzyl alcohol in 25 seconds or less,
It is disclosed in Japanese Patent Laid-Open No. 1-196044.

However, in the color developing solution using the conventional developing agent 4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline salt, the stability of the processing solution is maintained, and at the time of continuous processing. After ensuring the stability of photographic performance
It was difficult to achieve ultra-rapid processing within 30 seconds. In other words, using a silver halide photosensitive material with a high silver chloride content,
It was found that processing with a developing solution having a high pH or a high processing temperature accelerated the processing, but both the liquid stability and the processing stability deteriorated remarkably and were not practical.

As a method for suppressing fluctuations in photographic performance due to accumulated bromide ions in the development of a silver halide photographic material mainly composed of silver chlorobromide, N-hydroxyalkyl-substituted -p-
The use of a color developing agent of a phenylenediamine derivative is disclosed in JP-A-61-261740 and JP-A-61-275837. The specification describes that the storage stability of a color image is improved by performing color development in a short time to reduce the residual amount of the color developing agent in the light-sensitive material.

(Problems to be Solved by the Invention) However, it is said that when an N-hydroxyalkyl-substituted-p-phenylenediamine derivative is used, the storage stability of the obtained color image, particularly the fastness to light, is significantly reduced. ing. Actually, a color photographic material containing a silver halide emulsion containing 80 mol% or more of silver chloride, for example, 4-amino-3-methyl-N-ethyl-N, which is widely used as a developing agent for a current color negative film, is used.
When processed with a color developer containing -β-hydroxyethylaniline salt but no benzyl alcohol, an image was formed rapidly (within 30 seconds) and the processing stability was excellent, but the processing time was short. Nevertheless, the light fastness was found to be much lower than that of 4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline salt.

Generally, in printing materials such as color papers, storage stability of a color image is an important item, and thus it is a major issue to achieve not only rapidity and low replenishment but also improvement of light fastness.

Moreover, as a result of further studies, when a rapid development treatment was carried out in a short time within 30 seconds using a developing agent of these N-hydroxyalkyl-substituted-p-phenylenediamine derivatives, a color photosensitive material having at least three types of photosensitive layers was obtained. The shadow portion of the intermediate photosensitive layer of the material (for example, the red-sensitive layer, the green-sensitive layer and the green-sensitive layer when the blue-sensitive layer is present from the side farther from the support) is softened, resulting in a so-called multi-layer effect, which causes graying. It was found that a phenomenon that the balance was deteriorated occurred.
It is considered that such a layering effect is a unique phenomenon that occurs only when a rapid development treatment within 30 seconds is performed.

Furthermore, it has been found that when processing is performed at a high temperature in order to further speed up color development, the obtained image, particularly the minimum density of cyan, tends to increase.

Therefore, an object of the present invention is to provide a color photographic light-sensitive material capable of providing a color image having excellent gray balance and excellent long-term storage stability when the color photographic material is subjected to rapid development processing within 30 seconds using a color developing agent. It is to provide a processing method.

It is a further object of the present invention to provide a method for processing a color photographic light-sensitive material capable of suppressing an increase in the minimum density, especially the minimum density of cyan even when high-speed development rapid processing is performed.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide photographic emulsion layer containing substantially 90 mol% or more of silver chloride and a color coupler. After the exposure, at least one p-phenylenediamine derivative represented by the following general formula (I) and the following general formula (II
It has been found to be solved by a processing method of a silver halide color photographic light-sensitive material characterized by performing color development processing within 30 seconds using a color developing solution containing at least one compound represented by I). Was.

General formula (I) (Wherein, R ¹ and R ³ each represent an alkyl group having 1 to 4 carbon atoms, and R ² represents a linear or branched alkylene group having 3 or 4 carbon atoms.

General formula (II) (Wherein L represents an alkylene group which may be substituted;
Is a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphine group, a hydroxyl group, an amino group which may be alkyl substituted, an ammonio group which may be alkyl substituted, a carbamoyl group which may be alkyl substituted, or an alkyl substituted. Represents a good sulfamoyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. That is, as a result of various studies, surprisingly, among various p-phenylenediamine derivatives, particularly the above general formula (I)
As shown by N-hydroxyalkyl-substituted p-
The hydroxyalkyl group of the phenylenediamine derivative is specified as a hydroxypropyl group or a hydroxybutyl group, and the alkyl group is replaced by the benzene nucleus at the meta position of the hydroxyalkyl-substituted amine, which enables speedup and at the same time light fastness. It was found that an excellent color image of

On the other hand, it has been found that the use of the specific color developing agent according to the present invention makes the above-mentioned layering effect more remarkable. However, surprisingly, due to the presence of the compound represented by the general formula (II), such layering effect can be obtained. It was found that the effect disappeared.

The compound of the general formula (II) is partially described as a preservative for a color developing solution, for example, in JP-A No. 1-196044, and among the various known preservatives, the general formula (II)
It was completely unexpected that the compound of the formula (1) has the effect of eliminating the above-mentioned layering effect, that is, affects the developability of the intermediate photosensitive layer in the photosensitive material.

In the method of the present invention, the replenishing amount of the color developing solution is preferably 120 ml or less, more preferably 15 ml per 1 m ² of the light-sensitive material.
~ 60ml.

Furthermore, it is also one of the preferable modes to perform the treatment without replenishment (including the case of replenishing evaporated water).

In the present invention, the developing time means the time during which the photosensitive material stays in the developing solution.

Further, the color photographic light-sensitive material of the present invention is color developed,
It is preferable to perform bleach-fixing and washing (or stabilization). Bleaching and fixing may be performed separately rather than in one bath as described above.

 Hereinafter, the present invention will be described in detail.

Generally, the color development rate differs depending on the p-phenylenediamine derivative used, and it has been conventionally known that 4-amino-3-methyl-N, N-diethylaniline salt or 4-amino-3-methyl-N-ethyl-N-methoxyethyl is used. A color developing agent having a hydrophobic group at the N-substituted position such as an aniline salt is likely to be distributed to an oil droplet phase containing a coupler and the like, and therefore developability is enhanced and it has been considered advantageous for short-time development (US See Patents 3,656,950, 3,656,925 and 4,035,188). On the other hand, 4-amino-3-methyl-N-ethyl-N
When using a color developing agent having a hydrophilic group at the N-substituted position such as -β-methanesulfonamide ethylaniline salt or 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline salt In the above, benzyl alcohol has been used in combination in the developer to accelerate the distribution to the oil drop phase and accelerate color development. However, when color development was performed in a short time of 30 seconds or less using the color developing solution having the above-mentioned hydrophobic group, the development was delayed to the lowermost layer in the light-sensitive material, and only an image with extremely poor color balance was obtained. Further, the addition of benzyl alcohol to the developing solution increased the color density in the uppermost layer, but did not increase the color density in the lowermost layer, and on the contrary, the color balance was disturbed.

From what has been described above, the present inventor has concluded that the following two requirements are important to achieve a photographic performance with little fluctuation in continuous processing and to achieve ultra-rapid processing in 30 seconds or less.

First, to supply the color developing agent quickly to the bottom layer of the light-sensitive material. That is, it is preferable to use a color developing agent that is not easily trapped in the oil droplet phase and has high diffusivity, and not to use benzyl alcohol that promotes distribution of the color developing agent into the oil droplet phase.

Second, select a highly active color developing agent that has a hydrophilic group. For example, in the processing of color paper, the current 4-
It is necessary to replace the N-methanesulfonamide group of amino-3-methyl-N-ethyl-N-β-methanesulfonamide ethylaniline salt with an N-hydroxyalkyl group to enhance the developing activity. This replacement increases hydrophilicity and at the same time increases reducing power.

However, as described above, it is also unavoidable that the light fastness of the generated color image is deteriorated.

The present inventor has further studied various color developing agents in order to solve this problem. As a result, unexpectedly 4-
It has been found that the light fastness of a color image is greatly improved by simply replacing the hydroxyethyl group of amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline salt with a hydroxypropyl group or a hydroxybutyl group. . Thus compounds with straight-chain or branched alkylene group of R ² to 3 or 4 hydroxyalkyl group (R ² OH) is was surprising that it can provide excellent color images of long-term storage stability. That is, a compound having a linear or branched alkylene group in which R ² is 5 is
It was slightly inferior in light fastness and greatly inferior in quickness. As described above, it was found that the compound having a hydroxyalkyl group having 3 to 4, of which 4 is a linear or branched alkylene group is the best in both light fastness and ultra-rapid processability. Further, there is almost no conventional knowledge about such development as a developing agent, and it is considered that the development is peculiar to the produced color image obtained by ultra-rapid processing using a color developing solution containing substantially no benzyl alcohol. However, the details of the contents are unknown, and the present invention is not bound by this assumption.

Hereinafter, a specific configuration of the present invention will be described in detail.

The color developing agent effective in the present invention is represented by the following general formula (I).

General formula (I) (Wherein, R ¹ and R ³ each represent an alkyl group having 1 to 4 carbon atoms, and R ² represents a linear or branched alkylene group having 3 or 4 carbon atoms.

Specific examples of R ¹ and R ³ include, for example, a methyl group, an ethyl group,
Examples thereof include a propyl group, an isopropyl group, a butyl group, and a (sec) butyl group. Further, specific examples of R ² include, for example, a propylene group, a butylene group, a 1-methylethylene group,
2-methylethylene group, 1-methylpropylene group, 2-
Examples thereof include a methylpropylene group and a 3-methylpropylene group.

In formula (I), R ¹ preferably represents an ethyl group or a propyl group, and R ³ preferably represents a methyl group or an ethyl group. The main chain of R ² is preferably a propylene group or a butylene group, and most preferably a butylene group.

Since the compound represented by the general formula (I) is extremely unstable when stored as a free amine, it is generally produced or stored as a salt of an inorganic acid or an organic acid, and the free amine is not added until it is added to the treatment liquid. Is preferable. Examples of the inorganic / organic acid for forming the salt of the compound of the general formula (I) include hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like.

Specific examples of the color developing agent of the present invention will be given below.
The present invention is not limited to these.

The amount of the color developing agent of the present invention to be used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol, per developer.

The processing temperature of the developing solution is preferably 30 ° C. or higher in order to achieve development in a short time. Also, Dm for development exceeding 50 ° C
Since in (minimum concentration) becomes high, a temperature below that is preferable.

The color developing agent of the present invention is Journal of American Chemical Society, Volume 73, 3100 (1951).
It can be easily synthesized according to the method described in.

The color developing agent of the present invention is also preferably used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4-amino-N, N-diethyl-3-methylaniline D-3 4-amino-N- (β-hydroxyethyl)-
N-methylaniline D-4 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline D-5 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline D- 6 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline D-7 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline D-8 4 -Amino-N-ethyl-N- (β-methoxyethyl) -3-methyl-aniline D-9 4-amino-N- (β-ethoxyethyl) -N
-Ethyl-3-methylaniline D-10 4-amino-N- (3-carbamoylpropyl) -Nn-propyl-3-methylaniline D-11 4-amino-N- (4-carbamoylbutyl)
-N-n-propyl-3-methylaniline D-12 N- (4-amino-3-methylphenyl) -3
-Hydroxypyrrolidine D-13 N- (4-amino-3-methylphenyl) -3
-(Hydroxymethyl) pyrrolidine D-14 N- (4-amino-3-methylphenyl) -3
-Pyrrolidinecarboxamide As a compound to be combined, among the above-mentioned p-phenylenediamine derivatives, particularly preferred exemplified compounds D-5 and D-6
And D-10. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used.

The amount of the main drug used in combination is the same as the main drug 1 of the general formula (I) of the present invention.
It is preferable to use 0.1 to 10 mol per mol.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion has a function as a preservative of the developing agent and a function of dissolving the silver halide and reacting with the oxidized developing agent to reduce the success rate of dye formation. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

The developer used in the present invention contains a compound represented by the following general formula (II) as an organic preservative instead of the hydroxylamine or sulfite ion.

General formula (II) In the formula (II), L represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may be substituted, and has 1 carbon atom.
To 5 are preferred. Specifically, methylene, ethylene, trimethylene, and propylene are preferred examples. As the substituent, a carboxyl group, a sulfone group, a phosphon group, a phosphinic acid residue, a hydroxyl group, an alkyl (preferably having a carbon number of 1 to 5) ammonio group which may be substituted, and a carboxyl group, a sulfone group or a phosphon group are shown. A hydroxyl group is a preferred example. A
Is a carboxyl group, a sulfone group, a phosphon group, a phosphinic acid residue, a hydroxyl group, an amino group which may be substituted with an alkyl (preferably 1 to 5 carbon atoms) or an alkyl group (preferably having 1 to 5 carbon atoms) It represents a good ammonio group, a carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), a sulfamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and an alkylsulfonyl group which may be substituted. Preferred examples thereof include a carboxyl group, a sulfone group, a hydroxyl group, a phosphone group, and a carbamoyl group which may be alkyl-substituted. -LA
Examples of carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as preferred examples, carboxymethyl group, carboxyethyl group A group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms.

As the substituent, a carboxyl group, a sulfone group, a phosphone group, a phosphinic acid residue, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, an alkyl group. Sulfamoyl group which may be substituted, alkylsulfonyl group which may be substituted, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, amino group which may be alkyl substituted, arylsulfonyl group, nitro group, Represents a cyano group and a halogen atom. There may be two or more substituents. R
As a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, a hydroxyethyl group can be mentioned as a preferred example, a hydrogen atom, a carboxymethyl group. , A carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. L and R may combine to form a ring. When L and R form a ring, L and R directly form a ring to have A as a substituent, or A represents an amino group which may be alkyl-substituted, and L represents a nitrogen atom of the amino group. It is preferable that R and R form a ring (for example, piperazine ring formation).

Next, specific compounds of the present invention are described, but are not limited thereto.

(II-19) HO-NH -CH 2 CO 2 H (II-20) HO-NH-CH 2 CH 2 CO 2 H (II-26) HO-NH-CH ₂ CH ₂ SO ₃ H (II-28) HO-NH- (CH 2) 3 SO 3 H (II-29) HO-NH- (CH 2) 4 SO 3 H (II-30) HO-NH-CH 2 PO 3 H 2 (II-32) HO-NH -CH 2 CH 2 PO 3 H 2 (II-33) HO-NH-CH 2 CH 2 OH- (II-34) HO-NH- (CH 2) 3 OH (II- _{35) HO-NH-CH 2} -PO 2 H 2 (II-46) HONHCH ₂ CH (PO ₃ H ₂ ) ₂ The amount of the compound represented by the general formula (II) is preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developer. is there.

The compound represented by the general formula (II) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). West German Patent No. 1,159,634,
"Inorganica Chimika Attack" (Inorganica Chi
mica Acta), 93, (1984) 101-108, etc., and specific methods are described below.

Synthetic Example Synthesis of Exemplified Compound (II-7) Into 200 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride, 11.5 g of sodium hydroxide and sodium chloroethanesulfonate 9
Add 6g, keep at 60 ℃ 40m of aqueous solution of 23g of sodium hydroxide
l was added slowly over 1 hour. 3 hours at 60 ° C
, The reaction mixture is concentrated under reduced pressure,
Heated to ° C. Insoluble matter is filtered and the filtrate is methanol 500 ml.
The desired product (Exemplified Compound (II-7)) monosodium salt was obtained as crystals. 41 g (yield 53%) Synthesis of Exemplified Compound (II-11) Formalin 32.6 g was added to a hydrochloric acid aqueous solution of hydroxylamine hydrochloride 7.2 g and phosphorous acid 18.0 g, and the mixture was heated under reflux for 2 hours. The generated crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified compound (II-11).

Further, in the present invention, various organic preservatives can be used in combination with the hydroxylamine derivative represented by the general formula (II).

Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent. That is, it is an organic compound having a function of preventing oxidation of a color developing agent by air or the like, but among them, a hydroxylamine derivative (excluding the compound of the general formula (II) and hydroxylamine), a hydroxamic acid, a human lazine, Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines and the like are particularly effective. These are disclosed in JP-A Nos. 63-4235, 63-5341, and 63-30845.
No. 63-21647, 63-44655, 63-46454,
63-53551, 63-43140, 63-56654, 63
-58346, 63-43138, 63-146041, 63-44
No. 657, No. 63-44656, U.S. Pat.Nos. 3,615,503, 2,4
No. 94,903 and Japanese Patent Publication No. 48-30496.

Other preservatives include JP-A-57-44148 and JP-A-57-44148.
-53739, various metals, JP-A-59-180588, salicylic acids, JP-A-54-3532, alkanolamines, JP-A-56-94349, polyethyleneimines, U.S. Patents If desired, the aromatic polyhydroxy compounds described in No. 3,746,544 and the like may be contained. Especially alkanolamines such as triethanolamine,
The addition of dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the organic preservatives to be used in combination, hydrazine derivatives (hitrazines and hydrazides) are particularly preferable, and the details thereof are described in JP-A-1-97953, 1-18693 and 1-
No. 186940, No. 1-187557, Japanese Patent Application No. 1-185578, No. 1
-198676, 1-199646, 1-297659 and the like.

When used in combination, it is preferably used in an amount of 0.1 to 10 mol per 1 mol of the compound of the general formula (II) of the present invention.

A compound represented by the following general formula (A) is more preferably used in the color developing solution according to the present invention from the viewpoint of further improving the effects of the present invention.

General formula (A) (In the formula, R ²¹ represents a hydroxyalkyl group having 2 to 6 carbon atoms, R ^21
22 and R ²³ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula In the formula, n is an integer of 1 to 6, X and X'represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. Preferred specific examples of the compound represented by the general formula (A) are as follows.

(A-1) Ethanolamine (A-2) Diethanolamine (A-3) Triethanolamine (A-4) Di-isopropanolamine (A-5) 2-Methylaminoethanol (A-6) 2-Ethylaminoethanol (A-7) 2-Dimethylaminoethanol (A-8) 2-Diethylaminoethanol (A-9) 1-Diethylamino-2-propanol (A-10) 3-Diethylamino-1-propanol (A-11) 3- Dimethylamino-1-propanol (A-12) isopropylaminoethanol (A-13) 3-amino-1-propanol (A-14) 2-amino-2-methyl-1,3-propanediol (A-15) Ethylenediaminetetraisopropanol (A-16) benzylethanolamine (A-17) 2-amino-2- (hydroxymethyl) ) -1,
3-Propanediol (A-18) 1,3-Diaminopropanol (A-19) 1,3-Bis (2-hydroxyethylmethylamino) -propanol These compounds represented by the general formula (A) are From the viewpoint of the effect of the object of the present invention, it is preferably used in the range of 3 g to 100 g, and more preferably in the range of 6 g to 50 g per color developing solution.

In the color developer according to the present invention, the compounds represented by the following general formulas (III-1) and (III-2), from the viewpoint that the effects of the present invention, particularly the effect of improving gray balance, are better exhibited, More preferably used.

General formula (III-1) General formula (III-2) In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 oxygen atoms, -OR ⁸ , -COOR ⁹ , Or a phenyl group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ⁵ G-OH or a hydrogen atom is represented, R ⁴ is a halogen atom, a sulfonic acid group, or a carbon atom number of 1 to 1.
An alkyl group of 7, -OR ⁸ , -COOR ⁹ , Or a phenyl group.

The alkyl groups represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ include those having a substituent, for example, a methyl group, an ethyl group, iso-
A propyl group, an n-propyl group, a t-butyl group, an n-butyl group, a hydroxymethyl group, a hydroxyethyl group, a methylcarboxylic acid group, a benzyl group, and the like; and R ⁸ , R ⁹ ,
The alkyl groups represented by R ¹⁰ and R ¹¹ have the same number as described above, and further include an octyl group and the like.

Examples of the phenyl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(III-101) 4-isopropyl-1,2-dihydroxybenzene (III-102) 1,2-dihydroxybenzene-3,5-disulfonic acid (III-103) 1,2,3-trihydroxybenzene-5- Carboxylic acid (III-104) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (III-105) 1,2,3-trihydroxybenzene-5-carboxy-n
-Butyl ester (III-106) 5-t-butyl-1,2,3-trihydroxybenzene (III-107) 1,2-dihydrokinshibenzene-3,4,6-trisulfonic acid (III-201) 2,3-Dihydroxynaphthalene-6-sulfonic acid (III-202) 2,3,8-Trihydroxynaphthalene-6-sulfonic acid (III-203) 2,3-Dihydroxynaphthalene-6-carboxylic acid (III-204) ) 2,3-Dihydroxy-8-isopropyl-naphthalene (III-205) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, the compounds particularly preferably used in the present invention include: 2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can also be used as an alkali metal salt such as sodium salt and potassium salt (specifically exemplified compound (III-102)).

In the present invention, the general formulas (III-1) and (III-
The compound represented by 2) is 5 mg to 15 g per 1 color developer.
Can be used in the range, preferably 15mg ~ 10g,
More preferably, it is desirable to use in the range of 25 mg to 7 g.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, nitrilo-N, N, N-tris (methylenephosphonic acid), ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) ), 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid. , Ethylenediamine ortho-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-N,
N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

Among these chelating agents, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetotetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) are preferable. ) Hydroxyethyliminodiacetic acid is preferred.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block metal ions in the color developer. Eg 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat.No. 3,813,247, and JP-A Nos. 52-49829 and 50-15554. p-phenylenediamine compounds, JP-A-50-
137726, JP-B-44-30074, quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, p-aminophenols described in U.S. Patent Nos. 2,610,122 and 4,119,462; Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Shoko 4
1-111431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
532,501 polyalkylene oxide represented, etc.
In addition, 1-phenyl-3-pyrazolidones, hydrazines, meoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

Halogen ions (chlorine ions and / or bromine ions) are required in the color developer for the purpose of preventing fog.
In the present invention, preferably 3.5 × 10 as chlorine ion.
^{-3 to} 3.0 x 10 ^-1 mol /, more preferably 1 x 10 ^-2 to 2
× 10 ^-1 mol / content. Chloride concentration is 3.0 × 10 ^-1
If it is higher than the mol / mol, it has a drawback of delaying the development and does not achieve the object of the present invention of being fast and having a high maximum density. Further, at 3.5 × 10 ⁻³ mol / less,
Stain cannot be prevented, and furthermore, the photographic properties (especially the minimum density) associated with rapid processing are large, and the amount of residual silver is large, so that the object of the present invention is not achieved.

In the present invention, bromine ions are preferably contained in the color developing solution for color paper, preferably 0.5 × 10 ⁻⁵ mol / to 1.0 ×.
10 ^-3 mol / content. More preferably, 3.0 × 10 ^-5 ~
5 × 10 ^-4 mol / mol, more preferably 1.0 × 10 ^-4
~ 3 x 10 ^-4 mol /. Bromine ion concentration is 1 × 10 ^-3
If it is higher than 0.5 mol / l, the development is delayed and the maximum density and sensitivity are lowered. If it is lower than 0.5 × 10 ^-5 mol / h, stain cannot be prevented, and furthermore, the photographic properties associated with continuous processing The variation is large and does not achieve the object of the present invention.

Here, the chloride ions and / or bromine ions may be directly added to the developer or may be eluted from the photosensitive material during the development processing.

When added directly to the color developer, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Among them, preferred is sodium chloride. , Potassium chloride.

Further, it may be supplied in the form of a salt of a fluorescent whitening agent added to the developer. Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the photosensitive material at the time of development, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

In the present invention, an optional antifoggant can be added in addition to chlorine ions and bromine ions, if necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, isodazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 10 g /, preferably 0.1 to 6 g /.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

The effect of the present invention is remarkable when the processing time of the color developing solution of the present invention is 5 seconds to 30 seconds, preferably 10 seconds to 15 seconds. The treatment temperature is 33 to 55 ° C, preferably 40 to 50 ° C.
In the above, the effect of the present invention is particularly remarkable.

The replenishing amount of the color developing solution during continuous processing varies depending on the light-sensitive material, but it is 20 to 220 ml, preferably 25 to 160 ml per 1 m ^2.
However, 40 to 110 ml is particularly preferable in that the effects of the present invention can be effectively exhibited.

Further, the color developing solution of the present invention has relatively better performance than the combination outside the present invention in any state of the liquid opening ratio (air contact area (cm ² ) / liquid volume (cm ³ )),
From the viewpoint of the stability of the color developer, the liquid aperture ratio is 0 to 0.
1 cm ^-1 is preferred. In continuous processing, practically 0.0
The range of 01 cm ^{-1 to} 0.05 cm ^-1 is preferable, and more preferably
It is 0.002 cm ^{-1 to} 0.03 cm ^-1 .

In general, when hydroxylamine is used as a preservative, even if the liquid aperture ratio of the color developer is reduced,
It is widely known that decomposition by heat or trace metals occurs. However, in the color developer of the present invention,
These decompositions are very small, and the color developing solution can be stored for a long period of time, or even if it is continuously used as a replenisher for a long period of time, it can be sufficiently put to practical use. Therefore, in such a case, it is preferable that the liquid opening ratio is small, and it is 0 to 0.002c.
m ^-1 is most preferred.

Conversely, after processing a certain amount of processing, it may be processed at a wide aperture ratio under the condition of being discarded, but even in such a processing method, according to the configuration of the present invention, excellent performance is exhibited. Can be.

In the present invention, desilvering processing is performed after color development.
The desilvering step generally comprises a bleaching step and a fixing step, but it is particularly preferred that the steps are performed simultaneously. The desilvering step includes bleaching-fixing- (washing and / or stabilizing bath) bleaching-bleach-fixing- (washing and / or stabilizing bath) bleaching-bleach-fixing-fixing- (washing and / or stabilizing bath) bleach-fixing- (washing with water And / or stabilizing bath) Bleach-fixing-fixing- (washing and / or stabilizing bath) Fixing-bleaching-fixing- (washing and / or stabilizing bath) Fixing-bleach-fixing- (washing and / or stabilizing bath) It can be mentioned as.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of aethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.
An iron ion complex salt may be formed. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount added is 0.01 to 1.0 mol /, preferably
It is 0.005-0.50 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Compounds having a mercapto group or a disulfide bond described in 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), JP-B-45-8506, JP-A-52-50 -20832, 53-327
35, U.S. Pat. No. 3,706,561, etc., thiourea compounds, or halides of iodine and bromine ions. Rehalogenating agents such as ammonium iodide), or chlorides (eg potassium chloride, sodium chloride, ammonium chloride), or iodides (eg ammonium iodide). One or more inorganics with pH buffering capacity, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary. Acids, organic acids and their alkali metal or ammonium salts, or ammonium nitrate,
Corrosion inhibitors such as guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; It is a thioether compound such as bisthioglycolic acid and 3,6-dithia-1,8-octanediol and a water-soluble silver halide dissolving agent such as thioureas. These may be used alone or in combination of two or more. can do. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
In the range of ~ 1.0 mole.

In the present invention, the pH range of the bleach-fixing solution or the fixing solution is as follows:
3 to 8 are preferable, and 4 to 7 are particularly preferable. pH
If the content is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco formation of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stains are easily generated.

The pH range of the bleaching solution in the present invention is 8 or less,
7 is preferable and 2-6 is especially preferable. When the pH is lower than this, deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the contrary, when the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

In the present invention, the bleach-fixing solution or the fixing solution may be a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. ) And metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately
The content is preferably 0.02 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol. Particularly, addition of ammonium sulfite is preferable.

As a preservative, sulfite is generally added,
In addition, ascorbic acid, carbonyl bisulfite adducts, sulfinic acids, carbonyl compounds, sulfinic acids, and the like may be added.

Further, a buffer, an optical brightener, a chelating agent, a fungicide, and the like may be added as necessary.

The bleach-fix solution of the present invention has a processing time of 5 seconds to 120 seconds, preferably 10 seconds to 60 seconds. Temperature is 25 ℃ ~ 60 ℃, preferably 30
~ 50 ° C. The replenishment amount is ²⁰ ml to ² per 1 m ² of light-sensitive material.
It is 50 ml, preferably 30 to 100 ml.

In the present invention, the fresh water supplied to the washing (stabilizing) tank may be tap water, well water, etc. which are usually used for washing, but more completely prevent the generation of bacteria in the destination tank, and reverse From the viewpoint of prolonging the life of the osmotic membrane, it is preferable to use water in which calcium and magnesium are reduced to 3 mg / mg or less, specifically, ion-exchange resin or water deionized by distillation is used. preferable.

In the present invention, the water washed and / or stabilized may be treated with a reverse osmosis membrane. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether,
Although polysulfone, polyacrylic acid, polyvinylene carbonate, and the like can be used, a crosslinked polyamide-based composite membrane and a polysulfone-based composite membrane are preferable because the reduction of the amount of permeated water does not easily occur.

Also, from the viewpoint of reducing the initial cost, running cost, downsizing, and noise reduction of the pump, etc.
A low-pressure reverse osmosis membrane that can be used at a liquid sending pressure as low as 15 kg / cm ² is preferable. Furthermore, the structure of the membrane is preferably a spiral membrane in which a flat membrane is wound into a roll shape, because the amount of permeated water is less likely to decrease.

The liquid sending pressure in the use of these membranes is in the range as described above, but the preferable condition is ^{2 to} 10 kg / cm ² , and the particularly preferable condition is 3 to 7 kg / cm ² in terms of the stain prevention effect and the reduction of the permeated water amount. .

The washing and / or stabilizing step is preferably connected in a multi-stage countercurrent system with a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The treatment with the reverse osmosis membrane is preferably performed on water in the second and subsequent tanks for such multistage countercurrent washing and / or stabilization. Specifically, the water in the second tank in the case of the two-tank configuration, the second or third tank in the case of the three-tank configuration, and the water in the third or fourth tank in the case of the four-tank configuration is treated with a reverse osmosis membrane and permeated. This is carried out by returning the water to the same tank (a tank from which water was collected for reverse osmosis membrane treatment; hereinafter, referred to as a collection tank) or a washing and / or stabilization tank located thereafter. Further, returning the concentrated washing and / or stabilizing solution to the bleach-fix bath upstream of the collection tank is one measure.

The required amount of permeated water supply is determined by the quality of permeated water (removal performance of reverse osmosis membrane), the amount of photosensitive material processed by an automatic processor, the amount of pre-tank liquid brought in by the photosensitive material, and the amount of fresh water supplied. However, it is usually in the range of 1 to 100 times the supply amount of fresh water. In particular, in the case of a low supply amount (low replenishment amount), the amount is preferably 5 to 55 times, particularly 10 to 30 times.

It is known to add a fungicide, a chelating agent, a pH buffer, a fluorescent whitening agent and the like to the washing water and / or the stabilizing water, and it is optional to use these as needed. In order not to increase the load on the reverse osmosis membrane, it is preferable not to use a large amount of these additives.

When bacteria are generated in the storage tank for fresh water for supply, it is preferable to irradiate the storage tank with ultraviolet rays.

The amount of washing water and / or stabilizing water in the washing and / or stabilizing step is the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler) and application, the washing and / or stabilizing water temperature, and the number of washing (stabilizing) tanks. (Number of stages), countercurrent, forward flow, etc.
It can be set in a wide range depending on the various conditions. Of these, the relationship between the number of washing (stabilizing) tanks and the water volume in the multi-stage countercurrent system is shown in the Journal of the Society of Motion Picture and Television.
Engineers (journal of the Society of Motion Pic
ture and Televi-sion Engineers) Volume 64, p.248〜25
It can be obtained by the method described in 3 (May 1955 issue). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 5.

According to the multi-stage countercurrent method, the amount of washing water and / or stabilizing solution can be greatly reduced, and for example, 0.5 to 1 per 1 m ^{2 of the} light-sensitive material
The following are possible, and the effect of the present invention is remarkable, but due to the increase in the residence time of water in the tank, there are problems such as bacteria breeding and the produced suspended matter adhering to the photosensitive material. As a solution to such a problem, JP-A-62-288838
The method of reducing calcium and magnesium described in No. 1 can be used very effectively. In addition, JP
-8542 isothiazolone compounds and siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in 61-120145, benzotriazole described in JP-A-61-267761, copper ions and others Hiroshi Horiguchi, "The Chemistry of Antibacterial and Antifungal" (1986) Sankyo Publishing, edited by Sanitary Technology "Microbial sterilization, sterilization and antifungal technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal " Antibacterial and Antifungal Encyclopedia "(1986
Year), and the fungicide described in can also be used.

Further, for water and / or stabilized water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softening agent can be used.

It is also possible to perform the treatment with the stabilizing solution directly after the above washing and / or stabilizing step or without performing the washing and / or stabilizing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added.

The washing and / or stabilizing bath of the present invention preferably contains a chelating agent.

The chelating agent that can be used can be selected and used from aminopolycarboxylic acid, aminopolyosphonic acid phosphonocarboxylic acid, alkylidene diphosphonic acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, and the like.

In particular, it is preferable to contain the organic phosphonic acid compound described in Japanese Patent Application No. 2-40940.

The amount of the chelating agent used is preferably 1 to 100 g, more preferably 5 to 50 g, per stabilizing bath.

The preferred pH of the washing step and / or the stabilizing step is 4-10.
And more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 30 to 60 ° C.
It is preferably 35 to 50 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. It is preferably 10 seconds, more preferably 10 seconds to 35 seconds. The replenishment amount is
A smaller amount is preferable from the viewpoint of running cost, reduction of discharge amount, handleability, etc., and is also an object of the present invention. A specific preferable amount of replenishment is preferably 150 ml or less per 1 m ² of the light-sensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, an arbor flow of washing and / or stabilizing water, which is reduced by a multi-stage countercurrent method, is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated liquid to reduce the amount of waste liquid Can be mentioned.

 The drying step that can be used in the present invention will be described.

In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired.

As a means for shortening the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of the hydrophilic binder such as molatin. Further, from the viewpoint of reducing the carry-on amount, it is possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. Naturally, as a means for improving the dryer, it is possible to speed up the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the irradiation angle of the drying air to the light-sensitive material and the method of removing the discharged air.

The processing time of the present invention is such that the light-sensitive material is in contact with the color developing solution before the final bath (generally, washing or stabilizing bath).
The effect of the present invention can be remarkably exhibited in a rapid processing step such that the processing step time is 3 minutes or less, preferably 1 minute 30 seconds or less.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order.

The image forming system including the light-sensitive material and processing which can be used in the present invention can be used for rapid processing of commonly used color prints, but can be used for intelligent color hard copy applications where speeding is more desired.

In particular, as an aspect of the intelligent color hard copy, an aspect in which scanning exposure is performed using high-density light such as a laser (for example, a semiconductor laser) or a light-emitting diode is preferable.

Many semiconductor lasers have high photosensitivity in the infrared region, and a light-sensitive material used therefor can use an infrared-sensitive silver halide emulsion layer instead of at least one of the above emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

Further, depending on the required image quality and quality, the color coupler may be of two colors. In this case, the number of silver halide emulsion layers for each may be two. In this case, a full-color image is not obtained, but an image can be formed more quickly.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, and the core inside the silver halide grains and the shell surrounding them ( Shell) [a single layer or a plurality of layers] having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the surface of the particle,
A structure in which different composition parts are joined on corners or surfaces)
And the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
It is more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, it is also preferable to use the above monodisperse emulsion as a blend in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The photosensitive material according to the present invention has a hydrophilic colloid layer for the purpose of improving the sharpness and the like of an image.
No. 337,490A2, pp. 27-76, a dye capable of being decolorized by treatment (among others, an oxonol dye) is used as the photosensitive material.
Titanium oxide is added so that the optical reflection density at 0 nm is 0.70 or more, or titanium oxide surface-treated with a dihydric or tetrahydric alcohol (such as trimethylolethane) is added to the water resistant resin layer of the support. Weight% or more (more preferably 14% by weight
Above).

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Further, to the photosensitive material according to the present invention, an antifungal agent as described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferred.

The support used in the light-sensitive material according to the present invention may be a white polyester support for display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material according to the present invention may be exposed to visible light and infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In the exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726.
As a result, light color mixing is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, bleach-fix processing is preferably performed after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods and processing applied to process this light-sensitive material As the additives, those described in the following patent publications, in particular, EP 0,355,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

Reference Example 1 A multilayer color photographic paper having the following layer structure was prepared on a paper support screen-laminated with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Slov-1) 8.2 g, and this solution was added with 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of average grain size 0.88 μm and 0.70 μm (silver molar ratio). Coefficient of variation of grain size distribution was 0.08 and 0.10, and each emulsion was brominated. The following blue-sensitive sensitizing dyes (containing 0.2 mol% of silver localized on the grain surface) are added to a large-sized emulsion per mol of silver.
2.0 × 10 ⁻⁴ mol was added to each of the emulsions, and for small-sized emulsions, 2.5 × 10 ⁻⁴ mol was added and then subjected to sulfur sensitization. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-diclo-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

Blue sensitized emulsion layer (Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) Green-sensitive emulsion layer (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Each mol of silver halide is 7.0 × 10 ^-5 mol for large size emulsion, and each for small size emulsion.
1.0 × 10 ^-5 mol) Red sensitive emulsion layer (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively, in an amount of 8.5 × 10 ^-5 mol and 7.7 × 1 mol per mol of silver halide. 10 ⁻⁴ mol and 2.5 × 10 ⁻⁴ mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average particle size and 0.39 μm average particle size (Ag mol) The coefficient of variation of grain size distribution is 0.10 and 0.08, and each emulsion has ArBr 0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) ) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.04 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of average grain size 0.58 μm and 0.45 μm, Ag mole ratio) Variation of grain size distribution Coefficients are 0.09 and 0.11, and each emulsion is ArBr0.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.17 Liquid paraffin 0.03 (ExY) yellow coupler 1: 1 mixture (molar ratio) with (ExM) magenta coupler 1: 1 mixture (molar ratio) (ExC) cyan coupler 2: 4: 4 mixture by weight of each (Cpd-1) color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-6) color image stabilizer 2: 4: 4 mixture (weight ratio) (Cpd-7) color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (UV-1) UV absorber 4: 2: 4 mixture (weight ratio) (Solv-1) solvent (Solv-2) Solvent 2: 1 mixture (volume ratio) (Solv-4) solvent (Solv-5) Solvent (Solv-5) Solvent First, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) manufactured by Fuji Photo Film Co., Ltd. was used for each sample, and gradation exposure of a three-color separation filter for sensitometry was applied (this is [A ], Without using a separate 3-color separation filter,
Gradation exposure was given through a gray wedge (this is [B]
And The yellow, magenta filters were used to adjust the B, G, and R components of the light). The exposure at this time was performed so that the exposure amount was 2500 CMS with the exposure time of 0.1 seconds.

The sample after the exposure was processed using a liquid having the following processing step and processing liquid composition.

However, each type of developing agent was changed as shown in Table 1 and each processing was performed. Processing time Temperature Time Color development 38 ℃ 20 seconds Bleach fixing 35-40 ℃ 10 seconds Water wash 35-35 ℃ 10 seconds Stability 30-35 ℃ 10 seconds Dry 70-80 ℃ 20 seconds Composition of each processing solution It is as follows. Color developer tank Liquid water 800 ml Aminotri (methylenephosphonic acid) -5Na salt 3.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Potassium chloride 5.0 g Potassium carbonate 2 g Color developing agent 12 mmol (See Table 1) Diethylhydroxylamine 4.5 g (80% aqueous solution) Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Water added 1000 ml pH (25 ° C) 10.05 Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate 100 g Ammonium sulfite 16g Ethylenediaminetetraacetic acid iron (III) ammonium 80g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Water added 100ml pH (25 ℃) 6.0 Washing solution Tap water stabilizing solution 5-Chloro-2-methyl-4-isothiazoline-3 -One 0.02 g 2-methyl-4-isothiazolin-3-one 0.01 g hydroxyethylidene-1,1- diphosphonic acid (60% water Solution) 12 g Water is added to 1000 ml pH (25 ℃) 4.0 to 7.0 The obtained yellow, magenta, and cyan image densities are passed through the B, G, and R filters corresponding to the respective dyes in the respective halftone areas. The density (D ^* ) was measured. Next, after exposing the obtained sample under xenon light (300,000 lux) for 8 days,
The decrease in image density due to light irradiation was determined. (Density after photobleaching (FD): The density of the image in the exposed area giving an image density of 1.0 was shown after the light irradiation.) These results are shown in Table 1.

As shown in Table 1, the structure of the p-phenylenediamine derivative was changed and examined. As a result, in the sample exposed through the three-color separation filter, only the color developing agents (Sample No. 2 and No. 3) presented in the present invention were obtained. It was found that a short-time treatment of 20 seconds gives a sufficient D ^* and gives a color image with high light fastness. However, it was found that when this color developing agent was used, the intermediate density of the magenta color image of the GL layer was greatly reduced in the gray sample exposed through the gray optical wedge.

Example 1 The same light-sensitive material as in Reference Example 1 was used, except that diethylhydroxylamine in the color developer was replaced by equimolar amount as shown in Table 2, and the color developing agent used in Sample No. 3 of Reference Example 1 was used. (Processing was carried out in the same manner as in Reference Example 1 except that the above-exemplified compound (I-12) was used (Sample Nos. 12 to 19). In the samples of References 1 and 2, color developing agents were used. To 4-amino-3-methyl-N-ethyl-
Nβ-Hydroxyethyl) aniline sulphate was used and treated with exactly the same solution except that the preservative was used as in Table 2.

The relative values of the respective magenta densities are shown in Table 2 when the magenta density D ^* of the sample which was subjected to gradation exposure through the gray wedge of the sample No. 3 of Reference Example 1 was 100.

From Table 2, it was found that by using the preservative according to the present invention, the density of the halftone portion was increased and the gray reproduction was improved. Moreover, even if it replaces with the preservative according to the present invention,
The light fastness obtained when using the developing agent of the present invention was good.

Further, a color developing agent is used as the exemplified compound (I-2),
The same results as those of the above sample Nos. 14 to 19 were obtained even when the operations were performed in place of (I-4) and (I-11).

Example 2 The same light-sensitive material as in Reference Example 1 was used, and diethylhydroxylamine in the color developing solution was replaced with equimolar amounts as shown in Table 3, and the formula (III-1) or (III) of the present invention was used. -2) was treated in the same manner as in Reference Example 1 using exactly the same liquid except that 0.02 mol / addition of the compound (indicated by the exemplified compound number in Table 3) was added. However, as the color developing agent here, the compound used in Sample No. 3 of Reference Example 1 (the exemplified compound (I-12) was used.

From Table 3, it was found that the gray reproduction was further improved by using the compound according to the present invention in combination.

Example 3 The same light-sensitive material as in Reference Example 1 was used and processed according to the following procedure.

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed sample was subjected to continuous processing (running test) using a solution having the following processing step and processing solution composition until the tank volume of the color developing solution was replenished. However,
The composition of the color developing solution and the developing time temperature were changed as shown in Table 4, and each processing was performed.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sulfurous acid 16g Ethylenediaminetetraacetic acid iron (III) ammonium 80g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Water 1000ml pH (25 ℃) 6.0 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are 3ppm or less for each) At the end of the running test, the sensitometry is performed to determine the image density of each of yellow, magenta, and cyan dyes. Was measured through B, G, R. filters corresponding to.

The time (T) for which the image is collected is calculated from the development time dependency of the above measured value at each temperature. Further, the respective minimum densities (Dmin) at T were obtained. The results are shown in Table 4.

It can be seen from Table 4 that a development temperature of 40 ° C. or higher is necessary to achieve good image formation with ultra-rapid processing within 15 seconds. On the other hand, if the temperature exceeds 50 ° C, Dmin (R) suddenly rises, which is not preferable. Further, by using the preservative of the present invention, it is possible to suppress an increase in Dmin during high temperature short time treatment. The color developing agent is represented by the exemplified compound (I-2),
Similar results were obtained even when the operations were performed in place of (I-4) and (I-11).

Example 4 (Preparation of emulsion) 3.3 g of sodium chloride in a 3% aqueous solution of lime-processed gelatin.
And 3.2 ml of N, N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. Add silver nitrate to this solution
An aqueous solution containing 0.2 mol and an aqueous solution containing 0.2 mol of sodium chloride and 15 μg of rhodium trichloride were added and mixed at 56 ° C. with vigorous stirring. Then, with vigorous stirring, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were mixed under vigorous stirring.
Added and mixed at 6 ° C. Five minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, silver nitrate was further added to 0.
An aqueous solution containing 020 mol, potassium bromide 0.015 mol, sodium chloride 0.005 mol and hexachloroiridium (I
V) An aqueous solution containing 0.8 mg of potassium acid was added and mixed at 40 ° C. with vigorous stirring. Thereafter, desalting and washing were performed. Further, 90.0 g of lime-processed gelatin was added, and triethylthiourea was added to perform optimal chemical sensitization.

With respect to the obtained silver chlorobromide (A), the shape, the particle size and the particle size distribution of the particles were determined from an electron micrograph. Each of these silver halide grains was cubic, and the grain size was 0.52 μm. The coefficient of variation was 0.08. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring X-ray diffraction from silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic GuKα ray as the radiation source. Diffraction lines from crystals having a uniform halogen composition give a single peak, whereas diffraction lines from crystals having localized phases with different compositions give a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the measured diffraction angle of the peak, the halogen composition of the silver halide constituting the crystal can be determined. The measurement results of this silver bromide emulsion (A) are centered on 70% silver chloride (30% silver bromide) in addition to the main peak of 100% silver chloride and 60% silver chloride.
It was possible to observe a broad diffraction pattern with the hem stretched around (silver bromide 40%).

(Preparation of Sensitive Material) A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-1) 8.2 g,
This solution is 10% sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc.
On the other hand, an emulsion was prepared by adding the red-sensitive sensitizing dye (Dye-1) shown below to the silver chlorobromide emulsion (A). The above emulsified dispersion and this emulsion were mixed and dissolved, and the first coating was prepared so as to have the composition shown below.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-diclo-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(First layer, red-sensitive yellow coloring layer) (Dye-1) 1.0 × 10 ⁻⁴ mol per mol of silver halide 1.0 × 10 ⁻⁴ mol (third layer, infrared-sensitive magenta coloring layer) (Dye-2) 4.5 × 10 ^-5 mol per mol of silver halide (fifth layer infrared-sensitive cyan coloring layer) (Dye-3) When 0.5 × 10 ^-5 mol (Dye-2) and (Dye-3) were used per mol of silver halide, the following compounds were added in an amount of 1.8 × 10 ^-3 mol per mol of silver halide.

Further, 8.0 × 10 ^-4 mol of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan coloring emulsion layers per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (red-sensitive yellow coloring layer) Silver chlorobromide emulsion (A) 0.30 gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd- 5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (infrared-sensitive magenta coloring layer) Silver chlorobromide emulsion (A) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) ) Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (infrared-sensitive cyan color-developing layer) Silver chlorobromide emulsion A 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilization Agent (Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seven layers (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification
17%) 0.17 Liquid paraffin 0.03 Next, semiconductor laser AlGaInP (oscillation wavelength, about 670n
m), semiconductor laser GaAlAs (oscillation wavelength, about 750 nm), Ga
Using an AlAs (oscillation wavelength, about 810 nm), the laser light is rotated by a rotating polyhedron to assemble a device that can sequentially scan and expose on color photographic paper that moves in the direction perpendicular to the scanning direction. The photosensitive material was exposed.
For the exposure amount, the exposure time and light emission amount of the semiconductor laser were electrically controlled.

The exposed sample was processed using a solution having the following processing steps and processing solution composition.

However, the kind of the preservative in the developing solution, the addition amount, and the kind of the exemplary compound of the general formula (III-1) or (III-2) should be the fifth.
Each treatment was carried out by changing as shown in the table. Processing time Temperature Time Color development 38 ℃ 15 seconds Bleach fixing 35 to 35 ℃ 15 seconds Rinse 30 to 35 ℃ 7 seconds Rinse 30 to 35 ℃ 7 seconds Rinse 30 to 35 ℃ 7 seconds Rinse 30 to 35 ℃ 7 seconds Dry 60 to 70 ° C 15 (Rinse to 4 tank countercurrent system) The composition of each processing solution is as follows. Color developer tank Water 800 ml 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5 g Diethylenetriamine pentaacetic acid 1.0 g N, N, N-Trismethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Potassium chloride 5.0 g Potassium carbonate 40 g Sodium hydrogen carbonate 3.9 g 4-Amino-3-methyl-N-ethyl-N-4-hydroxybutyl) aniline 2.p-toluenesulfonic acid (I-12) 13.1 g Diethylhydroxyamine (80 % Aqueous solution) 6.3 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Water added 1000 ml pH (25 ° C) 10.15 Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate 100 ml Ammonium sulfite 16 g Ethylenediaminetetraacetate Iron (III) ammonium 80g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Water added 100ml pH (25 ℃) 6.2 Rinse solution (same as tank solution and replenisher solution) Tap water Rinse solution is reverse osmosis membrane (Daicel Chemical Co., Ltd. spiral RO module element DRA-80 (effective membrane area)
Liquid pressure of 4 kg / cm using a plastic pressure vessel Vessel PV-0321 manufactured by the same company loaded with 1.1 m ² , polysulfone-based composite membrane)
^2. Pumping was performed under the conditions of a liquid flow rate of 1.5 / min. (The permeated water was supplied to the fourth rinse tank, and the concentrated liquid was returned to the third rinse tank.) The results are shown in Table 5.

It is understood from Table 5 that by applying the present invention to a laser-exposed light-sensitive material and processing it, a gray gradation image having a sufficiently high magenta density can be obtained even in a halftone portion in a short time.

(Effect of the Invention) According to the present invention, when a color photographic material is subjected to rapid development processing within 30 seconds using a color developing agent, a color image having excellent gray balance and excellent long-term storage stability can be obtained. .

Further, the gray balance is further improved by incorporating the compound represented by the general formula (III-1) and / or (III-2) into the color developing solution.

Further, according to the present invention, it is possible to effectively suppress the increase of the minimum concentration even in the high temperature rapid processing.

Claims (3)

(57) [Claims] 1. After exposing a silver halide color photographic light-sensitive material having at least one silver halide photographic emulsion layer containing substantially 90 mol% or more of silver chloride and a color coupler,
A color developing treatment is performed within 30 seconds using a color developing solution containing at least one p-phenylenediamine derivative represented by the following general formula (I) and at least one compound represented by the following general formula (III). A method for processing a silver halide color photographic light-sensitive material, which is characterized. General formula (I) (In the formula, R ¹ and R ³ each represent an alkyl group having 1 to 4 carbon atoms, and R ² represents a linear or branched alkylene group having 3 or 4 carbon atoms.) General formula (II) (Wherein L represents an alkylene group which may be substituted;
Is a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphine group, a hydroxyl group, an amino group which may be alkyl substituted, an ammonio group which may be alkyl substituted, a carbamoyl group which may be alkyl substituted, or an alkyl substituted. Represents a good sulfamoyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. ) 2. The processing method according to claim 1, wherein the color developer contains at least one compound represented by the following general formulas (III-1) and (III-2). . General formula (III-1) General formula (III-2) (In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group, -OR ⁸ , -COOR ⁹ , Or represents a phenyl group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or an alkyl group. ) 3. The processing method according to claim 1, wherein the development processing is carried out at a color development temperature of 40 ° C. or higher and 50 ° C. or lower within 15 seconds.