JP3485146B2 - Photo processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an image-exposed halo.
Form high-contrast negative images from photographic silver halide materials
On how to make
High-contrast negative images suitable for photolithography for printing
The present invention relates to a method for stably forming the substrate. [0002] 2. Description of the Related Art Ultra-high contrast photographic features with gamma values exceeding 10
Whether it is a negative image or a positive image,
Photos of continuous tone images with useful dot images
It is extremely useful for objective reproduction or line drawing reproduction. That
Using a highly sensitive emulsion and a stable developer,
It is strongly necessary to obtain ultra-high contrast photographic properties that are useful for line art reproduction.
Is desired. Conventionally, ultra-high contrast images with gamma values exceeding 10
The true characteristics are silver chlorobromide (at least silver chloride content of 50%
The lith-type silver halide composed of
Is extremely low (usually 0.1 mol / L or less)
Developed with quinone developer and obtained by infectious development
I was However, this hydroquinone developer is
Hydroquinone is a preservative that does not disturb the image
Extremely poor preservation due to lower sulfate concentration, 3 days
Has the serious disadvantage that it cannot withstand the aging
Was. As a means for solving the above problems, hydrazine
Compounds in silver halide photographic materials and developers
And obtain ultra-hard photographic characteristics with gamma value of 10 or more
For example, U.S. Pat. Nos. 4,168,977 and 4,2
Nos. 24,401, 4,243,739 and 4,26
9,929, 4,272,614, 4,32
3,643, JP-A-62-178246, and JP-A-62-178246.
62-180361. Typically
Silver halide photographic material containing hydrazine compound
Has a specific problem that black spots are easily generated. [0005] Although the mechanism of black spot generation is not clear,
It looks like a non-image part sandy, so-called pepper shake
Is to form a developed silver image that looks like
This is a problem in making a film. From this, black
Tutu is sometimes called pepper fog. Reduce black pots
Development inhibitors, such as 5-methyl
Add a large amount of benzotriazole, etc.
Methods are generally known, but photographic properties and halftone dot quality
It has an adverse effect. In addition, various additives etc.
Are also disclosed in JP-A-63-34543,
-103232, etc., but still this problem
Has not been fully resolved. [0006] In the plate making process, a phototypesetting film,
Various silver halide photosensitive materials, such as shadow films and bright room light-sensitive materials
For those who work with the developer, several types of developer
Warehouse management is required. In order to eliminate this trouble, various photosensitive
It is desirable to be able to process the material with one developer.
As described above, a large amount of 5-methylbenzotriazole is contained in the developer.
In addition to the effect of suppressing the generation of black pot, adding to the amount,
General silver halide exposure without hydrazine derivatives
The effect of suppressing an increase in the minimum concentration of a material is also known.
Processable development of several types of silver halide photosensitive materials
It is an effective inhibitor in liquids, but as described above,
And has the disadvantage of adversely affecting dot quality
Was. [0007] SUMMARY OF THE INVENTION It is an object of the present invention to provide a halo.
Without adversely affecting the photographic characteristics of the silver gemide photosensitive material
Suppresses increase in minimum concentration and contains hydrazine derivative
Adversely affects the photographic properties of photographic silver halide materials
To provide a method for suppressing the occurrence of black spots without
It is in. [0008] SUMMARY OF THE INVENTION The above object of the present invention is an object of the present invention.
Method of developing illuminated silver halide photographic material
At or exposed to light containing a hydrazine derivative
Developed silver halide photographic material
A method for forming a high-contrast negative image, comprising:
Characterized by developing in the presence of the compound represented by Chemical Formula 1.
Achieved by a photographic processing method. [0009] BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the compound of formula 1
Developing in the presence of a compound of formula 1
In the medium or in the developing solution
Means that. In a preferred embodiment of the present invention,
The compound represented by is contained in the photosensitive material or the developer.
However, it is more preferable to add it to the developer.
Has little effect on true characteristics and eliminates dot quality degradation
Thus, the occurrence of black spots can be suppressed. In photosensitive material
If it is contained, the silver halide emulsion layer must be coated.
Layer, such as a silver halide emulsion layer, an undercoat layer, an intermediate layer
Layer, protective layer, etc. [0010] The amount of the compound of the present invention may be added to the developer.
If used, 1 mg / liter to 10 mg / liter
An addition amount in the range of 00 mg, preferably 10 mg to 50
0 mg. In addition, when it is contained in the photographic layer, 1 m^Two
With a content ranging from 0.1 mg to 100 mg per
Or 1 mg to 20 mg. The compound of the present invention is added to a silver halide emulsion.
When adding, it is preferable to add after chemical ripening,
Or methanol, ethanol, acetone, dimethyl
Dissolved in water-miscible organic solvent such as formamide and added
Just add. Next, the compound of formula 1 will be described. In the formula
L represents an alkylene group (eg, methylene, ethylene,
Etc.). Among them, preferred are those having 3 or more carbon atoms.
The following are preferred, and a methylene group is particularly preferred. M is hydrogen
Atoms, alkali metals (e.g. sodium, potassium
Etc.) or ammonium groups (eg ammonium, tet
Lamethylammonium, tetraethylammonium
Etc.). R₁, R_TwoRepresents a hydrogen atom and an alkyl group, respectively.
(E.g., methyl, ethyl, propyl, n-butyl,
Chlorohexyl group), alkenyl group (for example, allyl group)
Alkynyl group (eg, propargyl group),
Aryl groups (eg phenyl, tolyl, methoxyphenyl)
, A chlorophenyl group, etc.), a heterocyclic group (for example, pyridi
, Thiazolyl, tetrahydropyranyl, etc.)
However, they cannot be hydrogen atoms at the same time. Preferred
Is R₁, R_TwoIs the sum of the carbon numbers (including the substituents) of 3
10 And also connect to each other to form a ring
May be. Preferred in this case are 4- to 7-membered rings
In particular, those having a 5- or 6-membered ring are preferred. Where R₁,
R_TwoAt least one OH group, -COOH group, -S
O_ThreeH group, -SO_TwoNHR_ThreeGroup, -SO_ThreeH group, -NHSO
_TwoR_FourIt is assumed that Particularly preferred of these
The dissociating protons have a pKa value of 4 to 12.
(Eg, carboxy, phenolic hydro
Xy, sulfonamide, sulfamoyl, etc.)
You. These groups may be salts of alkali metals and the like.
No. M is a hydrogen atom, an alkali metal or ammonium group
Represents R_ThreeIs hydrogen atom, alkenyl group, alkynyl
Group, aryl group, alkyl group (R₁, R_TwoTo the alkyl group of
Synonymous) and a heterocyclic group. Preferred of these
Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
And an aryl group and an aryl group. R_FourIs an alkenyl group,
Alkynyl group, aryl group, alkyl group (R₁, R_TwoNo
And a heterocyclic group. Preferred among these
Preferred are alkyl groups having 1 to 6 carbon atoms and alkenyl.
And an aryl group. Hereinafter, specific examples of the compound represented by Formula 1 will be given.
However, the present invention is not limited to these. [0015] Embedded image [0016] Embedded imageThe following are representative examples of the synthesis of the compounds of the present invention.
State. 5-mercapto- (1H) -tetrazolyl
Sodium acetate 18.2 g, triethylamine hydrochloride
16.5 g, p-aminophenol 10.9 g, acetoacetate
The mixture was mixed with 200 ml of nitrile,
24.8 g of hexylcarbodiimide were added. Then warm
After incubating for 4 hours at a bath temperature of 60 ° C, the insoluble matter was removed.
After filtration, the filtrate was dried under reduced pressure. Then 100m of water for residue
l, 5 g of sodium hydroxide was added, and the insoluble material was filtered off.
The filtrate was washed with ethyl acetate (100 ml × 2 times).
Then, 15 ml of concentrated hydrochloric acid was added to the aqueous layer, and the precipitated crystals were collected by filtration.
After washing and drying, 13 g of T-1 was obtained. (Melting point 218
℃, decomposition) 5-mercapto- (1H) -tetrazolyl
2.7 g of sodium acetate sodium salt, triethylamine hydrochloride
2.5 g, p-methanesulfonamidoaniline 2.8
g, and 40 ml of acetonitrile, and stirred at room temperature.
3.7 g of dicyclohexylcarbodiimide were added. Less than
Below, the same process as above was performed to obtain 3.3 g of T-12.
Obtained. (Melting point 233 ° C, decomposition) As a developing agent used in the developing solution of the present invention,
Is a dihydroxybenzene-based developing agent such as hydroxy
Non, chlorohydroquinone, bromohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
2,3-dichlorohydroquinone, 2,5-dichloroha
Idroquinone, 2,3-dibromohydroquinone, 2,
5-dimethylhydroquinone, hydroquinone monosul
Although there are honates and the like, hydroquinone is particularly preferred. The present invention also relates to 3-pyrazolidone and also
Uses P-aminophenol-based developing agent as dihydroxyben
It can be used in combination with a zen developing agent or alone.
1-phenyl-3 as a 3-pyrazolidone developing agent
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydride
Roxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-dimethyl-3-pyrazolidone, 1-p-tolyl
-4,4-dimethyl-3-pyrazolidone and the like. Book
As the p-aminophenol-based developing agent used in the present invention,
N-methyl-p-aminophenol, N- (β-hydro
Xylethyl) -p-aminophenol, N- (4-hydrido)
Roxyphenyl) glycine, 2-methyl-p-aminophen
Phenol, p-benzylaminophenol, etc.
Among them, N-methyl-p-aminophenol is preferred.
No. Further, as a developing agent, ascorbic acid and
Its derivatives can be used. Ascorbic acid and
The derivative can be used alone or as a dihydroxybenzene developing agent
And / or 3-pyrazolidone or P-aminophenol
It can be used in combination with a developing agent. The developing agent is usually 0.03 mol / L to 1.0.
It is preferably used in an amount of mol / L. Also dihydro
Xybenzenes and 1-phenyl-3-pyrazolidones or
Is used in combination with p-aminophenols
The former is 0.1 mol / L to 1.0 mol / L, and the latter is 0.0 mol / L.
It is preferably used in an amount of from 01 to 0.1 mol / L. As the sulfite preservative used in the present invention,
Sulfites, such as sodium sulfite, potassium sulfite
System, sodium bisulfite, potassium metabisulfite,
Examples include sodium aldehyde and sodium aldehyde. Consumption
0.2 mol / L or more, preferably 0.3 mol / L or more
The range is 1.0 mol / L. The effect of the present invention is 0.2
Particularly, the effect is exhibited when the ratio is equal to or greater than 1 / L. In the developing solution, if necessary, a buffering agent (eg,
For example, carbonate, boric acid, borate, alkanolamine
, Sulfosalicylic acid), alkaline agents (eg, hydroxylated
Sodium, potassium hydroxide, lithium hydroxide, etc.)
Dissolving agents (polyethylene glycols, these
), PH adjuster (for example, organic acid such as acetic acid), development
It can contain accelerators, surfactants, hardeners, etc.
Wear. The developing solution may further contain an antifoggant (for example, 5
-Nitroindazole, 5-nitro-benzimidazo
5-methyl-benzotriazole, 5-nitroben
Benzotriazole such as zotriazole, benzothia
Sol, 1-phenyl-5-mercapto-tetrazole
Or tetrazole, thiazole or British Patent 1,2
69,268), chelating agents
(For example, diethylenetriaminepentaacetic acid, ethylenedia
Mintetraacetic acid, these alkali metal salts, polyphosphates,
Nitriloacetate). As additives used in addition to the above components,
Is a development inhibitor such as sodium bromide and potassium iodide
Agent, ethylene glycol, diethylene glycol, tri
Ethylene glycol, dimethylformamide, methyl
Losolve, hexylene glycol, ethanol, methano
May contain organic solvents such as
Color tone agent, defoamer, water softener, JP-A-56-1062
No. 44 may be included. The pH value of the developer thus adjusted is
Select enough to give the desired density and contrast.
But preferably in the range of about 10-13.
No. In particular, the present invention is applied to a pH range of 10 to 12.5.
It is suitable. It can be used in the process of the present invention.
As an automatic developing machine, L manufactured by Dainippon Screen Mfg. Co., Ltd.
D281Q, LD360, LD381, Fuji Photo Fill
FG680A, FG950A, FG710A
Etc., but is not limited to the type of automatic developing machine. These self
When processing using a dynamic developing machine, replenish the developer
Can be processed across. Replenishment is generally photosensitive material
Replenishment (treatment replenishment) with air treatment and replenishment with air oxidation
(Oxidative replenishment), the developer of the present invention
Both process replenishment and oxidation replenishment
It can be carried out. Processing replenishment rate is usually 60-500ml / m
^TwoCan be used in the range of
It is better to reduce as much as possible to reduce the amount. Through
Usually preferably 100-200 ml / m^TwoTo replenish
What is necessary is just to comprise the composition of a developing solution, such as raising a component concentration. The development processing temperature and time of the photosensitive material are mutually
Related and determined in relation to the total processing time,
Generally, it takes about 10 seconds to 3 minutes at about 20 to 50 ° C.
In the case of processing, it is 10 to 40 seconds at about 30 to 50 ° C.
You. Silver halide light-sensitive material used in the present invention
Is a black-and-white photographic material (eg, medical or industrial radiography)
Photo-sensitive materials for photoengraving such as true materials, squirrel-type photographic materials,
Micro photographic materials, micro reversal photographic materials for X-rays, computer photography
Planting paper, negative photographic material for general photography, photographic paper, etc.)
There is. The hydrazine derivative used in the present invention
The compound represented by the general formula 2 can be mentioned. [0033] Embedded image In the general formula 2, A¹, A^TwoAre both hydrogen atoms or
Is a hydrogen atom and the other is a sulfonyl group or an acyl group
And R⁷Represents an aliphatic group, an aromatic group, or a heterocyclic group.
Then G¹Is carbonyl, sulfonyl, sulfoxy
Group, phosphoryl group, oxalyl group or iminomethylene group
And R⁸Represents a hydrogen atom, an aliphatic group, an aromatic group,
A xy group, an aryloxy group, an amino group or
Represent. [0035] Embedded image In the general formula 3, Q⁺Contains a cationic group
Represents a group, A^-Represents an anion, but Q⁺Contains a sulfo group
Not needed when Next, the general formulas 2 and 3 will be described in detail.
explain. In the general formula 2, A¹, A^TwoIs hydrogen atom, carbon
An alkylsulfonyl group and an arylsulfo group having a number of 20 or less
A phenyl group (preferably a phenylsulfonyl group,
Σ_pAre replaced so that the sum of
Enylsulfonyl group) and an acyl group having 20 or less carbon atoms (preferably
Preferably a benzoyl group, or Hammett's σ_pIs the sum of
A benzoyl group substituted to be 0.5 or more)
Or unsubstituted or substituted aliphatic, straight-chain, branched or cyclic
A sil group (for example, a halogen atom, ether
Group, sulfonamide group, amide group, hydroxy group,
Examples include a ruboxyl group and a sulfo group. ) And A¹,
A^TwoIs most preferably a hydrogen atom. R⁷so
The aliphatic group represented is a linear, branched or cyclic alkyl group,
An alkenyl group and an alkynyl group. R⁷Yoshi represented by
The aromatic group is a monocyclic or bicyclic aryl group.
Examples include a phenyl group and a naphthyl group. R⁷Complex
As the ring group, at least one of N, O, and S atoms
A 3-10 membered saturated or unsaturated heterocyclic ring,
These may be monocyclic, or may further have another aromatic ring or
May form a condensed ring with a heterocyclic ring. Preferred as heterocycle
Or a 5- or 6-membered aromatic heterocyclic group.
For example, pyridyl group, imidazolyl group, quinolyl group, benz
Imidazolyl group, pyrimidyl group, pyrazolyl group,
Including noryl, thiazolyl, and benzothiazolyl groups
Is preferred. R⁷May be substituted with a substituent.
Examples of the substituent include the following. these
May be further substituted. For example, alkyl
Group, aralkyl group, alkoxy group, aryl group,
Mino group, acylamino group, sulfonylamino group, urea
Group, urethane group, aryloxy group, sulfamoyl
Group, carbamoyl group, alkylthio group, arylthio
Group, sulfonyl group, sulfinyl group, hydroxy group,
Logen atom, cyano group, sulfo group, carboxy group, ann
Monium group, pyridinium group, thyuronium group, isothione
An oleido group. These groups are mutually separated when possible
To form a ring. R⁷Preferred as
Is an aromatic group, more preferably an aryl group. or,
R⁷Is the smell of immobile photographic additives such as couplers
With ballast groups that are commonly used
Is also good. Ballast groups have photographic properties with 8 or more carbon atoms
Relatively inert to the group, for example, an alkyl group,
Alkoxy group, phenyl group, alkylphenyl group,
You can choose from nonoxy group, alkylphenoxy group, etc.
it can. Q in general formula 3⁺Has at least one
A group containing a cationic group having a quaternary nitrogen atom,
Linear or branched hydrocarbon having 1 to 4 carbon atoms
G through the strand¹And part or all of this chain is
And may form part of a heterocyclic ring having a secondary nitrogen atom.
Q⁺Preferred examples of trialkylammonio are
Alkyl group, pyridinium-1-ylalkyl group, 1-A
Rukypyridinium-2-yl group, 1-alkylpyridi
Ium-3-yl group, 1-alkylpyridinium-4-
Yl group, thiazolinium-3-ylalkyl group, oxa
Zolinium-3-ylalkyl group, 1-alkylimida
Zolium-3-ylalkyl groups and the like. this
These groups may be substituted, and the substituent may be R⁷of
Those mentioned as substituents are preferred. Furthermore, these
When a group forms a ring structure, it may be fused with another ring.
No. A^-Is Q⁺And a preferred example is
Cl^-, Br^-, P-toluenesulfonate, methylsulfur
Honart etc., but Q⁺As a substituent of
It does not exist when it has an E group and forms an inner salt. G¹Represents a carbonyl group, a sulfonyl group, a sulf
Oxy, phosphoryl, oxalyl or iminomethyl
Represents a len group, G¹Is a carbonyl group, oxalyl
Groups are preferred. R⁸As the aliphatic group represented by
Or an alkyl group having 1 to 5 carbon atoms,
Are preferably monocyclic or bicyclic aryl groups (for example,
Including a ring-ring). G¹Is a carbonyl group,⁸
Preferred among the groups represented by are a hydrogen atom and an alkyl
(For example, methyl group, trifluoromethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopro
Pill group, phenylsulfonylmethyl group, etc.), aralkyl
Group (eg, 2-hydroxybenzyl group), aryl
Group (for example, phenyl group, 3,5-dichlorophenyl
Group, 2-methanesulfonamidophenyl group, 4-methane
Sulfonamidophenyl group, 2-hydroxymethylphen
A general formula 3 or the like, particularly a hydrogen atom,
Equation 2 is preferred. R⁸May be substituted, and the substituent
As R⁷The substituents listed with respect to can be applied.
G¹Is an oxalyl group, R⁸Preferred as
Alkoxy group (for example, methoxy group, ethoxy group,
Propoxy group, methoxyethoxy group, etc.), aryloxy
Si group (for example, phenoxy group, 2-hydroxymethyl
Phenoxy, 4-chlorophenoxy, etc.), amino
(Eg, 3-hydroxypropylamino group, 2,3-
Dihydroxypropylamino group, 2-dimethylamino
Tylamino group, 3-diethylaminopropylamino group
Etc.), general formula 5, etc., and an amino group is particularly preferred. R
⁷, R⁸Adsorbs on the surface of silver halide grains
Those incorporating a strengthening group may be used. Such adsorption
Examples of the group include a thiourea group, a heterocyclic thioamide group,
U.S. Pat.
The groups described in US Pat. No. 5,105 are exemplified. Also, R⁸Is
G¹-R⁸Is split from the residual molecule, and -G¹-R⁸Department
Initiate a cyclization reaction that produces a cyclic structure containing a minute atom
Such as, for example, for example,
And those described in JP-A-63-29751.
You. Specific examples of the compound represented by the general formula 2 are shown below.
However, the present invention is not limited to the following compounds. [0039] Embedded image [0040] Embedded image [0041] Embedded image [0042] Embedded image [0043] Embedded image [0044] Embedded image [0045] Embedded image [0046] Embedded image [0047] Embedded image [0048] Embedded image [0049] Embedded image [0050] Embedded image [0051] Embedded image [0052] Embedded image [0053] Embedded image [0054] Embedded image [0055] Embedded image [0056] Embedded image [0057] Embedded image [0058] Embedded image [0059] Embedded image [0060] Embedded image [0061] Embedded image [0062] Embedded image The hydrazine compound of the present invention is described in, for example,
Nos. 61-213847 and 62-178246,
62-180361, 62-260153, 6
No. 3-253357, JP-A-1-269936, US
No. 4,684,604, No. 3,379,529
No. 4,377,634, No. 4,332,87
No. 8, No. 4,937,160
It can be synthesized by using the method. The hydrazine compound of the present invention is suitably mixed with water.
Organic solvents such as alcohols (methanol, ethanol
, Propanol, fluorinated alcohol), ketones
(Acetone, methyl ethyl ketone), dimethylforma
Amide, dimethylacetamide, dimethylsulfoxide,
It can be used by dissolving it in methylcellosolve or the like.
Also, by the well-known emulsification dispersion method,
Luphthalate, tricresyl phosphate, glycerin
Such as lutriacetate or diethyl phthalate
Use auxiliary solvents such as yl, ethyl acetate and cyclohexanone
Dissolve and mechanically create and use an emulsified dispersion
Can be. Or a method known as the solid dispersion method
The hydrazine compound powder into water
For dispersing with a tool, colloid mill, or ultrasonic
You can also be. The photographic emulsion used in the present invention is
, Alcohols, pyridines, onium salts, etc.
Can be included. Preferred
Various tertiary amine compounds (eg, tertiary amine compounds)
For example, U.S. Pat. No. 4,975,354, Japanese Patent Publication No. 6-124
06, Tokiko 7-36076, KD2354, KD
2462) and phosphonium salt compounds (eg,
Examples thereof include compounds described in JP-A-61-167939).
Can be High contrast accelerator is surface latent image type halogenated
Although it is preferable to incorporate it in a silver emulsion layer, a surface latent image type halo
In the hydrophilic colloid layer adjacent to the silver gemide emulsion layer
You may. The content of the hardening accelerator in the layer depends on the
Of silver halide emulsion, chemical structure of compound and development
Suitable content may vary over a wide range
In the surface latent image type silver halide emulsion
1 × 10 per mole of silver^-Five~ 1 × 10^-2Mol is preferred
No. Further, a high contrast accelerator may be added to the developer.
1 × 10 per liter of developer^-3~ 1 mole is preferred
Good. Light-sensitive silver halide milk of the light-sensitive material of the present invention
There is no particular limitation on the silver halide used in the agent, but the surface
Latent image type silver halide emulsions are often used.
Silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodobromide, bromide
Silver and the like can be used, but silver chloroiodobromide, silver iodobromide
Is used, the content of silver iodide is within a range of 5 mol% or less.
It is preferred that it is an enclosure. Morphology and crystal of silver halide grains
There is no particular limitation on the habit, size distribution, etc.
Those having a size of μm or less are preferred. Silver halide emulsion
Rhodium, iridium and gold compounds such as gold salts and gold trichloride
Form silver sulfide by reacting with salts of precious metals like silver and silver salts
Such as sulfur compounds, stannous salts and amines
Can increase the sensitivity without coarsening particles
it can. Also, salts of precious metals such as rhodium and iridium,
During the physical ripening of silver halide grains with iron compounds such as red blood salts
Alternatively, it can be present during nucleation. In particular, logistics
The addition of a potassium salt or a complex salt thereof can provide ultra-high contrast in a short development time.
Further enhance the effect of the present invention of achieving photographic characteristics
It is preferred. In the present invention, the surface latent image type silver halide milk
Is a silver halide grain with higher surface sensitivity than internal sensitivity
Consisting of, preferably, U.S. Pat.
Surface sensitivity and internal feeling specified in 4,224,401
They have different degrees. The silver halide emulsion is monodispersed
And particularly in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in US Pat. No. 4,401 are preferred.
New The silver halide emulsion used in the present invention is water-soluble
Rhodium salts (eg, rhodium dichloride, rhodium trichloride
System, potassium rhodium (III) hexachloride, rhodium hexachloride
(III) ammonium acid) is more preferable,
These rhodium salts are added at the time of addition during emulsion production.
It is preferable to add it before the completion of one ripening. Rhodium salt
The addition amount is 1 × 10 per mol of silver halide.^-7Mole to 1
× 10^-FourMolar is preferred. Halogen used in the present invention
The average grain size of silver halide is preferably 0.7 μm or less, particularly
Preferably, it is in the range of 0.1 to 0.4 μm. halogen
The shape of silver halide particles is regular like cube, octahedron
May be like a mixed crystal form, but relatively
A so-called monodisperse emulsion having a narrow size distribution is preferred.
New The monodisperse emulsion referred to herein means an average grain size of ±
90% of total number of particles in 40% particle size range, more preferable
Or an emulsion in which 95% is contained. The present invention
Silver salts and solubility for the preparation of silver halide emulsions in water
Single jet is used for reacting halogen salts
Method, double jet method, reverse formation under excess silver ion
Although any means such as a mixing method may be used, the purpose of the present invention is as follows.
For soluble silver salt and soluble halogen under acidic solution
Double jet method to add particles simultaneously to form particles
Particularly preferred. Silver halide milk prepared in this way
The agent may or may not be chemically sensitized. Chemistry
If sensitized, normal sulfur sensitization, selenium sensitization, reduction sensitization
Feeling and the like are used. The photographic emulsion used in the present invention has a methine color.
It may be spectrally sensitized by an element or the like. Used
Dyes include cyanine dyes, merocyanine dyes, and complex dyes.
Anine dye, complex merocyanine dye, horopora-sia
Nin dyes, hemicyanine dyes, styryl dyes,
Myoxonol dyes are included. Particularly useful dyes are
Cyanine dyes, merocyanine dyes, and complex merocyanines
It is a pigment belonging to nin pigment. These sensitizing dyes are simply
Although they may be used alone, a combination thereof may be used.
Combinations of sensitizing dyes are often used, especially for supersensitization.
You can. Along with the sensitizing dye, it itself has a spectral sensitizing effect.
Non-having dyes or substances that do not substantially absorb visible light
And a substance exhibiting supersensitization may be contained in the emulsion.
No. For use in the emulsion layer or intermediate layer of the light-sensitive material of the present invention.
Zera is a binder or protective colloid that can be used.
It is advantageous to use tin, but other hydrophilic rollers
Ids can also be used. For example, gelatin derivatives,
Graft polymer of ratine and other polymers, albumi
, Casein and other proteins, hydroxyethyl cellulose
, Carboxymethylcellulose, cellulose sulfate
Cellulose derivatives such as ters, sodium alginate, lees
Sugar derivatives such as powder derivatives, polyvinyl alcohol, poly
Partial acetal of vinyl alcohol, poly-N-vinyl
Pyrrolidone, polyacrylic acid, polymethacrylic acid, poly
There is a single such as acrylamide, polyvinylimidazole
Using various kinds of synthetic hydrophilic polymer materials such as
Can be As gelatin, lime-processed gelatin
In addition to acid-treated gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, enzymatically treated enzyme as described in P30 (1966)
Ratin may be used, and hydrolysates of gelatin and
Enzymatic degradation products can also be used. The photographic emulsion used in the present invention includes a photosensitive material.
To prevent fogging during the manufacturing, storage or photographic processing of pigments
To stop or stabilize photographic performance.
Compounds can be included. That is, azoles,
For example, benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazo
, Mercaptothiazoles, mercaptobenzothia
Sols, mercaptothiadiazoles, aminotria
Sols, benzotriazoles, mercaptotetrazo
And mercaptopyrimidines and mercaptotriazines
Turnips, thioketo compounds, azaindenes, etc.
Addition of many compounds known as antioxidants or stabilizers
Can be obtained. Of these, particularly preferred are:
Benzotriazoles (eg, 5-methylbenzotria
Sols) and nitroindazoles (e.g., 5-nitro
Londazole). These compounds are added to the processing solution
You may make it contain. The photographic light-sensitive material of the present invention comprises a photographic emulsion layer and
Contains inorganic or organic hardener in other hydrophilic colloid layers
May be. For example, chromium salt (chrome alum
Aldehydes (formaldehyde, glyoxa
), N-methylol compounds, dioxane derivatives
(2,3-dihydroxydioxane, etc.), active vinyl
Compound, active halogen compound (2,4-dichloro-6-
Hydroxy-S-triazine etc.) alone or in combination
They can be used together. Photosensitive silver halide emulsion layer
Or, in the adjacent layer, sensitivity increase, contrast increase or
Is Research Disclosure (R
esearch Disclosure) No. 17465 No. XXI B-D
Compounds can be added, especially polyethylene
It is preferable to add glycol or its derivatives
No. Photographic milk of photosensitive material prepared using the present invention
Coating agent, antistatic,
Stoppage, improvement of slipperiness, emulsification dispersion, prevention of adhesion and improvement of photographic properties
Various purposes such as good (eg, development acceleration, high contrast, sensitization)
May contain a surfactant. For example, saponin (Stero
And alkylene oxide derivatives (polyethylene)
Glycol, polyethylene glycol alkyl ether
And glycidol derivatives (alkenyl succinic acid
Liglycerides), fatty acid esters of polyhydric alcohols
Surfactants such as sugars and alkyl esters of sugars
Agent, alkyl carboxylate, alkyl sulfate,
Carboxy groups, such as alkyl phosphates,
Sulfo group, phospho group, sulfate group, phosphate ester
Anionic surfactants containing acidic groups such as groups, amino acids,
Aminoalkylsulfonic acids, aminoalkylsulfuric acid or
Amphoteric surfactants such as phosphate esters, aliphatic or
Is aromatic quaternary ammonium salts, pyridinium, imine
Heterocyclic quaternary ammonium salts such as dazolium
Cationic surfactants can be used. The photographic light-sensitive material used in the present invention includes photographic milk
Dimensional stability is improved on the agent layer and other hydrophilic colloid layers.
Including water-insoluble or poorly soluble synthetic polymer degradation products for any purpose
Can be taken. For example, alkyl (meth) acrylate
G, alkoxyalkyl (meth) acrylate, glyci
Jill (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefin, styrene
Alone or in combination, or these and acrylic acid,
Methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxy
Sialkyl (meth) acrylate, styrene sulfonic acid
It is possible to use a polymer with a combination of
it can. [0074] The present invention will be described more specifically with reference to the following examples.
This does not limit the embodiments of the present invention.
No. Embodiment 1 Adjustment of silver halide photosensitive material Irage by pAg controlled double jet method
Cubic unit containing 0.25 μm in average particle diameter
Dispersed silver chloroiodobromide emulsion (silver bromide 60 mol%, silver iodide 1.
5 mol%) and remove it by flocculation method.
Salt, washed with water and redissolved. After sulfur sensitization of this emulsion by a conventional method,
-Phenyl-5-mercaptotetrazole was added to increase
Anhydrous-5,5'-dichloro-9-ethyl-3,3 '
-Di- (3-sulfopropyl) -oxacarbocyanine water
Sodium oxide was added and the emulsion was dried at about 40 ° C for 45 minutes.
After 5 minutes to stabilize the spectral sensitizing effect,
Rubenzotriazole, 2-hydroxy-4,6-dic
Loro-1,3,5-triazine sodium salt and dode
After adding sodium silbenzenesulfonate,
5 g / silver nitrate on Tylene terephthalate film
m^Two3g / m gelatin^TwoWas applied. this
Gelatin 1 g / m 2 as a protective layer^Two, And surface activity
Add a surfactant, matting agent, and hardening agent, apply and dry to prepare a sample.
Done. Adjustment of developer A developer was prepared as shown below.   600 ml of water   Sodium sulfite 100g   Potassium carbonate 60g   Hydroquinone 40g   Sodium ascorbate 5g   1-phenyl-4-human-peroxymethyl-4-methyl-3-hydroxyperitone 0.7 g   Benzotriazole 0.2g   6.0 g of potassium bromide   6.6 g of diethylene glycol   2 g of diethylenetriaminepentaacetic acid   Water was added to make 1 liter, and the pH was adjusted to 10.60 (25 ° C.) with KOH. . Then, the above developer (D-1) was further added to
The amounts of Comparative Compound 30 and the compound of the present invention described in Table 1 were used.
The added developer solutions (D-2) to (D-8) were prepared. [0079] [Table 1] [0080] Embedded image After exposing the silver halide photosensitive material prepared above
After performing development processing, the sensitivity value, minimum density (Dmin), and
And the maximum concentration (Dmax) were measured. Exposure to color temperature 5
Using a 400 K light source, a red filter (Ratten N
o. 29) and exposed through a wedge. Sensitivity is transparent
Determined as the reciprocal of the amount of exposure necessary to obtain a density of 3.0,
The sensitivity at the time of development processing with the above developer D-1 was 100.
And expressed relatively. For processing, an automatic developing machine (Dainippon Screen)
LD221) and the following developer and
A liquid was used. Development and fixing conditions are 35 ° C for 30 seconds.
is there. As the fixing solution, the following fixing solution was used. <Fixing solution> Ammonium thiosulfate 120g Sodium thiosulfate pentahydrate 10g Sodium sulfite 25g Acetic acid 25g 6 g of tartaric acid Aluminum sulfate 8g 1 liter with water Adjust the pH to 5.0 ± 0.1 with sulfuric acid or sodium hydroxide
Made Results of processing with the developing solution shown in Table 1
Are shown in Table 2. [0085] [Table 2] No. 1 (comparative product) has a high minimum concentration and N
o. 2 (Comparative product) has low sensitivity, but low sensitivity
I can't get it. The present invention (No. 5 to No. 5)
No. 8) is sufficient without adversely affecting photographic characteristics
Sensitivity can be obtained. Embodiment 2 Adjustment of silver halide photosensitive material Iriji adjusted by the control double jet method
Monodispersed silver chlorobromide containing 0.25 μm in average particle diameter
Emulsion (silver chloride 70 mol%) was treated with 6-methyl-4-hydroxy
Si-1,3,3a, 7-tetrazaindene is equivalent to 1 mole of silver
1 g was added. Anhydro-5,5 'as sensitizing dye
-Dichloro-9-ethyl-3,3'-di- (3-sulfo
Propyl) oxacarbocyanine hydroxypyridini
300 mg of silver per mole of silver,
0.18 g of azine per mole of silver and the following nucleation accelerator
1.1 g was added per mole of silver. Further added hardener
Then, on a polyethylene terephthalate film with silver nitrate
4.0 g / m^Two2.5g / m gelatin^TwoTo be
Applied. [0088] Embedded imageThe silver halide light-sensitive material prepared above was used in Examples
In the same manner as in No. 1, development processing was performed with developing solutions D-1 to D-8. exposure
Is exposed using a high-intensity light meter using a xenon light source,
After development, the photographic properties and black spots were evaluated. Black pots are not
Develop the exposed sample and magnify the sample with a microscope
To increase the number of black pots per square centimeter
I counted. The evaluation was made in five stages. 5 is the best number
Is 0, 4 is 5 or less, 3 is 10 or less, 2
Is less than 15 occurrences, 1 is more and the worst quality
Represents The photographic characteristics include the highest density (Dmax) and the lowest density
(Dmin) and sensitivity were measured. Sensitivity is 3.0
The developer D-1 was determined as the amount of exposure necessary to obtain
100 and relatively described. For dot quality,
Using Rhinotronic 300 manufactured by Innotype Hell
Outputs 150 lines of square dots, visually 5 levels
evaluated. The evaluation criterion is "5" is the best and "1" is the worst.
Quality. As the halftone dot quality as a plate for plate making,
Evaluations "5" and "4" are practical, and evaluation "3" is net goods
Although the quality is not enough, it can be practically used, and the evaluation is “2”
"1" is a quality that cannot be practically used. The processing was performed in the same manner as in Example 1,
(Dainippon Screen Co., Ltd. LD221)
And the fixing solution used in Example 1. Development
And fixing conditions are 35 ° C. for 30 seconds. Table 3 shows the results.
Write. [0092] [Table 3] No. 1 (Comparative product) has many black spots
You. No. 2 (Comparative product) has less black spots, but
Degree, dot quality and maximum density are insufficient. No. 3 (ratio
The comparison product is a practically usable level with halftone dots and black pots.
But the minimum concentration is high. No. 4 (Comparative product) has the lowest concentration
High, poor dot quality, and high number of black spots.
On the other hand, no. 5 to 8 (invention), photographic properties, screen
Black spots are suppressed without adversely affecting point quality
It is. Embodiment 3 (Preparation of emulsion): 2.0 × 10 per mol of silver^-7Mole of water
Sodium chloride and potassium bromide containing soluble rhodium salts
PAg control double for mixed aqueous solution and silver nitrate aqueous solution
A cubic unit mixed with the jet method and having an average particle size of 0.20 μm
Silver chloroiodobromide emulsion composed of dispersed grains (coefficient of variation 13%)
(Silver chloride content: 70 mol%). This emulsion is
The precipitate was washed with water and re-dissolved by the roculation method. Iodination
The silver content is 0.2 mol% and is distributed throughout the grains.
I did it. This emulsion contains sodium thiosulfate per mole of silver.
And 6 mg of chloroauric acid at 60 ° C. for 50 minutes.
For 2 hours as a stabilizer.
Methyl-4-hydroxy-1,3,3a, 7-tetraza
Indene was added at 50 mg per mole of silver. A sensitizing dye was added to the emulsion obtained above.
As anhydrous-5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -oxacarbocyanine hydroxide
This emulsion was added with 300 mg of thorium per mole of silver.
To stabilize spectral sensitization by leaving at 40 ° C for 45 minutes
And then divide it into dodecinated surfactants.
20mg / m sodium rubenzenesulfonate^Two, Ha
100 mg / m of idroquinone^Two, With the following structural formula 32
10 mg / m of nucleation accelerator represented^TwoWas added. That
Later, the exemplified hydrazine derivative of Chemical Formula 29 was added. Soshi
The comparative compound added to the developer in Example 1
The compounds were added to the silver halide emulsion as described in Table 4
Was. Further, as a hardening agent, 1,3-divinylsulfonyl
-2-propanol 100 mg / m^TwoWas added. Like this
Emulsion obtained by using polyethylene terephthalate film
5g / m with silver nitrate on top^Two, Gelatin 2g / m^TwoWill be
Was applied. [0096] Embedded image On the emulsion layer, gelatin was used as a protective layer.
1g / m^Two, S-1 at 30 mg / m^TwoAnd fluorinated surfactant
5 mg / m^TwoIn addition, an average particle size of about 3.5 μm
Amorphous SiO_Two20mg / m matting agent^TwoIn addition,
1,3-divinylsulfonyl-2-propa as a hardener
50 mg / m of knol^TwoIn addition, the samples shown in Table 4 were prepared.
Was. [0098] [Table 4]The silver halide light-sensitive material prepared above was used as an example.
The developing process was performed with the comparative developer D-1 described in 1. processing
As in Example 1, an automatic developing machine (Dainippon Screen)
Using the above developer and Example 1
The fixing solution used in the above was used. Developing and fixing conditions are 35 ° C
-30 seconds. Photographic characteristics are maximum density (Dmax), minimum
The concentration (Dmin) and the sensitivity were measured. The sensitivity is transmission density 3.
Calculated as the exposure required to obtain 0,
Obtained when silver photosensitive material E-1 was processed with developer D-1.
Assuming that the sensitivity is 100, the values are relatively described. Dot quality, black
The potting was carried out in the same manner as in Example 2. This result
It is described in Table 5. [0100] [Table 5] From the results shown in Table 5, the present invention was obtained in the same manner as in Example 2.
Compound whose sensitivity is slightly lower than that of Example 2.
Black spots are suppressed without adversely affecting photographic characteristics.
You can see that [0102] As shown in the above embodiment, the hydrazine
In the processing of silver halide photosensitive materials containing halogenated derivatives
By treating in the presence of the compound of the present invention,
The effect on the true characteristics is extremely small, and the occurrence of black spots is suppressed.
You. Particularly, the compound of the present invention is added to a developer.
The effect is effective.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-212651 (JP, A) JP-A 64-80951 (JP, A) JP-A-6-67368 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03C 5/29 501 G03C 1/06 501 G03C 5/305

Claims (1)

(57) [Claim 1] A method for developing an exposed silver halide photographic light-sensitive material, characterized by developing in the presence of a compound represented by the following formula (1): Processing method. Embedded image In the formula, L represents an alkylene group. R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, but they are not hydrogen atoms at the same time. Alternatively, R ₁ and R ₂ may be linked to each other to form a ring. Provided that at least one OH group in R ₁ and R ₂ ;
COOH group, -SO ₃ H group, -SO ₂ NHR ₃ group, -NH
It has SO ₂ R ₄ . M represents a hydrogen atom, an alkali metal or an ammonium group. R ₃ represents a hydrogen atom, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R ₄ represents an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group