JPH11212220A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method capable of obtaining a clear and sharp image having discrimination between high density and low minimum density and improved image preservation in a short time, and also, whose work environment is improved, as for a monochromatic image forming method. SOLUTION: As for the image forming method, after image-exposing silver halide photosensitive material which is provided with at least one photosensitive silver halide emulsion layer and one hydrophilic colloid layer on a supporting body, the material is developed by developer so as to form a monochromatic image. In this case, the developer is applied on the silver halide photosensitive material by a processing liquid supply means for spraying the developer with gaseous phase, and also, the UV density and visual density of the layer opposite to the layer containing the photosensitive silver halide of the supporting body are controlled to be <0.3, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a black-and-white image using a silver halide light-sensitive material (hereinafter, also simply referred to as a light-sensitive material). The present invention relates to an image forming method capable of easily obtaining a sharp black-and-white image having excellent performance.

[0002]

2. Description of the Related Art At present, as image information, black and white images have largely changed from black and white images to color images due to the large amount of information and ease of expression. However, black and white images are preferred in specific fields such as medical fields. Rarely used. Further, in the printing field, plate making materials for color images are also used as black and white images for each printing ink, and there is still a great demand mainly for industrial applications.

Conventionally, a photosensitive material has been processed by immersing it in a processing solution stored in a processing tank for a predetermined time.
However, 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. Therefore, a method of replenishing a replenisher in order to keep the activity of the processing solution constant is generally widely used.
The replenishment of the replenisher is intended to dilute the eluate from the light-sensitive material, correct the amount of evaporation, and replenish the consumed components.

Particularly, in the field of printing plate making in which a high contrast image of gamma (γ) of 10 or more is formed, the effect of the activity of the processing solution is remarkable. In order to reduce the opening area of the processing tank and to shorten the renewal time of the processing solution in the processing tank, JP-A-9-212826 and JP-A-9-23056
No. 3 described in JP-A-9-13399.
A method using a sealed multi-stage treatment tank described in No. 3 is known. However, these methods basically use a processing tank, and thus cannot be a sufficient solution to the above problem.

In addition to such processing, there is a so-called one-bath processing in which development and fixing are performed with one processing solution.

The one-bath processing has the advantages of reducing the number of processing liquids and processing mechanisms by one compared with the ordinary two-bath processing, making it possible to reduce the size of an automatic developing machine, and reducing the preparation of a solution. In such a case, the reproducibility of fine halftone dots required for a printing photosensitive material is remarkably deteriorated, and there is a serious problem such as a large decrease in sensitivity.

In recent years, due to the growing interest in environmental issues,
There is a strong demand for reduction of photographic processing waste liquid. Further, the discharge of the developing solution is restricted, and there is a demand for low replenishment of the processing solution.

Therefore, the conventional replenishing amount of the processing solution is usually 350 ml or more per 1 m ^{2 of the} photosensitive material to be processed, but in recent years, it has become necessary to process at a rate of 250 ml or less per 1 m ² .

However, when such low replenishment is performed, the above-described faithful reproducibility of fine halftone dots and a decrease in sensitivity become more remarkable, which is a serious problem.

Also, the fact that a large amount of processing liquid is always present in the processing tank of the automatic processing machine is not preferable in terms of the working environment, and improvement has been desired.

Japanese Patent Application Laid-Open No. 9-80720 discloses a method in which a processing liquid is sprayed by an ink jet nozzle. However, there is no mention of a high-contrast black-and-white image forming method, and a minute halftone dot required for a photosensitive material for printing. Was insufficient to achieve reproducibility and sensitivity.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for forming a black-and-white image in which a high density and a minimum density can be distinguished in a short time. It is an object of the present invention to provide an image forming method capable of obtaining a sharp image excellent in image storability and further excellent in a working environment.

[0013]

[Means for Solving the Problems] A method for forming a black-and-white image by imagewise exposing a silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on a support, followed by processing using a developer, The developing solution is applied to a silver halide photographic material by a processing solution supply means that flies through a gas phase, and the UV of the layer on the support opposite to the layer containing the photosensitive silver halide is applied.
An image forming method, wherein each of the density and the visual density is less than 0.3.

2. 2. The image forming method according to claim 1, wherein the developer is processed using a developer containing at least one kind of silver halide solvent in an equimolar amount or more with a developing agent.

3. 3. The image forming method according to 1 or 2, wherein at least one of the silver halide solvents contained in the developer is an organic fixing agent.

4. The image forming method according to any one of claims 1 to 3, wherein the processing liquid is only one type of liquid.

5. The amount of the developing solution applied by the processing solution supply means for flying the silver halide photographic material through the gas phase is 1 per 1 m ^{2 of the} silver halide photographic material.
The image forming method according to any one of claims 1 to 4, wherein the amount is from 0 to 150 ml.

6. The image forming method according to any one of 1 to 5, wherein the amount of silver contained in the silver halide photographic material is from 0.3 to 3.4 per 1 m ^2.

[7] Any one of 1 to 6, wherein the silver halide photographic light-sensitive material contains a hydrazine derivative.
Item.

8. A layer opposite to the layer containing the photosensitive silver halide with respect to the support of the silver halide photographic light-sensitive material, wherein the layer has a water absorption of less than ² g per m2.
The image forming method according to claim 1.

9. After imagewise exposing the silver halide photographic light-sensitive material, the processing temperature for forming a black-and-white image is 25 ° C. to 50 °
The image forming method according to any one of claims 1 to 8, wherein the temperature is ° C.

10. In the processing for forming a black-and-white image after the imagewise exposure of the silver halide photographic light-sensitive material, the temperature before 30% of the total processing time from the start of processing is less than 40 ° C. and after 70% of the total processing time The image forming method according to any one of claims 1 to 9, wherein the temperature of the image is higher than 40 ° C.

11. 11. The method according to any one of 1 to 10, wherein after the imagewise exposure of the silver halide photographic light-sensitive material, a process of adding water is performed before the developer is applied to the silver halide photographic light-sensitive material. 2. The image forming method according to 1.

12. Any one of 1 to 11, wherein prior to processing of the silver halide photographic light-sensitive material, the silver halide photographic light-sensitive material is supported by a carrier provided with a rubber-containing layer capable of temporarily bonding and supporting. 2. The image forming method according to claim 1.

13. 13. The image forming method according to any one of 1 to 12, wherein the silver halide photographic material is exposed by a laser beam.

14. 600 silver halide photographic materials
The image forming method according to any one of claims 1 to 13, wherein the exposure is performed with light having a wavelength of from 700 nm.

15. Wherein the silver halide photographic material is processed with a liquid prepared from a solid processing agent.
15. The image forming method according to any one of 14.

Hereinafter, the present invention will be described in detail.

The processing liquid supply means for causing the developing solution of the present invention to fly on the photosensitive material through the gas phase may be a processing liquid having the same structure as the ink jet head of the ink jet printer or a liquid having a structure described in JP-A-6-324455. Examples thereof include those that generate pressure and actively fly by generating pressure, and those that fly by the liquid pressure of the processing liquid such as a spray bar. As a method to fly actively,
An object 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 easy to control the supply amount of the processing liquid, and the position of the processing position of the photosensitive material can be easily controlled. It is particularly preferably used because of its ease of selection.

The processing liquid supply means may be a means for supplying a processing liquid from a linear supply head to a photosensitive material via a gaseous phase, or a means for supplying a processing liquid from a planar supply head via a gaseous phase. , Or another method. When the photosensitive material is in the form of a sheet, the processing liquid is exposed from the supply head in a state where the positional relationship between the photosensitive material and the supply head is fixed using a planar supply head corresponding to the size of the photosensitive material. Although the material may be supplied via the gas phase, the supply head is smaller when the processing liquid from the supply head is supplied to the photosensitive material via the gas phase while shifting the positional relationship between the supply head and the photosensitive material. 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, but in order to quickly supply the processing liquid to the photosensitive material, the supply head is moved in a direction parallel to the linear supply head. It is preferable to move the photosensitive material.

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. Further, 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 processing liquid flying means exposes the processing liquid per second. The number of times the material is caused to fly through the gas phase is preferably at least one time, and particularly preferably at least ten times, in order to sufficiently supply the processing liquid to the surface of the photosensitive material. In addition, 1 × 10
^It is preferably 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, and 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 treatment liquid from being clogged with a little drying. Further, the area of each supply port is preferably 1 × 10 ⁻⁸ m ² or less, particularly preferably 1 × 10 ⁻⁶ m ² or less in order to uniformly supply a processing solution to obtain a photosensitive material. The distance between the supply ports is preferably 5 × 10 ⁻⁶ m ² or more in terms of the strength of the supply ports, and the average of the distance between the edges of the supply port and the nearest supply port. It is preferably 1 × 10 ⁻³ m ² or less for supplying a liquid.

The distance between the supply port after processing and the emulsion surface of the light-sensitive material 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). .

The amount of the processing liquid used is preferably small within a range that does not affect the image quality, from the viewpoint of the amount of waste liquid and the handleability. Specifically, the photosensitive material 1 m ² per 10
150 ml is preferred, and more preferably 15 to 110 m
1 and 20 to 80 ml are most preferred.

In the present invention, from the characteristics of the processing liquid supply means, it is preferable that only the emulsion surface of the photosensitive material be in contact with the processing liquid. Therefore, it is necessary that the layer on the opposite side does not cause any problems in the subsequent process even if it is not treated, that is, the UV and visible densities are sufficiently low. Specifically, the UV and visual densities are each 0.1.
It is necessary to be less than 3, preferably less than 0.2 and more preferably less than 0.1 each. Further, it is preferable that there is no specific color.

As the silver halide solvent of the present invention, general formulas (I) to (V) described in JP-B-7-120023 can be used.
And the like. In the present invention,
Thiosulfates (eg, sodium thiosulfate, ammonium thiosulfate), imide compounds (eg, uracil, 5-methyluracil, 6-methyluracil, 6-butylthiouracil), 4-substituted thiourea compounds, organic thioether compounds, thione compounds , Active methylene compounds and mesoionic compounds are preferably used. Preferably, sodium thiosulfate, ammonium thiosulfate, uracil, 5-methyluracil, 6-methyluracil, 6-butylthiouracil are used. Particularly, sodium thiosulfate is preferable.

In the present invention, as the silver halide solvent to be added to the developer, only one kind may be used, or a plurality of kinds of silver halide solvents may be used in combination. It is preferable to use a silver halide solvent in combination, and it is more preferable to use an organic fixing agent in combination.

The hydrazine derivative used in the silver halide photographic light-sensitive material of the present invention is preferably a compound represented by the following formula (H).

[0040]

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In the general formula (H), A is an aryl group,
Or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a — (CO) _n — group, a sulfonyl group, a sulfoxy group, a —P (＝ O) R ₂ — group, or an iminomethylene group. , N represents an integer of 1 or 2, A ₁ and A _{2 each} represent a hydrogen atom or one of which is a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group; Represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or 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).

[0043]

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In the general formula (Ha), R ¹ represents 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) , A thienyl group, a furyl group), and those groups further preferably substituted with a suitable substituent are preferably used. 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.

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 general 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 formula (H) are shown below, but the present invention is not limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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

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

In the present invention, the hydrazine derivative can be used in any photographic constituent layer on the side of the silver halide emulsion layer. Preferably, a silver halide emulsion layer and / or
Alternatively, it is used for at least two or more of the hydrophilic colloid layers adjacent thereto. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably in the range of 10 ^-5 to 10 ^-2 mol. And the amount of the hydrazine derivative contained in the photographic component layer closest to the support in the hydrazine derivative-containing photographic component layer is:
The molar equivalent is 0.2 to 0.8 times the total amount of the hydrazine derivative contained in the photographic constituent layer farther from the support. Preferably, it is 0.4 to 0.6 times molar equivalent. Even if the hydrazine derivative used in the present invention is one kind,
Two or more kinds may be used in combination.

In the light-sensitive material used in the image forming method of the present invention, a 5- or 6-membered nitrogen-containing heterocyclic derivative can be used as a contrasting agent. The 5- or 6-membered nitrogen-containing heterocyclic derivative used is represented by the following general formula (Pa), (Pb) or (Pc).

[0061]

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In the general formula (Pa), (Pb) or (Pc), A ₁ , A ₂ , A ₃ , A ₄ or A ₅ is a non-metal for completing a 5- to 6-membered nitrogen-containing heterocycle. Represents a group of atoms,
The hetero ring may contain an oxygen atom, a nitrogen atom and a sulfur atom, and the hetero ring 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 have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. ,
Sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group,
Represents a carbamoyl group, a ureido group, an amino group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group.

Examples of the 5- or 6-membered nitrogen-containing heterocycle 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), Bp
Represents a divalent linking group, and m is 0 or 1. The divalent linking group includes alkylene, arylene, alkenylene, -S
O _2- , -SO-, -O-, -S-, -CO-, -N
(R ₆ ) — and (R ₆ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of Bp include an alkylene group, an alkenylene group, and an alkyleneoxy group.

In the general formulas (Pa) and (Pc),
R ₁ , R ₂ or R ₅ represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ may be the same or different, and A ₁ , A ₂ And the same groups as those described as the substituent for A ₃ , A ₄ or A ₅ can be mentioned.

In a preferred example, R ₁ , R _{2 and} R ₅ each represent an alkyl group having 4 to 10 carbon atoms, and more preferably a substituted or unsubstituted aryl group or substituted alkyl group.

[0067] Formula (Pa), in (Pb) or (Pc), X _p ^- is a counter ion necessary to balance the charge of the whole molecule, such as chlorine ions, bromine ions, iodine ions, nitrate ions, represents sulfate ion, p- toluenesulfonate, oxalate, n _p represents the number of counter ions needed to balance the charge of the whole molecule, in the case of intramolecular salt n _p is 0. Specific examples of the compounds are shown below.

[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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In the present invention, hydrazine or 5 to 6
It is preferable to use a nucleation accelerator in order to effectively promote hardening of the member by the nitrogen-containing heterocyclic derivative.

As a preferable nucleation accelerator, a compound represented by the following general formula [Na] or [Nb] is preferably used.

[0075]

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In the general formula [Na], R ₃₁ , R ₃₂ , R
₃₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group, and R ₃₁ , R ₃₂ and R ₃₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group,
Examples include a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation promoting agent [Na] are shown below.

[0078]

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[0079]

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[0080]

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[0081]

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In the above formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₃₄ is a hydrogen atom, an alkyl group, an alkynyl group, an aryl group,
Ar and R ₃₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide-adsorbing group include groups having the same meaning as the silver halide-adsorbing group of the compound represented by formula (H).

Specific compounds of the general formula [Nb] include the following.

[0084]

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[0085]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258751.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5;
No. 8 thiosulfonic acid compound.

The nucleation accelerator used in the present invention can be used in any of the photographic constituent layers on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. Is preferred. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably in the range of 10 ^-5 to 10 ^-2 mol.

In the silver halide photographic light-sensitive material of the present invention, a tetrazolium compound can be used as a high contrast agent. The tetrazolium compound used in the present invention is represented by the following general formula [T].

[0089]

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In the triphenyltetrazolium compound represented by the general formula [T], the substituents R ₁ , R ₂ ,
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 sigma value of Hammett in the phenyl substitution, see, for example, Journal of Medical Chemistry.
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.

[0094]

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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.

In the present invention, other known toning agents may be used, and these may be used alone or in combination of two or more. Alternatively, transition metals of Groups 6 to 10 of the periodic rule may be used.

In the present invention, a processing mode in which water or a processing solution comes 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. Further, the supplied water can be heated to an arbitrary temperature as needed. 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 1 m ^{2 of the} photosensitive material.
It is preferably less than 2 g, more 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.

In the present invention, the photosensitive material to which the processing solution is applied and supplied is preferably heated. The heating may be started before the photosensitive material is applied and supplied with the processing liquid, may be started simultaneously with the application and supply of the processing liquid, or after the application and supply of the processing liquid. It is preferable to start before it is done. The heating may be continued at a constant temperature as needed, or the temperature may be changed over time. The heating temperature is preferably in the range of 25C to 50C, more preferably 35C to 46C. Also,
The temperature before 30% of the total processing time from the start of processing is 40 ° C
The heating is preferably such that the temperature after 70% of the total processing time is more than 40 ° C. and the temperature before 40% of the total processing time from the start of the processing is 40 ° C. or less and the total processing time is less than 40 ° C. Heating in which the temperature after 60% is a temperature above 40 ° C. is particularly preferred.

Examples of the means for heating the photosensitive material include a heat conduction heating means for contacting the photosensitive material such as a heat drum and a heat belt and overheating by heat conduction; a convection heating means for heating by convection such as a dryer; 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 the photosensitive material when the photosensitive material is present before the heating means can heat unnecessary heating. This is achieved by a conveying means for conveying the photosensitive material at a predetermined conveying speed, and a photosensitive material detecting means for detecting the presence of the photosensitive material at a predetermined position on the upstream side in the conveying direction of the conveying means from a position heated by the heating means. It can be achieved by controlling the heating control means based on the photosensitive material detecting means. In this case, the control may be such that the photosensitive material detecting means detects the presence or absence of the photosensitive material at the predetermined position after a lapse of a predetermined time after the photosensitive material detecting means detects the presence of the photosensitive material at the predetermined position. It is preferable to control the heating means to perform a predetermined heating until a predetermined time elapses after the detection of.

In the present invention, prior to processing of the photosensitive material, the photosensitive material is supported by a carrier having a rubber-containing layer capable of temporarily adhering and supporting the photosensitive material. -It is preferable from the viewpoint of stability.

The rubber-containing layer of the present invention is a slip preventing layer which contains rubber and uses this as a slip preventing effect.

As the rubber, natural rubber can be used.
Desirably, it is synthetic rubber. As the synthetic rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, urethane rubber, polysulfide rubber,
Tetrafluoroethylene-propylene rubber, acrylic rubber, epichlorohydrin rubber, ethylene-vinyl acetate rubber, 1,
2-polybutadiene rubber, thermoplastic elastomer (styrene, olefin, urethane, polyester,
Polyamide-based, fluorine-based, etc.), ethylene-propylene copolymer, ethylene-propylene-diene copolymer, nitrile-butadiene rubber, butyl rubber, fluorine rubber, chlorosulfonated polyethylene rubber, propylene oxide rubber, ethylene-acryl rubber, Examples include nobornene rubber and silicone rubber, and silicone rubber is particularly preferred. These rubbers may be used in combination.

In the displacement preventing layer, (a) rosin, polyterpene, phenol resin, xylene resin, epoxy resin,
Sticking resin such as petroleum carbonized resin, (b) plasticizer such as phthalate ester, phosphate ester, chloride paraffin, (c)
It is preferable to add oils and fats such as animal oils and fats and mineral oils to adjust the adhesiveness to the sheet. Further, an anti-aging agent, a stabilizer, a filler, a coloring agent and the like may be added.

As the silicone rubber suitable as the rubber contained in the shift preventing layer, a silicone rubber containing a linear organic polysiloxane having a repeating unit as shown below and having a molecular weight of several thousand to several hundred thousand is preferable.

[-(R) Si (R) -O-] _n wherein n is an integer of 2 or more, and R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a vinyl group or an aryl group. , And R are preferably methyl groups.

The silicone rubber useful in the present invention is obtained by a condensation reaction of such a silicone base polymer with the following silicone crosslinking agent.

1. R-Si-(-OR ') 2. 2. R-Si-(-OAc) R-Si-(-ON = CR ' ₂ ) ₂ where R has the same meaning as R described above, R' is an alkyl group such as a methyl group or an ethyl group, and Ac is an acetyl group.

These silicone rubbers are also available as commercial products, for example, “YS-308” manufactured by Toshiba Silicone Co., Ltd.
5 "and the like.

Other useful silicone rubbers include those obtained by reacting the above-mentioned base polymer with an H-type silicone oil having the following repeating units, or a silicone in which about 3% of R is a vinyl group. It can also be obtained by an addition reaction with a base polymer or a reaction between the H-type silicone oils.

[-(R) SiH-O-] _m [-(R) S
i (R) -O-] _{n wherein} R is as defined above, m is an integer of 2 or more, n
Is 0 or an integer of 1 or more.

In order to obtain a silicone rubber by such a crosslinking reaction, in addition to the above-mentioned components, an organic carboxylate of a metal such as tin, zinc, cobalt, lead, calcium, manganese or the like, for example, dibutyltin laurate, tin (II) A catalyst such as octoate, cobalt naphthenate or the like, or chloroplatinic acid is added.

In order to improve the strength of the silicone rubber, a filler may be mixed. Silicone rubber premixed with a filler is commercially available as a silicone rubber stop or silicone rubber dispersion. If it is preferable to provide a silicone rubber film by a coating, a dispersion of RTV or LTV silicone rubber can be used. John is preferably used. Such examples include “Syl Off-23” and “SRX-
There are silicone rubber dispersions for paper coating such as 257 and SH-237.

The silicone rubber layer preferably contains a silane coupling agent in order to further improve the adhesion to the support. The silane coupling agent includes the following.

A. H ₂ NCH ₂ CH ₂ N (CH ₃ ) (C
H ₂ ) ₃ Si (OCH ₃ ) ₃ b. GlyO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ [Gly = glycidyl group] c. HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ d. CH ₂ ＣＨCHSi (OCOCH ₃ ) ₃ e. CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH
₃ ) ₃ f. CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ g. H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₂
CH ₃ h. The chlorosilane slip-stopping layer may be simply layered on the drum,
It may be completely bonded (for example, by a lamination method) using an adhesive or a primer. Alternatively, a coating solution obtained by dissolving and dispersing a rubber-containing material for forming a shift preventing layer in a solvent may be applied on a drum and dried.

The drum is made of metal and has rigidity. The photosensitive material carried thereon is not easily deformed, and its surface is macroscopically smooth. In addition, instead of a cylindrical drum, a rotating body having another appropriate shape (such as an elliptical shape or a regular polygonal shape) can be used, or the processing can be performed on an endless belt serving as a rotating pressure receiving member. it can. Further, the processing can be performed on a pressure-receiving body that moves linearly, or can be performed on a pressure-receiving body that moves linearly.

The thickness of the shift preventing layer is not particularly limited as long as the photosensitive material can be adhered and supported, but is preferably 0.1 to 500 μm in order to maintain good smoothness of the photosensitive material. Also, the displacement preventing layer may be provided on a heat drum,
In this case, the thickness is 0.1 to 3 so as not to hinder the thermal conductivity.
00 μm is preferred.

Exposure light sources that can be used in the image forming method of the present invention include a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, a CRT light source, and a FO-C
An RT 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) or the like 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,
Particularly, a laser light source having a wavelength of 600 to 700 nm is preferably used.

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

Each part granule of the developer and the fixing agent used in the solid processing agent of the present invention is preferably 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 sugar alcohols are threitol, erythritol, arabitol, ribitol,
Xylitol, sorbitol, mannitol, iditol, talitol, galactitol, allozlicitol.

Preferred 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.

The granulation method preferably used in the present invention includes 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 vessel. This method is preferable in terms of high production efficiency and the effect of the present invention.

A fluidized-bed granulator can be used on the market.
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.

The photosensitive material used in the image forming method of the present invention contains photosensitive silver halide as a constituent. As the photosensitive silver halide, conventionally known photosensitive silver halides can be used. For example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide can be used. Silver chloride,
Silver chlorobromide is preferred, the Cl- content is more preferably 70% or more, and the Cl- content is more preferably 8% or more.
0% or more. Most preferably, the content of Cl- is 90% or more or silver chloride.

The silver halide has a uniform composition from the inside to the surface of the grain, a so-called core / shell type having a different composition between the inside and the surface, or a halogen having a multilayer structure in which the composition changes stepwise or continuously. Any of silver halide may be used.

Further, the silver halide may be monodisperse having a relatively uniform grain size or polydisperse having a wide grain size distribution.

The shape of silver halide is cubic, spherical, 8
Those having a clear crystal habit, such as a tetrahedron, dodecahedron, and tetrahedron, or those having no such crystal habit can be used. Also, for example, JP-A-58-111933 and JP-A-58-111934.
No., Research Disclosure (RD) 22534
No. 2, having two parallel crystal planes,
Each of these crystal planes is a grain having an area larger than that of the other crystal planes, and tabular silver halide having a diameter to thickness ratio of about 5 or more can also be used.

Further, for example, US Pat. No. 2,592,250
Nos. 3,220,613 and 3,271,257
No. 3,317,322 and 3,511,622
Nos. 3,531,291 and 3,447,927
Nos. 3,761,266 and 3,703,584
Nos. 3,736,140 and 3,761,276
No., JP-A-50-8524, JP-A-50-38525,
Internal latent image type silver halide emulsions in which the grain surface is not fogged in advance described in JP-A Nos. 52-15661 and 55-127549 can also be used.

The photosensitive silver halide may be formed at any stage of the grain formation by using iridium, gold, rhodium,
Metal ion species such as iron and lead can be added in the form of a suitable salt. In this case, these metal ions are generally added in a range of 10 ^-7 to 10 ^-5 mol per mol of silver.

The particle size of the above-mentioned photosensitive silver halide emulsion is preferably 0.01 to 2 μm, more preferably 0.1 to 2 μm.
05 to 1 μm. Further, for adjusting the gradation, it is possible to use silver halides having different average grain sizes in the same photosensitive layer in combination.

The photosensitive silver halide emulsion is chemically sensitized on the surface of silver halide grains with a known method and a sensitizer (active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate, etc.). Is preferred. Chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

These light-sensitive silver halide and light-sensitive silver salt-forming components are used in an amount of 0.3 to 3.4 g, preferably 0.9 to 3.0 g in terms of silver per m ² of the light-sensitive material. Used.

The photosensitive silver halide grains used in the image forming method of the present invention can be subjected to chemical sensitization using various known methods. In particular, chemical sensitization with a chalcogen compound can be performed. Chemical sensitization by a chalcogen compound includes a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method.

The sensitizer was added during the formation of silver halide grains.
It may be at any time after the formation of the particles and before or after the desalting, but preferably during the formation of the particles or after the desalting.

The photosensitive silver halide grains are preferably spectrally sensitized with a sensitizing dye.

Examples of the sensitizing dye to be used include all known sensitizing dyes which, when adsorbed on silver halide grains, spectrally sensitize the silver halide grains in a desired wavelength range according to the exposure light source. Can be mentioned.

The sensitizing dye can be used by a known method. Also, a desired spectral sensitization spectrum can be obtained by mixing a plurality of sensitizer colors.

In the present invention, it is preferred that a sensitizing dye is adsorbed on the photosensitive silver halide grains. The sensitizing dye may be added at any time, for example, during grain formation, before desalting after grain formation, before chemical sensitization after desalting, after chemical sensitization, and before mixing with an organic silver salt. . Preferably, after desalting and before mixing with the organic silver salt.

The addition amount of the sensitizing dye is preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, more preferably from 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, per mol of silver halide. , 1 ×
10 ^{-5 to} 2 × 10 ^-4 mol is preferred. If the amount of the sensitizing dye is too large, the residual color deteriorates, the storage stability deteriorates, and the printout deteriorates, which is not preferable. The use amount of the sensitizing dye is preferably reduced as long as the desired performance is obtained.

As the hydrophilic binder used in the present invention, preferred are ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol (having a molecular weight of about 2000 or more), gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, starch, agar, and the like. Synthetic or natural polymer substances such as gum arabic can be used, and these can be used alone or in combination of two or more. In particular, gelatin is preferably used, and as the gelatin, ordinary alkali-treated gelatin or acid-treated gelatin, or a gelatin derivative such as phenylcarbamoylated gelatin or phthalated gelatin is used.
These may be used in combination of two or more. Also, a combination of the above-mentioned various gelatins and a water-soluble polymer other than gelatin is preferably used.

The amount of the binder used is usually preferably 0.05 to 8 g per m ² of the support in each constituent layer.
0.2-5 g is more preferred. Incidentally, the total amount of the binder on the photosensitive layer side of the photothermographic material is 1 to 1 m ² per support.
30 g is preferable, and 2 to 15 g is more preferable.

The hydrophilic binder is preferably hardened with a known photographic hardener. As the hardener, for example, vinyl sulfone type, aldehyde type, epoxy type, N-
Methylol-based and halogen-substituted-s-triazine-based hardeners are exemplified. Further, a polymer hardener can also be used.

Suitable hydrophobic binders for use in the invention are transparent or translucent, generally colorless, natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, polyvinyl alcohol, Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Polyvinyl pyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, polyvinyl acetal (Polyvinyl formal, polyvinyl butyral, etc.), polyesters,
Examples include polyurethanes, phenoxy resins, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, polyamides, and the like. The binder may be coated from water or an organic solvent or emulsion.

An organic silver salt can be used in the light-sensitive material of the present invention. As an organic silver salt, it is relatively stable to light, but when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a photographic silver salt) and a reducing agent, a silver image can be formed. It is a silver salt that forms. The organic silver salt may be any organic substance including a source capable of reducing silver ions.
Among them, silver salts of organic acids, particularly long-chain fatty carboxylic acids having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms, are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a total stability constant in the range of 4.0 to 10.0 are also desirable.

In the light-sensitive material used in the present invention, other known additives can be optionally used. For example,
Antihalation dyes, matting agents, plasticizers, sliding agents,
Examples include a desensitizer, a plasticizer, and a development accelerator.

For the light-sensitive material and processing used in the present invention, various known techniques, formulas, additives and methods of adding the same can be used. Particularly, production of a silver halide light-sensitive material for forming a black-and-white image is possible. The known techniques, formulas, additives and methods for adding the same can be preferably applied.

[0151]

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0152] Example 1 (Preparation of silver halide emulsion A ₁₎ co-precipitation method a silver content of 70 mole% chloride with the remainder an average diameter silver chlorobromide core grains of 0.09μm comprising silver bromide Prepared. At the time of mixing the core particles, K ₃ Rh (NO) ₄ (H ₂ O) ₂ was added in an amount of 7 × 10 ⁻⁸ mol per mol of silver and 1 mol of silver at the end of grain formation.
40 ° C., p in the presence of 8 × 10 ^-6 mol of ₃ OsCl ₆
While maintaining H3.0 and a silver potential (EAg) of 160 mV, a silver nitrate aqueous solution and a water-soluble halide solution were simultaneously mixed. The core particles were shelled using a double jet method with EAg reduced to 123 mV with saline. At that time, K ₂
3 × 10 ⁻⁷ mol of IrCl ₆ per mol of silver, K ₃ RhC
9 × 10 ⁻⁸ mol of ₁₆ was added. Further, KI conversion was performed using silver iodide fine particles, and the resulting emulsion was a core / shell type monodisperse having an average diameter of 0.15 μm (coefficient of variation: 10
% Of silver chloroiodobromide (70 mol% of silver chloride, 0.2% of silver iodobromide)
(Mol%, the remainder being silver bromide). Subsequently, desalting was carried out using a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin was substituted with phenylcarbamyl, for example, exemplified compound G-8 described in JP-A-2-280139). EAg after desalination is 5
It was 190 mV at 0 ° C.

The obtained emulsion was added with 8.5 × 10 ^-4 mol of potassium bromide and mol of citric acid per mol of silver, and pH was adjusted.
5.6, adjusted to an EAg of 123 mV, and added with 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) to cause a reaction, and then solid-dispersed inorganic sulfur (S8) compound [ Seishin Enterprise Co., Ltd .;
PM-1200, saponin was added and dispersed to an average particle size of 0.5 μm] and chloroauric acid was 1.5 × 1
0 ^-5 mol was added up sensitivity exits at temperature 55 ° C. chemically ripened.

After the temperature was lowered to 40 ° C., 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver and 1-phenyl-5-mol.
-After adding 3 × 10 ^-4 mol of mercaptotetrazole and 5 × 10 ^-3 mol of potassium iodide, the mixture was adjusted to pH with citric acid.
Was adjusted to 5.1, and then 100 mg of sensitizing dye d-1 was added.

[0155] For (Preparation of silver halide emulsion B ₁₎ Silver Halide Emulsion A _1, K ₃ RhCl ₆ to 6 × 1 shell portion
0 ^-8 except that the mole was prepared a silver halide emulsion B ₁ in the same manner. When performing the same chemical sensitization, the emulsion of B ₁ represents 40% more sensitive than emulsion A _1.

(Preparation of Photosensitive Material 1) A gelatin subbing layer of the following formula 1 was coated on a support at a gelatin content of 0.55 g / m ^2.
The silver halide emulsion layer 1 of the following formula 2 was further provided thereon with a silver content of 1.73 g / m ² and a gelatin content of 0.66.
g / m ² , and further thereon a silver halide emulsion layer 2 of Formulation 3 so that the silver amount is 1.73 g / m ² and the gelatin amount is 0.66 g / m ^2. Formula 4
Was applied simultaneously so that the amount of gelatin was 1.3 g / m ² . On the undercoat layer of the support opposite to the emulsion layer, a backing layer of the following formula 5 was coated with a backing protective layer of the following formula 6 so that the amount of gelatin became 2.3 g / m ^2. It was applied so that the amount was 0.7 g / m ² .

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.55 g / m ² Saponin 56.5 mg / m ² Dye AD-8 (solid dispersion) 10 mg / m ² Dye SF (solid dispersion) 20 mg / m ² dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 10 mg / m ² Fungicide Z 0.5 mg / m ² Formulation 2 (Composition of silver halide emulsion layer 1) Silver halide emulsion A ₁ Equivalent amount of silver 1.45 g / m ² Hydrazine compound (Example H-15) 2 × 10 ⁻³ mol / Ag 1 mol Compound a 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex L1 ( particle size 0.25μm) 0.25g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxy-purine 2 mg / m ² 2-Merukaputopi Spermidine 1 mg / m ² gallate n- propyl ester 25 mg / m ² of ascorbic acid 20 mg / m ² EDTA 25 mg / sodium m ² of polystyrene sulphonic acid 15 mg / m ² coating solution pH was 5.2.

Formulation 3 (Composition of Silver Halide Emulsion Layer 2) Silver Halide Emulsion B ₁ Silver amount 1.45 g / m ² equivalent Hydrazine compound (Ex. H-15) 4 × 10 ⁻³ mol / Ag 1 mol Amino compound AM-1 7 mg / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 4 × 10 ⁻³ mol / Ag1 mol Saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 25 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Dye f5 15 mg / m ² Polymer latex L3 0.25 g / m ² Colloidal silica (average particles diameter 0.05μm) 150mg / m ² reduced dextrin (weight average molecular weight of 1000, reduced glucose component 0.2%) 0.3 g / ² gelatin with a phthalated gelatin, pH of the coating solution is 4.
It was 8.

Formulation 4 (Emulsion protective layer composition) Gelatin 1.0 g / m ² Amino compound AM-1 14 mg / m ² Matting agent: spherical polymethyl methacrylate having an average particle size of 2.8 μm 30 mg / m ² Surfactant S1 20 mg / M ² slip agent W1 75 mg / m ² Compound a 50 mg / m ² Polymer latex L3 (average particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² hardener h2 150 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² Formulation 5 (backing layer composition) Gelatin 0.5 g / m ² Sodium-iso-amyl-n-decyl sulfosuccinate 5 mg / m ² polymer latex L4 0.4 g / m ² colloidal silica (average particle size 0.05 μm) 100 mg / m ² polystyrene Nsuruhon Sodium 10 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² hardener h3 100 mg / m ² zinc hydroxide 50 mg / m ² Compound ^{D 10mg / m 2 EDTA 50mg /} m 2 formulation 6 (Backing protective Layer) Gelatin 0.05 g / m ² Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 5 μm 400 mg / m ² Polymer latex L4 1 g / m ² Average particle size 3 μm Indefinite silica 350 mg / m ² sodium-di- (2 -Ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant S1 18 mg / m ² Compound a 50 mg / m ² Hardener h1 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² UV concentration of the backing layer is 0.09 , Visual density is 0.0
It was 6.

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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Preparation of Photosensitive Material 1b Dyes f1, f2, and f3 were added to the backing layer for 30, respectively.
A light-sensitive material 1b was prepared in the same manner as the light-sensitive material 1, except that 120 and 150 mg / m ^{2 were} added. U of backing layer
The V density was 0.32 and the visual density was 0.96.

(Preparation of developer A)
Was prepared.

Diethylene-triaminepentaacetic acid / pentasodium salt 1 g per liter of liquid used 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g erythorbic acid 5 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g Sodium thiosulfate 50 g KOH was added so that the pH of the working solution was 10.4.

(Preparation of Developer B) Developer B was prepared in exactly the same manner as developer A except that 0.5 g of uracil was added per liter of working solution.

(Preparation of Developer C) Developer C was prepared in exactly the same manner as developer A except that sodium thiosulfate was removed.

(Composition of Fixing Solution) A fixing solution having the following composition was prepared.

Per liter of liquid used Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) ) The pH of the working solution was adjusted to 4.9 with 25 ml of sulfuric acid.

Exposure was performed using 633 nm He-Ne as a light source.
Step exposure was performed while changing the amount of light at 1.5 × 10 ⁻⁷ seconds with a laser sensitometer using laser light.

The developing process was evaluated using a prototype developing machine shown in FIG. In FIG. 1, a photosensitive material P is developed, fixed, rinsed,
Each process of drying is performed.

In FIG. 1, reference numeral 12 denotes a squeeze roller;
Is a conveying roller, 14 is a preheat drum for preheating, 15 is a drying air blowing nozzle, 16 is a washing water discharging nozzle, 17 is a developing solution discharging nozzle, and 18 is a fixing liquid discharging nozzle. Reference numerals 19 and 20 denote development unit heaters, and reference numeral 21 denotes a fixing unit heater. A panel heater for heating the photosensitive material is used. The surface of each roller is 3 with YS-3085 (manufactured by Toshiba Silicon Corporation).
It is coated to a thickness of 00 μm.

FIG. 2 is a conceptual view of a cross section showing the structure of the processing liquid supply device of the present invention.

The liquid is introduced by the chamber 23 from the liquid inflow passage 22 in which the area of the flow path is narrowed, the diaphragm 25 is deformed by the drive element 24, and a sudden change in volume in the chamber occurs. As a result, the processing liquid is ejected from the orifice 27. The orifice has an orifice channel 28.
And an orifice plate 29. The upper wall of the chamber 23 is formed by a diaphragm 25, through which the displacement of the drive element 24 is transmitted. Drive element 24
It is preferable that the upper part of the chamber is formed by the vibration plate 25 so that the processing liquid does not come into direct contact with the processing liquid. The wall material of the chamber is preferably made of vinylidene chloride, and the orifice channel portion is preferably made of vinylidene chloride. The material of the orifice plate is preferably nickel.

FIG. 3 is a plan view of FIG. 2. The contact angle of the processing liquid on the orifice plate 29 is 20 degrees, and the contact angle of the processing liquid on the wall surface of the chamber is 45 degrees.

Next, the configurations of the diaphragm 25 and the driving element 24 will be described. The vibration plate 25 is attached to the external member 26 of the processing liquid supply means with, for example, an epoxy resin adhesive. The diaphragm 25 is made of vinylidene chloride resin. The driving element is a piezo element. The piezo element expands and contracts in the horizontal direction and vibrates up and down, so that pressure can be applied to the processing liquid. The leads 31 and 32 are connected to an electronic pulse generator for generating an external pulse voltage.

The droplet 30 of the processing liquid is ejected from the orifice 27. The end of the orifice channel 28 is a circular orifice 27 having a small diameter, and the orifice channel 28 has a small diameter. The droplet diameter is controlled. At this time, the pressure in the processing chamber decreases, and flows into the chamber 23 from the external processing liquid tank through the liquid inflow passage 22.

As described above, the positive and negative voltages are alternately applied to the two piezo elements, so that the photosensitive material processing liquid is continuously supplied.

As the driving condition of the supply means, a serial type supply head using a piezo element is used. The number of orifices is 64, and a staggered pattern as shown in FIG. 4 is used. The drive voltage and the like were adjusted so that the volume of a droplet in one ejection was 150 picoliters. The injection frequency was set to 7500 Hz. .

The processing liquid was supplied to the entire surface of the photosensitive material by operating eight coating liquid supply units shown in FIGS. 2 and 3 in a direction perpendicular to the conveying direction of the photosensitive material.

The main processing conditions of the developing section at this time are shown below. However, the supply amount of the developer and the temperature and time of each of the development, fixing, washing, and drying processes are variable.

Temperature of heat roller (1) 40 ° C. Time from contact with heat roller to supply of developer 2 seconds Distance between developer supply and photosensitive material 3 mm Scanning speed of developer supply section 500 mm / sec Fixer supply section Scanning speed 500 mm / sec Fixing solution supply amount 60 ml / m ² Processing conditions (Process) (Temperature ° C) (Time sec) Developing 38 15 Fixing --- Washing Normal temperature 15 Squeeze / Drying 50 15 Processing described in Table 1 under the above processing conditions Are performed, and samples 101 to 101
109 was obtained. The amount of the developer applied was 1 m ² of the photosensitive material.
The volume was set to 60 ml.

(Evaluation of photographic performance) The obtained processed sample was measured for sensitivity, maximum density and minimum density using a densitometer PDA-65 (manufactured by Konica Corporation). Sensitivity is the sample No.
The reciprocal of the exposure amount that gives a blackening density of 1.0 to 101 is 100
And expressed as relative sensitivity. The sharpness (clearness) and fixability (clearness) were visually evaluated on a five-point scale. Level 5 is the highest quality, level 3 is the practical limit, and level 2 or less is a practically problematic level. After processing the photosensitive material by 20 m ² each, a line drawing pattern was processed as shown in Table 1, and the degree of image quality deterioration due to running was visually evaluated. Level 5 is not degraded at all, and level 2 and below are levels that are severely degraded and have practical problems.

Table 2 shows the above results.

[0187]

[Table 1]

[0188]

[Table 2]

As is clear from Table 2, it can be seen that a sharp black-and-white image excellent in discrimination can be obtained in a short time by the image forming method of the present invention.

Example 2 (Preparation of photosensitive material 2) Except that in Example 1, the silver content of silver halide emulsions A ₁ and B ₁ of silver halide emulsions 1 and 2 was 1.6 g / m ² respectively. A photosensitive material 2 was produced in exactly the same manner as in Example 1.

(Preparation of Photosensitive Material 3)
Light-sensitive material 3 was prepared in the same manner as in Example 1, except that the silver content of silver halide emulsions A ₁ and B ₁ of silver halide emulsions 1 and 2 was 1.85 g / m ² , respectively.

Processing Conditions Table 3 shows the amount of the developer applied.

(Step) (Temperature ° C.) (Time / Second) Developing 38 15 Rinsing at room temperature 15 Squeeze / Drying 50 15 The processing shown in Table 3 was performed using the developing solution B under the above processing conditions to obtain samples 201 to 212. . The obtained sample was evaluated in the same manner as in Example 1. Table 4 shows the results.

[0194]

[Table 3]

[0195]

[Table 4]

As is evident from Table 4, the image forming method of the present invention can provide a sharp black-and-white image excellent in discrimination in a short time.

Example 3 (Preparation of Photosensitive Material 4) In Example 1, gelatin for the backing layer and polymer latex L4 were added in amounts of 0.1% each.
A light-sensitive material 4 was produced in exactly the same manner as in Example 1 except that the amounts were 6 g / m ² and 0.4 g / m ² . The water absorption of the backing surface of this photosensitive material 4 was 3.5 g / m ² .

Processing conditions (Step) (Temperature ° C) (Time sec) Water immersion Table 5 Development Table 5 Water washing Room temperature 15 Squeeze / dry 50 15 Under the above conditions, processing was performed using developer B as shown in Table 5. This was performed to obtain samples 301 to 304. The same evaluation as in Example 1 was performed on the obtained sample. Table 6 shows the results.

[0199]

[Table 5]

[0200]

[Table 6]

As is clear from Table 6, it is clear that the image forming method of the present invention can provide a sharp black-and-white image excellent in discrimination in a short time.

Example 4 (Preparation of developer D) Preparation of granule A (for 1 liter) Sodium sulfite 23 g Sodium carbonate 12 g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone (dimesone S) 7 g Potassium bromide 5 g Diethylenetriaminepentaacetic acid / 5 sodium 3 g Benzotriazole 0.26 g Hydroquinone 10 g Mannit 10 g Compound A 70 g

[0203]

Embedded image

The above materials were placed in a commercially available stirring granulator, and
Mix and crush for minutes. Water of 5% of the total weight was gradually added, and the obtained granules were transferred to a fluidized bed drier and dried at a supply air temperature of 60 ° C for 2 hours. The granules thus obtained were again placed in a commercially available granulator and sized with a 5 mm mesh.

Preparation of Granule B (for 1 liter) Sodium sulfite 20 g Sodium carbonate 10 g Sodium thiosulfate 58 g Sodium acetate 15 g Mannit 10 g Powdered sorbite 5 g Uracil 0.5 g Put the above ingredients in a commercially available stirring granulator and mix for 3 minutes And crushed. Water of 5% of the total weight was gradually added, and the obtained granules were transferred to a fluidized-bed dryer.
Dried for hours. The granules thus obtained were again placed in a commercially available granulator and sized with a 5 mm mesh.

Each of the granules A and B was placed in a fluidized bed granulator GPCG-5 (manufactured by Pourex Corporation) in an amount of 5 liters, and fluidized at an air supply temperature of 60 ° C. and an air flow of 8 m ³ / min.

The surface of the granules was coated by spraying 20 g per liter of a 30% aqueous solution of sorbitol with a two-fluid spray. The resulting surface-coated granules are called a and b.

15 g of the two kinds of granules a and b obtained by the above operation were prepared, and 2% by weight of the combined weight of sodium 1-octanesulfonate was added thereto. Mix for minutes. This mixture was filled with an oil press machine at a filling amount of 1 tablet per 30 mm in diameter.
The tablets were compressed at 0 g under a compression pressure of 1 ton / cm ² .

[0209] Of the solid processing agents thus produced, 3
Developer D was prepared using 5 liters.

Processing (Step) (Temperature ° C.) (Time / Second) Development Table 7 15 Rinsing at room temperature 15 Squeeze / dry 50 15 401-404 were obtained. The same evaluation as in Example 1 was performed on the obtained sample. Table 8 shows the results.

[0211]

[Table 7]

[0212]

[Table 8]

As is clear from Table 8, the image forming method of the present invention can provide a sharp black-and-white image excellent in discrimination in a short time, and the same effect can be obtained by using a solid processing agent. It can be seen that it can be obtained.

[0214]

According to the present invention, a sharp black-and-white image having high density and low density discrimination and excellent image storability can be obtained in a short time, and an image forming method excellent in working environment can be obtained. .

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a developing machine using processing liquid supply means for flying a photosensitive material of the present invention through a gas phase.

FIG. 2 is a conceptual cross-sectional view of a processing liquid supply device of processing liquid supply means for flying a photosensitive material of the present invention via a gas phase.

FIG. 3 is a conceptual plan view of a processing liquid supply device of processing liquid supply means for causing a photosensitive material of the present invention to fly through a gas phase.

FIG. 4 is a view showing the concept of an orifice plate pattern of the present invention.

[Explanation of symbols]

 P Silver halide photographic light-sensitive material 12 Squeeze roller 13 Conveyance roller 14 Preheat drum 15 Dry air blowing nozzle 16 Rinse water discharging nozzle 17 Developer discharging nozzle 18 Fixing liquid discharging nozzle 19 Developing unit heater 20 Developing unit heater 21 Fixing unit heater 22 Liquid Inflow passage 23 Chamber 24 Drive element 25 Vibration plate 26 External member 27 Orifice 28 Orifice channel 29 Orifice plate 30 Droplet 31 Lead wire 32 Lead wire 33 Communication pipe

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/76 502 G03C 1/76 502 5/08 5/08 5/29 5/29 5/305 5/305 5/38 5 / 38 G03D 5/00 G03D 5/00

Claims (15)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on a support is imagewise exposed to light and then processed using a developer to produce a black-and-white image. In the forming method, the developing solution is applied to a silver halide photographic material by a processing solution supply means which flies through a gas phase, and a layer on the opposite side of the layer containing the photosensitive silver halide of the support is formed. An image forming method, wherein each of the UV density and the visual density is less than 0.3. 2. The image forming method according to claim 1, wherein the developer is processed using a developer containing at least one silver halide solvent in an equimolar amount or more with a developing agent. 3. The image forming method according to claim 1, wherein at least one of the silver halide solvents contained in the developer is an organic fixing agent. 4. The image forming method according to claim 1, wherein the processing liquid is only one type of liquid. 5. The amount of a developing solution applied by a processing solution supply means for flying a silver halide photographic light-sensitive material through a gas phase is 10 to 10 m ² per m ^{2 of the} silver halide photographic light-sensitive material.
The image forming method according to any one of claims 1 to 4, wherein the amount is from 150 to 150 ml. 6. The image forming method according to claim 1, wherein the amount of silver contained in the silver halide photographic light-sensitive material is 0.3 to 3.4 per m ^2. . 7. The image forming method according to claim 1, wherein the photographic light-sensitive material contains a hydrazine derivative. 8. The method according to claim 1, wherein the layer opposite to the layer containing the photosensitive silver halide with respect to the support of the silver halide photographic material has a water absorption of less than ² g per m ^2.
The image forming method according to any one of claims 1 to 7, wherein 9. A process temperature for forming a black-and-white image after imagewise exposing the silver halide photographic light-sensitive material is from 25 ° C. to 50 ° C.
The image forming method according to any one of claims 1 to 8, wherein the temperature is ° C. 10. A process for forming a black-and-white image after imagewise exposing a silver halide photographic light-sensitive material, wherein the temperature before 30% of the total processing time from the start of processing is less than 40 ° C.
10. The image forming method according to claim 1, wherein a temperature after 70% of the total processing time exceeds 40 ° C. 11. The method according to claim 1, wherein after the imagewise exposure of the silver halide photographic light-sensitive material, a process of adding water is performed before the developer is applied to the silver halide photographic light-sensitive material. 11. The image forming method according to any one of items 10 to 10. 12. Prior to processing of the silver halide photographic material, the silver halide photographic material is supported on a carrier provided with a rubber-containing layer capable of temporarily bonding and supporting. The image forming method according to claim 1. 13. The image forming method according to claim 1, wherein the silver halide photographic material is exposed by a laser beam. 14. A method for preparing a silver halide photographic material from 600 to
The image forming method according to any one of claims 1 to 13, wherein exposure is performed using light having a wavelength of 700 nm. 15. The image forming method according to claim 1, wherein the silver halide photographic material is processed with a liquid prepared from a solid processing agent.