JP2619262B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a method for producing less fog in unexposed areas and obtaining stable processing characteristics for a long period of time. And a method for processing a silver halide color photographic light-sensitive material.

[Background of the Invention]

Usually, in a method of forming a dye image by processing a silver halide color photographic light-sensitive material, an imagewise exposure is applied, and then an oxidized p-phenylenediamine-based color developing agent is reacted with a dye image forming coupler. A dye image is formed. In this method, a color reproduction method based on an ordinary color reduction method is applied, and cyan, magenta, and yellow dye images corresponding to red, green, and blue are formed on respective photosensitive layers. In recent years, in forming such a dye image, high-temperature development processing and elimination of processing steps have been generally performed in order to shorten development processing time. In particular, in order to shorten the development time, it is extremely important to increase the development speed in color development. The development speed in color development is affected in two directions. One is a silver halide color photographic light-sensitive material, and the other is a color developing solution. In the former case, in particular, the composition of the silver halide emulsion grains used greatly affects the development speed, and in the latter case, the conditions and composition of the color developing solution greatly affect the development speed.

Conventionally, hydroxylamine and sulfite have been used as preservatives for color developing solutions. Particularly, hydroxylamine is effective as a preservative for a p-phenylenediamine-based color developer.

However, hydroxylamine has the disadvantage that it is oxidized and decomposed to generate ammonia. This ammonia acts on the silver halide photographic light-sensitive material, causing ammonia fog on the light-sensitive material. In particular, the presence of heavy metal ions (such as iron ions and copper ions) in the color developing solution makes hydroxylamine more easily decomposed.

Various chelating agents have been considered and used to complex heavy metal ions and prevent their adverse effects. Specific examples of these chelating agents include aminopolycarboxylic acid, polyphosphoric acid, and organic phosphoric acid. However, although these chelating agents are effective for iron ions, they are not so effective for copper ions.

In addition, there is a tendency that the color developing solution is replenished at a low level due to recent economic efficiency and a small amount of waste liquid, and the concentration of heavy metal ions accumulated in the color developing solution tends to be high. Is increasingly desired.

On the other hand, silver halide color photographic materials in which the photosensitive silver halide emulsion is substantially composed of silver chloride (hereinafter referred to as silver chloride color photographic materials) are conventional silver chlorobromide and chloroiodobromide. Compared to a color photographic light-sensitive material comprising a silver halide emulsion containing silver bromide or silver iodide, such as silver or silver iodobromide emulsion, bromide or iodide ions which are developed more quickly and further control the development reaction are produced. Since it is not accumulated in the color developing solution, it is extremely useful as a photosensitive material for rapid processing. The present inventors have conducted various studies using a silver chloride color photographic light-sensitive material suitable for this rapid processing, and as a result, it has been found that it has the following disadvantages.

That is, firstly, the hydroxylamine, which has been conventionally used as one of the preservatives, acts as a silver chloride developer, progresses silver development, and develops the color of the finally obtained dye image. The concentration has dropped.

Secondly, sulfites, which are used as other conventional preservatives, act as a dissolving agent for silver chloride, causing physical phenomena to rapidly progress and disrupting the balance of the coupling reaction in the silver development reaction. In other words, the color density was lowered due to the silver reaction being too advanced and the coupling reaction being delayed.

Thirdly, according to the study by the present inventors, it has been found that fogging is likely to occur particularly when heavy metal ions are mixed. Although this fog was large as a whole, the fogging of cyan was particularly large when used to prevent a decrease in the density of the dye image.

The heavy metal ions are particularly problematic when a large amount of photosensitive material is continuously processed.

Further, in a developing method in which a silver halide photographic material is continuously processed by an automatic developing machine or the like, in order to avoid a change in development finish characteristics due to a change in the component concentration, the components of the color developing solution are kept within a certain concentration range. Means is required. As such means, a method is usually employed in which a replenisher for replenishing deficient components and diluting unnecessary increased components is replenished. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method is a serious problem in terms of economy and pollution. Therefore, in recent years, in order to reduce the overflow solution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in a small amount, or an electrodialysis method corresponding to substantially low replenishment or a regenerating method of a developer using an ion exchange resin. Is demanded as a social need, and in such a method, heavy metal ions are particularly easily accumulated, and it is strongly desired to solve the above problems.

Further, it has been found that such a low replenishment process has another disadvantage that the amount of evaporation increases, the color developing solution is concentrated, and it is difficult to obtain stable photographic characteristics (especially, the maximum density of yellow). . In particular, when a running process for performing a continuous process is performed intermittently for a long period of time, such as in a minilab, this disadvantage cannot be ignored.

(Object of the present invention)

Accordingly, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which generates less fog even when heavy metal ions are mixed in a color developing solution and provides stable photographic characteristics for a long period of time.

[Configuration of the invention]

The object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which a silver halide color photographic light-sensitive material is imagewise exposed and then processed with a color developing solution. 3.5, wherein at least one of the silver halide emulsion layers contains at least 90 mol% of silver chloride, further contains a nitrogen-containing heterocyclic mercapto compound in the photographic component layer of the light-sensitive material, and the color developing solution is as follows: A method for processing a silver halide color photographic light-sensitive material, comprising a compound represented by the formula [I]. Achieved by

In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

[Specific configuration of the invention]

Next, the compound represented by the general formula [I] according to the present invention will be described in detail. In the formula (I), R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. Also R ₁
And R ₂ may form a ring.

In formula (I), represent the R ₁ and R ₂ are each an alkyl group or a hydrogen atom are not hydrogen atoms at the same time, R ₁
And the alkyl groups represented by R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. R ₁
And the alkyl group of R ₂ includes those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, may form a heterocyclic ring such as piperidine, piperazine or morpholine. .

Specific compounds of the hydroxylamine derivative represented by the general formula [I] are described in U.S. Patent Nos. 3,287,125 and 3,293,0
No. 34 and 3,287,124, particularly preferred specific exemplary compounds are shown below.

These compounds are usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by the general formula [I] in the color developing solution is usually 0.2 g / to 50 g /, preferably 0.5 g / to 30 g /
And more preferably 1 g / to 15 g /.

In addition, a compound represented by the general formula [I] and a conventionally used hydroxylamine can be used in combination.

The color developing solution according to the present invention, when containing the compound represented by the following general formula [D], not only exerts the effect of the present invention better, but also against the air oxidation of the color developing solution. It is more preferably used to show an improvement effect.

In the formula, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms,
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 Wherein n ₁ is an integer of ₁ to 6, and X ′ and Z ′ each 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 [D] are as follows.

(D-1) ethanolamine, (D-2) diethanolamine, (D-3) triethanolamine, (D-4) di-isopropanolamine, (D-5) 2-methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol (D-9) 1-diethylamino-2-propanol, (D-10) 3-diethylamino-1- Propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) isopropylaminoethanol, (D-13) 3-amino-1-propanol, (D-14) 2-amino-2-methyl -1,3-propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzylethanolamine, (D-17) 2 Amino-2- (hydroxymethyl) -1,
3-propanediol.

From the viewpoint of the effects of the present invention, these compounds represented by the general formula [D] are used in an amount of 1 g to 10 g per color developing solution.
0 g is preferably used in the range, more preferably 2 g ~ 30 g
Used in the range.

One of the preferred embodiments of the present invention is that the color developing solution of the present invention contains bromide in an amount of 4 × 10 ^-4 mol or more per color developing solution. In this case, not only the effect of the object of the present invention is exhibited more favorably, but also another effect of improving the bleaching fog of the unexposed portion is exhibited. The bromide is preferably 8 × 10 ⁻⁴ mol / 〜1.2 × 10 ⁻² mol /, more preferably 1.6 × 10 ⁻³ mol / 〜1.0 × 10 ⁻² mol /, particularly preferably 3.2 × 10 ⁻³ mol /. ~ 8.4 × 10 ^-3 mol /
Used in the range.

The color development in the present invention is usually carried out at a temperature in the range of 20 ° C to 80 ° C, preferably in the range of 30 ° C to 50 ° C.

The pH of the color developing solution in which development is performed is generally 8 or more, preferably 9.5 or more.

Development is carried out in the presence of pH buffers, development inhibitors, antifoggants, complexing agents for softening, preservatives, development accelerators, competing couplers, fog agents, auxiliary developer compounds and viscosity modifiers. Research Disclosure 17544, December 1978, Section XXI, Industrial Opportunities, Inc. (I
ndustrial Oppotunities Ltd.), (Homewell Havant, H
Published by ampshire, GrentBritain and Ullmans Enchlopedy del Technischen Hemiy
Enzyklpudie der technisehen Chemie), 4th edition, 18 volumes,
See especially 451 pages 452 and 463-465 in 1979. Suitable developer compositions include Grant Haist and Modern Photographic Processing.
tographic processing), John Wiley &
John Willey and Sans, 1973, Vol. 1 and 2
Has been given to.

Particularly useful color developing agents used in the color developing solution of the present invention are N, N-dialkyl-p-phenylenediamine compounds, and the alkyl group and the phenyl group may be substituted with any substituent. Among them, particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N
-Dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecyl-N-dodecylamino) -toluene sulfate, N-ethyl-N-β-methanesulfonamidoethyl-3- Methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethyl-3
-Methyl-4-aminoaniline sulfate, 4-amino-3
-Methyl-N, N-diethylaniline sulfate, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate, and the like.

Other suitable color developers include, for example, the Journal of American Chemical Society (J. Amer. Chem. So
c.) 73 , 3100 (1951). Also, black and white developer materials can be used in addition.

According to a particularly preferred embodiment, the color developer contains a color developer A of the following formula:

These color developing agents are usually used in an amount of 1 to 1 per color developing solution.
It is preferably used in the range of × 10 ^-2 mol to 2 × 10 ^-1 mol, but from the viewpoint of rapid processing, 1.5 to 1.5 mol per color developing solution.
More preferably, the range is from × 10 ^-2 mol to 2 × 10 ^-1 mol.

Further, the color developing agents may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
-It may be used in combination with pyrazolidone or methol.

In the processing method of the present invention, the amount of the replenisher of the color developer to provide an advantage of particularly remarkably present invention when used in the range of the photosensitive material 1 m ² per 10Ml～300ml, very particularly 20ml~200m
The range of l is preferred, most preferably in the range of 30 ml to 100 ml.

One of the preferred embodiments of the present invention is that the processing time of the color development processing step is 90 seconds or more. In particular, a range of 100 seconds to 360 seconds is preferred, especially 12
A range from 0 seconds to 300 seconds is preferred, and most preferably 15 seconds.
The range is 0 to 240 seconds.

In the present invention, a bleach-fix solution after color development is preferably used from the viewpoint of rapid processing. When a high silver chloride photosensitive material is used and bleach-fix processing is performed immediately after color development as in the present invention, a stain called bleach fog is used. Tends to occur. Therefore, as a result of various studies, it was found that the use of the bleach-fixing solution having a pH in the range of 4.5 to 6.8 not only can solve this problem but also has the effect of reducing the silver bleaching speed.

In particular, this effect is good when the pH of the bleach-fix solution is 5 to 6.3.

In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution, as well as a washing solution or a stabilizing solution instead of a washing solution. For example, an electrolysis method (French Patent No. 2,299,667), a precipitation method (JP-A-5
2-73037, German Patent 2,331,220), ion exchange method (JP-A-51-17114, German Patent 2,548,237), metal replacement method (UK Patent 1,353,805) and the like can be effectively used.

In the processing method of the present invention, after bleaching and fixing (or bleach-fixing) processing after color development processing, stable processing may be performed without washing with water, or washing processing may be performed, and then stable processing may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and a small amount of water washing step may be added as necessary. The following steps are included as typical specific examples of a preferable treatment method.

(1) Color development → bleach-fix → washing with water (2) Color development → bleach-fix → small amount of washing → washing with water (3) Color development → bleach-fix → washing → stable (4) Color development → bleach-fix → stable (5) Color developing → Bleaching and fixing → First stable → Second stable (6) Color development → Washing (or stable) → Bleaching and fixing → Washing (or stable) (7) Color developing → Stop → Bleaching and fixing → Washing (or stable) (8) (9) color development → bleaching → fixing → washing → stable (10) color developing → bleaching → small amount of washing → fixing → first stable → second stable (11) color developing → bleaching → small amount washing → fixing → small amount stable → washing → stable (12) Color development → small amount washing → bleaching → small amount washing → fixing → small amount washing → water washing → stable (13) Color development → stop → bleach → → small amount washing → Fixing → small amount washing with water → washing with water → stable Among these processes, (4) to (5) Step is preferably used.

The silver halide grains used in the silver halide emulsion layer of the present invention contain at least 90 mol% of silver chloride, and the remainder may contain bromide or iodide, but is preferably substantially silver chloride. It is preferable that the iodide is extremely small.

In particular, when the amount of silver chloride is 95 mol% or more, the effect of the object of the present invention is favorably exhibited, and particularly preferably 98 mol% or more. In a special case, it is also preferable that the blue photosensitive layer is silver halide containing 30 mol% of bromide and the other two layers, for example, the green photosensitive layer and the red photosensitive layer have a chloride content of about 99 mol%. This is one of the embodiments. Silver halide is preferably a core-shell grain and has a double layer structure.

At least 90 mol% of the silver chloride used in the present invention;
A silver halide emulsion layer containing silver halide grains comprising a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously contained in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer can contain, for example, a non-diffusible color coupler which produces a cyan partial color image, generally a phenol or α-naphthol coupler. The green-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a magenta partial color image, usually a 5-pyrazolone based color coupler and a pyrazolotriazole. The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having a closed ketomethylene group. The color coupler can be, for example, a 6-, 4- or 2-equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications: Agfa's work report (Mitteilungln ausden Forsch
ungslaboratorien der Agta), Leverkusen /
Munich (Leverkusen / Munchen), Vol.III.p.111 (1
961) "Color coupler" (Farbkuppler) by W. Pelz; K. Venkataraman, "The Chemistry of Synthetic D"
yes), Vol. 4, 341-387, Academic Press (Acad
emic Press), (1971); TH James, "The Theory of the Photogragh Process"
phic Process), 4th edition, pages 353-362; and Research Disclosure No. 17643,
Section VII.

In the present invention, a magenta color represented by the general formula [MI] as described in JP-A-63-106655, p. JP-A-63-106655, pages 29 to 34
No. 1 to No. 77 are listed. ) A cyan coupler represented by the general formula [CI] or [C-II] also described on page 34 (specific examples of cyan couplers include (C ') described in the same specification, pages 37 to 42). -1) to (C'-82),
(C "-1) to (C" -36)), and 20
The high-speed yellow coupler described on page 21 (specific examples of cyan couplers include (Y'-1) to (Y'-39) described on pages 21 to 26 of the same specification) can be used as the light-sensitive material of the present invention. It is preferable to use them in combination from the viewpoint of the effects of the object of the present invention.

In the present invention, when a high-silver chloride light-sensitive material of the present invention is used in combination with a nitrogen-containing heterocyclic mercapto compound, not only the effects of the present invention can be achieved well, but also a bleach-fix solution in a color developing solution. Another effect is that the effect on the photographic performance caused by the inclusion of phthalocyanine is extremely small, which is a more preferable embodiment in the present invention.

In the nitrogen-containing heterocyclic mercapto compound, the nitrogen-containing heterocycle is an imidaline ring, an imidazole ring, an imidazolone ring,
Pyrazoline ring, oxazoline ring, oxazole ring, oxazolone ring, thiazoline ring, thiazole ring, thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzotriazole Ring, indazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, virazine ring, pyrimidine ring, pyritazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring ( For example, it is desirably selected from triazaindene ring, tetrazaindene ring, pentazaindene ring, etc.). Of these, particularly preferred nitrogen-containing heterocyclic mercapto compounds include oxazole rings, oxadiazole rings, thiadiazole rings,
A triazole ring, a tetrazole ring, a benzimidazole ring, a benzotriazole ring, a pyrimidine ring, a triazine ring, and a polyazaindene ring.

Hereinafter, specific examples of the nitrogen-containing heterocyclic mercapto compound useful in the present invention will be described.

The above compounds were obtained from the Journal of Chemical Society (J. Chem. Soc) 49, 1948, 1927, and the Journal of Organic Chemistry (J. Org. Chem.) 39, 246.
9, 1965, JP-A-50-89034, JP-A-55-79436, JP-A-51-1794
No. 02639, No. 55-59463, Annalen Hemy (Ann.
Chim.), 44-3, 1954, JP-B-40-28496, Chemical Berchte (Chem. Ber.) 20, 231, 1887, U.S. Pat.
No. 9,976, Chemical and Pharma-Tical
Buretane (Chemical and Pharmaceutical Bulleti
n) (Tokyo) Volume 26, 314 (1978), Berichte der Deutschen Hemischen Geelsläft (Beri)
chte der Deutscben Chemischen Gesellsdraft) 82, 12
1 (1948), U.S. Pat. Nos. 2,843,491, 3,017,270, British Patent 940,169, Journal of American Chemical Society, 44, 1502-1510 and the like.

The nitrogen-containing heterocyclic mercapto compound (hereinafter, simply referred to as a mercapto compound) is described in, for example, JP-A-51-1071129.
Nos. 48-102621, 55-594463 and 59-124333
It is described in each gazette of the issue.

In the present invention, the mercapto compound is preferably added to two or more photographic constituent layers.

The total amount of the mercapto compound used varies widely depending on the layer constitution of the silver halide photographic light-sensitive material, the type of the mercapto compound, the amount of silver halide, processing conditions, etc., and is generally from 10 ^-8 mol to 10 mol / m ^{2. -4} mol, preferably 10 ^-7 mol to 1
Although it is in the range of 0 to ⁵ mol, in the present invention, it is not limited to the total amount itself, but is defined by the degree of fog prevention of each emulsion layer and the magnitude of the effect of the mercapto compound between each layer.

The silver halide emulsion having a silver chloride content of 90 mol% or more in the present invention can be prepared by a conventional method (for example, single inflow or double inflow by constant or accelerated feeding of materials). pA
Particular preference is given to the preparation method by means of the double-flow method with adjustment of the g; see Research Disclosure No. 17643, sections I and II.

Emulsions can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, such as tin compounds as described in Belgian Patent Nos. 493,464 and 568,687, and polyamines such as diethylene triamine or aminomethylsulfinic acid according to Belgian Patent No. 547,323. It is a derivative. Gold, platinum, palladium,
Noble metals and noble metal compounds such as iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is described in Zeitschrift Fair Bissenshaftriche Photography (Z.Wiss.Photo.) 46 , 65-72.
(1951) in the article by R. Kosiovsky; see also Research Disclosure No. 17643, supra, section III.

Emulsions can be sensitized using optically known methods, for example, conventional polymethine dyes such as neuthocyanins, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like:・ FM Hamer's “Cyanine Dyes and Related Compounds” (19)
64) Ullmanns Enzyklpadie der t
echnischen Chemie), 4th edition, volume 18, p. 431 and following, and above, Research Tis Closure No. 17643, section IV.

Emulsions can use conventional antifoggants and stabilizers. Azaindene is a particularly suitable stabilizer, with tetra- and pentazaindene being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this kind are described, for example, in Birr's article,
Zeitschrift Fair Bissenshaftrichhe Photography (Z.Wiss.Photo.) 47, 1952, p.2-5
8, and the above Research Disclosure No. 17643,
Shown in Section IV.

The components of the light-sensitive material can be contained by a commonly known method; for example, US Pat. Nos. 2,322,027 and 2,53.
No. 3,514, No. 3,689,271, No. 3,764,336 and No. 3,76
See 5,897. Components of photosensitive material, such as couplers and UV
The absorbent can also be included in the form of a charged latex; see DE-A-2,541,274 and EP-A-14,921. The components can also be fixed in the light-sensitive material as polymers; see, for example, DE-A-2,044,992, U.S. Pat. Nos. 3,370,952 and 4,080,211.

On the other hand, the light-sensitive material used in the present invention has a swelling degree of the photographic layer of 1.5 to 3.5, preferably 2.0 to 3.2. The swelling degree as referred to herein means a value obtained by dividing the photographic layer thickness after immersing the photographic material in distilled water at 33 ° C. for 2 minutes by the dry layer thickness.

When the swelling degree of the photographic layer is more than 3.5, the fog density of the unexposed area is high, and when it is less than 1.5, a sufficient maximum density cannot be obtained. On the other hand, when the swelling degree of the photographic layer is more than 3.5, the density of yellow stain is undesirably high. Further, if the degree of swelling of the photographic layer is larger than 3.5, the mechanical strength of the photographic layer in the developing process is lowered, causing troubles such as generation of scratches, and the amount of water absorption increases, which is not preferable because it causes a drying load.

Here, the "photographic layer" refers to a laminated hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. It does not include the back layer provided on the side opposite to the photographic photosensitive layer across the support. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and includes an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like in addition to the silver halide emulsion layer.

Any method may be used to adjust the degree of swelling within the scope of the present invention. For example, the amount and type of gelatin used in the photographic layer, the amount and type of hardener, or drying after coating the photographic layer It can be adjusted by changing conditions and aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. be able to.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin oxygen-decomposed product can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are added to gelatin. What is obtained by reacting is used. Specific examples are U.S. Pat.Nos. 2,614,928, 3,132,945, and 3,186,846.
No. 3,312,553; British Patent Nos. 861,414, 1,033,189
No. 1,005,784 and JP-B No. 42-26845.

As the gelatin-grafted polymer, a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. Can be used. In particular, a graft polymer of a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferable. Examples of these are described in U.S. Pat. Nos. 2,763,625, 2,831,767, and 2,956,884. Representative synthetic hydrophilic polymer substances are described in, for example, West German Patent Issue (OLS) 2,312,708 and US Pat.
Nos. 0,751, 3,879,205 and JP-B-43-7561.

Examples of the hardener include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2 , 3-dihydroxydioxane), active vinyl compounds (1,3,5-
Triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., an active halogen compound (2,4-dichloro-6)
-Hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, mucophenoxycyclolic acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-
6-hydroxytriazinylated gelatin or the like can be used alone or in combination. Specific examples thereof are described in U.S. Patent Nos. 1,870,354, 2,080,019, 2,726,162,
2,870,013, 2,983,611, 2,992,109, 3,04
7,394, 3,057,723, 3,103,437, 3,321,313
No. 3,325,287, No. 3,362,827, No. 3,539,644,
No. 3,543,292; British Patent Nos. 676,628; 825,544;
No. 1,270,578, German Patent 872,153, No. 1,090,427,
It is described in JP-B Nos. 34-7133 and 46-1872.

Particularly preferred hardeners are aldehydes, active vinyl compounds and active halogen compounds.

As the support of the silver halide color photographic light-sensitive material in the present invention, a conventional support can be used, for example, a support of cellulose ester such as cellulose acetate and a support of polyester. Paper supports are also suitable, and they can be coated, for example, with polyolefins, especially polyethylene or polypropylene; in this regard, see Research Disclosure No. 17643, supra, section XVI.

Conventional hydrophilic film formers can be used as protective colloids or binders for the layers of the light-sensitive material, such as proteins, especially gelatin, alginic acid or derivatives such as esters, amides or salts thereof, carboxymethylcellulose and cellulose sulfate. Cellulose derivatives, starch or derivatives thereof, or hydrophilic synthetic binders; see also the binders shown in Research Disclosure No. 17643, Section IX, supra.

The layer of the photographic material provided on the support can be cured by a conventional method, for example, using an epoxide, a heterocyclic ethyleneimine or an acryloyl hardener. Furthermore,
The layers can be cured by a method according to DE-A-2,218,009 to produce a color photographic light-sensitive material suitable for high-temperature operation. The above layer can be cured with a diazine, triazine or 1,2-dihydroquinoline-based curing agent or a vinylsulfone-type curing agent. Other suitable curing agents are DE-A-2,439,551,
Nos. 2,225,230 and 2,317,672 and Research Disclosure No. 17643, Section XI.

(Specific embodiments of the invention)

Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Reference Example 1 An experiment was conducted using the following color paper, processing solution, and the following processing steps. The following layers were sequentially coated on a color paper polyethylene coated paper support from the support side to prepare a light-sensitive material.

The average molecular weight of polyethylene coated paper is 10
0000, 200 parts by weight of polyethylene of density 0.95 and average molecular weight 2
000, a mixture of 20 parts by weight of polyethylene having a density of 0.80, 7.5 wt% of anatase type titanium oxide was added, and a coating layer having a thickness of 0.035 mm was formed on the surface of a high-quality paper having a weight of 170 g / m ² by an extrusion coating method. The back surface was provided with a coating layer having a thickness of 0.04 mm using only polyethylene. After pretreatment by corona discharge was performed on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1, wherein the emulsion contains 350 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye 200 mg of 2,5-di-t-butylhydroquinone sensitized using 2.6 × 10 ^-4 mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate
/ m ² and the following yellow coupler Y containing 2.1 × 10 ^-1 mol per mol of silver halide as a yellow coupler, and coated so that the silver amount becomes 250 mg / m ² .

Second layer: 290 mg / m ^{2 of} di-t-octyl hydroquinone dissolved and dispersed in dibutyl phthalate, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
A mixture of (2-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole 190 mg /
The gelatin layer containing m ² is coated so as to have a gelatin of 1900 mg / m ² .

Third layer: A green-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1, wherein the emulsion contains 400 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye The following magenta coupler M (1) was sensitized using 2.6 × 10 ^-4 mol and dissolved and dispersed in a solvent in which dibutyl phthalate and tricresyl phosphate were mixed at a ratio of 2: 1. It is coated so as to contain 1.7 × 10 ⁻¹ mol and to have a silver amount of 250 mg / m ² . Here, 0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained as an antioxidant per 1 mol of the coupler.

Fourth layer: 35 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-tert-butylphenyl) -5 A mixture of chlorobenzotriazoles (2: 1.5:
1.5: 2) the amount of gelatin 1 at 500 mg / m ² gelatin layer containing
It is coated to be 900 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver halide emulsion having a silver halide composition shown in Table 1, which emulsion contains 460 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye The following cyan couplers C (1) and C (1) were sensitized using 2.2 × 10 ^-5 mol, and dissolved in dibutyl phthalate to disperse and disperse in 2,5-di-t-butylhydroquinone 150 mg / m ² and a cyan coupler. 2) (1: 1) is contained in an amount of 3.2 × 10 ⁻¹ mol per mol of silver halide and coated so that the silver amount is 305 mg / m ² .

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 900 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized, and 4-hydroxy-6-methyl-
It contained 1,3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardening agent and saponin as a coating aid.

The swelling degree of the photographic layer was adjusted as shown in Table 1 below by changing the amount of the hardener added to the photographic material and the drying conditions after coating the photographic layer.

The above photosensitive material (changes silver halide composition and swelling degree)
Was subjected to stepwise exposure, and processed with the following processing steps and processing solutions. The maximum density of the yellow dye of the obtained sample was measured. At the same time, the magenta dye density in the unexposed area was measured, and the results are summarized in Table 1 below.

Processing step (1) Color development 32.8 ° C 3 minutes 30 seconds (2) Bleaching and fixing 35 ° C 1 minute 30 seconds (3) Rinse 25 ° C to 35 ° C 3 minutes (4) Drying 60 ° C to 90 ° C About 2 minutes Liquid composition Color developing tank liquid Ethylene glycol 15 ml Potassium sulfite 1.0 g Sodium chloride 1.5 g Potassium carbonate 30.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.2 g Fluorescence Brightener (diaminostilbene) 1.0 g Hydroxylamine derivative (described in Table 1) 3.5 g Ethylenediaminetetraacetic acid 3.0 g Benzyl alcohol 1.0 g Potassium bromide 0.4 g Add water to make the total amount 1 and add KOH and H ₂ SO ₄ pH10.10.

Bleach-fix tank solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust pH to 6.0 with potassium carbonate or glacial acetic acid and water To make the total amount 1.

However, the color developing solution contains 2 ppm of ferric ion (added in the form of ferric ammonium ethylenediaminetetraacetate).
1ppm and 1ppm of copper ion (added in the form of copper sulfate)
What was stored for one week at room temperature at an opening ratio of 20 cm ² / (1 color developing solution was stored at an opening area of 20 cm ² ) was used.

As apparent from Table 1 above, the silver halide composition,
When both the degree of swelling of the photographic layer and the inclusion of the specific hydroxylamine derivative in the color developing solution are within the scope of the present invention, a sufficient yellow dye concentration is obtained only when heavy metals are mixed. It can be seen that magenta fogging is also good in the unexposed areas, and that it is good.

Reference Example 2 The magenta coupler M (1) in the color paper sample used in Experiment No. 1-8 of Reference Example 1 was prepared by using a pyrazolotriazole type described in JP-A-63-106655, pages 29 to 34. Magenta couplers (M'-1), (M'-2), (M'-
4), (M'-21), (M'-37), (M'-61),
(M'-63), and the same experiment was performed. The maximum density of yellow was found to be the highest in Experiment No. 1-
8, but the magenta dye density in the unexposed area was
0.02, which was extremely good.

Reference Example 3 In the color developer used in Experiment No. 1-8 of Reference Example 1, exemplary compounds D-2, D-3 and D- of alkanolamine derivatives (compounds represented by the general formula [D]) were added. 13 each 5g
When the same experiment as in Reference Example 1 was carried out except for the addition, the maximum of yellow increased by about 0.20 and the magenta dye density of the unexposed area decreased by 0.01 to 0.02. Further, the tar property and the generation of crystals generated in the color developing solution tank were also improved.

Example 1 In each emulsion layer of the color paper sample used in Experiment Nos. 1 to 8 of Reference Example 1, an exemplary compound (I-2) of a mercapto compound was added.
4), (I-41), (I-60), (I-66), (I-7
9) and (I-84) were added in the same manner as in Reference Example 1 except that 0.12 mg / m ^{2 was} added. The maximum yellow density was unchanged, and the magenta fog density in the unexposed area was 0.02. It fell to 0.01.

Reference Example 4 An experiment was carried out in the same manner as in Reference Example 1 except that the processing time in the color development processing step of Experiment No. 1-8 in Reference Example 1 was changed as shown in Table 2. The results are shown in Table 2 below.

From Table 2 above, from the reference data, the color development time
When 90 seconds or more, it can be seen that the data was effectively obtained.

〔The invention's effect〕

According to the present invention, even when heavy metal ions are mixed in the color developing solution, fog is less generated and stable photographic characteristics can be provided for a long period of time.

Claims (1)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material is imagewise exposed and then processed with a color developer, wherein the swelling degree of the photographic layer of the light-sensitive material is 1.5 to 3.5. Wherein at least one of the silver halide emulsion layers contains at least 90 mol% of silver chloride, further contains a nitrogen-containing heterocyclic mercapto compound in the photographic component layer of the photographic material, and the color developing solution has the following general formula: A method for processing a silver halide color photographic light-sensitive material, comprising continuously processing the light-sensitive material containing the compound represented by the formula (I). [Wherein, R ¹ and R ² each represent an alkyl group or a hydrogen atom. However, both R ¹ and R ² are not hydrogen atoms at the same time. R ¹ and R ² may form a ring. ]