JPH06175320A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent contamination of edges due to infiltration of a bleach-fixing liquid through cut edges of a supporting body by incorporating a specified sizing agent into the paper supporting body and incorporating a specified compd. into the bleach-fixing liquid. CONSTITUTION:The paper supporting body contains at least one kind of alkylketene dimer as a sizing agent. The supporting body is cut into the finish size of photograph in an automatic developing machine prior to the developing process and then subjected to developing process. The bleach-fixing liquid contains an iron (III) complex of a compd. expressed by formula I. In formula R1-R6 are hydrogen atoms, aliphatic groups, aromatic groups, or hydroxy groups, W is a connecting group expressed by formula II, M1-M4 are hydrogen atoms or cations, W1 is an alkylene group or single bond, W2 is an alkylene group or -CO-, and Z is a single bond, -O-, -S-, -CO-, etc. However, both of Z and W1 are not single bonds at one time (n)is an integer 1-3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material by an automatic processor, and more specifically, it is a method of immersing a bleach-fixing solution from a cut surface of an end of a support. The present invention relates to a development processing method capable of preventing edge stains due to scratches.

[0002]

2. Description of the Related Art Conventionally, as a photographic reflection support, so-called baryta paper in which one side of paper is coated with a baryta layer mainly composed of barium sulfate has been used. For speeding up, a waterproof support in which both sides of a base paper are coated with resin has come to be used. However, even when the above-mentioned waterproof support is used, the processing liquid permeates from the cut surface of the end of the support to stain the edge portion, significantly deteriorating its photographic value. In order to prevent this edge stain, a method of giving a high sizing property to the base paper layer has been attempted.

As disclosed in JP-B-47-26961, fatty acid soap type sizing agents and JP-A-51-13
As described in JP-A-2822 and JP-A-3-174152, it is described that an alkyl ketene dimer or the like is used as a sizing agent for photographic base paper to improve edge stains. In recent years, as a part of improving user service, photo processing requires quick processing such as finishing 30 minutes from the development reception time, and a small automatic developing machine called a minilab has spread to the market, and photo processing is performed in the development reception shop. An increasing number of systems are being returned to users. Generally, the width of photosensitive material of automatic developing machine for paper in minilab is 10 cm.
Supplied in rolls of about 20 cm, cut in the lengthwise direction in an automatic processor, and finished as a single photo. Cutting is performed after the processing is completed (hereinafter referred to as roll conveyance).
For example, a product of Fuji Photo Film Co., Ltd., PP-1040B type color paper processor) and a roll-shaped product are cut into a finished size in advance and then processed for development (hereinafter referred to as cut conveyance. For example, Fuji Photo Film) It is roughly classified into two types, a PP401B color paper processor manufactured by Co., Ltd. Due to its structure, the roll transfer type cannot be transferred unless it has a certain length, so when printing a small number of prints, there is much loss of the photosensitive material.
There is a great demand from lab users to reduce losses.

In an automatic developing machine usually called a minilab,
Width of the finished size of the photo in the photosensitive material manufacturing plant (eg 11.7 cm to get a service size print)
The photosensitive material cut into sheets is supplied in the form of a roll having a length of several tens of meters, and the sheet is cut into individual sheets by the cutting mechanism inside the automatic developing machine. As described above, in order to reduce the loss of the light-sensitive material, when the processing is performed after cutting to the finished size of the photograph prior to the processing, edge stains may occur on the cutting surface perpendicular to the transport direction. It has been found. This is because in the cutting in the automatic processor, the sharpness of the blade deteriorates when used under severe conditions and the cutting surface is rough, and the processing solution, especially the bleach-fixing solution, is impregnated from that part to cause edge stains. The effect of the sizing agent described above was insufficient when the cut surface was rough. In this case, the cut surface in the lateral direction with respect to the conveyance is cut in a well-controlled factory, and edge stains hardly occur. Therefore, there is a strong demand for a method of cutting and transporting a photosensitive material with less loss, which does not cause edge stains not only on the cutting surface in the lateral direction with respect to the transportation but also on the cutting surface perpendicular to the transportation direction. .

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to cut a photographic support having resin coated on both sides,
In particular, it is an object of the present invention to provide a photographic processing method by an automatic developing machine in which edge stains caused by a bleach-fixing solution on a rough cut surface with sharpness are remarkably suppressed.

[0006]

The above object of the present invention can be achieved by the following items (1) to (3). (1) A silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on a paper support whose both sides are coated with polyolefin is processed in a bleach-fixing step using an automatic processor after the color developing step. In the method, at least one alkyl ketene dimer is contained as a sizing agent in the paper support, and prior to the development processing step, the finished size of the photograph is cut in an automatic processor and then the development processing is performed, and the bleaching is performed. A method for processing a silver halide color photographic light-sensitive material, wherein the fixing solution contains a ferric complex salt of a compound represented by the general formula (I). General formula (I)

[0007]

[Chemical 2]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Each represents a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents a linking group represented by the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) In formula _{(W) - - (W 1} -Z) n -W 2 ( formula (W), W ₁ represents an alkylene group or a single bond.
W ₂ represents an alkylene group or -CO-. Z is a single bond,
It represents -O-, -S-, -CO-, or -N ( _Rw )-( _Rw represents a hydrogen atom or an alkyl group which may be substituted). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. (2) The method for processing a silver halide color photographic light-sensitive material as described in (1) above, wherein the conveying speed of the light-sensitive material in the automatic processor is 1.2 m / min to 3 m / min. (3) In the above (1) or (2), the aerial time between the color developing bath and the bleach-fixing bath in the automatic processor is 5 seconds to 15 seconds.
A method for processing a silver halide color photographic light-sensitive material, characterized in that the second is.

The compound of the general formula (I) of the present invention will be described in more detail below. R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And the aliphatic group represented by R ₆ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group,
Those having 1 to 10 carbon atoms are preferable. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. ,
A phenyl group is more preferred. R ₁ , R ₂ , R ₃ , R ₄ ,
The aliphatic group and aromatic group represented by R ₅ and R ₆ may have a substituent, for example, an alkyl group (for example, methyl,
Ethyl), aralkyl groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-methylphenyl), amino groups (eg dimethylamino), Acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl) ), Alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg methanesulfonyl), sulfinyl groups (eg methanesulfinyl), hydroxy groups, halogen atoms ( For example, chlorine atom, bromine atom, fluorine atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (eg acetyl, benzoyl), alkoxycarbonyl group (eg methoxycarbonyl). ), An acyloxy group (eg acetoxy), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group, and the like, and if possible, a dissociation product or a salt thereof.

When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ , R ₂ , R
₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom.

The linking group represented by W is represented by the following general formula (W). Formula _{(W) - (W 1 -Z} ) n -W 2 - W 1 represents an alkylene group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group, a propylene group), a cycloalkylene group having 5 to 10 carbon atoms (for example, 1, 2-cyclohexylene group).

W ₂ represents an alkylene group or --CO--.
The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ . The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent. As the substituent, those mentioned as the substituent for R ₁ are applicable, but an alkyl group, a hydroxy group or a carboxy group is preferable. More preferably, W ₁ and W ₂ are alkylene groups having 1 to 3 carbon atoms,
A methylene group or an ethylene group is particularly preferable.

Z is a single bond, --O--, --S--, --CO--,
Or -N (R _W) - represents a. R _W represents a hydrogen atom or an optionally substituted alkyl group. As the substituent, those mentioned as the substituent for R ₁ can be applied, but a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group is preferable. Z is preferably a single bond. n
Is preferably 1 or 2, and more preferably 1.

Specific examples of W in the above formula (I) include the following.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg lithium, sodium, potassium), ammonium (eg ammonium, tetraethylammonium) and pyridinium. it can.

In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited thereto.

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

The compounds represented by formula (I) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in Japanese Patent No. 3857 or the like. As described in these documents, the compound represented by the general formula (I) of the present invention includes optical isomers ([R, R], [S, S], [S, R] , [R, S])
Exists. For example, the exemplary compound (I-1) of the compound represented by formula (I) of the present invention has three optical isomers ([R, R], [S, S], [S, R]). Exist and these can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof.

In the present invention, a compound synthesized from an L-amino acid such as [S, S] -form as a starting material is preferable to other optical isomers. These compounds are described by Springer and Copecca in Chem. Zvesti. 20
(6): 414-422 (1966) and JP-A-3-
It can be synthesized based on the method described in No. 173857.

The iron (III) complex of the compound represented by the above general formula (I) of the present invention comprises a trivalent iron ion and the general formula (I).
It can be prepared by mixing the above compound with a compound in a bleach-fixing tank or a bleach-fixing replenishing tank. When used as a bleaching agent, it may be isolated and used as a chelating agent iron (III) complex. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt.

The amount of the iron (III) complex of the general formula (I) used is 0.02 mol to 1.0 per liter of the bleach-fixing bath.
The molar amount is preferably 0.04 to 0.5 mol, particularly preferably 0.08 to 0.3 mol. Also, iron (II
It is preferable that the compound of the general formula (I) is present in excess of about 1 to 20% in addition to the complex of I). In the compound of general formula (I), I-1, I-2, I-3, I-15, I-1
Particularly preferred are the compounds of 6 and I-17.

The ferric complex salt used in the bleach-fixing solution may be added as a complexed iron complex salt in advance and dissolved,
Also, complexing compounds and ferric salts (eg ferric sulfate,
Ferric chloride, ferric bromide, iron nitrate (III), iron sulfate (II
I) Ammonium and the like) may be coexistent to form a complex salt in the bleach-fixing solution.

The compound forming the ferric complex salt in the bleach-fixing solution (composition) of the present invention is preferably 50 mol% or more of the compound represented by the above-mentioned general formula (I). It is preferable to occupy 80 mol% or more.
In the present invention, as the compound forming the ferric complex salt in the bleach-fixing solution, the compound represented by the above general formula (I) may be used alone or in combination of two or more kinds. Good.

Within the scope of the present invention, as the compound forming the ferric complex salt in the bleach-fixing solution, a compound other than the compound represented by the general formula (I) may be used in combination. I do not care. Such compounds include EDTA,
1,3, -PDTA, diethylenetriaminepentaacetic acid,
1,2-Cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-carboxy) Examples thereof include, but are not limited to, methyl) iminodipropionic acid and the like.

In the present invention, as a bleaching agent for the bleach-fixing solution, an inorganic oxidizing agent may be used in combination as a bleaching agent, in addition to the above-mentioned ferric iron complex salt, as long as the object of the present invention is not impaired. Examples of such an inorganic oxidizing agent include hydrogen peroxide, persulfate, and bromate, but are not particularly limited thereto. The total concentration of ferric complex salt in the bleach-fixing solution of the present invention is 0.005
The range of 1.0 mol / liter is suitable, and 0.01 to
The range is preferably 0.70 mol / liter, more preferably 0.02 to 0.30 mol / liter.

Next, the desilvering process applicable to the present invention will be described. In the present invention, the desilvering step includes a bleach-fixing step, and includes a bleach-fixing step alone, a bleach-bleach-fixing step, a bleach-fixing step-fixing step, a bleaching step-bleach-fixing step-fixing step and the like. In the present invention, the bleach-fixing step alone is preferable in terms of simplifying and speeding up the desilvering step.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, it is described in US Pat. No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978). Compounds having a mercapto group or a disulfide bond, JP-B-45-8506 and JP-A-52-20832, 5
The thiourea compounds described in 3-32735, U.S. Pat. No. 3,706,561 and the like, or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or iodide (eg, ammonium iodide) or the like. If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
One or more kinds of inorganic acids having pH buffering ability such as citric acid, sodium citrate and tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

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

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide solubilizers such as thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing 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, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The bleach-fixing solution or fixing solution contains sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) and metas as preservatives. It preferably contains a sulfite ion-releasing compound such as bisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are converted to sulphite ion and the amount is about 0.0
The content is preferably 2 to 0.05 mol / liter, more preferably 0.04 to 0.40 mol / liter.

As a preservative for the bleach-fixing solution and the fixing solution,
Although sulfite is generally added, ascorbic acid, carbonyl bisulfite adduct, carbonyl compound, or the like may be added, and benzenesulfinic acids are also effective. Furthermore, a buffer for the bleach-fixing solution and the fixing solution,
A fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as necessary.

In the bleach-fixing solution of the present invention, the preferred p
The H region is 3 to 10, and more preferably 4 to 9.
Above all, when a high silver chloride emulsion is used in the light-sensitive material, the pH of the bleach-fixing solution is preferably 9.0 to 5.0, and 8.5.
-6.0 are more preferable, and 7.5-6.5 are the most preferable.

The replenishing amount of the bleach-fixing solution of the present invention is appropriately 20 to 500 ml, and particularly preferably 25 to 200 ml per 1 m ² of the light-sensitive material.
More preferably, it is 30 to 100 ml.

The processing temperature of the bleach-fixing solution applicable to the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. Treatment time is 10 seconds to 1 minute, preferably 20 seconds to 30
Seconds. The total treatment time of the washing and / or stabilizing step is 90 seconds or less, preferably 60 seconds or less.

Next, the color developer used in the present invention should be the one described in JP-A-4-145434, page 5, lower right column, line 16 to page 9, upper left column, line 20. You can The processing temperature of the color developer applicable to the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. Treatment time is 10 seconds to 1 minute, preferably 20 seconds to 30
Seconds. It is preferable that the replenishment amount is small, but the light-sensitive material 1
^{20 to} 600 ml per m ² is suitable, preferably 30 to 200 ml, more preferably 30 to 10 ml.
It is 0 ml.

In the present invention, after desilvering processing such as fixing or bleach-fixing, washing and / or stabilization processing is carried out. Regarding the washing process and the stabilizing process, JP-A-4-145434.
It is possible to use those described on page 10, lower right column, bottom line to page 11, lower right column, line 14.

The treating agent applicable to the present invention may be supplied as a concentrated liquid having a single or plural parts, or may be supplied as a dusting agent. Further, the liquid may be supplied in a used liquid state, or may be a combination of a concentrated liquid, a powder and a used liquid.

The material of the replenishing cartridge for filling the processing liquid used in the present invention may be any material such as paper, plastic, metal, etc., and particularly has an oxygen permeability coefficient of 50 ml / (m ² · atm · day). ) The following plastic materials are preferred. The oxygen permeability coefficient is "O
₂ Permeation of Plastic Container, Modern Packing "(O ₂ permeati
on of plastic container,
Modern Packing; J. Calya
n, 1968), December issue, pages 143-145.

Specific examples of preferable plastic materials include vinylidene chloride (PVDC) and nylon (N
Y), polyethylene (PE), polypropylene (P
P), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVAL), polyacrylonitrile (PAN),
Examples thereof include polyvinyl alcohol (PVA) and polyethylene terephthalate (PET).

In the present invention, PVDC, NY, PE, EVA, EVAL and PE are used for the purpose of reducing oxygen permeability.
The use of T is preferred. These materials may be used alone and may be shaped and used, or a method of forming a film and laminating a plurality of kinds (so-called composite film) may be used. Further, as the shape of the container, various types such as bottle type, cubic type, pillow type and the like can be used, but the present invention is a cubic type which is flexible and easy to handle and can be reduced in volume after use and Structures similar to are particularly preferred.

When used as a composite film, the structures shown below are particularly preferable, but not limited thereto.・ PE / EVAL / PE ・ PE / aluminum foil / PE ・ NY / PE / NY ・ NY / PE / EVAL ・ PE / NY / PE / EVAL / PE ・ PE / NY / PE / PE / PE / NY / PE ・PE / SiO ₂ film / PE ・ PE / PVDC / PE ・ PE / NY / aluminum foil / PE ・ PE / PP / aluminum foil / PE ・ NY / PE / PVDC / NY ・ NY / EVAL / PE / EVAL / NY ・NY / PE / EVAL / NY-NY / PE / PVDC / NY / EVAL / PE-PP / EVAL / PE-PP / EVAL / PP-NY / EVAL / PE-NY / Aluminum foil / PE-Paper / Aluminum foil / PE ・ Paper / PE / Aluminum foil / PE ・ PE / PVDC / NY / PE ・ NY / PE / Aluminum foil / PE ・ PET / EVAL / E · PET / aluminum foil / PE · PET / aluminum foil / PET / PE above thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns.
Further, the internal volume of the completed container is about 100 ml to 20 liter, preferably about 500 ml to 10 liter.

The container (cartridge) may have a cardboard or plastic outer box, or may be formed integrally with the outer box. Various processing liquids can be filled in the cartridge of the present invention. For example, color developing solution, black and white developing solution, bleaching solution, preparation solution, reversal solution, fixing solution,
Although a bleach-fixing solution, a stabilizing solution and the like can be mentioned, it is particularly preferable to use a color developing solution, a black-and-white developing solution, a fixing solution and a bleach-fixing solution for a cartridge having a low oxygen permeability coefficient.

The processing method of the present invention is carried out by using an automatic developing machine, preferably a cut-conveying type automatic developing machine. A known method can be used as a method for cutting the finished size of a photograph prior to the processing which is a feature of the present invention.
For example, a shear cut method, a rotary cut method, a push cut method, a punch cut method, etc. are used. The material of the blade of the cutter is high speed steel or cemented carbide. The angle of the cutting edge is preferably 30 ° to 60 °.

Examples of the structure of the cutting portion include those described in JP-A-63-2693 and JP-A-63-287853. Cutting may be performed at any time before entering the first bath of processing, and the roll-shaped photosensitive material set may be first cut and exposed to light, or exposed as it is in a strip shape to enter the processing bath. You may cut just before.

In the present invention, the aerial time when the photosensitive material moves between the processing solutions, that is, the crossover time is 5
The time of not less than 2 seconds is preferable because the effect of the present invention becomes more remarkable, but the time of not less than 7 seconds is more preferable. However, if it is 15 seconds or more, the processing speed and other adverse effects occur, which is not preferable. From this point, 10 seconds or less is more preferable. If it is 5 seconds or less, the wall between the processing liquid tanks is structurally lowered, and the risk of liquid mixing increases. In particular, if the bleach-fixing solution is mixed in the color developing solution, the photographic properties are greatly deteriorated even in a small amount.

The preferable conveying speed of the light-sensitive material in the automatic processor of the present invention is preferably 1.2 m / min or more. More preferably, it is 1.8 m / min or more. If the conveying speed is high, the physical addition applied to the end surface cut in the automatic processor during the conveying becomes large, and the effect of the present invention becomes more remarkable. However, if the conveying speed is increased, the size of the automatic processor itself increases in order to maintain a predetermined processing time, and the advantage of miniaturization of the processor called minilab is impaired, so 3.0 m / min or less is preferable. It is more preferably m / min or less.

As the transporting means, a roller transporting type of transporting the photosensitive material from the photosensitive material supplying portion to the drying end portion by means of a roller brings about a remarkable effect of the present invention. A guide for guiding the photosensitive material to the next roller may be provided between the rollers. It is preferable that the rollers in the crossover section have a squeeze function of suppressing the carry-in of the treatment liquid from the previous bath to the next bath. Resin, rubber or the like can be used as the material of the transport roller. In the case of opposing rollers having a structure sandwiching a photosensitive material, it is preferable to use a soft material such as resin on one side and rubber on the other side. Besides the flat roller shape, a crown roller or a warped roller may be used.

In the present invention, it is preferable that the stirring of each treatment liquid is strengthened as much as possible so that the effects of the present invention can be more effectively exhibited. Specific methods for strengthening stirring are disclosed in JP-A-62-183460 and JP-A-62-183.
No. 461, that is, a color negative film processor FP-56 manufactured by Fuji Photo Film Co., Ltd.
No. 0B, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, a method in which a stirring effect is increased by using a rotating means disclosed in JP-A-62-183461, and further, a method is provided in the solution. Examples include a method of moving the light-sensitive material while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of causing jetting of the processing liquid to collide is most preferable, and it is preferable to adopt this method for all processing tanks.

In particular, in processing with a processing solution having fixing ability, 15
The effect of the present invention is greatly improved by making the jets collide within seconds. More preferably within 10 seconds, even more preferably 5
Within seconds. It is better to circulate the entire processing liquid in order to make the liquid temperature uniform. The total circulation flow rate is 0.2 to 5 liters per minute, preferably 0.5 to 4 liters per 1 liter of tank volume for each processing tank, but bleaching, bleach-fixing,
In each desilvering step such as fixing, the circulation flow rate is preferably relatively high, and the preferable range is 1.5 to 4 liters.

It is preferable to carry out so-called evaporation correction by supplying water corresponding to the evaporation of the processing liquid to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed to monitor. A method of calculating the evaporation amount of water in the water tank, calculating the evaporation amount of water in the bleaching tank from this evaporation amount, and replenishing the bleaching tank with water in proportion to this evaporation amount or Japanese Patent Application No. 2-46743. , Same 2
-47777, 2-47778, 2-4777.
The evaporation correction method using a liquid level sensor or an overflow sensor described in Nos. 9 and 2-117922 is preferable. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in No. 4, the amount of water added is calculated by a coefficient previously obtained based on the information on the operating time, stop time and temperature control time of the automatic processor.

Further, it is necessary to devise a method for reducing the amount of evaporation, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable opening ratio of the color developing solution is as described above, but it is preferable to reduce the opening area of other processing solutions as well. The exhaust fan is attached to prevent condensation during temperature control,
Preferred emissions, per minute 0.1 m ³ to 1 m ^3, a particularly preferred engine displacement, a 0.2m ³ ~0.4 m ^3.

The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. As the drying method, it is preferable to use a ceramic warm air heater, and the supply air volume is 4 m ³ per minute
20 m ³ are preferred, particularly 6 m ³ through 10m ³ preferred. The heating prevention thermostat of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached to the leeward or upwind side through the heat radiation fins or the heat transfer portion. The drying temperature is preferably adjusted depending on the water content of the light-sensitive material to be processed, and is optimally 45 to 55 ° C for a 35 mm wide film and 55 to 65 ° C for a brownie film.

A replenishing pump is used for replenishing the processing liquid, but a bellows type replenishing pump is preferable. Also,
As a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

Although various parts materials are used in the automatic processor, preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include "Noryl" manufactured by GE Plastics Co., Ltd., and examples of the modified PPE include "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd. and "Yupiace" manufactured by Mitsubishi Gas Chemical Company. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers.

As the material of the roller of the processing section, resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable. Further, these materials can be used for other processing liquid contact portions. PE resin is also preferable as a material for the replenishment tank by blow molding. The processing parts, gears, sprockets, bearings, etc. are made of PA (polyamide), PBT (polybutylene terephthalate), UH.
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (whole aromatic polyester resin, liquid crystal polymer) are suitable.

PA resin is 66 nylon or 12 nylon, 6
Polyamide resins such as nylon that contain glass fibers or carbon fibers are strong against swelling by the treatment liquid,
It can be used. Also, high molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. Unreinforced products are suitable for UHMPE resin, such as "LUBMA" and "HIZEX Million" manufactured by Mitsui Petrochemical Co., Ltd., "New Light" manufactured by Shin Kogyo Co., Ltd.,
Asahi Kasei Co., Ltd. "Sunfine" and the like are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000.

The PPS resin is preferably reinforced with glass fiber or carbon fiber. Examples of the LPC resin include ICI Japan Co., Ltd. “Victorex”, Sumitomo Chemical Co., Ltd. “Econol”, Nippon Oil Co., Ltd. “Zyder”, Polyplastics Co., Ltd. “Vectra” and the like. As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicone resin, or a foamed urethane resin is suitable. Examples of the urethane foam resin include "Rubicel" manufactured by Toyo Polymer Co., Ltd.

EPDM is used as a rubber material such as a pipe joint, an agitation jet pipe joint, and a sealing material.
Rubber, silicone rubber, viton rubber and the like are preferable. The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds. Next, a silver halide photosensitive material using a support in which both sides of a base paper are coated with polyolefin will be described.

In the present invention, this support base paper preferably contains 0.05% by weight or more, more preferably 0.05 to 2.0% by weight, and particularly preferably 0.3 to 1.5% by weight, based on the absolute dry weight of pulp in paper. By containing at least one of the above, it is possible to achieve improvement of edge stains when treated with the treatment liquid. As the alkyl ketene dimer, any of the compounds known in this field can be used, but preferably those disclosed in JP-A-51-132822, Tappi Vol.39 No. 1 (1956), etc., It is preferable that the alkyl group has 8 to 30 carbon atoms. Among them, a compound having a structure represented by (Chemical Formula 10) is particularly preferable.

[0068]

[Chemical 10]

(Here, R ² is an alkyl group, preferably having 10 to 25 carbon atoms. For example, hexadecyl, octadecyl, eicosyl, docosyl, etc.), for example, Akobel 12, Hacon W, Hacon 602 (Dick Hercules Company), Saison H20 (Kao), SPK-903 (Arakawa Kagaku), and the like. Other additives for the support are preferably 0.1% by weight or more, more preferably 0.1 to 3% by weight, and particularly preferably 0.5 to 2% by weight or higher fatty acid salt or 0.1% by weight or more, preferably 0.1 to 2% by weight. , Particularly preferably 0.3 to
0.5% by weight or more of alkenylsuccinic anhydride or 0.01% by weight or more, preferably 0.01 to 1% by weight, particularly preferably
0.1 to 0.7% by weight of epoxidized higher fatty acid amide and the like can be used as a paper quality improving agent.

These base paper additives may be used in two or more kinds or in four kinds.
You may use together all the seeds. As the epoxidized higher fatty acid amide, any of the compounds known in the art can be used. In particular, a compound having a structure represented by (Chemical Formula 11) is preferable.

[0071]

[Chemical 11]

(Wherein R ¹ is a substituent such as an alkyl group, n is a positive integer, and X is an anion). n is preferably 2 to 10, more preferably 2 to 6. Examples of (Chemical Formula 11) include NS-715 (manufactured by Modern Chemical). As the higher fatty acid salt, any of the compounds known in this field can be used. In particular, alkali metal salts of saturated fatty acids (eg, sodium or potassium salts of hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, docosanoic acid, etc.) can be mentioned.

As the alkenyl succinic anhydride, any of the compounds known in the art can be used.
Compounds having the structure shown in 2) are preferred.

[0074]

[Chemical 12]

(Wherein R ³ is a substituent such as an alkyl group,
R ⁴ represents a divalent group such as an alkynyl group). Examples are Size Pine SA-850 and Size Pine SA-
810 (manufactured by Arakawa Chemical), RS-168E (manufactured by Sanyo Kasei)
And so on. These additives can be added by means such as mixing with pulp during papermaking of the base paper.

The base paper used in the present invention is NBKP or LB.
Although wood pulp such as KP, NBSP and LBSP is mainly used for paper making, it is also possible to mix synthetic fibers such as vinylon or synthetic pulp such as polyethylene. Considering the formation and the suitability for papermaking, 2
00-350 CSF is preferred. Further, in the present invention, in addition to the above additives, fillers such as clay, talc, calcium carbonate, urea resin fine particles, sizing agents such as rosin and paraffin wax, paper strength agents such as polyacrylamide, sulfuric acid bands, cationic polymers, etc. The fixing agent may be added if necessary.

Further, it is preferable to subject the film-forming polymer such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and polyvinyl alcohol modified product to surface size treatment, and polyvinyl alcohol or polyvinyl alcohol modified product is particularly preferred. Examples of the polyvinyl alcohol-modified product include a carboxy-modified product, a silanol-modified product, and a copolymer with acrylamide. The coating amount of the covering polymer is 0.1 to 5.0
It is g / m ² , preferably 0.5 to 3.0 g / m ² . In addition, if necessary, an antistatic agent, an optical brightener, a pigment, an antifoaming agent, a compound having a cation, etc. may be surface-sized in combination with the coating forming polymer.

As the equipment for making paper used in the present invention, an ordinary Fourdrinier paper machine can be used, and it is preferable that a calender is provided before winding the paper machine and before surface size. Paper basis weight of the water-resistant support of the present invention
The thickness is 60 g / m ² to 230 g / m ² and 55 μ to 230 μ, respectively.

Examples of the polyolefin resin used for coating both sides of the base paper include homopolymers of α-olefins such as polyethylene and polypropylene, and mixtures of these various polymers. Particularly preferred polyolefins are high density polyethylene, low density polyethylene and mixtures thereof. These polyolefins are usually coated on both sides of the base paper by an extrusion coating method, and therefore, the molecular weight thereof is not particularly limited as long as it can be extrusion coated, but the molecular weight is usually in the range of 10 ⁴ to 10 ⁶ . Certain polyolefins are used.

The thickness of the polyolefin coating layer is not particularly limited and can be determined according to the thickness of the polyolefin coating layer of the conventional photographic paper support, but usually 10 to
50 μm is preferred. The front surface, that is, the polyolefin coating layer on the side on which the photographic emulsion is coated, preferably contains a white pigment, and the type and amount of the white pigment are appropriately selected from known ones. be able to. Further, known additives such as a fluorescent whitening agent and an antioxidant may be added.

Further, the polyolefin coating layer on the back surface may be composed of only the above-mentioned polyolefin resin, but a coloring pigment, a white pigment or the like may be added, and the same addition as the polyolefin coating layer on the front surface is added. It is also possible to adopt a configuration in which an agent is added. As the equipment for extrusion coating when extrusion-coating the polyolefin, a usual polyolefin extruder and laminator are used.

In order to provide a silver halide emulsion layer on the polyolefin coating layer, the surface of the polyolefin coating layer is preferably subjected to corona discharge treatment, glow discharge treatment, flame treatment, etc., and if necessary, an undercoat layer or antihalation. The silver halide emulsion may be coated on the layer.

Next, the color photographic light-sensitive material used in the present invention will be described in detail. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are , The following patent publications, in particular European patent EP 0,355,660A2
Those described in Japanese Patent Application No. 1-107011 are preferably used.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

The silver halide emulsion used in the present invention is
It is preferable to have at least one emulsion layer containing silver halide grains of which silver chloride is 90 mol% or more.
An emulsion in which 95 to 99.9 mol% or more, and more preferably 98 to 99.9 mol% or more of silver chloride is preferably used, and chlorobromide in which all layers are composed of 98 to 99.9 mol% or more of silver chloride A silver emulsion is particularly preferable.

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in 33144, European Patent EP 0,333,185A2
3-Hydroxypyridine cyan couplers (especially couplers (42) listed as specific examples, which have been converted into 2-equivalent by attaching a chlorine-eliminating group to couplers (6) and (9)) Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image, etc.
A dye decolorizable by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane).

Further, 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, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically active and substantially colorless compound may be used simultaneously or alone. For example, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage after processing.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

In the present invention, the swelling degree of the photographic layer of the silver halide color light-sensitive material is 1.2 to 3.0,
It is particularly preferable in that the adhesion of the color light-sensitive material after processing is improved. The lubricity of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer. More preferably, it is 1.3 to 2.7.

The photographic layer referred to herein means a laminated hydrophilic colloid group layer containing at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can

As gelatin, lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

As the gelatin-graft polymer, a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination.

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

Examples of the color light-sensitive material used in the present invention include color papers, color reversal papers, direct positive color light-sensitive materials, and other light-sensitive materials having a reflective support. A color sensitive material for printing such as color paper is preferable. The support used in the light-sensitive material according to the present invention may be a support provided on a support having a silver halide emulsion layer on which a white polyester support or a layer containing a white pigment is provided for a display. You may use. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

Example 1 (Preparation of support base paper) 50% by weight of hardwood bleached kraft pulp (LBKP) and 50% by weight of softwood bleached sulfite pulp (NBSP) were mixed and beaten to 310 ml of Canadian Standard Freeness, As shown in the following and Table A, the raw materials for the support were prepared by internally mixing. The unit is% by weight in dry pulp display.

Pulp (LBKP / NBSP = 1/1) 100 Fluorescent whitening agent 0.15 Blue dye 0.00005 Anionic polyacrylamide (manufactured by Hamano Industries / Polyacron ST-13) 1.5 Polyamine polyamide epichlorohydrin (manufactured by Dikhhercules / Epinox P130) 0.25 Alkyl ketene dimer (listed in Table A) Listed in Table A Fatty acid soap Listed in Table A Bansulfate Soil Listed in Table A

[0106]

[Table 6]

Each of the above paper materials was made into paper, and carboxyl-modified polyvinyl alcohol 1.0 g / m ² ,
The thickness was adjusted with a calender coated with 1.0 g / m ² of calcium chloride, and the basis weight of 170 g / m ² and 150 μm were used as the base support paper. (Preparation of support) Next, regarding this support base paper,
A laminator was used to laminate polyethylene containing 10% by weight of titanium oxide on the front surface and 28 g / m ^{2 of} polyethylene on the back surface, respectively, to obtain a support. (Preparation of Light-Sensitive Material) Each of the supports using the above-mentioned support base papers was subjected to corona discharge treatment on the surface of polyethylene and then coated with the following silver halide emulsion layer to prepare a light-sensitive material. Support base paper ,,,
Photosensitive materials 101, 102, 103, 104 and 105 were used.

Preparation of First Layer Coating Solution Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-
7) 0.7 g of ethyl acetate 27.2 cc and solvent (S
olv-3) and (Solv-7) 4.1 g each
10% gelatin aqueous solution containing 10% sodium dodecylbenzene sulfonate 8cc 1
Emulsified dispersion A was prepared by emulsifying and dispersing in 85 cc. On the other hand, silver chlorobromide emulsion A (cube, average grain size 0.88
3: 7 mixture of large size emulsion (μm) and small size emulsion (0.70 μm) (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and silver bromide (0.3 mol% was locally contained in a part of the grain surface) was prepared in each size emulsion). In this emulsion, the blue-sensitizing dyes A and B shown below were 2.0 × 10 ⁻⁴ mol per mol of silver for the large-sized emulsion A, and for the small-sized emulsion A, respectively.
2.5 × 10 ⁻⁴ mol of each is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

Further, Cpd-10 and Cpd-11 are provided in each layer.
The total amount is 25.0 mg / m ² and 50.0 mg / m ² , respectively.
It was added so as to be m ² .

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0112]

[Chemical 13]

(2.0 × 10 ⁻⁴ mol for each large-sized emulsion A and 2.5 × 10 ⁻⁴ mol for each small-sized emulsion A per mol of silver halide)

[0114]

[Chemical 14]

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion B and 5.6 × 10 ⁻⁴ mol for small size emulsion B), and

[0116]

[Chemical 15]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion B, and 1.0 × 10 ^-5 mol for small size emulsion B)

[0118]

[Chemical 16]

(0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide)

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.

[0121]

[Chemical 17]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 × 10 ^-5 moles, 7.7 × 10 ^-4 moles per mole,
2.5 × 10 ⁻⁴ mol was added.

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

Further, the following dyes (in parentheses represent the coating amount) were added to the emulsion layer to prevent irradiation.

[0125]

[Chemical 18]

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

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) The silver chlorobromide emulsion A 0.30 gelatin 1.22 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-1) 0.19 solvent ( Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second Layer (Color Mixing Prevention Layer) Gelatin 0.64 Color mixing inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size 0.55 μm and small size emulsion with 0.39 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and in each size emulsion 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.12 Gelatin 1.28 Magenta coupler ( ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 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 1.41 Ultraviolet Absorber (UV-1) 0.47 Color Mixing Inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion with average grain size 0.58 μm and small size emulsion with 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution was 0.09 and 0.11, and in each size emulsion 0.6 mol% of AgBr was locally contained in a part of the grain surface.) 0.23 Gelatin 1.04 Cyan coupler ( ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorbing Agent (UV-1) 0.16 Color Mixing Inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh Layer (Protective Layer) Gelatin 1.10 Polyvinyl alcohol acryl-modified copolymer (Degree of modification 17%) 0.17 Liquid paraffin 0.03

[0135]

[Chemical 19]

[0136]

[Chemical 20]

[0137]

[Chemical 21]

[0138]

[Chemical formula 22]

[0139]

[Chemical formula 23]

[0140]

[Chemical formula 24]

Photosensitive materials 101 to 1 prepared as described above
No. 05 was processed into a roll having a width of 11.7 cm and a length of 30 m, and the PP-401B type color paper automatic developing machine manufactured by Fuji Photo Film Co., Ltd. was remodeled and treated with the following processing steps and processing solutions. The cutting method of the photosensitive material of this modified machine is to expose and cut the roll-shaped photosensitive material at 8.25 cm intervals under the control of the pulse motor, and cut it to a size called 11.7 × 8.25 cm service size, and then cut it. The obtained light-sensitive material enters the color developing solution. In addition, the cutter part is a shear cutter type, the material of the blade is high speed steel and the angle of the blade edge is 45 °. Moreover, in order to simulate the deterioration of the sharpness of the blade in the market, the experiment was performed after cutting 500,000 times in advance. This corresponds to the number of times of use for about 2 years with an average throughput.

Treatment process Temperature Time Color development 38 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Stability (1) 35 ℃ 30 seconds Stability (2) 35 ℃ 30 seconds Stability (3) 35 ℃ 30 seconds Dry 80 ℃ 60 seconds

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] Water 800 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 0.8 ml Lithium sulfate (anhydrous) 2.7 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium bromide 0.03 g Diethylhydroxylamine 4.6 g Potassium carbonate 27 g Sodium sulfite 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 4.5 g Fluorescent brightening Agent (4,4'-diaminostilbene type) 2.0 g Water added 1000 ml pH (added potassium hydroxide) 10.25

[Bleach-fixing solution A] [Tank solution] Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 17 g Ethylenediaminetetraacetic acid ferric ammonium monohydrate 0.16 mol Glacial acetic acid 9 g Water was added 1000 Milliliter pH (25 ℃) See Table 7

[0145] [Stabilizing Solution] (tank solution and replenisher are the same) ortho-phenylphenol _{0.15g ZnSO 4 · 7H 2 O 0.2} g bismuth chloride 0.5 g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1 -Diphosphonic acid (60% solution) 3.8 g Ethylenediaminetetraacetic acid 2.0 g Optical brightener (Tinopearl SFP Ciba Geigy) 2.0 g Ammonia water or 50% sulfuric acid is added to pH 7.8 and water is adjusted to 1 liter.

Then 0.16 mol of ethylenediaminetetraacetic acid ferric ammonium monohydrate in the bleach-fixing solution A was added to ferric ammonium 0.16 of the compound I-1 of the general formula [I] of the present invention.
The bleach-fixing solution B was replaced with the bleaching-fixing solution B, and the bleaching-fixing solution C was replaced with the ferric ammonium salt of I-2 (0.16 mol). Edges of samples obtained by subjecting the light-sensitive materials 101 to 105 to automatic processing while changing the bleach-fixing solution to A to C with the above-mentioned automatic developing machine unexposed, and aged for 3 days at 80 ° C. and 70% RH after processing. The degree of dirt was checked. The evaluation method is the distance from the edge of the side of the sample (11.7 cm × 8.2 cm) cut in the automatic processor perpendicular to the transport direction to the point where the processing solution penetrates deepest (liquid penetration distance). ) Was measured.

The results are shown in Table B.

[0148]

[Table 7]

As described above, according to the method of the present invention,
When the bleach-fixing solution containing the iron complex salt of the compound of the general formula (I) is used, the edge stain is remarkably improved. Further, the effect is further improved when the pH is within the preferred range of the present invention.

Example 2 The same experiment as in Example 1 was carried out by changing the conveying speed of the automatic processor as shown in Table C. The pH of the bleach-fixing solutions A to C was adjusted to 6.7 before use. The other treatment solutions used were the same as those used in Example 1. Similarly, the processed photosensitive material was aged at high temperature and high humidity in the same manner as in Example 1, and then the same measurement was performed to examine the liquid penetration distance. The results are shown in Table C.

[0151]

[Table 8]

As shown in Table C, when the bleach-fixing solution A is used, the edge stain is increased by increasing the conveying speed, but when the compound of the present invention is used, the edge stain is not increased at all.

Example 3 For the same light-sensitive materials 101 to 102 as in Example 1, the bleach-fix solution was changed as shown below and in Table D, and the same color developer as in Example 1 was used, instead of the stabilizing bath. The treatment was performed using a washing bath. [Bleaching and fixing solution 3A] Addition amount Water 400 ml Ammonium thiosulfate (700 g / l) 110 ml Ammonium sulfite 18 g Ethylenediaminetetraacetic acid ferric ammonium monohydrate As shown in Table D 9.0 g glacial acetic acid 1000 ml pH ( 25 ° C) 6.7

[Bleach-fixing solution 3B] Water 400 ml Ammonium thiosulfate (700 g / l) 110 ml Ammonium sulfite 18 g Ferric ammonium of compound I-1 Described in Table D 9.0 g glacial acetic acid Water 1000 ml pH ( 25 ° C) 6.7 pH was adjusted with acetic acid and ammonia.

At this time, the air time (crossover time) during which the photosensitive material moved between the baths of the automatic processor used in Example 1 was changed as shown in Table D. The sample of this experiment was also aged under high temperature and high humidity conditions, and then the liquid permeation distance was measured. The results are shown in Table D.

[0156]

[Table 9]

As shown in Table D, edge smearing is further reduced for the preferred crossover time of the present invention.
Further, when the concentration of the iron complex salt of the compound (I) of the present invention is within the preferable range, the edge stain is reduced.

[0158]

As described above, according to the embodiments of the present invention, the edge stains caused by the permeation of the processing liquid are greatly improved, especially when the development processing is performed by using the roller transport type automatic developing machine. be able to.

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Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on a paper support coated on both sides with a polyolefin is subjected to a color developing step and a bleach-fixing step using an automatic processor. In the processing method, the paper support contains at least one alkyl ketene dimer as a sizing agent, and prior to the development processing step, it is cut into a finished size of a photograph in an automatic processor, and then development processing is performed. A method for processing a silver halide color photographic light-sensitive material, characterized in that the bleach-fixing solution contains a ferric complex salt of the compound represented by formula (I). General formula (I) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group.
W represents a linking group represented by the following general formula (W). M ₁ ,
M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) In formula _{(W) - - (W 1} -Z) n -W 2 ( formula (W), W ₁ represents an alkylene group or a single bond.
W ₂ represents an alkylene group or -CO-. Z is a single bond,
It represents -O-, -S-, -CO-, or -N ( _Rw )-( _Rw represents a hydrogen atom or an alkyl group which may be substituted). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. ) 2. The method of processing a silver halide color photographic light-sensitive material as claimed in claim 1, wherein the speed of conveyance of the light-sensitive material in the automatic processor is 1.2 m / min to 3 m / min. 3. The aerial time between the color developing bath and the bleach-fixing bath in the automatic developing machine according to claim 1,
A method for processing a silver halide color photographic light-sensitive material, which is characterized by being 15 seconds.