JPH11202455A - Developer for silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the image forming method by using the silver halide photographic sensitive material having high-contrast photographic characteristics and uniformizing a processing solution and to provide the developer for this photosensitive material to be used for this image forming method. SOLUTION: This silver halide photographic sensitive material having at feast one silver halide emulsion layer on a support is imagewise exposed and an image is formed by coating the photosensitive material with the developer represented by the formula in which each of R1 and R2 is, independently, an alkyl, amino, alkoxy, or alkylthio group each optionally substituted, and each may combine with each other to form a ring; (k) is 0 or 1; (k) is 0 or 1 and when (k)= 1, X is a -CO- or -CS- group; and each of M1 and M2 is an H or alkali metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming method using a silver halide photographic material and a developer for the silver halide photographic material used in the image forming method.

[0002]

2. Description of the Related Art Hitherto, a silver halide photographic light-sensitive material has been processed by immersing it in a processing solution stored in a processing tank for a predetermined time.

However, in recent years, the discharge of the developing solution has been restricted, and a low replenishment of the processing solution has been demanded. Further, the method using a treatment tank has a problem that the activity of the treatment liquid is different between the new liquid state and the running state, or the composition of the treatment liquid changes due to evaporation or air oxidation during storage in the treatment tank. In particular, when a high-contrast image of γ10 or more was formed, the effect was remarkable.

[0004] For this reason, in order to reduce the opening area of the processing tank and to shorten the renewal time of the processing liquid in the processing tank, a slit processing tank system described in JP-A-9-212826 and JP-A-9-230563 is used. A method using a sealed multi-stage treatment tank described in Japanese Patent Application Laid-Open No. 9-1331993 is known. However, since the system basically uses a processing tank,
It cannot be a sufficient solution to the above problem.

[0005] Japanese Patent Application Laid-Open No. 2-64637 and Japanese Patent Application Laid-Open
No. 80720 discloses a method of applying and supplying a processing liquid, but there is a problem that unevenness of the processing liquid easily occurs. This was a serious problem particularly in a photosensitive material having a high photographic characteristic of γ10 or more.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is that the activity of a processing solution differs between a new solution state and a running state, or the composition of a processing solution changes due to evaporation or air oxidation during storage in a processing tank. The method for forming an image for a silver halide photographic light-sensitive material which does not cause unevenness of a processing solution, particularly in a light-sensitive material having high contrast photographic characteristics of γ10 or more, and a silver halide used in the image forming method An object of the present invention is to provide a developer for a photographic light-sensitive material.

[0007]

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

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed, and a developer represented by the formula (A) is coated on the light-sensitive material. An image forming method comprising supplying an image to form an image.

[0009]

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[In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. Or R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X is-
Represents CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. (2) A silver halide photographic light-sensitive material comprising a compound represented by the formula (A) as a developing agent, wherein the developer is coated on a light-sensitive material and supplied to form an image. Developer.

(3) The image forming method according to (1), wherein an image is formed by applying and supplying a developer containing the compound represented by the general formula (A) and an alkaline aqueous solution.

(4) The image according to (3), wherein after the developer containing the compound represented by the general formula (A) is supplied, an image is formed by applying and supplying an alkaline aqueous solution. Forming method.

Next, the above-mentioned general formula (A) used in the present invention
The compound represented by is described.

[0014]

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In the general formula (A), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and k =
When it is 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

In the compound represented by the general formula (A),
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is particularly preferred.

[0017]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the general formula (A) or the general formula [A-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Preferred examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or [Aa] according to the present invention are shown below.
The present invention is not limited to these.

[0021]

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[0022]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

The developer of the present invention is preferably used under alkaline conditions of pH 9 or more. In the method of applying and supplying a coating solution, the alkaline agent and the developer containing the general formula (A) are separately supplied. Is preferred. Particularly preferably, the developer containing the general formula (A) has a pH of 8 or less, and it is preferable to separately supply an alkaline solution having a pH of 9 or more for supplying alkali. Alkaline liquid and general formula (A)
The order of application and supply of the developer liquid containing (A) may be simultaneous or different, but more preferably, the alkali liquid is supplied after the application and supply of the developer containing the general formula (A).

In the present invention, a processing mode in which water and a processing solution come into contact with both surfaces of the light-sensitive material can be adopted, if necessary. It is preferable to supply water to the photosensitive material prior to the application and supply of the processing liquid for speeding up the processing. A tank may or may not be provided for supplying water, and a known method and technique can be used as appropriate. The supply amount of water is preferably 0.5 to 100 g per 1 m ² of the photosensitive material,
40 g is more preferred.

The water to be supplied can be heated to an arbitrary temperature as required. In this case, the layer on the opposite side of the layer containing the photosensitive silver halide preferably has a small water absorption. Specifically, the water absorption is ² g per 1 m ^{2 of the} photosensitive material.
Is preferably less than 1 g. Such an amount of water absorption can be realized by the technique described in JP-A-9-90584 or other techniques known in the art.

Supply of Processing Solution In the present invention, "application and supply" refers to a process in which a processing is performed with a processing solution applied to a photosensitive material. Specifically, it indicates a state in which the processing liquid is supplied to the photosensitive material in an amount of 1 ml / m ² or more and 200 ml / m ² or less.

In the present invention, the processing step may be a developing step alone, but may be suitably used in a fixing step or the like.

Treatment liquid supply means Various treatment methods can be used as the treatment liquid supply means. A method of supplying a processing solution directly from a processing solution supply port to a photosensitive material or while forming beads, a method of supplying a processing solution to a photosensitive material via a gas phase, such as a method of supplying a processing solution from a slit or a hole, are preferably used.

In the case of slits and holes When the liquid is supplied directly from the slits or holes or while forming beads, the shape of the liquid supply section is not particularly limited as long as it can supply the processing liquid. For porous nozzles, the preferred hole diameter is between 0.03 mm and 1.0 mm. More preferably, it is 0.05 mm to 0.5 mm. Further, a preferable interval between the holes is 0.1 mm to 1.0 mm, more preferably 0.15 mm to 0.5 mm.

In the case of a slit-shaped nozzle, the preferred slit width is from 0.03 mm to 1.0 mm. If the width is too small, it is not preferable for the uniform application of the treatment liquid. If the width is too large, liquid dripping will occur. Occur. The slit width is more preferably 0.05 mm to 0.5 mm, and more preferably 0.10 mm to 0.3 mm. The distance between the liquid supply port and the photosensitive material is 0.03 mm to 10 mm, preferably 0.05 mm to 5 mm, and more preferably 0.1 mm to 5 mm.
3 mm is preferred from the viewpoint that uniform application of the treatment liquid can be improved.

In the case where the processing liquid is supplied through a gaseous phase, a method of supplying the processing liquid through a gaseous phase includes a processing liquid applying means for applying a processing liquid to a photosensitive material through a gaseous phase, such as a curtain coater. Can be

The processing liquid supply means for causing the processing liquid to fly onto the photosensitive material through the gas phase may have the same structure as that of the ink jet head of the ink jet printer or the structure described in JP-A-6-324455. As described above, there is a type in which a pressure is generated to actively fly, and a type such as a spray bar, which is caused to fly by the liquid pressure of a processing liquid. As a method for actively flying, a method utilizing vibration by a piezoelectric element or a method utilizing bumping is preferably used.

The method of supplying the processing liquid by actively flying the processing liquid with the same structure as the ink-jet head of the ink-jet printer is based on the ease of controlling the supply amount of the processing liquid and the control of the processing position of the photosensitive material. It is particularly preferably used because of its ease of selection. Further, as the processing liquid supply means, a processing liquid is supplied from a linear supply head to the photosensitive material via a gas phase, or a processing liquid is supplied from the planar supply head to the photosensitive material via a gas phase. Or a method in which a processing liquid is supplied from a point-like supply head to a light-sensitive material via a gaseous phase, or another method. Further, when the photosensitive material is a sheet, the processing liquid is sensed from the supply head using a planar supply head corresponding to the size of the photosensitive material in a state where the positional relationship between the photosensitive material and the supply head is fixed. Although the supply of the processing liquid from the supply head to the photosensitive material via the gas phase while shifting the positional relationship between the supply head and the photosensitive material may be possible, the supply head is smaller. However, it is preferable because the processing solution can be sufficiently supplied to the photosensitive material. When a linear supply head is used, the supply head may move.However, in order to quickly supply the processing liquid to the photosensitive material, a linear supply head and a linear supply head are used. It is preferable to move the photosensitive material in directions other than the parallel direction. In particular, in order to keep the processing time constant, it is preferable to move the photosensitive material in a direction perpendicular to the linear supply head. When the processing liquid is caused to fly from the supply head to the photosensitive material via the gas phase while shifting the positional relationship between the supply head and the photosensitive material as the processing liquid flying means,
The number of times the processing liquid is caused to fly through the gas phase to the light-sensitive material per second is preferably at least one time, particularly preferably at least 10 times, in order to sufficiently supply the processing liquid to the surface of the light-sensitive material. Further, in order to fly from the supply head, the number is preferably 1 × 10 ⁶ times or less, particularly preferably 1 × 10 ⁵ times or less.

When the processing liquid supply means supplies the processing liquid to the photosensitive material through the supply port, the supply port may have any shape such as a circle, a square, or an ellipse. And
The area of each supply port is preferably 1 × 10 ⁻¹¹ m ² or more, particularly preferably 1 × 10 ⁻¹⁰ m ² or more, in order to prevent the processing liquid from being clogged in a slightly dried state. Also,
The area of each supply port is preferably 1 × 10 ⁻⁸ m ² or less, and particularly preferably 1 × 10 ⁻⁸ m ² or less, in order to uniformly supply the processing solution to the photosensitive material.
× 10 ⁻⁶ m ² or less is preferable. In addition, the interval between the supply ports is preferably 5 × 10 ⁻⁶ m or more in terms of the strength of the supply ports and the like, on the average of the distance between the edges of the supply port and the nearest supply port. 1 × for supplying processing solution
It is preferably 10 ^-3 m or less.

The distance between the supply port after processing and the emulsion surface is preferably 50 μm or more (especially 1 mm or more) for easy control of this distance, and more preferably 10 mm or less (especially 5 mm or less).

Further, the photosensitive material to which the processing liquid is applied and supplied is preferably heated.

Heating means The temperature of the photosensitive material heated by the heating means may be about 40 ° C. or lower, preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and particularly preferably 50 ° C. or higher. The temperature is preferably 150 ° C. or lower from the viewpoint of heat resistance of the photosensitive material and ease of processing control.
0 ° C. or lower, particularly 90 ° C. or lower is preferable.

As the heating means for heating the photosensitive material, a conductive heating means such as a heat drum or a heat belt for heating by conduction in contact with the photosensitive material, a convection heating means for heating by convection such as a dryer, an infrared ray or a high frequency Radiant heating means for heating by radiation such as electromagnetic waves.

It is preferable to have a heating control means for controlling the heating means to heat when the silver halide photographic material is present before the heating means heats, because unnecessary heating can be prevented. This is because the conveying means for conveying the silver halide photographic material at a predetermined conveying speed, and the presence of the silver halide photographic light-sensitive material at a predetermined position on the upstream side in the conveying direction of the conveying means from the destination heated by the heating means And a heating material control means based on the detection of the photosensitive material detection means. In this case, the control is such that the photosensitive material detecting means detects the presence of the silver halide photographic light-sensitive material at the predetermined position from the absence of the silver halide photographic material at a predetermined time and then the photosensitive material detecting means detects the silver halide at the predetermined position. It is preferable to control the heating means to perform a predetermined heating until a predetermined time has elapsed after detecting the presence or absence of the photographic light-sensitive material.

When the treatment liquid is applied and supplied, the surface tension of the liquid is preferably adjusted to 40 dyn / cm or less. Particularly preferably, it is 30 dyn / cm or less. Various surfactants are used to change the surface tension. Particularly, a fluorine-based surfactant is preferable.

The method of the present invention uses γ1
The effect is great in an image forming method having a high contrast of 0 or more.

Light-sensitive material according to the present invention The light-sensitive material according to the present invention contains a transition metal selected from elements of Groups 6 to 10 of the periodic table in a silver halide emulsion layer.

The silver halide emulsion containing a transition metal used in the present invention contains silver halide grains in the periodic table 6 to
A transition metal selected from Group 10 elements can be introduced into the silver halide in the form of a complex. As the transition metal complex used in the present invention, a six-coordinate complex represented by the following general formula is preferable.

[ML ₆ ] ^{m In the} formula, M represents a transition metal selected from elements of Groups 6 to 10 of the periodic table, L represents a bridging ligand, and m represents 0, -1, -2 or -3. As specific examples of the ligand represented by L, preferable specific examples other than nitrosyl and thionitrosyl bridging ligands include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, Thiocyanate,
Examples include selenocyanate, tellurocyanate, azide and aquo ligands, nitrosyl, thionitrosyl and the like. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), osmium (Os) and iridium (Ir).

The following are specific examples of the transition metal coordination complex.

[0048] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O) _2] ^- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru _(NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeC )] ^2- 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir The (NO) Cl ₅ ] ^2- metal complex can be added to silver halide during the preparation of silver halide grains. The timing of addition may be such that it is uniformly distributed throughout the silver halide grains, or it may be such that it is present in the inner shell of the silver halide grains. The transition metals preferably used in the present invention are Ru, Rh and Ir. Although there is no particular limitation, it is preferable to add at the time of particle formation.

The addition amount is 10 ^-8 per mol of silver halide.
10 ^-3 mol, preferably 10 ^-8 to 10 ^-6 mol.

Organic Hardening Agent The organic hardening agent used in the present invention includes, for example, Journal of the Printing Society of Japan, 24, 299 (1987), Imaging Sc.
i. Techniques utilizing nucleation development as described in Technol 40, 70 (1996), and compounds exhibiting a selective development mechanism as described in Journal of the Printing Society of Japan 24, 307 (1987) are used. .

Specific examples of these compounds include hydrazine derivatives, 5- and 6-membered nitrogen-containing heterocyclic compounds, tetrazolium compounds and the like, and it is preferable to use a nucleation accelerator together with these compounds.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0053]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₂ — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group. A carbamoyl group or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0056]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and preferably both are hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵ ) groups. R ³ represents an alkynyl group or a saturated heterocyclic group; R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group.

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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Specific examples of other preferable hydrazine derivatives are described in US Pat. No. 5,229,248, columns 4 to 60, (1) to (252).
Can be mentioned.

The above hydrazine derivative can be synthesized by a known method. For example, US Pat.
No. 9,248, column 59 to column 80, can be synthesized by the method as described.

In the present invention, the amount of the hydrazine derivative to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like. The range is preferably from 10 ^-6 to 10 ^-1 mol, and particularly preferably from 10 ^-5 to 10 ^-2 mol. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

It is preferable that the hydrazine derivative used in the present invention is contained in a solid dispersion state from the viewpoint of storage stability of the light-sensitive material. As a method of dispersion, the hydrazine derivative does not substantially contain an organic solvent such as ethyl acetate, methanol, and methyl ethyl ketone and a high boiling point organic solvent,
A method of removing an organic solvent by depressurization after mixing with an aqueous solution which may contain one or more stabilizers or a pulverizing agent, or a method of removing one or more stabilizers or pulverizing solids of a hydrazine derivative It is prepared by repeatedly colliding with a hard inorganic grinding medium in an aqueous solution which may contain an agent. Hard inorganic grinding media include sand, silica spheres,
Stainless steel, silicone carbide, glass,
Beads such as zirconium, zirconium oxide, alumina, and titanium are used. These bead sizes are between 0.25 and
It is in the range of 3.0 mm. Ball mill, media mill,
A method of reducing the particle size using an attritor mill, a jet mill, a vibration mill or the like is also often used.

The average particle size of the hydrazine derivative of the dispersion obtained as described above can be in the range conventionally obtained by this method, and is generally 0.05 to 1.
5 μm, preferably between 0.1 and 1.0 μm.

For the dispersion used in the present invention, a stabilizer or a dispersion aid is used. As the stabilizer or the dispersing aid, a surfactant or a hydrophilic colloid is preferable.

As the surfactant, known anionic, cationic, nonionic, betaine surfactants and fluorine surfactants can be used. For example, surfactants include alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyltaurine, sulfosuccinic acid Carboxyl groups, such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates,
Anionic surfactants containing an acidic group such as a sulfonic acid group, a phosphoric acid group, a sulfate ester group, and a phosphate ester group, or alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic activators such as heterocyclic quaternary ammonium salts and aliphatic or heterocyclic-containing phosphonium or sulfonium salts, or saponins (steroids), alkylene oxide derivatives, glycidol derivatives, fatty acid esters of polyhydric alcohols, sugars Nonionic surfactants such as alkyl esters of the above can be used.

The hydrophilic colloid is a known water-soluble polymer,
For example, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonate, gelatin, derivative gelatin (phthalated gelatin, phenylcarbamoylated gelatin),
Synthetic or natural polymer substances such as cellulose derivatives (cellulose ether, cellulose ester, etc.), starch, gum arabic, pullulan, dextran, dextrin and the like are used.

A form in which the hydrazine derivative is emulsified and dispersed in a high-boiling solvent is also preferably used from the viewpoint of the storage stability of the light-sensitive material. The method of dissolving and emulsifying and dispersing the hydrazine derivative in a high boiling point solvent is the same as the method conventionally used for oil-soluble couplers and oil-soluble ultraviolet absorbers. That is, the hydrazine derivative is dissolved in a high boiling organic solvent together with a low boiling organic solvent if necessary, mixed with a gelatin aqueous solution containing a surfactant, and emulsified and dispersed by a colloid mill or the like. Examples of the high boiling organic solvent used at this time include carboxylic esters, phosphoric esters, carboxylic amides, and hydrocarbons. For reference, specific examples of the high-boiling organic solvent advantageously used in the present invention are shown below.

[0079]

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Film pH of the silver halide light-sensitive material of the present invention
Is preferably 6 or less, and the pH of the film surface as used herein means an aqueous solution (3.3 mol in the case of GS-5013F) having the same concentration and composition as the internal solution of the comparative electrode per 1 cm ² on the surface of the photosensitive material to be measured. / L of KCl) was added dropwise in an amount of 0.5 cc.
After leaving for 5 minutes in an atmosphere of 0% RH, a silver chloride electrode (AgC
1 / KCl) as a reference electrode, an integrally formed flat glass electrode (flat composite electrode) is brought into contact with the measurement surface, and 5
This is the value measured after minutes. As a specific example of the flat composite electrode, a flat composite electrode GS-50 manufactured by Toa Denpa Kogyo KK
13F and the like.

In the present invention, in order to adjust the film surface pH, a method of adding an acid, a method of adding a volatile alkali during coating and drying of a film, or a compound which releases an acid by a reaction after coating and drying is used. Various methods, such as a method using, are used.

The hydrazine derivative of the present invention can be contained in any layer of the silver halide light-sensitive material. However, from the viewpoint of storage stability of the light-sensitive material, it may be added to a layer other than the silver halide emulsion layer. preferable.

The following are preferred as the 5- to 6-membered nitrogen-containing heterocyclic contrasting agent.

The photosensitive material according to the present invention is excellent in storage stability by using a specific nitrogen-containing heterocyclic compound represented by the general formula [Pa], [Pb] or [Pc] as a high contrast agent. , Sensitivity and Dmax can be provided, and an image forming method exhibiting hard photographic characteristics can be provided.

[0085]

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The formula [Pa], [Pb] or [P
c), A ₁ , A ₂ , A ₃ , A ₄ or A ₅ is 5-6
Represents a group of non-metallic atoms for completing a membered nitrogen-containing heterocycle, the heterocycle may contain an oxygen atom, a nitrogen atom, a sulfur atom, and the heterocycle may be condensed with a benzene ring . ₅ composed of A ₁ , A ₂ , A ₃ , A ₄ or A 5
The 6-membered nitrogen-containing heterocyclic ring may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkyl group,
Alkenyl, alkynyl, halogen, acyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, carboxy, hydroxy, alkoxy, aryloxy, amido, sulfamoyl, carbamoyl, ureido, amino Group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group.

Examples of the 5- to 6-membered nitrogen-containing heterocyclic ring composed of A ₁ , A ₂ , A ₃ , A ₄ or A ₅ include pyridine,
Imidazole, thiazole, oxazole, pyrazine,
Examples thereof include a pyrimidine ring, and a pyridine ring is preferable.

In the general formulas [Pa] and [Pb], B _p
Represents a divalent linking group, a divalent linking group is an alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O -, - S -, - CO -, - N (R 6) -, represents what is configured alone or in combination (R ₆ represents an alkyl group, an aryl group, a hydrogen atom). A preferred example is B _p
Represents an alkylene group, alkenylene group, or alkyleneoxy group. m is an integer of 0 or 1.

In the general formulas [Pa] and [Pc],
R _1, R ₂ and R ₅ each represent an alkyl group or an aryl group of saturated and unsaturated having 1 to 20 carbon atoms, and these groups may have a substituent, examples of the substituent A ₁ , A ₂ , A ₃ , A ₄ or A ₅ may be the same as those mentioned above.

Preferred examples of R ₁ , R ₂ and R ₅ are an alkyl group having 4 to 10 carbon atoms or a substituted or unsubstituted aryl group. More preferred examples are a substituted or unsubstituted phenyl group and an unsaturated group. Represents an alkyl group or a phenyl-substituted alkyl group.

[0091] In general formula [Pa], [Pb] or [Pc], X _p ^- is a counter ion necessary to neutralize the charge of the whole molecule, such as chlorine ions, bromine ions, iodine ions, nitrate ions , Sulfate ion, p-toluenesulfonate, oxalate, n _p represents the number of counter ions required to neutralize the charge of the whole molecule, and n _p is 0 in the case of an internal salt. Specific examples of the compounds are shown below.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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As more preferred embodiments of the present invention, general formula (I) described in quaternary salt compounds described in US Pat. No. 3,719,494, general formula (I) described in US Pat. No. 4,115,122, Heterocyclic quaternary salt compounds described in U.S. Pat. No. 4,877,723, general formula (I) described in JP-A-4-437, and general formula (I) described in JP-A-8-220706.
(II) (III) and nicotinamide derivatives described in JP-A-7-92598 are preferably used.

In the present invention, the general formulas [Pa] and [Pb]
Or preferably is 1 × 10 ^-1 mol content to 1 × 10 ^-6 mol absence per mole of silver as the addition amount of the compound represented by [Pc], in particular 1 × 10 ^-5 mol to 5 × 10 ^{- Two}
The molar range is a preferable addition amount.

The compound represented by the general formula [Pa], [Pb] or [Pc] of the present invention may be a suitable organic solvent such as alcohols (methanol, ethanol, propanol,
It can be used by dissolving in fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of the compound represented by the general formula [Pa], [Pb] or [Pc] can be dispersed and used by a ball mill, a colloid mill or an ultrasonic wave by a method known as a solid dispersion method.

The light-sensitive material of the present invention has a general formula [P
It is preferable to add a nucleation accelerator such as a hydrazine derivative, an amine derivative, an onium salt compound, a disulfide derivative, or a hydroxyamine derivative in combination with the compound represented by a), [Pb] or [Pc]. Examples of the compound of the nucleation accelerator include compounds described in paragraph numbers [0062] to [0077] of JP-A-8-314066 and
(2-1)-described in US Pat.
(2-20) and (3-1) to (3-6);
Compound of general formula I disclosed in JP-A-10104420
No. 3536, page 17, lower right column, line 19 to page 18, upper right column 4
Line and the lower right column, lines 1 to 5;
The thiosulfonic acid compound described in 237538 is preferably used. Particularly preferably, the compounds described in JP-A-8-314066 are used.

The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol per mol of silver, more preferably 1 × 10 ^−5.
２2 × 10 ⁻² mol is more preferred, and 2 × 10 ^-5 −1 × 1
0 ^-2 mol is most preferred.

As the tetrazolium compound, a compound represented by the following general formula [T] is preferable.

[0103]

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The phenyl group substituents R ₁ , R ₂ , and R ₃ of the triphenyltetrazolium compound represented by the general formula [T]
R ₃ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

Regarding the Hammett's sigma value in the phenyl substitution, for example, Journal of Medical Chemistry (Journal of Medical C)
hemistry) Volume 20, page 304, 1977,
C. of the description. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, all σP values) and an ethyl group (−0) can be seen in reports such as C. Hansch. .15), cyclopropyl group (-0.21), n-propyl group (-0.13), i
So-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which is useful as a substituent of the compound of the general formula [T] of the present invention.

N represents 1 or 2, and the anion represented by X _T ^n- includes, for example, chloride ion, bromide ion,
Halogen ions such as iodide ions; acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid; acid radicals of organic acids such as sulfonic acid and carboxylic acid; anionic activators, specifically p-toluenesulfonic acid anion Lower alkylbenzene sulfonate anions, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate, higher alkyl sulfate anions such as lauryl sulfate anion, borate anions such as tetraphenylboron, di-2-ethylhexyl sulfo. Dialkyl sulfosuccinate anions such as succinate anions, polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion, higher aliphatic anions such as stearic anion, and polymers such as polyacrylate anion With ones, and the like can be given.

Hereinafter, specific examples of the compound represented by the general formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0108]

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The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Vol. 55, pp. 335-483.

As the tetrazolium compound represented by the general formula [T], one kind may be used, or two or more kinds may be used in combination at an appropriate ratio.

These organic contrast agents may be used alone or in combination of two or more.

Solid Disperse Dye The average particle size of the solid disperse dye used in the present invention is 0.2 μm.
m, particularly preferably 0.05 to 0.15 μm
It is. In the particle size distribution, 0.3 μm or less of the scattering intensity distribution preferably occupies 70% or more. As a method for measuring the average particle size and the particle size distribution of the solid disperse dye according to the present invention, the average particle size was determined using ELS-800 manufactured by Otsuka Electronics Co., Ltd. The particle size distribution was obtained from the scattering intensity distribution obtained by the same method.

The preferred addition position of the solid disperse dye of the present invention is on the side of the silver halide emulsion layer with respect to the support and farther from the support than the silver halide emulsion layer.
In that case, the solid disperse dye may be a single layer or may be added to the protective layer.

In the present invention, the preferable addition amount of the solid disperse dye varies depending on the absorbance of the solid disperse dye and varies, but is preferably not more than 200 mg / m ^2, more preferably 5 to 50 mg / m ^2. It is preferably used in the range of m ² . More preferably, the dye is used in a more preferable particle size range.

The concentration of the solid disperse dye is 0.05 to 1.0 at the absorption maximum of the silver halide emulsion.
However, it is preferably 0.1 to 1.0, and particularly preferably 0.3 to 1.0.

In the present invention, the hydrophilic colloid layer serving as a solid disperse dye layer provided at a position farther from the silver halide emulsion layer side with respect to the support than the silver halide emulsion layer includes:
It is a commonly used hydrophilic colloid layer containing a hydrophilic polymer substance such as gelatin and polyacrylamide, and a synthetic polymer such as latex.

As the solid disperse dye used in the present invention, fine dye particles represented by the following general formulas (1) to (6) are preferably used.

[0118]

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Hereinafter, the compounds represented by formulas (1) to (6) used in the present invention will be described.

In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus,
Q represents an aryl group or a heterocyclic group, B ′ represents a heterocyclic group, X and Y may be the same or different, each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent Represents a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 0 or 1. However, the general formula (1)
The dye represented by (6) has at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nucleus represented by A and A 'in the general formulas (1), (2) and (3) is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thione Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas (3) and (5) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in the general formulas (1) and (4) include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q in the general formulas (1) and (4) include a pyridyl group, a quinolyl group,
Examples include an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group, and a thienyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, and a cyano group. Group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfamoyl group, and a sulfonamide group. Good. Preferably, it has 1 carbon atom
To 6 alkyl groups (for example, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (for example, fluorine atom, chlorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group) , Methylenedioxy group, 2-hydroxyethoxy group, n-butoxy group, etc.), substituted amino group (for example, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino Group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, Sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.) There may be a combination of these substituents.

The electron-withdrawing groups represented by X and Y in formulas (4) and (5) may be the same or different and include, for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group, acyl group, alkylsulfonyl group, arylsulfonyl group,
And a sulfamoyl group.

The heterocyclic ring represented by B 'in the general formula (6) is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole, indole and the like.

L ₁ , L ₂ and L _{3 in the} general formulas (1) to (5)
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, etc.),
Aryl group (eg, phenyl, p-tolyl, p-chlorophenyl, etc.), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenyl group, etc.), aralkyl group (eg, benzyl group, etc.) Group, phenethyl group, etc.), heterocyclic group (eg, pyridyl, furyl, thienyl, etc.), substituted amino group (eg, dimethylamino, diethylamino, anilino group, etc.), and alkylthio group (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas (1) to (6), a dye having at least one carboxyl group in the molecule is preferably used, and more preferably a dye having the general formula (1) And particularly preferably a dye in which Q in the formula (1) is a furyl group.

Specific examples of preferably used dyes are shown below, but the present invention is not limited to these.

[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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Other preferred specific examples of the compounds represented by formulas (1) to (6) are described in, for example, JP-A-7-12.
No. 8793, pages (6) to (18). I-1 to N
o. I-30, II-1 to II-12, III-1 to III-8,
Examples include, but are not limited to, IV-1 to IV-9, V-1 to V-8, and VI-1 to VI-5.

As a method for producing a solid fine particle dispersion of a dye according to the present invention, JP-A-52-92716, JP-A-52-92716,
5-155350, 55-155351, 63
Nos. 197943, 3-182743, and World Patent WO 88/04794 can be used. Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound dispersed in solid fine particles is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, after dissolving the compound in a weakly alkaline aqueous solution,
A method of precipitating a particulate solid by lowering the pH to make it weakly acidic, or a method of simultaneously preparing a weakly alkaline solution of the compound and an acidic aqueous solution while adjusting the pH to produce a particulate solid, A dispersion can be obtained. The solid fine particle dispersion of the present invention may be used alone, or may be used as a mixture of two or more kinds, or may be used by mixing with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

When the solid fine particle dispersion used in the present invention is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant is present during or after the dispersion.
As such surfactants, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates , Alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N
Anionic surfactants such as -acyl-N-alkyltaurines and nonionic surfactants such as saponins, alkylene oxide derivatives and alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, for example,
Compounds 1 to 32 described in pages 128793 (26) to (32) are exemplified, but not limited thereto.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye, but is usually preferably from 0.1 to 2000 mg per g of the dye. , More preferably 0.5 to 1000 mg, particularly preferably 1 to 50 mg.
0 mg may be sufficient.

The concentration of the dye in the dispersion is 0.01
使用 50% by weight is preferably used,
More preferably, it is 0.1 to 30% by weight. The addition position of the surfactant is preferably added before the start of dispersion of the dye,
If necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone, respectively, or two or more kinds may be combined, and both activators may be combined.

The dispersion of solid fine particles used in the present invention may be added with a hydrophilic colloid used as a binder in a photographic component layer before or after the start of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin.In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, and gelatin having a polymerizable ethylene group-containing monomer. Graft polymer, carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, polymethacrylic acid, etc. Agar, gum arabic, alginic acid, albumin, casein and the like. These may be used in combination of two or more. The amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is preferably 0.1% to 12% by weight, more preferably 0.5% to 12%.
8%.

A particularly preferred addition position of these solid disperse dyes is between the support and the emulsion layer.

When the processing agent is applied and supplied, the maximum concentration of the dye in the hydrophilic colloid layer on the side opposite to the emulsion layer with respect to the support is preferably 0.5 or less, more preferably 0.1 or less, and further preferably 0.1 or less. Preferably, it is substantially free of a dye.

Built-in developing agent As the developing agent that can be used in the present invention, an appropriate one can be selected from conventionally known ones. The developing agent referred to here includes a developing agent precursor that releases the developing agent during development.

Examples of the developing agent which can be used in the present invention include, for example, US Pat. Nos. 3,351,286, 3,761,270, 3,764,328, and 3,342,599. No. 3,719,492, Research Disclosure 12146, No. 1
Nos. 5108 and 15127 and JP-A-56-271.
No. 32, No. 53-135628, No. 57-79035
P-phenylenediamine and p-aminophenol-based developing agents, phosphoramidophenol-based developing agents, sulfonamidoaniline-based developing agents, and hydrazone-based developing agents, phenols, sulfonamidophenols, polyhydroxy Benzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols,
There are ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various developing agents.

Two or more developing agents may be used in combination, and 1-aryl-3-pyrazolidone or a derivative thereof and a hydroquinone derivative are particularly preferred.

The developing agent incorporated in the light-sensitive material according to the present invention preferably contains the silver halide emulsion contributing to image formation in an amount capable of developing 15% or more, preferably 50% or more, particularly preferably 100% or more. An acceptable amount is preferred.
Here, the developable amount means the number of moles of silver which can be reduced when the developing agent has theoretically reacted to the maximum with respect to the silver halide emulsion contained in the light-sensitive material.

These developing agents can be contained in the silver halide emulsion layer and other hydrophilic colloid layers. Preferably, the same side of the support as the silver halide emulsion layer is used, and more preferably, a hydrophilic colloid layer other than the silver halide emulsion layer is used. Particularly preferred is any layer between the support and the silver halide emulsion layer.

It is preferable that the developing agent used in the present invention is contained in a solid dispersion state from the viewpoint of storage stability of the light-sensitive material. As a method of dispersion, an aqueous solution containing a developing agent substantially free of an organic solvent such as ethyl acetate, methanol, methyl ethyl ketone and the like and a high boiling point organic solvent and optionally containing one or more stabilizers or pulverizers may be used. Or a method of removing the organic solvent under reduced pressure after mixing with water, or repeatedly subjecting the solid of the developing agent to a hard inorganic grinding medium in an aqueous solution which may contain one or more stabilizers or grinding agents Prepared. As the hard inorganic grinding medium, beads such as sand, silica spheres, stainless steel, silicon carbide, glass, zirconium, zirconium oxide, alumina, and titanium are used. These bead sizes range from 0.25 to 3.0 mm. A method of reducing the particle size using a ball mill, a media mill, an attritor mill, a jet mill, a vibration mill, or the like is often used.

The average particle size of the dispersion obtained as described above can be in the range usually obtained by the conventional method, and is generally 0.05 to 1.5 μm, preferably 0.1 to 1.5 μm. It is between 1 and 1.0 μm.

For the dispersion used in the present invention, a stabilizer or a dispersion aid is used. As the stabilizer or the dispersing aid, a surfactant or a hydrophilic colloid is preferable.

Techniques Used for Image Formation of the Present Invention Exposure light sources that can be used include a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, and a CR lamp.
A T light source, a FO-CRT light source, a light emitting diode, a laser light source (for example, a gas laser, a dye laser, a YAG laser, a semiconductor laser, or the like) can be used alone or in combination. In addition, semiconductor laser and S
A light source in combination with an HG element (second harmonic generation element) can also be used. Among them, a laser light source can be preferably used, and in particular, a laser light source having a wavelength of 600 to 700 nm can be preferably used.

In the present invention, it is preferable to use a solid processing agent.

It is preferable that each part granule of the developer and the fixing agent used in the solid processing agent of the present invention is coated. Sugars or water-soluble polymer compounds preferably used for coating include sugar alcohols, monosaccharides (eg, glucose, galactose, etc.), disaccharides (eg, maltose, sucrose, lactose, etc.), polysaccharides, polyalkylene glycols, polyvinyl alcohol, Examples include polyvinylpyrrolidone, polyvinyl acetal, polyvinyl acetate, aminoalkyl methacrylate copolymer, methacrylic acid-methacrylic acid ester copolymer, methacrylic acid-acrylic acid ester copolymer, and a vinyl polymer having a betaine structure. Preferred among these are sugar alcohols, polysaccharides and polyalkylene glycols.

Preferred as sugar alcohols are threitol, erythritol, arabitol, ribitol,
Xylitol, sorbitol, mannitol, iditol, talitol, galactitol, allozlicitol.

Preferred as polysaccharides are pullulan, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose,
Examples include cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose succinate, carboxymethylethylcellulose, dextrins, cyclodextrins, and starch degradation products. Particularly preferred starch decomposed products include Pine Flow and Paindex manufactured by Matsutani Chemical.

Specific preferred examples of the polyalkylene glycol include polyethylene glycol # 2000, # 4000, and # 6000 manufactured by Kanto Chemical.

Examples of the granulation method preferably used in the present invention include rolling granulation, extrusion granulation, spouted bed granulation, fluidized bed granulation, pulverized granulation, stirring granulation, and compression granulation. Can be applied. In addition, as a method of coating the saccharide or the water-soluble polymer compound on the granules in the present invention, the granules granulated by any method can be coated with pan coating, tumbling coating, fluid coating and the like.

By using a fluidized-bed granulator, a tumbling fluidized-bed granulator, or the like, granulation and coating can be continuously performed in the same container. This method is preferable in terms of high production efficiency and the effect of the present invention.

A fluidized-bed granulator may be a commercially available one.
More specifically, Powrex multiplex series,
Examples include the GPCG series, WST / WSG series, Fujimaru's New Malmerizer series, Ogawara's Mixgrade series, Freund's Spiral flow series, and flow coater series.

Light-sensitive Material The light-sensitive material used in the present invention preferably uses a silver halide emulsion having a silver chloride content of 60 mol% or more. Specifically, silver chloride or 60 mol% or more of silver chloride is used. It is preferable to use a silver halide emulsion having a composition of silver chlorobromide containing silver bromoiodide and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 0.6 μm.
m or less, especially 0.5 to 0.05 μm
m is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size.

For details of the method for determining the average particle size, see
Mies, James: The Theory of the Photographic Process (CE Mees & THJ)
ames: The theory of the p
photographic process), 3rd edition,
36-43 (1966 (Macmillan "Mcmill"
an ", published by the company)).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

Among the above tabular grains, tabular grains having a (100) plane having 90 mol% or more of silver chloride as a main plane can be used, and these are described in US Pat. No. 5,264,3.
No. 37, 5,314,798, 5,320,95
No. 8, etc., and desired tabular grains can be easily obtained.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

The silver halide emulsion is preferably chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used.

Examples of the combination used in combination with these chemical sensitizers include, for example, a combination of a sulfur sensitizer and a noble metal sensitizer,
Examples include a combination of a selenium sensitizer and a noble metal sensitizer, and a combination of a reduction sensitizer and a noble metal sensitizer.

These chemical sensitizers can be added at any time during the preparation of the silver halide emulsion, but preferably at the time of chemical sensitization. The addition amount of these chemical sensitizers is preferably in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole); mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion according to the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like may be used. it can.

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide] and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like) ), Mucohalogenic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener, etc., alone or in combination Can be used. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C.

The photosensitive material used in the present invention contains various other additives. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

The support used in the present invention may be either permeable or non-permeable, but for the purpose of the present invention, preferably a permeable plastic support. For the plastic support, a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.),
A support made of a triacetate compound (eg, triacetate cellulose or the like), a polystyrene compound (eg, syndiotactic polystyrene), or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In the present invention, the compounds described below are preferably contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4)
Compounds described on pages [0013] to (14), page [0039] (5) Supersensitizers JP-A-6-347938, page (3) [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
To (32) [0157] Compound described in JP-A-9-90538, page (23) [0091] to
(42) Compound described on page [0163] (7) Nucleation promoting agent JP-A-7-114126, page (32) [0158]
Compound described on page [36] to page [0169] JP-A-9-90538, page (36) [0164]
(52) Compound described on page [0186] (8) Tetrazolium compound JP-A-6-208188, page (8) [0059] to
(10) Compound [9] described on page [0067] (9) Pyridinium compound JP-A-7-110556, (5) page [0028]-
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (11) Syndiotactic polystyrene (SPS) support and undercoating JP-A-9-80664, page (3) [0022]-
(8) Compound described on page [0077] Regarding the aforementioned additives and other known additives,
For example, Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The types of compounds and the locations described in these three research disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Top right 996
III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Top right Fog inhibitor / stabilizer 24 IV 649 Top right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII As an exposure light source that can be used in the image forming method of the present invention, a tungsten lamp, a halogen lamp, Xenon lamps, mercury lamps, CRT light sources, FO-CRT light sources, light emitting diodes, laser light sources (eg, gas lasers, dye lasers, YAG lasers, semiconductor lasers, etc.) can be used alone or in combination. Further, a light source in which a semiconductor laser and an SHG element (second harmonic generation element) are combined can also be used. Among them, a laser light source can be preferably used.
A laser light source having a wavelength of 0 to 850 nm is preferably used.

Processing Technology According to the Present Invention The developing solution used in the present invention can use a known developing agent in combination. Specifically, dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (eg, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3
-Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-
Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc., ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complexes (EDTA iron salt, DTPA iron salt, DTPA nickel salt) Etc.) can be used alone or in combination. Among them, it is preferable to use a developer containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as developing agents and are described, for example, in US Pat. No. 2,688,548.
Nos. 2,688,549 and 3,022,168
Nos. 3,512,981, 4,975,354, and 5,326,816 can be used.

In the present invention, a developing agent of ascorbic acid or a derivative thereof and a 3-pyrazolidone (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like and dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate, sodium salt of hydroquinone monosulfonic acid, potassium salt of 2,5-hydroquinone disulfonic acid and the like) It is more preferred to use the developing agents in combination. When used in combination, the developing agents such as 3-pyrazolidones, aminophenols and dihydroxybenzenes are usually used in an amount of 0.01 to 0.1 per liter of developer.
Preferably it is used in an amount of less than 2 mol. In particular, combinations of ascorbic acid and its derivatives with 3-pyrazolidones and ascorbic acid and its derivatives with 3
-Combinations of pyrazolidones and dihydroxybenzenes are preferably used.

In the present invention, the developing solution contains an alkaline agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine). And the like are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
Molar range. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole,
Benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, biodegradable chelating agents, etc.), development accelerators (eg, U.S. Pat. No. 2,304,025, Japanese Patent Publication No. 47
45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

As the fixing solution, those having a commonly used composition can be used. Fixers generally have a pH of 3
８8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

As the fixing agent used in the one-bath treatment, the above-mentioned fixing agent is preferably used. Also, Japanese Unexamined Patent Publication No. 8-1794
Uracil, hydantoin and the like as described in No. 58 are also preferably used.

The fixing solution contains a water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, an aldehyde compound (for example, glutaraldehyde or a sulfurous acid adduct of glutaraldehyde).
Etc. can be added.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent capable of softening hard water. A compound such as an agent can be included.

The fixing solution contains salts such as acetic acid, citric acid, tartaric acid, malic acid and succinic acid, and optical isomers thereof. As the salts of acetic acid, citric acid, tartaric acid, malic acid, succinic acid and the like, these lithium salts, potassium salts,
Lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartaric acid, sodium potassium tartaric acid, and the like such as sodium salt and ammonium salt may be used.

As the developing solution and / or the fixing solution, a solution obtained by dissolving a solid processing agent such as a tablet or a granule in a solvent such as water can be used.

After the fixing treatment, it is washed and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt) , Polyphosphates, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophen, dichlorophen, formaldehyde, P-hydroxybenzoate, 2- (4-thiazoline) -benzo) Imidazole, benzoisothiazolin-3-one, dodecyl-benzyl-methylammonium-chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.).
Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In view of the demand for reducing the amount of waste liquid, the present invention is processed while performing a fixed amount of replenishing fixation in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² . Preferably 30 to 25 per m ² each
0 ml.

The temperature of the fixing, washing and / or stabilizing bath is preferably in the range of 30 to 45 ° C., and each may be separately adjusted.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film to the automatic developing machine until it comes out of the drying zone when processing using the automatic developing machine is 60 due to the demand for shortening the developing time. It is preferably 10 seconds or less and 10 seconds or more. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is a time including all the time of the process, that is, a time of Dry to Dry. Total processing time is 1
If the time is less than 0 second, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dr)
y) is 15 to 50 seconds. Further, in order to stably process a large amount of photosensitive material of 100 m ² or more, the developing time is preferably 18 seconds or less and 2 seconds or more.

In order to remarkably exert the effects of the present invention, a heat conductor (for example, 60 ° C.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

Examples of the heat transfer material at 60 ° C. or higher include:
A heat roller is mentioned as an example. It is preferable that the outer periphery of the hollow roller made of aluminum is covered with silicone rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

It is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a driving unit and a driving transmission unit. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

A thermistor arranged in contact with the outer peripheral surface of the heat roller is connected to the temperature controller. The temperature controller detects the temperature from the thermistor at 60 ° C. to 150 ° C., preferably 70 ° C. to 130 ° C. Thus, it is preferable that the halogen heater be turned on and off.

The following examples are given as radiating objects emitting radiation temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer material of 60 ° C. or more and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regenerating purifying agent and apparatus: JP-A-6-250352, page (3), “0011” to page (8), “0058”.

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between the developing bath and the fixing bath: JP-A-4-313949, page (18), “0054” to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) A method for controlling the drying air of an automatic developing machine by detecting the outside air temperature and humidity: Japanese Patent Laid-Open No. 1-315745.
6 (2) lower right column to 501 (7) lower right column and JP-A-2-108051, 588 (2) lower left column to 589
(3) The lower left column of the page.

(7) Method of recovering silver from fixing waste liquid:
No. 27623, page (4) “0012” to page (7) “00”
71 ".

[0211]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to embodiments, but embodiments of the present invention are not limited thereto.

Example 1 Preparation of silver halide (Preparation of silver halide emulsion A) Aqueous silver nitrate solutions B and N
A water-soluble halide solution C consisting of aCl and KBr was prepared at pH 3.
The mixture was added at a constant flow rate of 0.35 ° C. at a constant flow rate in Solution A for 15 minutes by a simultaneous mixing method.
Was obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Thereafter, the pH is adjusted to 5.6 with a 1N-NaOH aqueous solution, and
Aged at 10 ° C for 10 minutes. After this, unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin was added per mole of silver to adjust the pH to 5.7, followed by dispersion at 55 ° C. for 30 minutes. After dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per mol of silver. The silver potential of the finished emulsion is 190 mV
(40 ° C.).

A: ossein gelatin 25 g nitric acid (5%) 6.5 ml ion-exchanged water 700 ml B: silver nitrate 170 g nitric acid (5%) 4.5 ml ion-exchanged water 200 ml C: NaCl 47.5 g KBr 51.3 g ossein gelatin 6 g Na [RhCl ₅ (H ₂ O)] 0.05 mg ion-exchanged water 200 ml 4-hydroxy-6 per mole of silver was added to the obtained emulsion.
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
× 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. 2 × 10 ⁻⁵ mol of sulfur dispersed in the form of fine particles as sulfur atoms and 1.5 × 10 ⁻⁵ mol of chloroauric acid were added, and the temperature was ^{adjusted to 5 °} C.
After chemical ripening at 0 ° C for 80 minutes, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was 2 × 10 ⁻³ mol per mol of silver, 1 × phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 1.5 × 10 ⁴ mol. ^-3 mol was added. After cooling down to 40 ° C,
The sensitizing dyes S-2 and S-3 were each added in an amount of 1 × per mole of silver.
10 ^-4 mol and 1.5 × 10 ^-5 mol were added.

Using the emulsion thus obtained, a support was prepared on a subbed support from the support side in the following formulation so that the coating weight per m ² was as shown below.
Layers), [second layer] and [third layer] are coated simultaneously and set by cooling. Then, [backing layer] is coated on the undercoat layer on the opposite side from the support side, and the temperature is set at -1 ° C. Sample 101 was obtained by cooling and setting, and drying both sides simultaneously.

[0215]

Embedded image

First layer Gelatin 0.50 g Phenylcarbamoylated gelatin 0.10 g Polyvinylpyrrolidone (PVP) 0.10 g Polyethylene glycol (molecular weight 2000) 0.15 g 1-Phenyl-4,4'-dimethyl-3-pyrazolidone 07 g sodium-iso-amyl-n-decylsulfosuccinate 0.05 g sodium dodecylbenzenesulfonate 0.02 g 2-methylhydroquinone 0.70 g AM 0.05 g Second layer (emulsion layer) gelatin 0.90 g silver halide emulsion A 2.75 g as silver amount Hydrazine derivative H-7 0.12 g Phenylcarbamoylated gelatin 0.30 g Suspension polymer of 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, and 12.5% by weight of vinyl pivalinate 1.0g polymer latte L1 (particle size 0.10 μm) 0.5 g polyvinylpyrrolidone (PVP) 0.15 g surfactant (SU-1) 0.09 g 4-mercapto-3,5,6-fluorophthalic acid 0.05 g dye (f -1) 0.05 g Sodium polystyrene sulfonate (average molecular weight: 500,000) 0.015 g The coating solution pH was 5.2.

Third layer (protective layer) Gelatin 0.90 g Polyvinyl pyrrolidone (PVP) 0.05 g Ammonium polyacrylate 0.25 g Colloidal silica 0.20 g Surfactant (SU-2) 0.02 g Sodium dihexyl sulfosucci 0.010 g Disinfectant Z 0.005 g Hardener (1) 0.07 g PMMA latex (size 3 μm) 0.01 g Backing layer Gelatin 3.0 g Sodium dihexyl sulfosuccinate 0.020 g Polymer latex (L3) 30 g Colloidal silica (average particle size: 0.05 μm) 0.50 g Sodium polystyrene sulfonate 0.010 g Carnauba wax dispersion 0.2 g PEG 4000 (polyethylene glycol molecular weight 4000) 0.2 g Matting agent: single unit having an average particle size of 3 μm Polymethylmethacrylate 0.045g hardener (1) 0.05 g Hardener (2) 0.07 g

[0218]

Embedded image

[0219]

Embedded image

[0220]

Embedded image

Evaluation of photosensitive material The obtained silver halide photosensitive material was subjected to wedge exposure using a 780 nm semiconductor laser, and subjected to the following treatment using a one-bath developer having the following composition.

One-bath developer Pure water 200 ml DTPA / 5Na 1.0 g Sodium sulfite 20 g KBr 4 g Potassium carbonate 40 g Diethylene glycol 40 g 5-Methylbenzotriazole 0.21 g 8-Mercaptoadenine 0.07 g 1-Phenyl-5-mercaptotetrazole 0 0.03 g Developing agent Amount in Table 1 Sodium thiosulfate 100 g Sodium thiocyanate 20 g Fluorine-based activator S-141 0.5 g KOH 18 g manufactured by Asahi Glass Co., Ltd. Dissolved to 500 ml according to the above formula. The pH of the working solution was 11.0.

Processing Process The developing section is processed using the developing solution supply section and the developing apparatus shown in FIGS. 1 and 2, and then immediately washed with water and dried using an automatic plate making machine GR960 manufactured by Konica Corporation. Was.

FIG. 1 is a schematic sectional view of the developing process of the automatic developing device. In the developing step 1 of the automatic developing device, a transport path 3 for transporting the silver halide photographic material P by a plurality of transport rollers 2 is formed, and the transport path 3 is provided in a horizontal direction. The silver halide photographic light-sensitive material P is in the form of a sheet cut before being carried into the developing step 1, and is conveyed with the image forming surface P1 facing upward. The transport path 3 for transporting the silver halide photographic light-sensitive material P includes a preheating unit 1
0, a coating section 20 and a squeeze section 30 are arranged in the order of the photosensitive material transport direction.

In the preheating section 10, the transport roller 2 is disposed above the transport path 3, and the heat roller 11 is disposed below the transport path 3 in opposition to the transport roller 2.
The heat roller 11 has a built-in heater 12, and the heat roller 11 constitutes a heating means for applying heat for processing the silver halide photographic material P. The silver halide photographic light-sensitive material P is heated to 35 ° C. to 90 ° C. by the heat roller 11, preferably 40 ° C. to 60 ° C.
The development is further promoted by heating to.

In the coating section 20, the processing liquid supply means disposed above the transport path 3 has a liquid supply section 21, and the transport roller 2 is provided below the transport path 3 opposite to the liquid supply section 21. Are located. The liquid supply unit 21 is arranged such that the axial direction thereof extends along the width direction of the silver halide photographic light-sensitive material P, and the liquid supply unit 21 is provided on the downstream side in the photosensitive material transport direction with respect to the heating means. The liquid supply section 21 has a supply port 22 formed along the axial direction toward the image forming surface P1 of the silver halide photographic light-sensitive material P. From this supply port 22, the image forming surface of the silver halide photographic light-sensitive material P is formed. The processing liquid is applied and supplied to P1.

In the squeeze section 30, squeeze rollers 31 are disposed opposite to each other above and below the transport path 3, and if at least the upper side of the squeeze roller which is in contact with the image forming surface P1 of the silver halide photographic material P is used as the squeeze roller Often, in this case, the lower side is constituted by the transport roller 2. Squeeze roller 31
Is arranged downstream of the liquid supply section 21 in the photosensitive material transport direction, and squeezes the developer supplied on the silver halide photographic material P to make it uniform.

The squeeze roller 31 is preferably a roller having little water absorption, and is preferably a metal roller such as SUS, a plastic roller, a rubber roller, a woven fabric roller, a nonwoven fabric roller, or a sintered roller. Specifically, stainless steel (SUS316L, SUS316, S
US304, SUS303), titanium (Ti), brass (Bs) and the like. As the plastic roller, the material of the squeeze roller is polyethylene terephthalate (PET), polyethylene (PE), ethylene tetrafluoride / perfluoroalkoxyethylene copolymer resin (PFA), polyacetal (POM), polypropylene (PP) , Polytetrafluoroethylene (PTFE),
Polyvinyl chloride (PVC), phenolic resin (PF),
Modified polyphenylene ether (PPE), modified polyphenylene oxide (PPO), polyurethane (PU),
Polycarbonate (PC), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene tetrafluoride / propylene hexafluoride copolymer resin (FE
P), ethylene tetrafluoride / ethylene copolymer resin (ETF
E) and the like are preferred. As rubber rollers, ethylene propylene rubber (EPDM, EPM), silicone rubber (S
i), nitrile rubber (NBR), chloroprene rubber (C
R) and the like are preferred. The material of the woven or nonwoven fabric is preferably a polyolefin fiber, a polyester fiber, a polyacrylonitrile fiber, an aliphatic polyamide fiber, an aromatic polyamide fiber, a polyphenylene sulfide fiber, or the like.
Further, a roller coated with Teflon is more preferable.

Heating means 13 and 14 for heating the silver halide photographic light-sensitive material P are arranged between the liquid supply section 21 and the squeeze roller 31 and at a stage subsequent to the squeeze roller 31.

Next, the configuration of the liquid supply section disposed in the coating section will be described with reference to FIG. The supply port 22 formed in the liquid supply section 21 sets the distance L1 between the tip 22a and the silver halide photographic material P to 0.03 mm to 10 mm. The processing liquid supplied from the liquid supply unit 21 is applied and supplied so as to flow in a curtain shape on the image forming surface P1 of the silver halide photographic light-sensitive material P, and becomes uniform.

If the distance L1 between the leading end 22a of the supply port 22 and the silver halide photographic material P is smaller than the set value, the end of the liquid supply part 21 is changed due to the thickness variation or swelling of the silver halide photographic material P. When the distance L1 is set to 0.03 mm to 10 mm, these problems can be solved.

At this time, the processing conditions of the developing section are as shown below.

Temperature of heat roller (11) 50 ° C. Time from contact with human roller to supply of developer 2 seconds Distance between developer supply port and photosensitive material (L1) 3 mm Slit width of developer supply port (22) 0.10 mm Time from supply of developer to water washing 15 seconds Temperature of developer supply (5 seconds after application of developer) 35 ° C. 5 seconds after supply of developer to start of water washing 45 ° C. Washing conditions 20 ° C./9 seconds Drying conditions 45 ° C. / 15 sec Supply rate: 1 bath developer 50 ml / m ² Rinse water 5 L / min Sensitivity, Dmax, Dmin The obtained sample of the developed photosensitive material is blackened with a PDA-65 (Konica Corporation, digital densitometer). Of the sample No. The reciprocal of the amount of exposure at which 101 gives a blackening density of 1.0 is expressed as a relative sensitivity with the reciprocal of 100 being taken as 100.

Γ (gamma) γ = (3-1) / [Log (exposure amount giving D = 3) −
Log (exposure amount giving D = 1)] Image setter Doveve8 manufactured by Mura Scitex Co., Ltd.
With the use of 00, a square dot of 175 L with a halftone of 50% was output at an appropriate exposure amount, the above processing was performed, and unevenness was visually evaluated.
A sample having no unevenness at all was assigned a rank of 5, and a practically usable lower limit level was assigned a rank of 3, and was visually evaluated.

[0235]

[Table 1]

From Table 1 above, it can be seen that unevenness does not occur in the development containing the compound represented by the general formula (A) in the coating and developing system, and γ is high.

Example 2 Preparation of Silver Halide (Preparation of Silver Halide Emulsion B) Aqueous Solutions A and N of Silver Nitrate
The water-soluble halide B consisting of aCl and KBr is converted to a silver potential (E
Ag) at 120 mV, pH 3.0, 35 ° C. in liquid C for 7 minutes by the simultaneous mixing method, and 0.09 μm of AgCl was 70;
AgBr formed 30 nuclei. Thereafter, the silver potential was adjusted to 100 mV with NaCl, an aqueous silver nitrate solution D and a water-soluble halide solution E were added again for 15 minutes, and a silver halide emulsion having a particle diameter of 0.20 μm (coefficient of variation: 15%), AgCl of 70 and AgBr of 30 was added. Obtained. Then pH is adjusted with 1N-NaOH aqueous solution.
The temperature was adjusted to 5.6 and aged at 50 ° C. for 10 minutes. Thereafter, denatured gelatin treated with phenyl isocyanate was added, and the pH was adjusted.
4.2 Wash the block with water and after washing with water, 15
g of gelatin was added to adjust the pH to 5.7, and the mixture was dispersed at 55 ° C. for 30 minutes. After dispersion, chloramine T was added at 4 × per mole of silver.
10 ^-4 mol was added. The silver potential of the resulting emulsion was 19
0 mV (40 ° C.).

A: silver nitrate 16 g nitric acid (5%) 5.3 ml ion-exchanged water 48 ml B: NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g ion-exchanged water 48 ml C: NaCl 1.4 g ossein gelatin 7 g nitrate (5%) 6.5 ml K ₂ RhCl ₅ (H ₂ O) 0.06 mg ion exchange water 700 ml D: silver nitrate 154 g nitric acid (5%) 4.5 ml ion exchange water 200 ml E: NaCl 37 g KBr 33 g ossein gelatin 6 g K ₂ RhCl ₅ (H ₂ O) 0.04 mg ion-exchanged water 200 ml 4-hydroxy-6 per mole of silver was added to the obtained emulsion.
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
The pH was adjusted to 5.6 and the EAg was adjusted to 123 mV by adding × 10 ^-3 mol and 8.5 × 10 ^-4 mol of potassium bromide. 2 × 10 ⁻⁵ mol of sulfur dispersed as fine particles and 1.5 × 10 ⁻⁵ mol of chloroauric acid are added as sulfur atoms, and the temperature is adjusted to 60.
After ripening at 80 ° C for 80 minutes, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was 2 × 10 ⁻³ mol per mol of silver, 1 × phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 1.5 × 10 ⁴ mol. ^-3 mol was added. After cooling down to 40 ° C,
Sensitizing dye S-1 was added in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver.

(Preparation of Silver Halide Emulsion C) Aqueous silver nitrate solution B and a water-soluble halide solution C comprising NaCl and KBr were added at a constant flow rate of 3.0 at 35 ° C. in Solution A for 15 minutes by a double jet method. 0.09 μm AgCl70, Ag
A cubic crystal of Br30 was obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Then, the pH is adjusted to 5.6 with 1N-NaOH aqueous solution.
And aged at 50 ° C. for 10 minutes. This ultrafiltration removes unnecessary salts, and then 15% per mole of silver.
g of gelatin was added to adjust the pH to 5.7, and the mixture was dispersed at 55 ° C. for 30 minutes. After dispersion, chloramine T was added at 4 × per mole of silver.
10 ^-4 mol was added. The silver potential of the resulting emulsion was 19
0 mV (40 ° C.).

A: ossein gelatin 25 g nitric acid (5%) 6.5 ml ion-exchanged water 700 ml B: silver nitrate 170 g nitric acid (5%) 4.5 ml ion-exchanged water 200 ml C: NaCl 47.5 g KBr 51.3 g ossein gelatin 6 g K ₃ [RhCl ₆ ] 0.06 mg ion-exchanged water 200 ml 4-hydroxy-6 per mole of silver was added to the obtained emulsion.
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
The pH was adjusted to 5.6 and the EAg was adjusted to 123 mV by adding × 10 ^-3 mol and 8.5 × 10 ^-4 mol of potassium bromide. 2 × 10 ⁻⁵ mol of sulfur dispersed as fine particles and 1.5 × 10 ⁻⁵ mol of chloroauric acid are added as sulfur atoms, and the temperature is adjusted to 50 ^° C.
After ripening at 80 ° C for 80 minutes, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene per mol of silver was 2 × 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 1.5 × 10 ⁴ mol. ^-3 mol was added. After cooling down to 40 ° C,
The hydrazine derivative H-6 was added in an amount of 3.5 × 10
^-3 mol was added.

Using the emulsion thus obtained, a support was prepared on a subbed support from the support side in the following formulation so that the coating weight per m ² was as shown below.
Layers), [second layer], [third layer] and [fourth layer] are simultaneously coated and cooled and set, and then a [backing layer] is placed on the opposite undercoat layer from the support side. The sample 201 was obtained by applying, cooling and setting at -1 ° C, and simultaneously drying both surfaces.

First Layer (Developer-Containing Layer) Gelatin 0.50 g Phenylcarbamoylated gelatin 0.10 g Polyvinylpyrrolidone (PVP) 0.10 g Polyethylene glycol (molecular weight 2000) 0.15 g Sodium-iso-amyl-n-decyl sulfo Succinate 0.05 g Sodium dodecylbenzenesulfonate 0.02 g Developing agent Amount in Table 1 AM 0.05 g Solid disperse dye (f-2) Average particle size 90 nm 0.05 g Second layer (emulsion layer) Gelatin 0.90 g Halogen Silver halide emulsion B 0.30 g in terms of silver amount Silver halide emulsion C 2.40 g in terms of silver amount Hydrazine derivative H-7 0.020 g Phenylcarbamoylated gelatin 0.30 g 75% by weight of colloidal silica and 12.5% by weight of vinyl acetate Suspension of 12.5% by weight of vinyl pivalinate Compound 1.0 g Polymer latex (L1) (particle size 0.10 μm) 0.5 g Polyvinylpyrrolidone (PVP) 0.15 g Surfactant (SU-1) 0.09 g 4-mercapto-3,5,6-fluoro Phthalic acid 0.05 g Dye (f-1) 0.02 g Sodium polystyrene sulfonate (average molecular weight 500,000) 0.015 g The coating solution pH was 5.2.

Third layer (protective layer) Gelatin 0.70 g Polyvinylpyrrolidone (PVP) 0.04 g Polyacrylic acid 0.15 g Colloidal silica 0.15 g Disinfectant Z 0.005 g Hardener (1) 0.07 g PMMA latex (Size 3 μm) 0.01 g Fourth layer (protective layer) Gelatin 0.20 g Polyvinylpyrrolidone (PVP) 0.01 g Polyacrylic acid 0.05 g Colloidal silica 0.05 g Dimethylsiloxane (average molecular weight 100,000) dispersion (average particle size) Diameter 0.2 μm) 0.03 g Surfactant (SU-2) 0.01 g Sodium-dihexyl sulfosuccinate 0.005 g Fungicide Z 0.001 g Backing layer Gelatin 3.0 g Sodium dihexyl sulfosuccinate 0.020 g Polymer Latex (L3) 0.30g roller Dal silica (average particle size: 0.05 μm) 0.50 g Sodium polystyrene sulfonate 0.010 g Carnauba wax dispersion 0.2 g PEG 4000 0.2 g Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 3 μm 0.045 g Hardener (1) 0.05 g Hardener (2) 0.07 g Evaluation of photosensitive material The obtained silver halide photosensitive material was treated with He-N of 633 nm.
Wedge exposure was carried out using an e-laser, and after treatment with a developing solution and a fixing solution according to the following processing processes 2 and 3, washing and drying were performed.

Processing Process 1 Developer Pure Water 150 ml DTPA · 5Na 1.0 g Sodium sulfite 20 g KBr 4 g Potassium carbonate 40 g Diethylene glycol 20 g 5-Methylbenzotriazole 0.21 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S (1 -Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone) 0.85 g Sodium erythorbate 30.0 g Fluorinated activator S-141 manufactured by Asahi Glass Co., Ltd. 0.5 g KOH 18 g According to the above formula, dissolve and 400 ml. Finished. The pH of the working solution was 11.0.

Fixing solution Pure water 200 ml Sodium thiosulfate 120 g Sodium sulfite 20 g Disodium citrate 20 g Fluorinated activator S-141 manufactured by Asahi Glass Co., Ltd. 0.5 g According to the above-mentioned formulation, dissolve and add citric acid to pH 5.3. The volume was adjusted to 400 ml with pure water.

Stabilizing liquid (per liter of liquid used) Biodegradable chelating agent (Ch) 40 g Potassium sulfite 35 g Potassium carbonate 25 g 8-Mercaptoadenine 0.1 g Sanbac-P (manufactured by San-ai Sekiyu KK) 20 g The evaluation was performed using a prototype developing machine as shown in FIG. In the drawing, the photosensitive material P is subjected to development, fixing, stabilization, and drying along a route indicated by an arrow with the emulsion coated surface facing upward. In the figure, reference numeral 41 denotes a driving roller for transporting a photosensitive material, and reference numeral 42 denotes a preheat drum for preheating. Reference numeral 43 denotes a drying air outlet, and reference numeral 44 denotes a stabilizing liquid discharge nozzle. Reference numeral 45 denotes a developer discharge nozzle, and reference numeral 46 denotes a fixer discharge nozzle. h-
1, h-2 and h-3 represent panel heaters for heating the photosensitive material.

The structure of the discharge nozzles indicated by 45 and 46 is shown in FIG.

In the figure, 53 is a piezo element, 51 is a liquid inlet passage, 54 is a vibration plate, 52 is a chamber, 57 is an orifice channel, 56 is an orifice, and 58 is a droplet.

Eight nozzles shown in FIG. 4 were bundled and operated in the direction perpendicular to the direction of transport of the photosensitive material to supply the processing liquid to the entire surface of the photosensitive material.

The settings at this time are shown below.

Heat drum temperature 40 ° C. Time from contact of heat drum to supply of developer 2 seconds Distance between developer supply port and photosensitive material 3 mm Scanning speed of developer supply section 500 mm / s Developer supply 40 ml / m ² Time from liquid supply to fixing 10 seconds Temperature from developing liquid supply to fixing 50 ° C. Scanning speed of fixing liquid supply section 500 mm / s Fixing liquid supply amount 40 ml / m ² Time from fixing liquid supply to water washing 10 seconds Fixing liquid supply Temperature until post-water washing 45 ° C Water washing time 4 seconds Water washing temperature 40 ° C Drying time 10 seconds Drying temperature 45 ° C Processing process 2 Developer A Pure water 120ml DTPA / 5Na 1.0g Sodium sulfite 20g KBr 4g Diethylene glycol 20g Dimesone S 0.85g Sodium erythorbate 30.0 g Fluorinated activator S-141 manufactured by Asahi Glass Co., Ltd. In accordance with .5g the above formulation, finished in 200ml dissolved. The pH of the working solution was 6.3.

Developer B Pure water 120 ml Potassium carbonate 40 g 5-Methylbenzotriazole 0.21 g 1-Phenyl-5-mercaptotetrazole 0.03 g KOH 18 g According to the above-mentioned formulation, the solution was dissolved to a final volume of 200 ml. The pH of the working solution was 11.8.

The same fixing solution and stabilizing solution as those used in Process 1 were used.

Developing machine The processing liquid supply section was combined as shown in FIG. 5, except that developer A was supplied from the portion represented by a and developer B was supplied from the portion represented by b. went.

Replenishing Amount of Developer A 20 ml / m ² Replenishing Amount of Developer B 20 ml / m ² Processing Process 3 Using developer, fixing solution, and stabilizing solution used in Process 2 Developer of developing machine in FIG. 3 The processing was performed using a developing machine whose supply part was modified as shown in FIG. The process was performed in the same manner as in the process 1 except that the developer A was supplied from the portion represented by 5c and the developer B was supplied from the portion represented by 5d.

Each of 5c and 5d is a bundle of five nozzles shown in FIG.

Amount of replenishment of developer A 20 ml / m ² Amount of replenishment of developer B 20 ml / m ² Supply time of developer B after supply of developer A 2 seconds Time from supply of developer B to supply of fixer 10 seconds Processing Process 4 The developing process, fixing solution, and stabilizing solution used in the processing process 3 were used, and the developing solution B was supplied from the portion represented by 5c and the developing solution A was supplied from the portion represented by 5d. The same was done.

Amount of replenishment of developer A 20 ml / m ² Amount of replenishment of developer B 20 ml / m ² Supply time of developer A after supply of developer B 2 seconds Time from supply of developer A to supply of fixer 10 seconds The sensitivity, gamma, and unevenness were evaluated in the same manner as in Example 1. In addition, black pots were evaluated by the following method.

Black Pot The non-image portion of the obtained sample was visually observed with a magnifying glass of 40 times, and a sample having no black pot was ranked 5 and the practical lower limit was set to rank 3.

[0260]

[Table 2]

As can be seen from Table 2, the occurrence of unevenness is improved by separating the developer solution containing the compound represented by the general formula (A) from the alkali solution. In particular, it can be seen that the developer supplied with the developer containing the compound represented by the general formula (A) and then supplied with the alkali liquid is excellent in sensitivity, γ and unevenness.

[0262]

According to the present invention, there is no problem that the activity of the processing liquid is different between the new liquid state and the running state, and the composition of the processing liquid changes due to evaporation or air oxidation during storage in the processing tank. An image forming method using a silver halide photographic light-sensitive material that does not cause processing unevenness in a light-sensitive material having high photographic characteristics of γ10 or more, and a developer for the silver halide photographic light-sensitive material used in the image forming method Can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a developing device according to the present invention.

FIG. 2 is a schematic sectional view of a developer supply unit according to the present invention.

FIG. 3 is a schematic sectional view of a developing device according to the present invention.

FIG. 4 is a schematic sectional view of a developer supply unit according to the present invention.

FIG. 5 is a schematic sectional view of a developer supply unit according to the present invention.

FIG. 6 is a schematic sectional view of a developing device according to the present invention.

[Explanation of symbols]

3 Conveyance path for transporting silver halide photographic light-sensitive material P 21 Liquid supply unit 22 Supply port 22a Tip P Silver halide photographic material P1 Image forming surface of silver halide photographic material P L1 Tip 22a of supply port 22 and halogen Distance from silver halide photographic material P

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed, and then a developer represented by the formula (A) is applied and supplied onto the light-sensitive material. Forming an image by forming the image. Embedded image [Wherein, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 2. A silver halide photographic light-sensitive material comprising a compound represented by the general formula (A) as a developing agent, wherein the developer is applied on a light-sensitive material to form an image. Material developer. 3. The image forming method according to claim 1, wherein an image is formed by applying and supplying a developer containing the compound represented by the general formula (A) and an alkaline aqueous solution. 4. The image forming apparatus according to claim 3, wherein an image is formed by supplying a developer containing the compound represented by the general formula (A) and then applying and supplying an alkaline aqueous solution. Method.