JPH11271941A - Automatic developing machine for silver halide color photographic sensitive material and processing method therefore - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize an automatic developing machine and a processing method for a silver halide photographic sensitive material by which the processing stability of bleaching liquid is improved, to put it concretely, the bleaching liquid is not deposited to a processing tank and the like and it is not deteriorated caused by contamination firstly, bleaching performance becomes excellent and processing can be quickly executed secondly, fogging density is reduced and irregularity is prevented from occurring thirdly and the automatic developing machine can be made compact lastly. SOLUTION: This automatic developing machine for a silver halide photographic sensitive material is provided with at least three processes being the developing process, the bleaching process and the fixing process. Besides, it is provided with a process that the bleaching liquid C is applied. Then, the film surface pH of the photosensitive material P is >=7.0 before it arrives at the applying process and the weight thereof is decreased to 3.0 to 150 g/m<2> after it is dried.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automatic processor for processing silver halide color photographic light-sensitive materials (hereinafter also referred to simply as "light-sensitive materials" or "light-sensitive materials" for simplicity). And, for the sake of simplicity, may be referred to as an automatic developing machine, a self-developing machine or a developing machine) and a processing method for a silver halide color photographic light-sensitive material. The present invention relates to an automatic processor for a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material, in which the generation of tar is less likely to occur and the tar generated in the processing tank is not stained.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is transported by, for example, a roller transport mechanism and immersed in a sufficient amount of processing solution stored in a processing tank such as a developing tank, a bleaching tank, or a fixing tank for a predetermined time. Let it be processed. Due to the processing of this silver halide color photographic light-sensitive material, fatigue deterioration due to consumption of the effective components in the processing solution stored in the processing tank, and unnecessary components because the components of all baths are brought in by the photographic material after the bleaching tank. The bath components cause dilution or deterioration of the active ingredients.
Particularly, in the bleaching solution, unnecessary developing agent components accumulate because the developing solution components are mixed in, and the bleaching agent is unnecessarily consumed by a redox reaction with the bleaching agent, and the developing agent component itself is It becomes tar and causes deposition on the processing tank wall and adhesion stains on the photosensitive material surface. Furthermore, there is a problem that the pH of the bleaching solution rises due to the introduction of an alkaline component, and the bleaching ability decreases. Generally, a certain amount of fresh solution is replenished to compensate for deterioration due to fatigue.However, in order to reduce the amount of developer solution carried in the bleaching solution, it is necessary to increase the amount of replenishment or replenish it. This is achieved by increasing the concentration of the bleaching agent in the liquid, but the amount of waste liquid increases and the amount of solid components in the waste liquid increases. There is also a machine equipped with a mechanism for aerating the bleaching solution in order to oxidize and recover the bleaching agent reduced and consumed by the developing agent. However, it is not preferable because it complicates the apparatus and promotes the generation of tar. Further, the mixing of alkali has been solved by adding a large amount of a buffer agent to the bleaching solution, but this also causes the deterioration of the bleaching performance, so that the bleaching agent needs to be further concentrated.

In order to solve such a problem, a silver halide photographic method is disclosed in Japanese Patent Application Laid-Open No. 2-99945 as a method in which a small amount of processing solution is used and a tired solution can always be replaced with a new solution. An application roller is arranged on the photosensitive material transport path, a supply roller for supplying the processing liquid to the application roller is provided, a processing liquid reservoir is provided between the supply roller and the application roller, and the processing liquid is halogenated by rotating the application roller. There has been proposed a material which is applied and supplied to an image forming surface of a silver halide photographic material. Also, Japanese Patent Application Laid-Open No. 9-43
Japanese Patent Application Publication No. 814 proposes a method of supplying a developing solution via a gas phase.

[0004]

By the way, in any case, most of the description is actually about a color developing solution, and does not take into account the harmful effects brought in from a prebath such as a bleaching step. As described in JP-A-2-99945, in the roller coating method using a color developing solution, the photosensitive material is conveyed in a dry state, so that the coating tends to be uniform. However, in systems where the color development step is performed in advance, such as in the bleaching step, the photosensitive material introduces the components of the pre-bath, and the penetration or replacement of the liquid on the coating surface is not performed well, which raises a new problem. became. In particular, in a system in which a highly alkaline solution such as a color developing solution is converted into a solution having a relatively low pH such as a bleaching solution, fog density due to uneven coating is uneven, which is likely to occur. Also, Japanese Patent Application Laid-Open No. 9-4
There is no particular problem with the color developing solution even in the method using a gas phase as described in No. 3814, but it is unnecessary due to the reaction between the bleaching agent and the color developing agent which is a component brought in from the previous bath such as a bleaching solution. It does not work well in a system where a serious reaction (fogging) occurs.

[0005] The present invention has been made in view of such circumstances, and an object of the present invention is to firstly improve the processing stability of the bleaching solution, and specifically, to the processing tank or the like. No precipitation, no deterioration due to liquid contamination, second, excellent bleaching performance and rapid processing, third, reduction of fog density and occurrence of unevenness, fourth, An object of the present invention is to provide an automatic developing machine for a silver halide color photographic light-sensitive material and a processing method of the silver halide color photographic light-sensitive material, which can make the automatic developing machine compact.

[0006]

The above object of the present invention has been attained by the following constitutions.

[0007] 1. A developing step, a bleaching step, and an automatic processor for a silver halide color photographic light-sensitive material having at least three steps of a fixing step, comprising a step of applying a bleaching solution,
The film surface pH of the photosensitive material immediately before reaching the coating step is 7.0 or more, and the weight loss after drying of the photosensitive material immediately before reaching the coating step is 3.0 to 150 g / m ^2. An automatic developing machine for silver halide color photographic light-sensitive materials, characterized in that:

[0008] 2. 2. The automatic developing machine for silver halide color photographic light-sensitive materials according to 1, wherein the supply outlet of the coating solution in the step of applying the bleaching solution is a slit.

3. 3. The automatic developing machine for silver halide color photographic light-sensitive materials according to 1 or 2, further comprising a heating means for directly heating the silver halide color photographic light-sensitive materials.

[0010] 4. 4. The automatic developing machine for a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, further comprising a heating means for heating the silver halide color photographic light-sensitive material to 45 ° C. or higher.

5. Halogen wherein the total processing solution supply amount from the supply outlet of the coating liquid in the step of applying a bleaching solution, the photosensitive material 1m claimed 1-4 any one of and sets the ² per 10ml~250ml Automatic developing machine for silver halide color photographic light-sensitive materials.

6. The bleaching solution has the following general formula (A):
Second compound of (I), (II) or (III)
1 characterized by containing at least one of iron complex salts
6. The automatic developing machine for a silver halide color photographic light-sensitive material according to any one of items 1 to 5,

[0013]

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Wherein A ₁ , A ₂ , A ₃ and A ₄ may be the same or different, and are represented by —CH ₂ OH, —COO
Represent M or -PO ₃ M ₁ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. ]

[0015]

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Wherein A ¹ , A ² , A ³ and A ⁴ each represent —CH ₂ OH, —PO ₃ (M ⁰ ) ₂ or —COOM, and may be the same or different. Good. M
Represents a cation. X ¹ is an alkylene group having 2 to 6 carbon atoms ^{- (B 1 O) n-} B 2 - represent. n represents an integer of 1 to 8, and B ¹ and B ² may be the same or different. B ¹ and B ² each have 1 to 5 carbon atoms
Represents an alkylene group. ]

[0017]

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Wherein n ₁ represents 1 or 2, and A represents —COOM ³ , —OH, —NH ₂ or —PO ₃ (M ³ ) ₂
Represents M ¹ , M ² , and M ³ represent a hydrogen ion, an ammonium ion, a sodium ion, a potassium ion,
Represents lithium ion or organic ammonium ion. ]

[0019]

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[Wherein A ⁵ and A ⁶ each represent —COOM
_{^{7, -PO 3 (M 7)}} 2, -SO 3 M 7, a hydroxyl group or a mercapto group, may each be the same or different. M ⁶ and M ⁷ each represent a cation. R represents a hydrogen atom, an aliphatic group or an aromatic group;
₁ and X ₂ each represent a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of an aliphatic group and an aromatic group. ] 7. The automatic developing machine for silver halide color photographic light-sensitive materials according to any one of claims 1 to 6, wherein the bleaching solution contains at least one compound represented by the following general formula (B).

General formula (B) A (-COOM) _{n wherein} A represents an n-valent organic group, n represents an integer of 1 to 6, and M represents an ammonium, an alkali metal or a hydrogen atom. ] 8. An automatic developing machine for a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step, and a fixing step, comprising a processing liquid supply means for supplying a bleaching liquid via a gas phase, before the bleaching step Has a pH of 7.0 or more and a weight loss of 3.0 to 15 after drying.
An automatic developing machine for a silver halide color photographic light-sensitive material, wherein the automatic developing machine has a constitution of 0 g / m ² .

9. 9. The automatic developing machine for a silver halide color photographic light-sensitive material according to claim 8, further comprising a heating means for directly heating the silver halide color photographic light-sensitive material.

10. 10. The automatic developing machine for silver halide color photographic light-sensitive materials according to 8 or 9, further comprising heating means for heating the silver halide color photographic light-sensitive material to 45 ° C. or higher.

11. The amount of the processing solution supplied from the liquid supply means of the bleaching solution via the gas phase is set to 10 ml to 250 ml per 1 m ^{2 of the} photosensitive material.
The automatic developing machine for a silver halide color photographic light-sensitive material according to any one of claims 10 to 10.

12. The bleaching solution has the general formula (A),
Second compound of (I), (II) or (III)
9 characterized by containing at least one of iron complex salts
12. The automatic processor for a silver halide color photographic light-sensitive material according to any one of items 1 to 11.

13. The automatic developing machine for a silver halide color photographic light-sensitive material according to any one of claims 9 to 12, wherein the bleaching solution contains at least one compound represented by the general formula (B).

14. In a method for processing a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step, and a fixing step, a bleaching solution is supplied by a coating means, and the pH of the film surface of the light-sensitive material before reaching the coating step is 7. 0
And the weight loss after drying is 3.0 to 150 g /
The method for processing a silver halide color photographic material, which is a m ^2.

15. 15. The method for processing a silver halide color photographic light-sensitive material according to claim 14, wherein the silver halide color photographic light-sensitive material is directly heated.

16. 14 or 1 wherein the silver halide color photographic material is heated to 45 ° C. or higher.
5. The method for processing a silver halide color photographic light-sensitive material according to item 5.

17. The total processing liquid supply from the supply outlet of the coating liquid in the step of applying the bleaching solution, a halogenated according to any one of 14 to 16, characterized in that said photosensitive material 1 m ² per 10ml~250ml A processing method for silver color photographic light-sensitive materials.

18. The bleaching solution has the following general formula (A):
Second compound of (I), (II) or (III)
1 characterized by containing at least one of iron complex salts
18. The method for processing a silver halide color photographic light-sensitive material according to any one of 4 to 17.

19. 19. The method for processing a silver halide color photographic light-sensitive material according to any one of 14 to 18, wherein the bleaching solution contains at least one compound represented by the following general formula (B).

20. In a method for processing a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step, and a fixing step, a bleaching solution is supplied via a gas phase;
The film surface pH of the light-sensitive material before reaching the bleaching step is 7.0 or more, and the weight loss after drying is 3.0 to 150 g / m ^2.
A method for processing a silver halide color photographic light-sensitive material, characterized in that:

21. 2. A heating means for directly heating the silver halide color photographic material.
0. The method for processing a silver halide color photographic light-sensitive material according to item 0.

22. 22. The method for processing a silver halide color photographic light-sensitive material according to 20 or 21, further comprising heating means for heating the silver halide color photographic light-sensitive material to 45 ° C. or higher.

23. The amount of the bleaching solution supplied via the gas phase is 10 ml to 250 ml per 1 m ^{2 of the} photosensitive material.
23. The method for processing a silver halide color photographic light-sensitive material according to any one of 20 to 22, wherein

24. The bleaching solution has the following general formula (A):
Second compound of (I), (II) or (III)
2 characterized by containing at least one of iron complex salts
24. The method for processing a silver halide color photographic light-sensitive material according to any one of 0 to 23.

25. 25. The method for processing a silver halide color photographic light-sensitive material according to any one of 20 to 24, wherein the bleaching solution contains at least one compound represented by the following general formula (B).

Hereinafter, the present invention will be described in detail.

[Silver halide photographic light-sensitive material] As an example of the silver halide photographic light-sensitive material processed by the automatic processor for silver halide photographic light-sensitive material of the present invention, a silver halide color photographic light-sensitive material containing a silver chloride emulsion. And silver halide color photographic light-sensitive materials containing silver iodobromide or silver bromide emulsion.

[Processing Step] The structure of the processing step of the present invention is as follows.
It is essential to have at least three steps of a developing step, a bleaching step, and a fixing step, and preferably comprises the following specific processing steps. Of these, the bleaching step is essential to be constituted by a coating step by a coating means, but other development steps and the like may be performed by a coating means.

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → first Stable → Second stable (5) Color development → Bleaching → Bleaching and fixing → Fixing → First stable → Second stable (6) Color developing → Bleaching and fixing → Stable (7) Color developing → Bleaching → First fixing → Second Fixing → Stable (8) Color development → Bleaching → Fixing → First stable → Second stable → Third stable [Film surface pH] The photosensitive material before the step of applying the bleaching solution of the present invention has a film surface pH. It is indispensable for the effect of the invention to be 7.0 or more, and more preferably p
H is 8.0 or more, more preferably 9.0 or more.

In order to measure the pH of the film surface, the photosensitive material immediately before reaching the bleaching step was first taken out, excess liquid on the surface was removed by pressing it with a silicone rubber spatula, and then the thermostat kept at 65 ° C. Let dry for 30 minutes. Thereafter, a commercially available electrode for surface measurement (flat type) is pressed against the surface of the light-sensitive material, 100 μl of water is dropped into a gap between the light-sensitive material and the electrode, and measurement is performed after waiting for 1 minute until the numerical value is stabilized.

[Weight of photosensitive material after drying] Before the step of applying the bleaching solution of the present invention, the weight of the photosensitive material before and after drying can be reduced in the range of 3.0 to 150 g / m ^2. Indispensable for achieving the effects of the invention, more preferably 1
0.0 to 100 g / m ² .

In the method for measuring the weight loss by drying, first, the light-sensitive material immediately before reaching the bleaching step is taken out and the weight is measured.
Thereafter, the photographic material is placed in a thermo machine maintained at 65 ° C. for 30 minutes and dried, and the weight is measured again. This is calculated as the weight loss per unit area.

[Coating means] The coating means in the present invention is means for applying and supplying a predetermined amount of a processing solution to the emulsion surface of a silver halide photographic light-sensitive material. The coating material is immersed in a tank filled with the processing solution. It does not include a method of infiltrating components into a photosensitive material by diffusion from a bulk liquid or a method of supplying a processing liquid via a gas phase.

As a specific application means, there is a method of applying a liquid through a member such as a roller, or a method of directly supplying a liquid such as curtain application. Air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnated coater, reverse roller coater, transfer roller coater, cartin coater, double roller coater, slide hopper coating, gravure Coater,
Examples include a kiss roll coater, a bead coater, a cast coater, a spray coater, a calendar coater, and an extrusion coater. In the effects of the present invention, particularly preferred systems include a squeeze coater, a gravure coater, an impregnated coater, a bead coater, and a blade coater.

The contact angle of the coating roller with the treatment liquid is preferably 45 ° or less, more preferably 20 ° to 40 °, which is preferable in that the supplied appropriate amount of the coating liquid becomes uniform on the coating roller. . The application roller is preferably a metal roller such as SUS, specifically, stainless steel (SUS
316L, SUS316, SUS304, SUS30
3), titanium (Ti), brass (Bs) and the like are preferable. In the case of a plastic roller or an elastic Teflon, an activator is coated so as to lower the contact angle. Also,
An application roller having a hydrophilic material is preferred. That is,
It is also preferable to laminate 6 nylon, N-methoxymethyl polyamide, polyurethane, polyacetal and the like. Preferably, the active agent to be coated is oriented on a hydrophobic roller to direct hydrophilic groups to the surface. Therefore, it is preferable to coat an amphoteric surfactant or an alkylamine ethylene oxide compound.

The contact angle between the coating roller and the treatment liquid was determined by using a plate sample obtained by the same material and the same forming method as the surface of the roller, "New Experimental Chemistry Course 18, Interface and Colloid", page 97 (October 1977). The contact angle is measured based on the droplet method according to the method of measuring contact angles described in Mar. 20, Maruzen. That is, a flat specimen having a mirror-finished smoothness is placed horizontally in a container filled with saturated vapor of a liquid to be measured, and a small amount of droplets are formed thereon using a syringe. The size of the droplet should be such that the contact diameter is about 3 mm or less (some reports indicate that the droplet volume should be 0.1 cm ³ or less). The contact angle is generally measured by a reading microscope equipped with a goniometer (magnification: about 20 times). Measurement accuracy is ±
It is 1 °, and if possible, it can be made ± 0.5 °.
Measure the left and right angles of the droplet, and if they differ significantly, discard the measurements from that droplet. The angle of the droplet is measured by adding an additional amount of the droplet or leaving the droplet for a while after the droplet is formed to check whether or not the angle has changed. In addition, measurement is performed at several different places on the same solid surface, and at least ten values are obtained to obtain an average value. The water used for the measurement shall be distilled water.

The shape of the liquid supply outlet is a slit formed in the axial direction of the coating roller, so that the contamination of the automatic developing machine member due to dripping of the coating liquid can be reduced. The processing liquid can be uniformly applied and supplied to the image forming surface of the photosensitive material. The preferred slit width is from 0.03 mm to 1.0 mm. If the width is too narrow, the uniformity is deteriorated, and if it is too large, liquid dripping occurs. More preferably, 0.05 to 0.5 mm, more preferably 0.10 to 0.5 mm
0.30 mm.

Further, since the liquid supply outlet can be made single, the single liquid supply outlet can reduce the contamination of the automatic developing machine member due to the dripping of the coating liquid and the like. The processing liquid can be uniformly applied and supplied to the image forming surface of the photographic material.

The total supply amount of the processing liquid from the liquid supply outlet to the coating roller is 10 ml to 250 m per 1 m ² of the photosensitive material.
l, the supply amount of the processing liquid is insufficient when the supply amount is smaller than the setting, and the supply is insufficient when the supply amount is larger than the setting. However, by setting the total supply amount of the processing liquid to 10 ml to 160 ml per 1 m ² , an appropriate amount can be obtained. The processing liquid can be applied and supplied, and the size of the automatic developing machine can be reduced. More preferably, the amount is 50 ml to 150 ml per 1 m ² , and it is preferable to supply a more appropriate amount of the processing liquid onto the coating roller. .

[Heating Means] The temperature of the photosensitive material heated by the heating means is preferably 45 ° C. or higher, more preferably 60 ° C.
The above is preferred. The temperature is preferably 95 ° C. or lower, particularly preferably 80 ° C. or lower, in view of the ripening resistance of the photosensitive material and the ease of processing control.

Examples of the heating means for heating the photosensitive material include a conductive heating means such as a heat drum and a hot belt for heating by conduction in contact with the photosensitive material, a convection heating means for heating by convection such as a drier, an infrared ray heating means and the like. Radiation heating means for heating by radiation such as high-frequency electromagnetic waves may be used.

In order to prevent the conductive heating means from being adversely affected, and to prevent the photosensitive material to be processed from having an adverse effect on the emulsion surface, the heat source to be heated is from the base side of the photosensitive material to be processed which is not coated with the emulsion. Preferably, they are in contact.

In the present invention, when the photographic material is heated before the processing solution is supplied to the emulsion side of the photographic material,
In order to reduce the influence of the difference in photosensitivity due to the temperature during exposure of the photosensitive material, it is preferable to heat the photosensitive material after the exposure of the photosensitive material is completed.

Further, it is preferable that the heating means has a heating control means for controlling the heating means to heat based on the presence information of the silver halide photographic material, because unnecessary heating can be prevented. This is to detect the presence of a silver halide photographic light-sensitive material at a predetermined position upstream of a heating section of a heating means in a transportation direction of the transportation means with a conveying means for conveying the silver halide photographic light-sensitive material at a predetermined conveyance speed. This can be achieved by having photosensitive material detecting means and controlling the heating control means based on the detection of the photosensitive material detecting means. The control in this case is performed immediately after the photosensitive material detecting means detects the presence of the silver halide photographic material at the predetermined position from the absence, or
Immediately after the photosensitive material detecting means detects the presence or absence of the silver halide photographic light-sensitive material at a predetermined position after a predetermined time has elapsed, or until the predetermined time has elapsed, the heating means performs a predetermined heating. Is preferred.

[Supplying means via gaseous phase] The processing liquid supply means of the processing apparatus of the present invention may be, for example, a processing liquid flying means for flying a processing liquid onto a photosensitive material via a gaseous phase, or a curtain coater. And a processing liquid application unit for applying a processing liquid to the photosensitive material via a gas phase. Examples of the processing liquid flying means for flying the processing liquid to the light-sensitive material via the gaseous phase include a means such as a spray bar that applies a sudden pressure to the processing liquid by compressed air or a solenoid to fly the processing liquid. Further, there is a method of injecting the processing liquid by pressurizing the processing liquid due to volume fluctuation by the piezoelectric element or bumping of a very small amount of liquid. More specifically, it causes volume fluctuation and bumping of a very small amount of liquid,
A driving element serving as a driving force of the flight of the liquid, a chamber that is a small processing liquid chamber in which the processing liquid is pressurized, an orifice that is an outlet of the pressurized processing liquid, and a liquid supply device in which the liquid is replenished, When the pressure is generated by the driving element, a sharp pressure is applied to the processing liquid in the chamber, and the processing liquid is ejected from the processing liquid supply port.

Specific means for supplying the processing liquid to the emulsion surface include vibration and bumping. From the viewpoint of durability of the processing liquid supply means, it is preferable to supply the processing liquid by vibration. In addition, as a method of generating vibration, it is preferable to use one that is deformed by electromechanical conversion means, and it is particularly preferable to use a piezo element.

Next, the material of the liquid contact portion will be described. The liquid contact portion according to the present invention is a member that constitutes a path from a tank in which the processing liquid is stored to be ejected by the supply device, and refers to a member that directly contacts the processing liquid. The contact angle of the processing solution to these members is 70 degrees or less, specifically, the entrance of the chamber of the supply device, the wall surface of the chamber,
It is a wall or the like that forms an orifice, and is a member that comes into contact with a pressurized liquid. Specific materials of these members are shown in the following groups A, B, and C. Preferably, in {Group A}, vinylidene chloride resin, vinyl chloride resin,
Epoxy resin, liquid crystal polyester, polyimide resin, polystyrene, polyethylene terephthalate, polyphenylene sulfide.
For glass ceramics, FOTFORM Glass, F
OTOFORM OPAL GLASS-Cerami
c, FOTOCREAM Glass-Ceramic
(Hora glass) is preferred. FOTFO for glass
RM Glass is preferred. In group C, SUS
316, nickel, tantalum, chromium, silicon, silicon dioxide are preferred.

In the present invention, the contact angle with the surface of the liquid contact portion is 70
Degree or less is preferable. This eliminates injection failure due to air bubble adhesion and improves injection stability. The contact angle to the surface of the liquid contact portion is more preferably 50 degrees or less and 10 degrees or more,
Particularly preferably, the angle is 35 degrees or less and 15 degrees or more. In order to prevent air bubbles from adhering, more preferably, the contact angle with the surface of the material forming the chamber is 70 degrees or less.

{Group A} Vinylidene chloride resin Vinyl chloride resin Epoxy resin Liquid crystal polyester ABS resin Phenol resin Polyimide resin Polyamide imide resin Melanin resin Acrylic resin Polyethylene Polypropylene Polyurethane triacetate Cellulose polystyrene Polyethylene terephthalate Polyphenylene sulfide {Group B} Ceramic glass ceramic C Group II SUS316 SUS306 Nickel Chromium Tantalum Silicon Silicon Dioxide Silicon Carbide [Bleaching Process] In this bleaching process, the bleaching agent is ferric iron of the compound represented by the general formula (A), (I), (II) or (III). A partial solution of a bleaching agent containing at least one complex salt and containing at least one ferric complex salt of a compound represented by formulas (A), (I), (II) and (III) By mixing immediately before being supplied to the silver photographic light-sensitive material, the storage stability of the liquid is improved, and specifically, there is no precipitation of the liquid, no oxidative deterioration of the liquid, and the mixing ratio of the two liquids varies. Is prevented.

Preferred specific examples of the compound represented by the general formula (A) are shown below, but the compound represented by the general formula (A) which can be used in the present invention is not limited thereto.

[0064]

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[0065]

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Among these, a particularly preferred compound is (A-10).

Preferred examples of the compound represented by formula (II) are shown below, but the compound represented by formula (II) which can be used in the present invention is not limited to these.

[0068]

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[0069]

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Of these, particularly preferred compounds are (I-1), (I-3), (I-5) and (I-15), and more preferred compounds are (I-1) and (I- 3).

The compound represented by the above general formula is described in Zh. O
bshch. Khim. , 49, 659 (1979),
Inorganic Chemistry, Vol.
7, 2405 (1968), Chem. Zresti,
32, 37 (1978); U.S. Pat. No. 3,158,635
And JP-A-5-303186.

Preferred examples of the processing solution for a silver halide photographic light-sensitive material having the bleaching ability of the present invention and the compound represented by the formula (II) used for processing the silver halide photographic light-sensitive material are described below. However, the compound represented by the general formula (II) that can be used in the present invention is not limited thereto.

[0073]

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Among these, particularly preferred compounds are (II-1), (II-2) and (II-3).

Preferred examples of the processing solution for a silver halide photographic light-sensitive material having the bleaching ability of the present invention and the compound represented by the formula (III) used for processing the silver halide photographic light-sensitive material are described below. However, the compound represented by the general formula (III) that can be used in the present invention is not limited thereto.

[0076]

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Usually, the bleaching agent is a sodium salt or
Used as ammonium salt and potassium salt.

Further, the bleaching solution preferably contains an organic acid compound represented by the following general formula (B).

Formula (B) A (—COOM) _{n wherein} A represents an n-valent organic group, n represents an integer of 1 to 6, M represents ammonium, an alkali metal (sodium,
Potassium, lithium, etc.) or a hydrogen atom. In the general formula (B), as the n-valent organic group represented by A, an alkylene group (for example, a methylene group, an ethylene group,
Trimethylene group, tetramethylene group, etc.), alkenylene group (eg, ethenylene group), alkynylene group (eg, ethinylene group), cycloalkylene group (eg, 1,4
-Cyclohexanediyl group, etc.), arylene group (eg, o-phenylene group, p-phenylene group, etc.), alkanetriyl etc. (eg, 1,2,3-propanetriyl group etc.), arenetriyl group (eg, 1, 2,3-benzenetriyl group).

The n-valent group represented by A is a substituent (eg, a hydroxy group, an alkyl group, a halogen atom, etc.)
(E.g., 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,2,
3-propanetriyl, methyl-p-phenylene, 1-
Hydroxy-2-chloroethylene, chloromethylene, chloroethenylene, etc.).

Preferred specific examples of the compound represented by the formula (B) are shown below, but the compounds represented by the formula (B) which can be used in the present invention are not limited thereto.

[0082]

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[0083]

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Among the above exemplified compounds, particularly preferred are the exemplified compounds (B-1), (B-2), (B-3),
(B-4), (B-5), (B-6), (B-13),
(B-14), (B-15) and (B-20), and particularly preferred are (B-1), (B-5) and (B-
6), (B-13), (B-14), and (B-20). Examples of the salt of the acid include an ammonium salt, a lithium salt, a sodium salt, and a potassium salt, and a sodium salt and a potassium salt are preferable from the viewpoint of storage stability. These organic acids or salts thereof can be used alone or in combination of two or more.

The bleaching solution may contain a rehalogenating agent. Known rehalogenating agents can be used, for example, ammonium bromide, potassium bromide, sodium bromide, potassium bromide, sodium chloride, ammonium chloride, potassium iodide, sodium iodide, ammonium iodide and the like. The compound of.

The ferric organic acid complex salt is preferably added in an amount of 0.1 mol to 2.0 mol per liter of the partial solution containing the bleaching agent, more preferably 0.15 mol to 2.0 mol. It is in the range of 1.5 mol / l.

The bleaching solution contains at least one of imidazole and derivatives thereof described in JP-A-64-295258, compounds represented by the general formulas [I]-[IX] described in the same specification and at least one of these exemplified compounds. By containing one kind, an effect can be obtained for quickness.

In addition to the above accelerators, JP-A-62-1234
Illustrative compounds described on pages 51 to 115 of JP-A-59-59, and exemplified compounds described on pages 22 to 25 of JP-A-63-17445, and JP-A-53-9563.
Compounds described in JP-A Nos. 0 and 53-28426 can be similarly used.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less.

The bleaching solution of the present invention may contain at least one compound selected from compounds represented by the following general formula [I], [SI] or [SII], or water-soluble siloxane compounds. preferable.

[0091]

Embedded image

In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom, preferably having 4 to 12 carbon atoms, more preferably 6 to 6 carbon atoms.
9 alkyl groups. X is a sulfonamide,

[0093]

Embedded image

Y is, for example, an alkylene oxide group or an alkylene group. Rf 'represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. Furthermore, A is _{-SO 3 M, -OSO 3 M,} -
_{COOM, -OPO 3 (M 1)} (M 2), - PO 3 (M 1)
It represents a hydrophilic group such as (M ₂ ), preferably -SO ₃ M. M, M ₁ and M ₂ are H, Li, K, Na or NH
₄ , preferably Li, K, Na most preferably L
i. m represents 0 or 1, n represents 0 or an integer of 1 to 10, and preferably m = 0 and n = 0.

[0095]

Embedded image

In the formula, R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group. E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents an oxygen atom or a —R ³ N— group, and R ³ represents an aliphatic group, a hydrogen atom or

[0097]

Embedded image

And R ⁴ represents a hydrogen atom or an aliphatic group. l ₁ , l ₂ , m ₁ , m ₂ , n ₁ , n ₂ are each 0 to 300
Represents the value of

[0099]

Embedded image

In the formula, A ₂ is a monovalent organic group, for example, an alkyl group having 6 to 50, preferably 6 to 35 carbon atoms (for example, hexyl, heptyl, octyl, nonyl, decyl,
Each group such as undecyl or dodecyl) or 3 carbon atoms
It is an annealed group substituted with an alkyl group having up to 35 or an alkenyl group having 2 to 35 carbon atoms. Further, when A ₂ is an annealing group substituted with an alkyl group or an alkenyl group, it includes those substituted with a fluorine atom.

As a preferable group to be substituted on the annealing group, an alkyl group having 1 to 18 carbon atoms (for example, methyl,
An unsubstituted alkyl group such as propyl, butyl, benzyl, hexyl, hexyl, octyl, nonyl, decyl, undecyl or dodecyl), a substituted alkyl group such as benzyl, phenethyl or an alkenyl group having 2 to 20 carbon atoms (eg, oleyl, cetyl) , Unsubstituted alkenyl groups such as allyl group, and substituted alkenyl groups such as styryl group). Examples of the aryl group include phenyl, biphenyl, naphthyl and the like, and a phenyl group is preferable. As the position to be substituted with the aryl group, ortho,
Any of meta and rose positions may be used, and a plurality of groups can be substituted.

B or C is ethylene oxide or propylene oxide or

[0103]

Embedded image

(Where n ₁ , m ₁ and l ₁ each represent 0, 1, 2 or 3). m and n are 0 to
Represents an integer of 100. X ₁ is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and examples thereof include the groups described for A ₂ .

As the water-soluble siloxane compound, a compound represented by the following general formula [SU-I] is preferable.

[0106]

Embedded image

In the formula, R ₉ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group,

[0108]

Embedded image

Represents the following. R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or a lower alkyl group, and R ₁₀ , R ₁₁ and R ₁₂ may be the same or different. l ₁ ~
l ₃ represents an integer of 0 to 30, and p, q ₁ and q
₂ represents 0 or an integer of 1 to 30;

[0110]

Embedded image

Represents the following.

Specific examples are described in Japanese Patent Application Laid-Open No. 4-299340, and include the general formulas [I], [SI],
Particularly preferred specific examples of the compound represented by [SII] and the water-soluble siloxane compound are shown below.

[0113]

Embedded image

Among the compounds represented by the above general formula [I], the most preferable ones are [I] -1, [I] -2,
Compounds represented by [I] -4 and [I] -9.

These compounds can be synthesized by a usual method, and are also available as commercial products.

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Embodiment 1 [Apparatus] FIG. 1 is a schematic configuration diagram of a main part of a self-developing machine of Embodiment 1. A heating means 10 for heating the silver halide photographic light-sensitive material P is provided upstream of the transport path of the silver halide photographic light-sensitive material P to be processed by the processing liquid. The heating means 10 includes a heating drum 11. An outlet roller 12 is provided below the heating drum 11. On the left side of the heating drum 11 is an inlet roller 13. A pressure belt drive roller 14 is provided on the left side of the exit side roller 12 and above the entrance side roller 13. Crimping belt 15 is used for exit-side roller 1
2. Inlet roller 13 and pressure belt drive roller 1
4 and is moved while being pressed against the heating drum 11 over a 90 ° section of the peripheral surface of the heating drum 11, whereby the emulsion surface of the photosensitive material P is pressed onto the heating drum 11 and transported. Thus, the photosensitive material P is heated.

Downstream of the heating drum 11 in the conveyance path of the photosensitive material P, there are a color developing solution applying means 20 and a bleaching solution applying means 40 following the developing means. The color developing solution applying means 20 has a processing solution container 25 containing a developing solution a for processing the photosensitive material P.
The processing liquid container 25 is sealed from the outside air and is a flexible container. As the processing liquid supply means 26, a slit coater is used. Thus, the processing liquid supply unit 26 supplies the first developer a to the emulsion surface of the photosensitive material P heated by the heating unit 10.

Subsequently, the second developing solution b is similarly supplied to the emulsion surface of the photosensitive material P by a tube pump (BP) as a processing liquid supply means 28 using a slit coater.
The developer b is supplied 2.0 seconds after the supply of the developer a.

Thereafter, the bleaching solution c is similarly supplied from a flexible container 43 sealed with the outside air to the emulsion surface of the photosensitive material P by a tube pump (BP) as a processing liquid supply means 41 by a slit coater. After the color developing step, a squeeze 50 for removing an excess processing solution is provided.

The second heating means 30 and the third heating means for heating from the upstream side to the downstream side of the photosensitive material conveying path where the developing liquids a, b and the bleaching liquid are supplied by the processing liquid supplying means 26, 28, 41, respectively. There are 60. The second heating means 30 includes a heating roller 31, a driving roller 32, and a heating belt 33. The third heating means 60 includes a heating roller 61, a driving roller 62, and a heating belt 63. Heating belt 33,
63 is stretched over the heating rollers 31 and 61 and the driving rollers 32 and 62, respectively. The heating roller 31
The heating belt 33 is located upstream of the transport path of the photosensitive material P to which the processing liquid N1 is supplied by the processing liquid supply means 26 and 28.
Heat. Similarly, the heating roller 61 is located upstream of the transport path of the photosensitive material P to which the processing liquid N2 is supplied by the processing liquid supply unit 41, and heats the heating belt 63. Driving rollers 32, 62 located downstream of the heating rollers 31, 61 on the transport path of the photosensitive material P drive the heating belts 33, 63. Thus, the photosensitive material P is heated on the heating belts 33 and 63. Then, the processing liquid supply means 26, 28, 41 supplies the processing liquid to the emulsion surface of the silver halide photographic material being heated by the heating means 30, 60. In this way, after the developing solution is supplied by the processing liquid supply means 26 and 28 and the development processing is completed, the bleaching liquid is supplied by the processing liquid supply means 41 and the bleaching processing is performed. Fixing process in tank FIX, stabilization tank ST
Is stabilized.

[Heating Condition] The photosensitive material emulsion surface temperature is set to 80 ° C. by the heating drum 11 having a surface temperature of 80 ° C.

[Second and Third Heating Conditions] The heating belts 33 and 63 having a surface temperature of 80 ° C. are used to heat the support of the photosensitive material P from the support side, and the emulsion surface of the photosensitive material is maintained at 80 ° C.

[Supply Head] A supply head of a slit coater is used. FIGS. 2 and 3A and 3B show a cross-sectional view and an external view of an example of the slit-shaped coater head. N2 is a processing liquid, P is a photosensitive material, and 63 is a heating belt. The supply head is perpendicular to the photosensitive material transport direction. On the other hand, a supply head (linear head) of a porous coater can be used in addition to the supply head of the slit coater. In this case, as shown in FIG. Is the distance between the nearest supply port and the edge 2
00 μm. The supply amount of each of the processing solutions a, b, and c per 1 m ^{2 of the} silver halide photographic light-sensitive material was 80 ml each.

[Photosensitive material] Konica Color LV100 color negative film manufactured by Konica Corp. exposed by a usual method is used. [Prescription of processing solution in processing solution containers (a), (b) and (c)] Color developing solution (A) water 500 ml sodium sulfite 1.0 g L-cysteine 0.5 g sodium p-toluenesulfonate 20.0 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 80. Adjust the pH to 1.50 with potassium hydroxide or 50% sulfuric acid by adding 0 g of water to make 1 liter.

Color developer (b) Water 500 ml Diethylenetriaminepentasodium pentasodium 3.0 g Potassium carbonate 100.0 g Sodium p-toluenesulfonate 15.0 g Sodium sulfite 15.0 g Potassium bromide 5.0 g Potassium iodide 0.1 g The pH was adjusted to 13.50 with potassium hydroxide or 50% sulfuric acid using water to make 1 liter.

Bleaching solution (c) Water 400 ml Ferric ammonium salt of Exemplified compound A-6 0.65 mol Ammonium bromide 100 g Exemplified compound (B-6) 80 g Imidazole 10 g 3-mercapto-1,2,4-triazole 5 g Water was added to make 1 liter, and the pH was adjusted to 2.00 using 25% aqueous ammonia or 50% sulfuric acid.

Fixing solution Water 500 ml Ammonium thiosulfate 200 g Sodium sulfite 18 g Ethylenediaminetetraacetic acid disodium 2 g 3-mercapto-1,2,4-triazole 2 g Add water to make 1 l, pH 7 using 25% aqueous ammonia or 50% sulfuric acid. Adjusted to .50.

Stabilization solution Water 500 ml m-Hydroxybenzaldehyde 1.5 g Disodium ethylenediaminetetraacetate 0.6 g β-cyclodextrin 0.2 g Water was added to make 1 liter, and the pH was adjusted to 7.00 with potassium hydroxide or 50% sulfuric acid. It was adjusted.

[Processing conditions] Processing step Processing time Processing temperature Replenishment amount (per 1 m ² ) Color development 60 seconds 80 ° C. 160 ml Bleaching 20 seconds 80 ° C. 80 ml Fixing 1 20 seconds 40 ° C. Fixing 2 20 seconds 40 ° C. 500 ml Stable 1 15 seconds 40 ° C. Stable 2 15 seconds 40 ° C. Stable 3 15 seconds 40 ° C. 800 ml Drying 30 seconds 65 ° C. Fixing 2 → 1, stable 3 → 2 → 1 was replenished by a multi-stage AC system.

The processing was performed under the above processing conditions, and as shown in Table 1, the pH of the film surface of the light-sensitive material before entering the bleaching step and the weight loss after drying were adjusted. The pH of the film surface was adjusted by immersing it in a solution (adjusted with sulfuric acid and potassium hydroxide) adjusted to the pH shown in Table 1 after completion of color development. The weight loss after drying was adjusted by drying after dipping in the above solution. Dmin density of magenta of the photosensitive material after processing, 1000n of Dmax part
m, the transmission absorbance (desilverability) was measured, and the occurrence of density unevenness on the surface of the light-sensitive material was visually evaluated according to the following evaluation criteria.

<Evaluation Criteria for Density Unevenness> A: Density unevenness has not occurred. O: Slight density unevenness has occurred other than on the image surface. Δ: Slight density unevenness has occurred on the image surface but on print. There is no problem. X: Density unevenness occurs on the image surface and is observed on the print in several frames. XX: Density unevenness occurs on the image surface and is observed on the print in all frames. The results are shown in Table 1.

[0136]

[Table 1]

As is clear from Table 1, when the film surface pH and the weight loss after drying were within the ranges of the present invention, satisfactory results were obtained as the BL performance (bleaching performance). When the membrane surface pH is lower than 7.0, the penetration and liquid exchange by the application of the BL liquid are not performed well, and when the loss on drying is less than 3.0 g / m ² , the liquid permeation speed is slow and the bleaching is not sufficiently performed.
If the amount is more than 150 g / m ² , the bleaching solution will be diluted and the bleaching ability will decrease. Therefore, the film surface pH and the weight loss after drying are within the range of the present invention, so that the BL performance is only satisfied. The result was obtained. A more preferred range of the film surface pH is 8.0 or more, and further more preferably 9.0 or more. A more preferable range of the loss on drying is in the range of 10.0 to 100 g / m ² .

Embodiment 2 FIG. 4 is a schematic configuration diagram of a main part of a self-developing machine of Embodiment 2. A heating unit 10 for heating the exposed silver halide photographic light-sensitive material P is provided upstream of the transport path of the silver halide photographic light-sensitive material P processed by the processing liquid. Heating means 10
Has a heating drum 11. An outlet roller 12 is provided above the heating drum 11. There is an entrance-side roller 13 on the left side of the heating drum 11. Outlet roller 12
There is a pressure belt driving roller 14 on the left side of the upper side of the entrance side roller 13. The pressure belt 15 is wrapped around the exit roller 12, the entrance roller 13 and the pressure belt drive roller 14, and the 90 °
The photosensitive material P is pressed onto the heating drum 11 and transported by being moved while being pressed by the heating drum 11 over the section. Thus, the photosensitive material P is heated.

Downstream of the heating drum 11 in the conveying path of the photosensitive material P, there are a developing means 70 and a bleaching means 80. The development processing means 70 has a processing container 75 for storing a developer a for processing the photosensitive material P and a processing container 77 for storing a developer b for processing the photosensitive material P. The bleaching means 80 has a processing vessel 85 containing a bleaching solution c for processing the light-sensitive material P. Processing container 7
5, a processing liquid supply means 76 for supplying the developer a to the photosensitive material P, a processing liquid supply means 78 for supplying the developer b contained in the processing vessel 77 to the photosensitive material P, and a processing vessel As the processing liquid supply means 88 for supplying the bleaching liquid c contained in the photosensitive material P to the photosensitive material P, a linear supply head of a piezo ink jet system is used. Thus, the processing liquid supply means 76 and the processing liquid supply means 78 supply the developer and the processing liquid supply means 88 supply the bleaching liquid via the gas phase to the emulsion surface of the photosensitive material P heated by the heating means 10, respectively. . The processing liquid overflowing from the photosensitive material P is discharged to a waste liquid section (not shown).

The photosensitive material P which has been color-developed by the developing means 70 and bleached by the bleaching means 80 is fixed in the fixing tank FIX, stabilized in the stabilizing tank ST, and dried in the drying unit DRY. You.

[Heating Conditions] The photosensitive material emulsion surface temperature is set to 80 ° C. by the heating drum 11 having a surface temperature of 80 ° C.

[Second and Third Heating Conditions] The heating belts 33 and 63 having a surface temperature of 80 ° C. are used to heat the photosensitive material P from the support surface, and the photosensitive material emulsion surface is maintained at 80 ° C.

[Supply Head] A piezo inkjet linear head is used. The linear supply head is perpendicular to the photosensitive material transport direction. The arrangement of the supply ports is a two-row staggered arrangement as shown in FIG. The distance between the supply ports is 200 μm as the distance between the edge and the nearest supply port. The supply port diameter is 100 μm (area: 7.85 × 10 ⁻⁹ m ² ), the number of processing liquid supply times per second is 7,500, and the supply amount of processing liquid per 1 m ^{2 of} silver halide photographic material is 75 ml.

[Photosensitive Material] The same photosensitive material as in Example 1 was used.

[Treatment Solution Composition] The same treatment solution composition as in Example 1 was used.

[Treatment Conditions] A similar experiment was conducted under the same treatment conditions as in Example 1.

Table 2 shows the above progress and results.

[0148]

[Table 2]

As is clear from Table 2, when the film surface pH and the weight loss after drying were within the range of the present invention, satisfactory results were obtained as the BL performance (bleaching performance). If the membrane surface pH is lower than 7.0, the permeation and liquid exchange by injection of the BL liquid are not performed well, and if the loss on drying is less than 3.0 g / m ² , the permeation speed of the liquid is slow and bleaching is not sufficiently performed.
If the amount is more than 150 g / m ² , the bleaching solution will be diluted and the bleaching ability will decrease. Therefore, the film surface pH and the weight loss after drying are within the range of the present invention, so that the BL performance is only satisfied. The result was obtained.

Example 3 Experiment No. 1 in Example 1 was performed. 1-9
And Experiment No. 2 of Example 2. Example 1 or 2 in 2-9, except that the temperature of the heating means 63 for heating the silver halide photosensitive material shown in FIGS. 1 and 4 was changed as follows, and the processing conditions were changed as follows. The same experiment was performed.

<Processing Conditions> Processing Step Processing Time Processing Temperature Replenishment Rate (per 1 m ² ) Color Development 65 seconds 70 ° C. 160 ml Bleaching 22 seconds Listed in Table 3 80 ml Fixing 1 22 seconds 40 ° C. Fixing 2 22 seconds 40 ° C. 500 ml Stable 1 20 Second 40 ° C. Stable 2 20 seconds 40 ° C. Stable 3 20 seconds 40 ° C. 800 ml Drying 20 seconds 65 ° C. Fixing 2 → 1, stable 3 → 2 → 1 was replenished by a multi-stage AC system.

Table 3 shows the above progress and results.

[0153]

[Table 3]

As apparent from Table 3, the heating temperature was set to 45.
C. or higher, the density unevenness generated in the bleaching step is improved, and the effect of the present invention is more remarkably exhibited.
It is preferably in the range of from 95 to 95C, more preferably from 60 to 80C.

Example 4 Experiment No. 1 of Example 1 1-9 and the experiment Nos. 2
In -9, the same experiment as in Example 1 or 2 was carried out except that the amount of liquid supplied to the silver halide light-sensitive material was changed as shown below, and the light-sensitive material to be processed was changed to LV400 color negative film manufactured by Konica Corporation. Was done. Table 4 shows the results.

[0156]

[Table 4]

[0157] As apparent from Table 4, a necessary and sufficient treatment solution by the process liquid supply amount 10ml / m ² ~250ml / m ² is supplied to desilvering performance, and more the effect of the present invention noticeable in, the more effective 50 ml / m ² to 15
It is preferably at 0 ml / m ² .

Example 5 Experiment No. 1 of Example 1 1-9 and the experiment Nos. 2
-9, the exemplified compound I-1 used in the bleaching solution.
Was carried out in the same manner as in Example 1 or 2, except that the pH of the bleaching solution was changed to 2.50 by changing the pH of the bleaching solution to the equimolar amount of the compound shown below. Table 5 shows the results.

[0159]

[Table 5]

As is clear from Table 5, the bleaching solution contains a ferric complex salt of a compound represented by any one of the general formulas (A), (I), (II) and (III) to increase the Dmin of magenta. Can be suppressed, and the effect of the present invention appears more remarkably.

Example 6 Experiment No. 1 of Example 1 1-9 and the experiment Nos. 2
-9, Exemplified Compound B-6 used in the bleaching solution
Was carried out in the same manner as in Example 1 or 2, except that squeezing after color development was not performed by changing the compound to an equimolar amount of the compounds shown below. Table 6 shows the results.

[0162]

[Table 6]

As is clear from Table 6, the bleaching solution contains the compound represented by the general formula (B), so that the magenta D
min rise can be suppressed more effectively.

[0164]

According to the present invention, firstly, the processing stability of the bleaching solution is improved. Specifically, there is no precipitation in a processing tank or the like, and there is no deterioration due to contamination of the solution. Silver halide color photographic light-sensitive materials, which have excellent bleaching performance and enable rapid processing. Third, can reduce fog density and prevent unevenness, and fourth, can reduce the size of automatic developing machines. And a processing method for a silver halide color photographic light-sensitive material.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a main part of an automatic machine according to a first embodiment.

FIG. 2 is a sectional view showing an example of a slit-shaped coater head.

FIG. 3 is a sectional view showing another example of the slit-shaped coater head.

FIG. 4 is a schematic configuration diagram of a main part of an automatic machine according to a second embodiment.

FIG. 5 is a diagram illustrating an arrangement of supply ports of a piezo-type inkjet linear supply head of a self-developing machine according to a second embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Heating means 11 Heating drum 12 Outlet roller 13 Inlet roller 14 Pressure belt drive roller 20 Color developing solution applying means 25 Processing liquid container 26 Processing liquid supply means 28 Processing liquid supply means 30 Second heating means 31 Heating roller 32 Drive roller 33 Heating belt a First developer b Second developer c Bleach P Silver halide photographic light-sensitive material (light-sensitive material)

Claims (25)

[Claims] 1. An automatic developing machine for a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step and a fixing step, comprising a step of applying a bleaching solution, and immediately before reaching the coating step. Silver halide having a film surface pH of 7.0 or more and a weight loss after drying of the photosensitive material immediately before reaching the coating step of 3.0 to 150 g / m ^2. Automatic developing machine for color photographic photosensitive materials. 2. The automatic developing machine for a silver halide color photographic light-sensitive material according to claim 1, wherein the coating solution supply outlet in the step of applying the bleaching solution is a slit. 3. An automatic developing machine for silver halide color photographic materials according to claim 1, further comprising a heating means for directly heating said silver halide color photographic materials. 4. The automatic silver halide color photographic light-sensitive material according to claim 1, further comprising heating means for heating the silver halide color photographic light-sensitive material to 45 ° C. or higher. Developing machine. 5. The photosensitive material 1 according to claim 1, wherein a total supply amount of the processing liquid from a supply outlet of the coating liquid in the step of applying the bleaching liquid is determined.
5. The automatic developing machine for a silver halide color photographic light-sensitive material according to claim 1, wherein the amount is set to 10 ml to 250 ml per m < ² >. 6. The bleaching solution according to the following general formula (A):
Second compound of (I), (II) or (III)
6. The automatic developing machine for a silver halide color photographic light-sensitive material according to claim 1, further comprising at least one iron complex salt. Embedded image [In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different, and each represents —CH ₂ OH, —COOM or —PO ₃
Represents M ₁ M ₂ . M, M ₁ and M ₂ are each a hydrogen atom,
Represents a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms. [Chemical formula 2] [Wherein A ¹ , A ² , A ³ , and A ⁴ are each —CH ₂ O
H, -PO ₃ (M ⁰⁾ represents ₂ or -COOM, may each be the same or different. M represents a cation. X ¹ is an alkylene group having 2 to 6 carbon atoms or-
(B ¹ O) represents n-B ^2- . n represents an integer of 1 to 8, and B ¹ and B ² may be the same or different. B ¹ and B ² each represent an alkylene group having 1 to 5 carbon atoms. [Chemical formula 3] [Wherein, n ₁ represents 1 or 2, A represents —COOM ³ ,
-OH, represent -NH ₂ or -PO ^₃ (M _{3) 2.}
M ¹ , M ² and M ³ each represent a hydrogen ion, an ammonium ion, a sodium ion, a potassium ion, a lithium ion or an organic ammonium ion. [Formula 4] [Wherein, A ⁵ and A ⁶ are -COOM ⁷ , -PO
₃ (M ⁷ ) ₂ , —SO ₃ M ⁷ , a hydroxyl group or a mercapto group, which may be the same or different. M ⁶ and M ⁷ each represent a cation. R represents a hydrogen atom, an aliphatic group or an aromatic group; X ₁ and X ₂ each represent a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of an aliphatic group and an aromatic group; Represents ] 7. The silver halide color photographic material according to claim 1, wherein the bleaching solution contains at least one compound represented by the following general formula (B). Automatic developing machine. General formula (B) A (-COOM) _n [In the formula, A represents an n-valent organic group, n represents an integer of 1 to 6, and M represents an ammonium, an alkali metal, or a hydrogen atom. ] 8. An automatic developing machine for a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step and a fixing step, comprising a processing liquid supply means for supplying a bleaching liquid via a gas phase. A silver halide color photograph characterized in that the photosensitive material has a film surface pH of at least 7.0 before reaching the bleaching step and a weight loss after drying of 3.0 to 150 g / m ^2. Automatic developing machine for photosensitive materials. 9. An automatic developing machine for a silver halide color photographic light-sensitive material according to claim 8, further comprising a heating means for directly heating said silver halide color photographic light-sensitive material. 10. An automatic developing machine for a silver halide color photographic light-sensitive material according to claim 8, further comprising a heating means for heating said silver halide color photographic light-sensitive material to 45 ° C. or more. 11. The method according to claim 9, wherein the amount of the processing liquid supplied from the liquid supply means of the bleaching liquid via the gas phase is set to 10 ml to 250 ml per 1 m ^{2 of the} light-sensitive material. 3. The automatic developing machine for silver halide color photographic light-sensitive materials according to claim 1. 12. The bleaching solution according to the general formula (A),
Second compound of (I), (II) or (III)
The automatic developing machine for a silver halide color photographic light-sensitive material according to any one of claims 9 to 11, further comprising at least one iron complex salt. 13. A silver halide color photographic light-sensitive material according to claim 9, wherein said bleaching solution contains at least one compound represented by the general formula (B). Automatic developing machine. 14. A method for processing a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step, and a fixing step, wherein a bleaching solution is supplied by a coating means, and the film of the light-sensitive material before reaching the coating step. Surface pH is 7.0
And the weight loss after drying is 3.0 to 150 g /
The method for processing a silver halide color photographic material, which is a m ^2. 15. The method for processing a silver halide color photographic light-sensitive material according to claim 14, wherein the silver halide color photographic light-sensitive material is directly heated. 16. The method for processing a silver halide color photographic light-sensitive material according to claim 14, wherein the silver halide color photographic light-sensitive material is heated to 45 ° C. or higher. 17. The method according to claim 14, wherein a total supply amount of the processing solution from a supply outlet of the coating solution in the step of applying the bleaching solution is 10 ml to 250 ml per 1 m ^{2 of the} photosensitive material. The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2. 18. The bleaching solution according to the following general formula (A):
Second compound of (I), (II) or (III)
18. The method for processing a silver halide color photographic light-sensitive material according to claim 14, comprising at least one of an iron complex salt. 19. The silver halide color photographic material according to claim 14, wherein the bleaching solution contains at least one compound represented by the following general formula (B). Processing method. 20. A method for processing a silver halide color photographic light-sensitive material having at least three steps of a developing step, a bleaching step, and a fixing step, wherein a bleaching solution is supplied via a gaseous phase and before the bleaching step is reached. A film surface pH of 7.0 or more and a weight loss after drying of 3.0 to 150 g / m ² . 21. The processing method for a silver halide color photographic light-sensitive material according to claim 20, further comprising heating means for directly heating said silver halide color photographic light-sensitive material. 22. The method for processing a silver halide color photographic material according to claim 20, further comprising heating means for heating the silver halide color photographic material to 45 ° C. or higher. 23. The silver halide according to claim 20, wherein the amount of the bleaching solution supplied via the gas phase is 10 ml to 250 ml per 1 m ^{2 of the} light-sensitive material. Processing method for color photographic light-sensitive materials. 24. The bleaching solution according to the following general formula (A):
Second compound of (I), (II) or (III)
The method for processing a silver halide color photographic light-sensitive material according to any one of claims 20 to 23, comprising at least one of an iron complex salt. 25. The silver halide color photographic light-sensitive material according to claim 20, wherein the bleaching solution contains at least one compound represented by the following general formula (B). Processing method.