JP2000241942A - Treatment of silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To avoid contamination, residual colors, transfer failure or production of roller marks by using a specified silver halide photographic material and coating the surface of a squeeze roller in an automatic developing machine with a specified material after completing a water washing process and before starting a drying process. SOLUTION: A silver halide photographic material containing sensitizing dyes expressed by formulas I, II or the like is developed, fixed, washed with water and dried by using an automatic developing machine. The surface of a squeeze roller disposed in the automatic developing machine is coated with a material having a contact angle θ with water ranging 0<θ<60 deg. after completing the washing process and before starting the drying process. In formula I, X is -S- or -Se-, two or more groups of R1 to R5 are org. groups having water-soluble groups and other groups of R1 to R5 are hydrogen atoms, alkyl groups or the like, each of R6 and R7 is a hydrogen atom, hydroxyl group or the like and these groups may be coupled to form a ring. In formula II, Y is -S- or -S2-, two or more groups of Z1 to Z6 are org. groups having water-soluble groups and other groups of Z1 to Z6 are hydrogen atoms, alkyl group or the like, and each of Z7 and Z8 is of the same meaning as R6 and R7 in formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic material (hereinafter, also referred to as a "photosensitive material").
More particularly, the present invention relates to a method for processing a silver halide photographic light-sensitive material which does not cause stains on a formed image even when a large-sized light-sensitive material for printing plate making is rapidly processed using an automatic developing machine.

[0002]

2. Description of the Related Art In recent years, photosensitive materials used for printing plate making have been increasingly processed by automatic developing machines connected to a laser output device called an image setter. A processed photosensitive material having a halftone image output by this imagesetter is often used as an exposure original to a lithographic printing plate material as a final plate, and it is important performance to obtain a clear image. .

[0003]

On the other hand, since exposure by an image setter can be performed at a high speed, there is a demand for correspondingly increasing the transport speed of an automatic developing machine and shortening the processing time. However, when high-speed transport and rapid processing are performed in accordance with the output speed, dirt adheres to the processed photosensitive material.
Problems such as occurrence of residual color, occurrence of jamming, and occurrence of roller marks will occur.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to solve the problems of dirt, residual color, poor conveyance, and roller marks even when rapid processing is performed in accordance with the output speed of an imagesetter. An object of the present invention is to provide a method for processing a photosensitive material for printing plate making which does not occur.

[0005]

The object of the present invention is to provide a silver halide photographic light-sensitive material containing a sensitizing dye represented by a general formula selected from the above (1) to (6) by using an automatic developing machine. In developing, fixing, washing and drying using the squeeze roller, the surface of the squeeze roller installed in the automatic developing machine between the end of washing and the start of drying has a contact angle (θ) with water of 0 ° <
A method for processing a silver halide photographic material covered with a material satisfying θ <60 °, the silver halide photographic material contains a hydrazine derivative represented by the above general formula (H), and development is started and drying is completed. 15 to 60 seconds, and at least 80% of the surface area of the first roller of the transport rack during the drying step has a contact angle with water of 0 ° <θ <60.
°, and 80% or more of the surface area of all rollers of the transport rack during the drying process is covered with a material having a contact angle with water of 0 ° <θ <60 °. That a fixing solution containing substantially no aluminum compound was used, that the water content of the silver halide photographic light-sensitive material after development, fixing and washing was 18 g / m ² or less, and that the silver halide photographic material passed through the squeeze roller. This is achieved by the fact that the water content of the silver halide photographic material immediately after is 50% or more of the water content after the development, fixing and washing processes.

That is, the inventor of the present invention considers that the dye stain of the processed photosensitive material is related to the behavior of the moisture from the photosensitive material squeezed by the squeeze roller on the roller, and adjusts the wettability of the surface of the roller. The present invention has been found that the dye stain can be improved by improving the residual color property and the transportability at the time of high-speed processing, and that the surface streaks (roller marks) due to the roller pressure can be prevented.

Hereinafter, the present invention will be described in detail.

First, in the present invention, the light-sensitive material has a general formula (1)
In the case of containing a sensitizing dye represented by any of (6), where the dye stain is particularly conspicuous, the characteristics of the squeeze roller are set and eliminated, and the surface has a contact angle with water ( θ) is covered with a material satisfying 0 ° <θ <60 °. The contact angle here is synonymous with a general definition, and is an angle θ formed by a water drop and a plane when the water drop is placed on a plane and stopped. Further, in addition to the squeeze roller, it is preferable that 80% or more of the surface area of the first roller of the transport rack during the drying process is covered with a material having a contact angle with water of 0 ° <θ <60 °. And more preferably 80 of the surface area of all the rollers of the transport rack during the drying process.
% Or more is covered with a material having a contact angle with water of 0 ° <θ <60 °.

The means for adjusting the contact angle of the surface material of the roller of the present invention can be generally adjusted by adjusting the surface chemical composition. For example, the smaller the critical surface tension on the roller surface, the more the water contact is made. The corners get bigger. Examples of the material of the surface effective for adjusting the critical surface tension include a phenol resin (baked), a silicone resin, a rubber, and a fluororesin. In the present invention, the surface is preferably processed with a water-repellent resin. Is a rubber roller that does not have natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), olefin rubber, styrene butadiene rubber (SBR), high styrene rubber, ethylene-propylene rubber ( EPM, EPD
M), chlorosulfonated polyethylene, butyl rubber (I
IR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), polysulfide rubber (T), acrylic rubber (AM, ANM), silicon rubber (Si), fluoro rubber (FPM), etc. Preferred are ethylene-propylene rubber, natural rubber and chloroprene rubber.

Hereinafter, the sensitizing dye will be described.

R _{1 to} R ₅ of the general formula (1) and the general formula (2)
Wherein at least two of Z _{1 to} Z ₅ represent an organic group carrying a water-soluble group, and the term “water-soluble group” as used herein refers to a so-called structure-activity relationship based on the relationship between the structure of the compound and the physiological activity. The π value of the Hansch method used in the above has a negative value. The Hansch method is described in J. Am. Me
d. Chem, 16, 1207 (1973) and 20,
304 (1979).

Among these water-soluble groups, dyes that are ionized in an aqueous solution and have two or more dyes having a pKa of 4 to 11 are preferable. Particularly preferably, two or more are 4-1.
An organic group having a pKa of 1 and at least one having a pKa of 4 or less has features of excellent spectral sensitivity and low residual color contamination.
Examples of specific functional groups exhibiting preferable pKa are shown below, but the present invention is not limited only to these.

[0013] pKa those _{4~11 - (CH 2) n COOM} , -C 6 H 4 COOM, -CH 2 C 6
_{H 4 COOM, -CH 2 -CH =} CH-CH 2 COOM, -
_{(CH 2) 2 SO 2 NHC} 6 H 4, -CH 2 CH 2 CONH 2 pKa of 4 or less things _{- (CH 2) n SO 3} M, -C 6 H 4 SO 3 M, -CH 2 C 6 H
_{4 SO 3 M, -CH 2 CH} = CH-CH 2 SO 3 M, CH 2 C
_{H (SO 3 M) CH 3} ( wherein, n represents 2 to 4, M is a hydrogen atom, an alkali metal atom or an ammonium group,. Represents an organic amine radical) R ₁ is not an organic group having a water-soluble group; R ₅ and groups Z _{1 to} Z ₆ are hydrogen, an alkyl group (eg, a methyl group or an ethyl group), a substituted alkyl group, an alkenyl group (eg, an allyl group), a substituted alkenyl group, an aryl group (eg, a phenyl group), or It is selected from substituted aryl groups (p-tolyl group and the like).

R ₆ and R ₇ in the general formula (1) and Z ₇ and Z ₈ in the general formula (2) are the same or different and are each a hydrogen, a hydroxy group, a halogen atom, an alkyl group (a methyl group, an ethyl group). , A propyl group, etc.), a substituted alkyl group (a trifluoromethyl group, a 2,2,2-trifluoroethyl group, etc.), an alkenyl group (an allyl group, etc.), a substituted alkenyl group, an alkoxy group (a methoxy group, an ethoxy group, etc.) ,
Alkylthio group (such as ethylthio group), substituted alkylthio group, arylthio group (such as phenylthio group), substituted arylthio group, aryl group (such as phenyl group), substituted aryl group (such as p-tolyl group), acyl group (such as acetyl group and propionyl) Group), acyloxy group (acetoxy group, propionyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), alkylsulfonyl group (methylsulfonyl group, etc.), carbamoyl group, substituted carbamoyl group, amide group, It represents a substituted amide group, a sulfamoyl group, a substituted sulfamoyl group, a sulfonamide group, a substituted sulfonamide group, a carboxy group and a cyano group. Or R ₆ and R ₇ together and Z ₇
And Z ₈ together represent the atoms necessary to complete a carbocyclic ring system (such as a benzene or naphthalene ring system), which may be the same or different. And R ₆ , R ₇ and Z
₇ and Z ₈ each may carry one or more substituents selected from the groups described above.

Hereinafter, specific examples of the compounds represented by formulas (1) and (2) will be given.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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In the general formula (3), Y ₁ and Y ₂ each represent a nonmetallic atomic group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring or a quinoline ring. And these heterocycles include a lower alkyl group (eg, a methyl group or an ethyl group), an alkoxy group (eg, a methoxy group, an ethoxy group), a hydroxyl group, an aryl group (eg, a phenyl group), and an alkoxycarbonyl group (eg, a methoxy group). , A halogen atom, or the like. R ₁ and R ₂ are a lower alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), an alkyl group having a sulfo group {β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ- Sulfobutyl group,
Sulfoalkoxyalkyl groups (sulfoethoxyethyl group, sulfopropoxyethyl group) and the like; alkyl groups having a carboxyl group (β-carboxylethyl group, γ-
Carboxypropyl group, γ-carboxybutyl group, δ-
Carboxybutyl group). R ₃ represents a methyl group, an ethyl group, or a propyl group. X ₁ represents an anion (eg, a halogen ion, a benzenesulfonate ion, a p-toluenesulfonate ion, etc.) commonly used for cyanine dyes. m ₁ represents 1 or 0, and when it is an inner salt, m ₁ = 0.

Hereinafter, specific examples of the compound represented by formula (3) used in the present invention will be shown.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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In the present invention, of the compounds represented by the general formulas (1) to (3), preferred are those represented by the general formulas (1) and (2).

In the general formula (4), the aliphatic group represented by R ₁ , R ₂ , R ₃ or R ₄ has 1 to 1 carbon atoms.
0 branched or straight-chain alkyl group (methyl group, ethyl group,
n-propyl group, n-pentyl group, isobutyl group, etc.),
Vinyl group, alkenyl group having 3 to 10 carbon atoms (such as 3-butenyl group and 2-propenyl group), and 7-14 carbon atoms
Aralkyl groups (benzyl group, phenethyl group, etc.).

Examples of the water-solubilizing group possessed by at least one of R ₂ and R ₄ include a sulfo group, a carboxy group, a phosphono group, a sulfate group and a sulfino group, and an aliphatic group having a water-solubilizing group as a substituent. Specific examples of the group include carboxymethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, sulfopentyl group, 3-sulfobutyl group, 6-sulfo-3-oxahexyl group, ω-
Sulfopropoxycarbonylmethyl group, ω-sulfopropylaminocarbonylmethyl group, 3-sulfinobutyl group, 3-phosphonopropyl group, 4-sulfo-3-butenyl group, 2-carboxy-2-propenyl group, o-sulfo Examples include a benzyl group, a p-sulfophenethyl group and a p-carboxybenzyl group.

The aliphatic group represented by R ₁ , R ₂ , R ₃ or R ₄ includes a hydroxy group, a halogen atom, an alkoxy group (such as a methoxy group and an ethoxy group) and an aryloxy group (such as a phenoxy group and a p- Sulfophenoxy group, etc.), cyano group,
A carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.),
Sulfamoyl group (sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (phenyl group, carboxyphenyl group, etc.) , An acyl group (acetyl group, benzoyl group, etc.) and an acylamino group (acetylamino group, etc.).

The substituent represented by V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ or V ₈ is represented by a Hammett σ _{p of} V _{1 to} V ₄ and V _{5 to} V _8. An electron-donating or electron-withdrawing group selected so that the sum of the values is greater than 0.12;
Specifically, a cyano group, a carboxy group, a linear or branched alkyl group (methyl group, ethyl group, iso-propyl group, t-butyl group, iso-butyl group, t-pentyl group, hexyl group, etc.), Alkoxy group (methoxy group, ethoxy group, propoxy group, etc.), alkylthio group (methylthio group, etc.), halogen atom, carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-pentamethylenecarbamoyl group, etc.), sulfamoyl group (N-methylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), acylamino group (acetylamino group, propionylamino group, benzoylamino group, etc.), sulfonylamino group (methanesulfonylamino group, benzenesulfonyl) Amino group, m-chlorobenzenesulfonylamino group, A fluoromethanesulfonylamino group, an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc.), an alkylsulfonyl group (a methanesulfonyl group, an ethanesulfonyl group, a trifluoromethanesulfonyl group, etc.), an arylsulfonyl group (benzene) Sulfonyl group, acyl group (acetyl group, benzoyl group, etc.), perfluoroalkyl group (trifluoromethyl group, pentafluoroethyl group, etc.), perfluoroalkoxy group (trifluoromethoxy group, pentafluoroethoxy group, etc.),
Perfluoroalkylthio group (trifluoromethylthio group, pentafluoroethylthio group, etc.), aryl group (phenyl group, m-chlorophenyl group, etc.), heterocyclic group (pyrrolyl group, pyridyl group, imidazolyl group, furyl group, thienyl group, etc. ) And the like.

The Hammett's σ _p value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the rate of hydrolysis of ethyl benzoate, and the value of each group is defined in Chemical Reviews vol.
7, 125-136 (1935), Journal o
f Organic Chemistry vol2
3, 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co., Ltd.), Physical Organic
Chemistry; McGraw Hill Boo
k (1940), Drug design VII Ac
ademic Press; New York (197
0), Structure-activity relationship of drug (Nankodo: 1979), Su
bstudent Constants for C
orlation Analysis in Ch
emistry and Biology; John
It is described in detail in Wiley and Sons (1979) and the like.

When V _{1 to} V ₈ are an aryl group, a heterocyclic group or an alkyl group, they may have a substituent as described above.

The ring formed by the condensation of V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ , V ₅ and V ₆ , V ₆ and V ₇ or V ₇ and V ₈ is 5 Examples thereof include a 7 to 7-membered saturated carbocycle, aromatic carbocycle, heterocycle and the like, and may have a substituent as described above.

Examples of the group substituted on the methine carbon of L ₁ , L ₂ , L ₃ , L ₄ and L ₅ include a lower alkyl group (methyl group,
Ethyl group), cyclic alkyl group (cyclopropyl group, cyclopentyl group, etc.), substituted alkyl group (2-methoxyethyl group, 2-thienylmethyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group ( Examples include a phenyl group, a carboxyphenyl group, etc., a heterocyclic group (thienyl group, furyl group, imidazolyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), a fluorine atom and the like. L ₁ may be fused with R ₁ or R ₂ , and L ₂ may be fused with R ₃ or R ₄ to form a ring.

As M ₁ , proton, organic ammonium ion (triethylammonium ion, triethanolammonium ion, etc.), cation of inorganic cation (lithium ion, sodium ion, calcium ion, etc.), halogen ion, p-toluenesulfonic acid Ion, perchlorate ion, and acid anion such as boron fluoride ion.

1 is 0 when an internal salt is formed to neutralize the charge.

Specific examples of the spectral sensitizing dye represented by the general formula (4) are shown below, but it should not be construed that the invention is limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[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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[0057]

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[0058]

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[0059]

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[0060]

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These compounds are described in "Cyanine Soybeans and Related Compounds" by FM Hama (1964, published by Inter Science Publishers), Ukr. Khim. Zh. , 1977,
43 (4) 381-4, British Patent No. 980,234,
U.S. Pat. No. 3,684,517, JP-A-61-203
No. 446, etc., and can be synthesized.

In the general formula (5), R ₁ is preferably an unsubstituted alkyl group having 18 or less carbon atoms (methyl group,
A propyl group, a pentyl group, a decyl group, an octadecyl group, etc. or a substituted alkyl group (substituents include carboxy group, sulfo group, cyano group, halogen atom, hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms, and 8 carbon atoms)
The following alkane sulfonylaminocarbonyl groups, acylaminosulfonyl groups having 8 or less carbon atoms, alkoxy groups having 8 or less carbon atoms, alkylthio groups having 8 or less carbon atoms, 2 carbon atoms
Aryloxy group having 0 or less, acyloxy group having 3 or less carbon atoms, acylthio group having 3 or less carbon atoms, acyl group having 8 or less carbon atoms, carbamoyl group, sulfamoyl group, 2 carbon atoms
An alkyl group having 18 or less carbon atoms substituted with an aryl group having 0 or less), among which an unsubstituted alkyl group, a carboxyalkyl group (such as a 2-carboxyethyl group, a carboxymethyl group or a salt thereof), and a sulfoalkyl group (A 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group or a salt thereof), a methanesulfonylcarbamoylmethyl group or a salt thereof is preferred. More preferably, it is a sulfoalkyl group (particularly a 2-sulfoethyl group).

The nucleus formed by Z includes a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a benzoxazole nucleus,
Naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tetrazole nucleus, benzotetrazole nucleus, tellrazoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, A pyridine nucleus, a quinoline nucleus, an isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus,
A thiadiazole nucleus, a tetrazole nucleus, a pyrimidine nucleus, and preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus, and a 4-quinoline nucleus; A nucleus is preferred.

D and Da represent an atomic group necessary for forming an acidic nucleus. The term “acid nucleus” used herein means “The Theory of the Photog”, edited by James.
graphic Process "4th edition, Macmillan Publishing Company, 1977, p. 198. Preferably, 2-pyrazolin-5-one, pyrazolidin-3,
5-dione, imidazolin-5-one, hydantoin,
2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazolidine-5-one, 2-thiooxazolidine-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, Thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1- Dioxide, indoline-2-one, indoline-3-one, indazolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3, 2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinoline-
4-one, 1,3-dioxane-4,4-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,
4-dione, indazolin-2-one, pyrido [1,2
-A] pyrimidine-1,3-dionepyrazolo [1,5-
b] Quinazolone, pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-
Nuclei such as dihydrobenzo [d] thiophen-1,1-dioxide and 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide; -Oxazolin-5-one nucleus and rhodanine nucleus are preferable, and rhodanine nucleus is particularly preferable.

The representative examples of the dye represented by formula (5) are shown below, but the invention is not limited thereto.

[0066]

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[0067]

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[0068]

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[0069]

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In the compound represented by the general formula (6), R
Examples of the water-solubilizing group substituted for ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include a sulfo group, a carboxy group, a phosphono group,
Each acid group such as a sulfate group and a sulfino group is exemplified.

As the aliphatic group represented by R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ , for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl) , N-pentyl, isobutyl, etc.), having 3 to 3 atoms
Examples thereof include a 10 alkenyl group (for example, each group such as 3-butenyl and 2-propenyl) and an aralkyl group having 3 to 10 carbon atoms (for example, each group such as benzyl and phenethyl). R ¹¹ is an aliphatic group having 8 or less carbon atoms substituted with a water-solubilizing group (eg, carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, etc.).

Examples of the aryl group represented by R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-) and a furyl group ( 2-), a thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group, a piperidinyl group and the like may be substituted. Each group represented by R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ may be further substituted with another substituent (for example, a halogen atom, an alkoxy group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p Specific examples of the aryl group substituted with a water-solubilizing group include each group such as -carboxybenzyl and the like, and examples thereof include a p-sulfophenyl group and a p-carboxyphenyl group, each of which is substituted with a water-solubilizing group. Specific examples of the heterocyclic group include groups such as a 4-sulfothienyl group and a 5-carboxypyridyl group. .

Examples of the condensable 5- or 6-membered nitrogen-containing heterocycle represented by Z ¹¹ include benzoxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d Oxazole, naphtho [2,
3-d] oxazole, benzothiazole, 4,5
6,7-tetrahydrobenzothiazole, naphtho [1,
Condensed rings such as 2-d] thiazole, naphtho [2,3-d] thiazole, benzoselenazole and naphtho [1,2-d] selenazole.

Examples of the group substituted on the methine carbon represented by L ¹¹ and L ¹² include, for example, a lower alkyl group (for example,
Groups such as methyl and ethyl), phenyl groups (such as phenyl and carboxyphenyl), alkoxy groups (such as methoxy and ethoxy), aralkyl (such as benzyl) and the like; There is.

Examples of the electron-withdrawing group represented by E ¹ and E ² include a cyano group.

The compound represented by the general formula (6) generally has high spectral sensitivity when one of the methine carbons represented by L ¹¹ and L ¹² is substituted. Gives a characteristic of being easily bleached in the processing bath, and has a favorable effect of reducing residual color contamination.

M ¹¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium) and an inorganic cation (for example, lithium, sodium, calcium and the like). Cation), and specific examples of the acid anion include, for example, a halogen ion (eg, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like. Can be n ¹¹ is 0 when an internal salt is formed to neutralize the charge.

Specific examples of the compound represented by the general formula (6) of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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The above compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by F.M.Hama (1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
The compound can be easily synthesized with reference to a conventionally known method described in JP-A-2,493,748 and the like.

To use these sensitizing dyes in a silver halide emulsion, the sensitizing dyes are added to and dissolved in a coating solution, or dissolved in water or an organic solvent such as methanol, ethanol or acetone alone or a mixed solvent thereof. What is necessary is just to add. It may be added in the form of a powder, and if necessary, it can be added to a layer adjacent to the silver halide emulsion layer, for example, a protective layer or an intermediate layer, as long as the photographic performance is not affected.

The amount of the sensitizing dye used in the present invention when it is added to the silver halide emulsion varies depending on the type of the silver halide emulsion and the type of the sensitizing dye. The range of 5 × 10 ^{-6 to} 2 × 10 ^-1 mol is good.

In the present invention, a so-called dry-to-dry process from the start of development to the end of drying of a super-high contrast type photosensitive material containing a hydrazine derivative represented by the general formula (H) is carried out.
When the processing is performed quickly with the time taken as 15 to 60 seconds, the effect is exhibited without regret.

Among the hydrazine derivatives represented by the general formula (H), a compound represented by the following general formula (Ha) is more preferable.

[0092]

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In the formula, R ¹¹ 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, chenyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Furthermore, the R ¹¹ preferably contains at least one ballast group or a silver halide adsorption accelerating group.

As the ballast group, those commonly used in immobile photographic additives such as couplers are preferable, and those having 8 carbon atoms are preferable.
For example, alkyl, alkenyl, alkynyl, alkoxy, phenyl, phenoxy, alkylphenoxy and the like which are relatively inert to the above photographic properties can be mentioned.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples 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 both are preferably 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 ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, allyl group, heterocyclic group, alkoxy group, hydroxyl group, amino group, carbamoyl group, Represents an oxycarbonyl group. Desirable R ¹² is a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, a —COOR ¹³ group, and a —CON
(R ¹⁴⁾ (R ¹⁵⁾ group (R ¹³ represents an alkynyl group or a saturated heterocyclic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ¹⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group). More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. R ¹²
The electron withdrawing group for substituting the carbon atom substituted with G preferably has a σp value of 0.2 or more and a σm value of 0.3 or more, for example, halogen, cyano, nitro, nitrosopolyhaloalkyl, polyhaloaryl, Alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group,
A carbamoyl group, an alkyl or aryl sulfinyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfonyloxy group, a sulfamoyl group, a phosphino group, a phosphine oxide group, a phosphonate ester group, a phosphonamide group, an arylazo group,
It represents an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group.

R ^{12 in the} formula (Ha) particularly preferably represents a fluorine-substituted alkyl group, a monofluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

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

[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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Specific examples of other preferred hydrazine compounds are described in US Pat. No. 5,229,248, columns 4 to 60, (1) to (252).
It is. These hydrazine compounds can be synthesized by known methods, for example, by the methods described in the above-mentioned U.S. Pat. Nos. 59 to 80 columns.

The amount of addition may be an amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. The hydrazine compound is added to at least one layer on the silver halide emulsion layer side, preferably to the silver halide emulsion layer and / or a layer adjacent thereto, more preferably to the emulsion layer. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. .2
0.8 molar equivalent. Preferably, it is 0.4 to 0.6 molar equivalent. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

It is preferable to employ the following technique for the photosensitive 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) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Nucleation promoting agent JP-A-7-114126, page (32) [0158]
(7) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (8) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (9) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (10) SPS support Support described in JP-A-3-54551. Other known additives include, for example, (RD) N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989).

In the present invention, an automatic developing machine having at least four processes of development, fixing, washing with water (including stabilization) and drying is employed.

In the developing solution, known developing agents, specifically, dihydroxybenzenes, 3-pyrazolidones, aminophenols, ascorbic acids and metal complex salts can be used alone or in combination. In addition, alkaline agents (sodium hydroxide, potassium hydroxide, etc.) and pH
It is preferable to add a buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.).

If necessary, a preservative, a dissolution aid, a sensitizer, a surfactant, an antifoaming agent, an antifoggant, a chelating agent, a development accelerator, a hardening agent or an antifoaming agent is added. be able to. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH 8.5
It is not less than 10.4.

As the fixing solution, those having a commonly used composition can be used. Usually the pH is between 3 and 8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum, or an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde). Even without these additions, the images formed by the method of the present invention are excellent.

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

In the present invention, the concentration of ammonium ion in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution. Particularly preferably, it is in the range of 0 to 0.05 mol. Also, when the acetate ion concentration in the fixing solution is 0.3
Preferably it is less than 3 mol / l.

The water washing treatment is preferably carried out with washing water containing a purifying agent containing an oxidizing agent and a bactericide. Examples of the oxidizing agent used include metal or nonmetal oxides, oxyacids or salts thereof, peroxides, and compounds containing an organic acid system. From the viewpoint of discharging to the drainage pipe, the oxyacid is preferably sulfuric acid, nitrous acid, nitric acid, hypochlorous acid and the like, and the peroxide is particularly preferably hydrogen peroxide solution or fentonic acid. Most preferred is hydrogen peroxide.

The bactericide may be any as long as it does not adversely affect photographic performance. Specific examples include thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothiane. Acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts,
Active halogen compounds such as organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, sodium chlorinated isocyanurate, chelating agents, sulfite compounds, antibiotics represented by penicillin, etc. Antibacterial and antifungal agents. Other L. E. FIG. We
st. “Water Quality Criteri
a "Photo. Sci. and Eng. Vol.
No. No. 6 (1965);
No. 542, No. 58-105145, No. 59-1265
No. 33, No. 55-111942, and No. 57-157
No.244 various anti-bacterial agents; described in "Bactericidal and Fungicide Chemistry" written by Hiroshi Horiguchi and published by Sankyo Publishing Co., Ltd. (Showa 57); Compounds such as those described above can be used.

In the present invention, the silver halide photographic light-sensitive material after the development, fixing and washing treatments has a water content of 18 g / m ^2.
Hereinafter, the water content of the silver halide photographic light-sensitive material immediately after passing through the squeeze roller is preferably 50% or more of the water content after the development, fixing, and washing processes. Here, the water content is determined by the following measurement method.

Emulsion layer side of photosensitive material (size 8 cm × 1
(2.5 cm) is prepared, and after the process for obtaining the water content is completed, the sample is sandwiched between blotting papers and passed between two opposed rollers to remove water droplets adhering to the surface. . After removing the water droplets, the sample was stuck on the glass plate so that the emulsion layer side was in contact with it to prevent evaporation of water,
The weight is measured (weight 1). 23 samples after measurement
After drying for 24 hours in a room conditioned at 48 ° C. and a relative humidity of 48%, the weight is measured together with the glass plate (weight 2).
The difference is converted to 1 m ² .

[0129]

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

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and Na
A water-soluble halide solution C composed of Cl and KBr is adjusted to pH 3.
The mixture was added at a constant flow rate of 0, 40 ° C. and a constant flow rate in Solution A for 30 minutes, and 0.18 μm of AgCl 70 mol%, AgBr 3
0 mol% of cubic crystals were obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. 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 resulting emulsion was 190 mV (40 ° C.).

A: ossein gelatin 25 g nitric acid (5%) 6.5 ml ion-exchanged water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg B: silver nitrate 170 g nitric acid (5%) 4.5 ml ion-exchanged water 200 ml C: 47.5 g of NaCl 51.3 g of KBr 6 g of ossein gelatin 0.15 mg of Na ₃ [IrCl ₆ ] 200 ml of deionized water 200 ml of 4-hydroxy-6 per mole of silver in 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. Next, the sulfur dispersed in the form of fine particles was converted into sulfur atoms by 2 × 10
^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid were added and chemically ripened at a temperature of 50 ° C. for 60 minutes, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrahydrofuran was added. Seindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and 1.5 × 10 ⁻³ mol of potassium iodide. After cooling to 40 ° C., the sensitizing dyes listed in Table 1 were added in an amount of 1 × 10 ^-4 per mol of silver.
Mole was added.

Emulsion A thus obtained was mixed with 1 m ²
The following first layer and second layer were simultaneously coated on one side of the undercoated support from the side of the support so as to have the following amount per unit by the following formula, followed by cooling and setting (emulsion formula A-1). .

Thereafter, the following backing layer and backing protective layer are coated on the undercoating layer having the antistatic layer on the opposite side at a coating speed of 200 m / min, cooled at -1 ° C., and simultaneously dried on both sides. To obtain a sample. The emulsion formulation A except that it did not contain a hydrazine derivative
Exactly the same as (Emulsion Formulation A-2).

(Support) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) is provided with 30 W /
After a corona discharge of (m ² · min), an undercoat layer having the following composition was applied on both sides and dried at 100 ° C. for 1 minute.

(Undercoat layer) 2-Hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) copolymer (numbers are weight ratio) 0.5 g / m ² Surfactant A 3.6 mg / m ² Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ² (Antistatic layer) 10 W / (m ² ··· min), an antistatic layer having the following composition was applied on one side to 70 m / m.
in, using a roll-fit coating pan and air knife, drying at 90 ° C. for 2 minutes,
Heat treatment was performed at 40 ° C. for 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² Hydrophobic polymer particles C 0.4 g / m ² Polyethylene oxide compound (MW 600) 0.1 g / m ² Curing agent E 0.1 g / m ² First layer (Emulsion layer) Gelatin 1.0 g Silver halide emulsion A 3.3 g as silver amount 5-nitroindazole 0.01 g 2-mercaptohypoxanthine 0.02 g 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, and vinyl Pivalinate 12.5% by weight suspension polymer 1.4 g Dextran (weight average molecular weight 65,000) 0.10 g 4-mercapto-3,5,6-fluorophthalic acid 0.05 g Sodium polystyrene sulfonate ( (Average molecular weight: 500,000) 0.015 g The coating solution pH was 5.8.

Second layer (protective layer) Gelatin 0.90 g Dextran (weight average molecular weight 65,000) 0.20 g Resorcinol 0.15 g 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 005 g Nucleation promoter Na 0.20 g Sliding agent S 0.012 g Fungicide Z 0.005 g Sodium polyoxyethylene lauryl ether sulfonate 0.010 g Sodium dihexylsulfosuccinate 0.015 g Silica (average particle size 5 μm) 0.01 g Silica (Average particle size 8 μm) 0.015 g Hardener (1) 0.15 g (Backing layer) Gelatin 1.8 g F-1 0.080 g F-2 0.050 g F-3 0.020 g Colloidal silica 75% by weight 12.5% by weight of vinyl acetate and 12.5% by weight of vinyl pivalinate Suspended polymer 0.7 g Sodium polystyrene sulfonate 0.010 g Hardener (2) 0.05 g (backing protective layer) Gelatin 1.8 g Matting agent: monodispersed polymethyl methacrylate having an average particle diameter of 3 μm 0.045 g polyoxyethylene Sodium lauryl ether sulfonate 0.005 g Sodium dihexyl sulfosuccinate 0.005 g Hardener (1) 0.15 g

[0138]

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[0139]

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[0140]

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(Developer) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium carbonate 65 g 1-phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 1.5 g Hydroquinone 40 g 1-phenyl-5-mercaptotetrazole 0.025 g Potassium bromide 4 g 5-Methylbenzotriazole 0.21 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.07 g KOH was added to the solution to a pH of 9.8 to make 1 L.

(Fixing solution) Ammonium thiosulfate (59.5% w / v aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% w / v aqueous solution) 82 g Citric acid (50% w / v) / V aqueous solution) 15.7 g gluconic acid (50% w / w aqueous solution) 8.55 g aluminum sulfate (48% aqueous solution) 13 ml glutaraldehyde 3 g sulfuric acid Amount to bring pH to 4.6 when used 1 L by adding water at the time of use Finished.

(Processing conditions) Temperature Processing time Replenishment amount Development 38 ° C. 25 seconds 130 ml / m ² Fixing 37 ° C. 25 seconds 130 ml / m ² Washing 5 ° C. 15 seconds Drying 50 ° C. 20 seconds Automatic processing machine manufactured by Dainippon Screen Co., Ltd. LD-M1060
Was modified and the first roller inside the transport rack in the drying zone was changed to a material having a contact angle shown in Table 1 and used.

(Measurement of Contact Angle) The contact angle was measured at 23 ° C. using a contact angle measuring device CA-Z manufactured by Kyowa Interface Chemical Co., Ltd.

(Evaluation Method) The prepared black-and-white silver halide photographic light-sensitive material was exposed so that the blackening ratio was 10%, and 500 sheets were continuously processed in all sizes. The obtained processed unexposed sample was visually evaluated, and the degree of adhesion of dye stain and roller mark stain was evaluated by rank. If it is less than 2, there is a problem in practical use, 3 is a level that can be used, but the dirt is clearly recognizable, 4 is a level that there is dirt but is not noticeable unless you look closely, and 5 is a level that does not have any dirt. It is desired that 10 or less stains adhere to the total number of processed 500 sheets, more preferably 5 or less.

Regarding the remaining color, the unexposed processed sample was subjected to a sensory evaluation and a rank evaluation. Below 2 there is a practical problem and 3
Is a level that can be used but cares about sex appeal, 4 is a level that has sex appeal but does not notice much if you do not look carefully, and 5 is a level that does not have residual color at all.

[0147] In addition, the transportability is limited to the case where normal processing cannot be performed due to the stuck inside the automatic developing machine even after continuous processing.
Depending on the number of samples that can be output normally and processed continuously until the end of drying, the superiority was evaluated by the following symbols.

0 to 10 sheets or less = xx 11 to 50 sheets =
× 51-250 sheets = △ 251-499 sheets = ○
500 sheets = ◎ The results are shown in Table 1.

[0149]

[Table 1]

[0150]

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Example 2 The formulation and processing conditions of the developing solution were changed as follows, except that the hydrazine compound shown in Table 2 was added to the emulsion coating solution of the photosensitive material in an amount of 4 × 10 ⁻⁵ mol per mol of silver. Is Example 1
The evaluation was performed in the same manner as described above.

(Developer) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium carbonate 95 g 1-phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 2.5 g Na erythorbic acid monohydrate 60 g Potassium bromide 4 g Benzotriazole 0.21 g Potassium hydroquinone monosulfonate 10 g 8-Mercaptoadenine 0.07 g KOH was added to the solution to a pH of 10.0 to make it 1 L.

(Processing conditions) Temperature Processing time Replenishment amount Developing 38 ° C. 15 seconds 130 ml / m ² Fixing 37 ° C. 10 seconds 130 mL / m ² Washing 5 ° C. 15 seconds Drying 50 ° C. 10 seconds The results are shown in Table 2.

[0154]

[Table 2]

Example 3 The components of the fixing solution were changed to the following formulation, and the EPDM having a contact angle with water of 20 ° occupied in the surface area of all the rollers inside the transport rack in the drying zone of the automatic developing machine. Evaluation was performed in the same manner as in Example 2 except that the ratio was changed as shown in Table 3.

(Fixing solution FA-1) Ammonium thiosulfate 200 g Sodium sulfite 15 g Sodium metabisulfite 25 g Citric acid 5 g Aluminum sulfate / 18-hydrate salt 15 g Boric acid 12 g KOH pH 4.7 Add water at the time of use to finish to 1 L Was.

(Fixer FA-2) Sodium thiosulfate 180 g Sodium sulfite 15 g Sodium metabisulfite 5 g Citric acid 5 g DTPA · 5H 5 g N-acetylpenicillamine 0.5 g KOH pH 5.8 Add water when used to make 1 L Finished.

Table 3 shows the results.

[0159]

[Table 3]

Example 4 The replenishment amounts of the developing solution and the fixing solution were both set to 80 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material, and the amount of the hardener (1) of the light-sensitive material was adjusted. The total water content of the emulsion side and the backing side immediately after passing through the squeeze roller installed before the start was changed as shown in Table 4, and the same as Example 3 except that the percentage of EPDM was changed to 80%. Was evaluated.

Table 4 shows the results.

[0162]

[Table 4]

Example 5 The replenishment amounts of the developing solution and the fixing solution were both set to 80 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material, and the strength of the squeeze roller installed between the end of washing and the start of drying was adjusted. Then, when the ratio of (water content immediately after passing) / (water content before passing) d was changed and evaluated in the same manner as in Example 3, the same result as in Example 4 was obtained.

[0164]

According to the processing method of the present invention, even when the photosensitive material for exposure is promptly processed by an image setter, problems such as stains, residual colors, defective conveyance, and roller marks do not occur.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/26 G03C 1/26 1/30 1/30 G03D 3/00 G03D 3/00 B

Claims (7)

[Claims] 1. A method for developing, fixing, washing and drying a silver halide photographic material containing a sensitizing dye represented by a general formula selected from the following (1) to (6) using an automatic developing machine: The surface of the squeeze roller installed in the automatic processor between the end of washing and the start of drying is covered with a material having a contact angle (θ) with water of 0 ° <θ <60 °. Processing method for a silver halide photographic light-sensitive material. Embedded image [Wherein, X is -S- or -Se-, and R ₁ , R ₂ , R
_At least two of ₃ , R ₄ and R ₅ represent an organic group having a water-soluble group. However, neither R ₃ nor R ₄ is an organic group having a water-soluble group. R ₁ , R ₂ , R ₃ , R ₄ and R _{5 which} are not the organic group having a water-soluble group represent a hydrogen, an alkyl group, an alkenyl group or an aryl group, and these may have a substituent. R ₆ and R ₇ each represent hydrogen, a hydroxy group, a halogen atom, a carboxy group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group which may have a substituent; Represents a group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylsulfonyl group, a carbamoyl group or a sulfamoyl group, and R ₆ and R ₇ may combine with each other to form a ring. [Chemical formula 2] Wherein Y is —S— or —S ₂ —, and Z ₁ , Z ₂ ,
At least two of Z ₃ , Z ₄ , Z ₅ and Z ₆ represent an organic group having a water-soluble group. However, neither Z ₄ nor Z ₅ is an organic group having a water-soluble group. Z _{1 to} Z _{6, which} are not the organic group having a water-soluble group, represent hydrogen, an alkyl group, an alkenyl group, or an aryl group, and these may have a substituent.
Z ₇ and Z ₈ have the same meanings as R ₆ and R _{7 in} formula (1). [Chemical formula 3] Wherein Y ₁ and Y ₂ each represent a non-metallic atomic group necessary to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring or a quinoline ring; May be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.
R ₁ and R ₂ each represent a lower alkyl group, an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R ₃ represents a methyl group, an ethyl group or a propyl group. X ₁ represents an anion. n ₁ and n ₂ represent 1 or 2. m ₁ represents 1 or 0, and m ₁ =
Represents 0. [Formula 4] [Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent a substituted or unsubstituted aliphatic group, and at least one selected from R ₂ and R ₄ has a water solubilizing group as a substituent. . V _1, V _2, V
₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ each represent a hydrogen atom or a substituent, and represent V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ , V ₅ and V ₆ , fused together in V ₆ and V ₇ or V ₇ and V ₈ may form a ring, each V ₁ ~V ₄ and V ₅ ~V ₈ is the sum of the Hammett sigma _p value for each group It is larger than 0.12. L _1, L
₂ , L ₃ , L ₄ and L ₅ represent a methine group. M ₁ represents an ion necessary to neutralize the charge in the molecule, and l represents the number of ions required to neutralize the valence in the molecule. [Chemical formula 5] [In the formula, R ₁ represents a substituted or unsubstituted alkyl group.
Z represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. D and Da each represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. L ₁ , L ₂ , L ₃ ,
L ₄ , L ₅ and L ₆ represent a methine group. M ₁ represents a counter ion necessary for neutralizing the charge, and m ₁ is a number of 0 or more required for neutralizing the charge in the molecule. n is 0 or 1
Represents [Formula 6] Wherein Y ¹¹ , Y ¹² and Y ¹³ are each independently —N (R
¹⁰ )-represents a group, oxygen atom, sulfur atom, selenium atom, tellurium atom. R ¹¹ represents an aliphatic group having 8 or less carbon atoms substituted with a water solubilizing group, and R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ each independently represent an aliphatic group, an aryl group or a heterocyclic group; And at least three groups of R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ substitute a water solubilizing group. Z ¹¹ is a 5-membered or 6-membered which may be condensed
L ¹¹ and L ¹² each independently represent a substituted or unsubstituted methine carbon. M ¹¹ represents an ion necessary to offset the total charge of the molecule, and n ¹¹ represents a number required to neutralize the charge of the molecule. ] 2. The silver halide photographic light-sensitive material contains a hydrazine derivative represented by the following general formula (H), and the time required from the start of development to the end of drying is 15 to 60 seconds. A method for processing a silver halide photographic light-sensitive material according to claim 1. Embedded image [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) R ₅₂
A or an iminomethylene group, n represents an integer of 1 or 2, and A ₁ and A ₂ are each a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents a substituted acyl group, R is a hydrogen atom, each substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group,
Represents a carbamoyl group or an oxycarbonyl group. R ₅₂
Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, and amino group. ] 3. The contact angle with water of at least 80% of the surface area of the first roller of the transport rack during the drying step is 0 ° <θ <.
3. The method for processing a silver halide photographic material according to claim 1, wherein the material is covered with a material having an angle of 60 [deg.]. 4. At least 80% of the surface area of all the rollers of the transport rack during the drying step has a contact angle with water of 0 ° <θ <6.
The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the material is covered with a material having an angle of 0 °. 5. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein a fixing solution containing substantially no aluminum compound is used. 6. The halogen according to claim 1, wherein the water content of the silver halide photographic material after the development, fixing and washing treatments is 18 g / m ² or less. Processing method of silver halide photographic light-sensitive material. 7. The silver halide photographic light-sensitive material immediately after passing through the squeeze roller has a water content of 50% or more based on the water content after development, fixing and washing. 7. The method for processing a silver halide photographic light-sensitive material according to 1, 2, 3, 4, 5, or 6.