JP3468981B2 - Processing method of silver halide photographic material for plate making - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic
For materials, more specifically in the printing and plate making industry
Silver halide photographic light-sensitive material used therefor and its processing
It is about the method. [0002] 2. Description of the Related Art In recent years, in the printing prepress industry, printed matter
The colorization and complexity of are becoming extremely advanced. For that reason
With the aim of shortening the working time as the number of printing points increases,
Demand for reduction in development processing time has increased, and automatic developing machines have been used.
When processing, the leading edge of the film is inserted into the automatic processor.
Total processing time from exit to the drying zone is 90
Processing within seconds is becoming common, and the total processing time
However, rapid processing of less than 60 seconds has been performed. Only
However, in such a developing process by the automatic developing machine,
If a large amount of development processing is performed continuously,
Where it exits and enters the fixing tank,
Fogging due to physical development occurs at the rear end, and halogenation for printing plate making
Has become a serious quality problem for silver halide photographic materials.
Was. As a method of suppressing these physical development fogs,
Commonly known as an antifoggant in silver halide emulsions
It is conceivable to use compounds that
That all things work to control the physical development fog
Absent. In addition, even those that act to suppress physical development fog,
In order to suppress it effectively, it is necessary to use a large amount,
Influence of silver halide emulsion on photographic properties, especially sensitivity
Greatly affected the sensitivity. [0003] On the other hand, a printing plate making c is an intermediate medium for printing.
Improving the quality and stabilizing the quality of silver halide photographic materials
Demands for it are increasing year by year. More halo than before
In order to achieve high quality silver photographic materials,
Various hydrazine compounds for the purpose of
It is known to be used. Halogenating hydrazine compounds
Additions to silver halide photographic emulsions and developers are described in U.S. Pat.
3,730,727 (Ascorbic acid and hydra
Gin and developer), 3,227,552
Fine text (as an auxiliary developer for obtaining a positive color image directly)
Hydrazine), and 3,386,831
(The use of aliphatic carboxylic acids as stabilizers for silver halide photographic materials
Β-monophenylhydrazide), 2,41
9,975, and Mees, The Theory of Photog
raphic process ", 3rd edition (1966), page 281
Have been. [0004] Among them, in particular, US Patent No. 2,41
No. 9,975 describes a hydrazine compound added to a silver chlorobromide emulsion.
And develop with a high pH developer such as 12.8.
In this case, gamma (γ) exceeds 10
It is described that the property can be obtained. However, p
Strong alkaline developing solutions with H close to 13 are susceptible to air oxidation.
It is unstable and does not withstand long-term storage and use. to this
In contrast, U.S. Patent Nos. 4,168,977 and 4,22
4,401, 4,243,739, 4,26
9,929, 4,272,614, 4,32
No. 3,643, the pH is from 11.0 to 12.3.
Gives extremely hard negative photographic characteristics by using
A silver halide photographic light-sensitive material is disclosed. This new
In a new image forming system, an extremely hard image
Use only silver chlorobromide with a high silver chloride content to obtain
No, but silver iodobromide and silver iodochlorobromide can be used.
There is a feature that can be. In addition, the conventional squirrel developer
Amount of sulfite preservatives
Storage stability because it can contain
Another characteristic is that it is good. The above-mentioned physical development fog is caused by these
Extremely high contrast photosensitive material containing azine compound
This was a particularly serious problem. That is, physical development
Compounds that are thought to be effective in controlling fog are
The hydrazine compound significantly inhibits the contrast enhancement effect,
It is difficult to control both physical development fog and high contrast
Met. [0006] In the case of a developing process using an automatic developing machine,
A fixed amount of developer and fixer in proportion to the area of the photosensitive material
While replenishing it to ensure stable photographic performance.
It is generally managed. Low fixer capacity
1m to prevent fixing failure^Two400 per
The processing was performed while replenishing the fixer of at least ml. However
However, in recent years, the amount of developer waste
Along with the reduction in the amount of toner, there is an urgent need to reduce the amount of fixing waste liquid.
1 m of the photosensitive material containing the hydrazine compound as described above^Two
Of replenishment amount of fixer less than 300ml per unit
As the continuous processing is continued, the pH of the fixer rises,
If fogging due to the above physical development is more likely to occur
1m^TwoLess than 300ml per bottle
Physical development even if continuous processing is continued under conditions of no fixing replenishment
Obtain high-contrast photographic characteristics without fogging
There has been a demand for a processing method that can perform the above. [0007] SUMMARY OF THE INVENTION The object of the present invention is as follows.
Continuously, without fluctuations in sensitivity and photographic characteristics
Which does not cause physical development fog
A silver halide photographic light-sensitive material. [0008] The object of the present invention is, secondly, that a high contrast is sufficient
It has a high density and can be physically developed
Provide silver halide photographic light-sensitive materials that do not generate fog
Is Rukoto. Third, the object of the present invention is to fix by an automatic developing machine.
The replenishment amount of the liquid is 1m^TwoLess than 300ml per
Even when processing while supplementing with
Halogen that prevents physical development fog while maintaining
An object of the present invention is to provide a method for processing a silver halide photographic material. [0010] The above objects of the present invention are:
At least one photosensitive silver halide emulsion layer on a support
When,Of undercoat layer, intermediate layer and protective layerAt least one parent
For silver halide photographic materials having an aqueous colloid layer
AndIn at least one of the hydrophilic colloid layersMelka
At least one nitrogen-containing heterocyclic compound having a
And the emulsion layer orLess of the hydrophilic colloid layer
At least one layerAt least one organosiloxane compound
Silver halide photographic material characterized by containing
Is achieved by Nitrogen-containing heterocyclic compounds having a mercapto group
Will be described in detail. In the photosensitive material of the present invention,
As a nitrogen-containing heterocyclic compound having a mercapto group,
The compound of the general formula (1) is preferably used. [0012] Embedded image [In the general formula (1), M represents a hydrogen atom or a cation;
Represents a heterocyclic residue containing at least one nitrogen atom,
Ring residues may be further fused. ] In the general formula (1), M is a hydrogen atom,
Ions (eg, alkali metal ions, ammonium ions
Heterocyclic residue represented by Z is further fused
And specifically, imidazole, tria
Sol, tetrazole, thiazole, oxazole,
Lenazole ring, benzimidazole, benzoxazo
Benzothiazole, thiadiazole, oxadiazo
Benzoselenazole, azaindene (for example,
Riazaindene, tetrazaindene, pentazaindene
Etc.) are preferred. Further, these heterocyclic residue and fused ring
May be substituted with a suitable substituent. Examples of substituents
Represents an alkyl group (eg, a methyl group, an ethyl group,
Loxyethyl group, etc.), alkenyl group (for example, allyl group
Aralkyl group (eg, benzyl group), aryl
Group (for example, phenyl group, naphthyl group, etc.), heterocyclic residue
(For example, pyridine group), halogen atom, mercapto
Group, cyano group, carboxyl group, sulfo group, hydroxy
Group, amino group, nitro group, alkoxy group (for example, methoxy
And the like). Specific examples of the compound represented by the general formula (1)
It is shown below. However, the present invention is limited to the following compounds
Not. [0016] Embedded image [0017] Embedded imageIn the light-sensitive material of the present invention, a mercapto group
Having a nitrogen-containing heterocyclic compound includes a silver halide emulsion.
Not included in the hydrophilic colloid layer. More preferably,
An adjacent layer of a silver halide emulsion layer, for example, an undercoat layer,
Or it is good to make it contain in a protective layer. The invention in layers
The content of the mercapto compound is determined by the halogenation used.
It depends on the characteristics of the silver emulsion and the chemical structure of the compound.
Suitable contents can vary over a wide range, but
About 5 × 10 per mole of silver in silver halide emulsion^-Five~ 1 × 1
0^-1Molar ranges are useful in practice, more preferably
4 × 10^-Four~ 5 × 10^-2The molar range is good. Further, the present invention relates to a nitrogen-containing compound having a mercapto group.
The heterocyclic compound is generally used as a stabilizer for the silver halide emulsion.
As described above, the sensitivity, tone, etc.
Include in the silver halide emulsion layer to the extent that the true characteristics are not impaired.
You may have. Its content depends on the silver halide used
It depends on the characteristics of the emulsion and the chemical structure of the compound.
2 × 10 per mole of silver in silver gemide emulsion^-3Preferably less than mole
In particular, 8 × 10^-FourMole or less is more preferred
New Next, the photosensitive material of the present invention is used.
The organic siloxane-based compound will be described. Of the present invention
It is generally known as an organosiloxane compound.
Polydimethylsiloxane, polydiethylsiloxane, etc.
Polyalkylsiloxane, polydiphenylsiloxa
Polyarylsiloxanes such as polymethylphenylsiloxane
In addition to Roxane, JP-B-53-292, JP-B-55-
49294, JP-A-60-140341 and the like.
Organic policy having an alkyl group having 5 or more carbon atoms
Roxane, alkoxy, hydroxy, hydrogen, cal on the side chain
Organic compounds having a boxyl, amino or mercapto group
It is also possible to use modified polysiloxanes such as
Block copolymers having kiru and siloxane units
Or a system as disclosed in JP-A-60-191240.
Uses a graft copolymer having a siloxane unit on the side chain
Can also be. Of these, modified polysiloxanes are preferred.
In particular, a compound represented by the following general formula (2) is preferable.
Commonly used. [0022] Embedded image In the general formula (2), R¹¹Represents a divalent linking group
Then R¹²Represents a hydrogen atom, a hydroxy group, a lower alkyl group,
Represents an alkoxyl group or the like, and m and n are each 1 to 20
Represents an integer, p is 0 or an integer of 1 to 12, and q is 1 to 2
An integer of 0 and r represents an integer of 1 to 15. In general formula (2)
Specific examples of the represented compounds are shown below. However, the present invention
It is not limited to the compounds below. [0024] Embedded image [0025] Embedded imageFurther, the organic siloxane compound of the present invention
Some are generally available from Shin-Etsu Chemical Co., Ltd.
Can be. For example, commercially available from Shin-Etsu Chemical Co., Ltd.
Product Name Silicone Oil, KF-352, KF-3
55, KF-615, KF-618, KF-851, X
-70-901 and the like. The method for producing the organosiloxane compound of the present invention is as follows:
For example, E.G.Rochou, Chemistry of the Silico
(Chapman and Hall, 1951
Edition) “P.66-70,“ Processing and Application of Silicone ””
West Plastics Technical Society 1954) p. 26, F.G.A.
"Inorganic Poly" by Stone and V.A.G.Graham
Mars "(Academic Press 1962) 230-
Pages 231 and 288-295, etc.
Or Japanese Patent Publication No. 35-10771, 43-28694
No. 45-14898
Catalysis of olefins to siloxane containing SiH
Method by addition reaction, or JP-B-36-22361
Each component organofluorosilane as described in
Can be synthesized by applying the method of co-hydrolysis of
Wear. The organosiloxane compound of the present invention is
Either a silver gemide emulsion layer or another hydrophilic colloid layer
Layer, but preferably silver halide milk
Preferably contained in a hydrophilic colloid layer that does not contain
No. More preferably, adjacent to the silver halide emulsion layer
Layer, such as an undercoat layer or a protective layer.
And more preferably a nitrogen-containing compound having a mercapto group.
In the same hydrophilic colloid layer as the heterocyclic compound
Is good. The addition amount of the organosiloxane compound of the present invention is
Although not particularly limited, 0.0005 to 2 g / m^TwoIs preferred
And more preferably 0.001 to 1 g / m^TwoEspecially good
Preferably 0.005 to 0.5 g / m^TwoIt is. Its addition
The method is to convert the siloxane compound to water, an organic solvent or
After previously dissolving in a mixed solvent of
Add to coating solution or disperse appropriately such as surfactant
As a pre-prepared aqueous dispersion in the presence of the agent
Can be added. Silver halide containing hydrazine compound
Photosensitive material containing a compound having a mercapto group
This is described in JP-A-60-153039 and JP-A-63-10.
3232 etc., but these are all
Compounds having a capto group act as organic antifoggants
Things. Japanese Patent Application Laid-Open No. 6-75319 discloses that hydrophilic
A mercapto compound having a functional group in an amount of 90 mol% or more.
Silver chloride having a particle size of 0.2 μm or less and containing a hydrazine compound
It has been disclosed that it is contained in silver
You. This is a mercapto compound having a hydrophilic group.
Included in the hydrophilic colloid layer on the opposite side of the
This is to prevent this. Also, JP-A-6-75
At 320, a silver halide containing a hydrazine compound
In a photographic material, a mercapto compound and tetra
It is disclosed that it contains a Zaindene compound. This
Even if it is processed with a developer whose activity has increased due to fatigue over time,
That is, stable photographic performance can be obtained. However, the physical expression which is the object of the present invention
Effective amount of mercapto compound to prevent image fog
When added to the emulsion layer, photographic properties such as a decrease in sensitivity
Has adverse effects or contains hydrazine compounds
Hydrazine in photographic silver halide photographic materials
Nucleation action is inhibited, and sufficiently high photographic characteristics are obtained.
Can not be. Therefore, a similar anti-fogging effect is obtained.
First, a mercapto compound was added to a hydrophilic colloid other than the emulsion layer.
It is often used by those skilled in the art to add
To be added to hydrophilic colloid layers other than the emulsion layer.
Then, the effect of preventing physical development fog becomes weaker,
Increasing the amount of addition also results in photographic properties and nucleation
Had the problem of adversely affecting On the other hand, the organic siloxane compound is
Surface characteristics of drawing paper and photographic film, such as stickiness
With the aim of improving the feeling, sticking resistance, scratch resistance, slipperiness, etc.
Used in silver halide photographic materials
Was. JP-A-50-117414, JP-A-60-14034
No. 1, No. 60-191240, No. 62-203152
No. 62-203155, JP-A-2-2933843
No., etc., describe their application in detail. this
The technology described in these publications is mainly photographic film.
Has been applied to In the present invention, in addition to these effects described above,
When used together with a mercapto compound,
Loxane compounds do not adversely affect photographic properties,
Alternatively, do not impair nucleation by hydrazine.
And that it is possible to prevent physical development fog.
I found it. The effect of this organosiloxane compound is
This is a new effect not expected from technology. The hydrazine compound used in the present invention
And will be described in detail. Hydrazination used in the present invention
Compounds include U.S. Pat. Nos. 4,224,401 and 4,224,401.
No. 243,734, No. 4,272,614, No.
No. 4,385,108, No. 4,269,929, same
No. 4,323,643 and JP-A-56-10624
No. 4, No. 61-267759, No. 61-230145
No. 62-270953, No. 62-178246
No. 62-180361, No. 62-275247
Nos. 63-253357 and 63-265239
And Japanese Patent Application Nos. 1-92356 and 1-99822.
There are hydrazine compounds described in the specification, etc.
It can be used clearly, and in particular, is represented by the following general formula (3).
It is preferable to use a hydrazine compound to be used. [0033] Embedded image In the general formula (3), A₁ , A_Two Is a hydrogen atom,
Alkylsulfonyl groups and aryls having 20 or less carbon atoms
A rufonyl group (preferably a phenylsulfonyl group, or
Replaced so that the sum of Hammett's σp becomes -0.5 or more.
Phenylsulfonyl group), acyl having 20 or less carbon atoms
Group (preferably a benzoyl group, or Hammett's σp
Benzoyl substituted so that the sum is -0.5 or more
Group), or unsubstituted or substituted linear or branched or cyclic
A substituted aliphatic acyl group (for example, a halogen atom
, Ether group, sulfonamide group, amide group, hydro
Examples include an xyl group, a carboxy group, and a sulfo group. )
A₁ , A_Two Is most preferably a hydrogen atom.
New R₁ The aliphatic group represented by is linear, branched or cyclic
Alkyl, alkenyl, and alkynyl groups. R
₁ The aromatic group represented by is a monocyclic or bicyclic aryl
A phenyl group and a naphthyl group.
It is. R₁ Among the N, O and S atoms
3-10 member saturated or unsaturated, including at least one
Which may be a single ring, or
A condensed ring may be formed with another aromatic ring or hetero ring.
As the heterocycle, preferably a 5- or 6-membered aromatic heterocycle
A pyridyl group, an imidazolyl group, a quino group
Linyl, benzimidazolyl, pyrimidyl, pyra
Zolyl group, isoquinolinyl group, thiazolyl group, benzti
Those containing an azolyl group are preferred. R₁Is substituted with a substituent
The substituent may be, for example,
No. These groups may be further substituted.
For example, an alkyl group, an aralkyl group, an alkoxy group,
Reel group, substituted amino group, acylamino group, sulfonyl
Amino group, ureido group, urethane group, aryloxy
Group, sulfamoyl group, carbamoyl group, alkylthio
Group, arylthio group, sulfonyl group, sulfinyl group,
Hydroxy group, halogen atom, cyano group, sulfo group,
Ruboxy group, ammonium group, pyridinium group, thiuro
And an isothioureido group. These groups
May be linked together to form a ring when possible. Ma
R₁ Is used for immobile photographic additives such as couplers.
Ballast groups that are commonly used in
May be. The ballast group has 8 or more carbon atoms
Groups that are relatively inert to the nature, such as alkyl
Group, alkoxy group, phenyl group, alkylphenyl group,
Choose from phenoxy group, alkylphenoxy group, etc.
Can be. Y₁ The divalent organic group represented by is an aliphatic group
And a group represented by an aromatic group. As the aliphatic group,
Linear, branched or cyclic alkylene group, alkenylene
A alkynylene group. In addition, as the aromatic group,
A ring or bicyclic arylene group such as phenylene
And a naphthylene group. Y₁ As more preferred
Or an arylene group, especially a phenylene group.
No. Also, Y₁ May have a substituent, and as a substituent
Is, for example, R₁ Those listed as substituents for
Wear. G₁ Represents a carbonyl group, a sulfonyl group, a sulf
Oxy, phosphoryl, oxalyl or imino group
Represents a tylene group;₁ As a carbonyl group,
Preferred is a thiol group. R_Two As the aliphatic group represented by
It is preferably an alkyl group having 1 to 5 carbon atoms, and an aromatic group and
Are preferably monocyclic or bicyclic aryl groups (eg,
For example, those containing a benzene ring). G₁ Is a carbonyl group
If R_Two Preferred among the groups represented by are alkyl
Group (for example, methyl group, trifluoromethyl group,
Droxypropyl group, 3-methanesulfonamide propyl
Group, phenylsulfonylmethyl group, etc.), aralkyl
Groups (eg, 2-hydroxybenzyl group), aryl
Group (for example, phenyl group, 3,5-dichlorophenyl
Group, 2-methanesulfonamidophenyl group, 4-methane
Sulfonamidophenyl group, 2-hydroxymethylphen
And a general formula (4). R_Two Is replaced
And the substituent may be R₁ Enumerate with respect to
Substituents can be applied. G₁Is an oxalyl group, R_Two
 Are preferably alkoxy groups (for example,
Xy, ethoxy, isopropoxy, methoxy
Xy group), aryloxy group (for example, phenoxy
Group, 2-hydroxymethylphenoxy group, 4-chlorofu
Enoxy group), amino group (for example, 3-hydroxypro
Pillamino group, 2,3-dihydroxypropylamino
Group, 2-dimethylaminoethylamino group, 3-diethyl
Aminopropylamino group), general formula (4), etc.
And an amino group is particularly preferred. R₁ , R_Two Is in it
Incorporation of a group that enhances adsorption to the surface of silver logenide grains
May be used. Such adsorbing groups include thiourine
Element group, heterocyclic thioamide group, mercapto heterocyclic group, tri
Azole groups and the like are described in US Pat. No. 4,355,105.
Groups. Also, R_Two Is G₁ -R_Two Part of
From the residual molecule, and -G₁ -R_Two Including partial atoms
That cause a cyclization reaction that produces a cyclic structure
And examples thereof include, for example,
29751 and the like. [0037] Embedded image Q in the general formula (4)⁺ Is at least
A group containing a cationic group having one quaternary nitrogen atom
Yes, straight or branched having 1 to 4 carbon atoms
G through the hydrocarbon chain₁ And a part of this chain or
All are part of a heterocycle with a quaternary nitrogen atom
Is also good. Q⁺ Preferred examples of
Monioalkyl group, pyridinium-1-ylalkyl
Group, 1-alkylpyridinium-2-yl group, 1-al
Kylpyridinium-3-yl group, 1-alkylpyridini
Um-4-yl group, thiazolinium-3-ylalkyl
Group, oxazolinium-3-ylalkyl group, 1-al
And a kilimidazolium-3-ylalkyl group.
It is. These groups may be substituted, and
Is R₁ Preferred as the substituents are: Change
When these groups form a ring structure,
May be. A^- Is Q⁺ Is a counter anion of
A good example is Cl^- , Br^- , P-toluenesulfoner
And methylsulfonate.⁺ Place
When it has a sulfo group as a substituent and forms an inner salt,
not exist. Next, specific examples of the compound represented by the general formula (3)
Examples are shown below, but the present invention is limited to the following compounds
Not something. [0040] Embedded image [0041] Embedded image[0042] Embedded image[0043] Embedded imageThe hydrazine compound of the present invention is described in, for example,
Sho 61-218474, 62-178246, 62
-180361, 62-260153, 63-25
3357, U.S. Pat. Nos. 4,684,604, 3,
No. 379,529, No. 4,377,634, No.
No. 4,332,878, No. 4,937,160,
Utilizing the method described in No. 63-98803, etc.
Can be synthesized. In the light-sensitive material of the present invention, the hydrazine compound
Is preferably contained in the silver halide emulsion layer.
May be contained in other hydrophilic colloid layers. layer
The content of the hydrazine compound of the present invention in
Of silver halide emulsion, chemical structure of compound and development
The appropriate content may vary over a wide range
1 mole of silver in silver halide emulsion
About 5 × 10^-6~ 8 × 10^-2Molar range is practically useful
And more preferably 5 × 10^-Five~ 1 × 10^-2Mole
Range is good. The silver halide emulsion used in the present invention includes
There is no particular limitation, and silver chlorobromide, silver chloroiodobromide, silver bromoiodide,
Silver iodide, silver chloride, etc. can be used.
When silver chloroiodobromide is used, the content of silver iodide is 5 moles.
% Or less. Shape of silver halide grains used in the present invention
There are no particular restrictions on the state, crystal habit, size distribution, etc.
With a diameter of 0.7 micron or less, especially 0.5 micron or less
The following are preferred, and 90% or more of the total number of particles is flat.
Those having a particle diameter in the range of ± 10% of the average particle diameter are preferred.
New The preparation method of the silver halide emulsion is normal mixing, reverse mixing,
Any of known methods such as simultaneous mixing may be used. Physics
The ripened emulsion is desalted and then added with necessary additives.
But desalting is omitted.
You can also. The silver halide emulsion used in the present invention is:
Chemical sensitization can be performed by a known method. Sulfur increase
Sensitizers include, for example, thiosulfate, thiourea, allyl
Sothocyanate, cystine, rhodanine and US patents
Nos. 1,574,944 and 2,278,947
No. 2,410,689, No. 2,440,206, No.
No. 3,187,458, No. 3,415,649, No.
Sulfur-containing as described in 3,501,313 and the like
Compounds can be used. Also, with sulfur sensitization, rice
Patents 2,448,060 and 2,540,086
Nos. 2,556,245 and 2,566,263
Platinum palladium, iridium, rhodium described in
Sensitization method using noble metal salt such as ruthenium
It can be used in combination. Also, potassium chloro
Compounds of various golds such as Aurate and Auric trichloride
Substances or palladium compounds such as palladium chloride
A combination of sensitization methods can be used. The silver halide emulsion of the present invention can be used in the photographic industry.
Spectral sensitization using dyes known as sensitizing dyes in
I can feel it. These pigments have cyanine color
Element, merocyanine dye, complex cyanine dye, complex melody
Anine dye, holo-holer cyanine dye, hemicyanine
Dyes, styryl dyes, hemioxanol dyes, etc.
You. These sensitizing dyes may be used alone,
May be used. Combinations of sensitizing dyes are particularly strong
Often used for color sensitization purposes. With sensitizing dye
Dyes or visible dyes that do not themselves have spectral sensitization
A substance that does not substantially absorb light and exhibits supersensitization
Substances may be included in the emulsion. The silver halide photographic light-sensitive material of the present invention includes:
In addition to the photosensitive emulsion layer, the overcoat layer, intermediate layer, and back
Provide a coating layer, undercoat layer and other hydrophilic colloid layers
be able to. And those layers contain a matting agent
You can do it. Emulsion of the silver halide photographic light-sensitive material of the present invention
For layers, overcoat layers, intermediate layers, backcoat layers, etc.
Binders or protective colloids that can be
It is advantageous to use gelatin, but other hydrophilic
Colloids can also be used. For example, gelatin induction
Body, graft polymer of gelatin and other macromolecules,
Proteins such as bumin and casein; hydroxyethyl cellulose
Carboxymethylcellulose, cellulose sulfate
Cellulose derivatives such as steles; sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol,
Partial acetal of poly (vinyl alcohol), poly-N-vinyl
Lupyrrolidone, polyacrylic acid, polymethacrylic acid,
Single acrylamide, polyvinylimidazole, etc.
Or a variety of synthetic hydrophilic polymer materials such as copolymers
Can be. As gelatin, lime-processed gelatin
Acid-treated gelatin, Bull.Soc.Sci.Phot.Japan, N
o. 16, Enzyme treatment as described in P30 (1966)
Gelatin may be used, or a hydrolyzate of gelatin
And enzymatic degradation products can also be used. The silver halide photographic light-sensitive material of the present invention comprises
High-contrast photographs using a stable developer with a pH of less than 11.0
To obtain the properties, a silver halide emulsion layer or other parent
Nucleation of amine derivatives, onium salts, etc. in aqueous colloid layers
It can be contained as an accelerator. Amine derivatives
For example, JP-A-60-140340 and JP-A-60-140340
No. 50829, No. 62-222241, No. 63-12
Nos. 4045, 63-286840, etc.
Can be used. Onium salt
Is preferably an ammonium salt or a phosphonium salt.
Preferred examples of the ammonium salt are described in JP-A-62-2.
Nos. 50439 and 62-280733.
The listed compounds can be used. Also good
Preferred examples of phosphonium salts include those described in JP-A-61-16.
No. 7939, 62-280733, etc.
The compounds described above can be used. Next, specific examples of the nucleation accelerator are shown below.
The present invention is not limited to the following compounds. [0054] Embedded image[0055] Embedded image[0056] Embedded image[0057] Embedded imageIn the light-sensitive material of the present invention, the nucleation accelerator is
It is preferable that the silver halide emulsion be contained in the silver halide emulsion layer.
It may be contained in another hydrophilic colloid layer. Building in layers
The content of the nucleus accelerator depends on the characteristics of the silver halide emulsion used.
Depends on chemical properties, chemical structure of compound and development conditions
And the appropriate content can vary over a wide range
Is about 6 × 10 per mole of silver in the silver halide emulsion.^-6~
6 × 10^-2Molar range is practically useful and more preferred
Ha, 6 × 10^-Five~ 2 × 10^-2The molar range is good. 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. Photosensitive material of the present invention
Ingredients include inorganic emulsions in photographic emulsion layers and other hydrophilic colloid layers.
Alternatively, an organic hardening agent may be contained. For example chromium salt
(Chrome alum, etc.), aldehydes, (forma
Aldehyde, glyoxal, etc.), N-methylol compound
Compound, dioxane derivative (2,3-dihydroxydioxa
Active vinyl compounds, active halogen compounds
(2,4-Dichloro-6-hydroxy-S-triazine
Etc.) can be used alone or in combination.
You. The photographic emulsion used in the present invention includes
Image quality, character extraction performance, etc.
To increase performance required in other printing and plate making industries
Suitable for emulsion layers, overcoat layers, backing layers, etc.
Other hydrophilic colloid layers may be filled with fillers known to those skilled in the art.
Ter dyes can be included. Further, a light-sensitive material produced by using the present invention
Photographic emulsion layers or other hydrophilic colloid layers
Agent, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention and
Improvement of photographic characteristics (eg, development acceleration, high contrast, sensitization), etc.
Surfactants may be included for various purposes. For example, saponin
(Steroids), alkylene oxide derivatives (poly
Ethylene glycol, polyethylene glycol alkyl
Ethers), glycidol derivatives (alkenyl
Succinic acid polyglycerides), fatty acids of polyhydric alcohols
Nonionics such as esters and sugar alkyl esters
Surfactant; alkyl carboxylate, alkyl sulfate
Carboki such as ters and alkyl phosphates
Sil group, sulfo group, phospho group, sulfate group, phosphoric acid
Anionic surfactant containing an acidic group such as an ester group;
No acids, aminoalkylsulfonic acids, aminoalkyl
Amphoteric surfactants such as sulfuric acid or phosphate esters; fats
Aliphatic or aromatic quaternary ammonium salts, pyridini
Heterocyclic quaternary ammonium such as uranium and imidazolium
Cationic surfactants such as salts can be used. The photographic light-sensitive material used in the present invention includes photographic milk
Dimensional stability is improved in the agent layer and other hydrophilic colloid layers.
For any purpose, decompose water-insoluble or poorly soluble synthetic polymer
Can be included. For example, alkyl (meth) acryle
, Alkoxyalkyl (meth) acrylate,
Sidyl (meth) acrylate, (meth) acrylamide
, Vinyl acetate, acrylonitrile, olefin, styrene
Alone or in combination, such as
Acid, methacrylic acid, α, β-unsaturated dicarboxylic acid,
Droxyalkyl (meth) acrylate, styrene sulf
Use a polymer that uses a combination of folic acid and the like as the monomer component
be able to. The photographic light-sensitive material used in the present invention includes those skilled in the art.
Any support known in can be used
You. As the support, glass, cellulose acetate fill
Film, polyethylene terephthalate film, paper, bary
Coated paper, polyolefin (eg polyethylene, poly
Propylene etc.) Laminated paper, polystyrene fill
Metals, polycarbonate films, metal plates such as aluminum, etc.
No. These supports may be corona treated in a known manner.
And, if necessary, substract in a known manner.
It may be processed. Using the silver halide light-sensitive material of the present invention,
To obtain high-contrast photographic characteristics, use a conventional lith developer or US
PH 13 described in Japanese Patent No. 2,419,975.
It is not necessary to use a highly alkaline developer close to
An image liquid can be used. That is, the halogenation of the present invention
Silver photographic materials have sufficient sulfite ions as preservatives.
(Especially 0.15 mol / l or more)
PH 9.5 or more, especially 10.5-1
Sufficiently ultra-high contrast negative image is obtained with 2.3 developer
be able to. There are no special restrictions on developing agents,
Roxybenzenes, 3-pyrazolidones, aminopheno
Can be used alone or in combination.
You. Other developers include alkali metal sulfites and carbonic acid.
PH buffers such as salts, borates and phosphates, bromide
Substances, iodides, and organic antifoggants (particularly preferably,
Nitroindazoles or benzotriazoles)
Contains a development inhibitor or an antifoggant, etc.
Can be. Also, if necessary, water softener, dissolution aid
Agent, color tone agent, development accelerator, surfactant, defoamer, hardening
Agent, silver stain preventing agent (eg, 2-mercaptoben)
Benzoimidazole acids) and the like. this
Examples of the additives are Research Disclosure 17
No. 6, 17643. Further, in order to obtain photographic properties of ultra-high contrast
In addition, the developing solutions are described in JP-A-56-106244 and JP-A-61-2.
67759, 61-230145, 62-2116
47, JP-A-2-50150, JP-A-2-208652, etc.
The amine compounds described can also be added.
The typical ones are listed below. [0066] a-1) Nn-butyldiethanolamine a-2) 3-Diethylamino-1,2-propanediol
Le a-3) 2-Diethylamino-1-ethanol a-4) 2-Diethylamino-1-butanol a-5) 3-Diethylamino-1-propanol a-6) Triethanolamine a-7) 3-Dipropylamino-1,2-propanedio
Rule a-8) 2-Dioctylamino-1-ethanol a-9) 3-Amino-1,2-propanediol a-10) 1-Diethylamino-2-propanol a-11) n-Propyldiethanolamine a-12) 2-Di-isopropylaminoethanol a-13) N, N-di-n-butylethanolamine a-14) 2-Methylamino-1-ethanol a-15) 3-Dimethylamino-1,2-propanediol
Le a-16) 4-Dimethylamino-1-butanol a-17) 1-dimethylamino-2-butanol a-18) 1-dimethylamino-2-hexanol a-19) 5-Dimethylamino-1-pentanol a-20) 6-Dimethylamino-1-hexanol a-21) 1-dimethylamino-2-octanol a-22) 6-Dimethylamino-1,2-hexanediol
Le The amount of addition may be any amount that promotes high contrast, but is generally 0.1%.
005-1.0 mol / l can be added. In the present invention, a developing agent is incorporated in the photosensitive material.
And treated with alkaline activator solution
May be adopted. (Japanese Unexamined Patent Publication No. 57-129436,
Nos. 57-129433, 57-129434, 5
7-129435, U.S. Pat.
Etc.). The processing temperature is usually selected between 18 ° C and 50 ° C.
Temperature below 18 ° C or above 50 ° C
It may be a degree. Fixing processing of the silver halide light-sensitive material of the present invention
As a fixing solution used when performing, generally used
A composition can be used. Fixer is generally fixed
An aqueous solution consisting of an agent and others, and the pH is usually 3.8 to
5.8. Sodium thiosulfate,
Thiosulfuric acid such as potassium thiosulfate and ammonium thiosulfate
Salt, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate,
An organic sulfur compound that forms a soluble stable silver complex and acts as a fixing agent.
What is known can be used. The fixing solution has a water-soluble property which acts as a hardener.
Aluminum salts, such as aluminum chloride, aluminum sulfate
, Alum, etc. can be added. The fixing solution may contain a preservative (for example,
Sulfate, bisulfite), pH buffer (eg, acetic acid), p
H adjuster (for example, sulfuric acid), chelating agent capable of softening water
And the like. Fixing processing of the silver halide light-sensitive material of the present invention
In doing so, the replenishment rate of the fixer is 300 ml / m^Two
The effects of the present invention are particularly exhibited when the following conditions are satisfied. Departure
In light-sensitive materials, replenishment depends on the processing area of the light-sensitive material.
It is preferable that the replenishment is performed according to the blackening rate,
May be combined. In these cases, all
The total amount of replenished material processed during that time
Defined by the value divided by the area. The silver halide light-sensitive material of the present invention can be used for fixing
300ml / m^TwoWhen processing that exceeds
Although good photographic performance can be obtained,
Is 300ml / m^TwoGood photographic performance
Particularly preferred replenishment rates are 100-300 ml / m^Two
It is. It is preferable to use an automatic developing machine for photographic processing.
New In the present invention, the photosensitive material is put into an automatic developing machine and then discharged.
Even if you set the total processing time until
A photographic characteristic of a super-high contrast negative gradation can be obtained. [0074] The present invention will be described below in detail with reference to examples.
However, of course, this description limits the present invention.
There is no. Embodiment 1 <Preparation of emulsion> 5 g of sodium chloride in 600 ml of water,
PAg 8.5 at 40 ° C in an aqueous solution containing 40g of gelatin
Silver nitrate aqueous solution by controlled double jet method
3.25 × 10^-6Mol / mol Ag water-soluble iridium salt
And 1.8 × 10^-7Mol / mol Ag of a water-soluble rhodium salt
And a halogen solution containing 0.25 μm average particle diameter.
A silver chlorobromide (silver bromide 30 mol%) emulsion was prepared and 1 mol of silver was prepared.
Potassium iodide aqueous solution to be 0.2 mol% with respect to
Was added, and the precipitate was washed with water and redissolved. One mole of silver was added to this emulsion.
2mg sodium thiosulfate and 4mg chloroauric acid
In addition, after heating at 55 ° C. for 60 minutes and performing chemical sensitization,
4-hydroxy-6-methyl-1,3,3 as stabilizer
150 mg of a, 7-tetrazaindene was added. This milk
The compound of formula 17 as a sensitizing dye was added to the^-FiveMo
Ag / mol Ag, add compound of formula 18 as surfactant
And 2-hydroxy-4,6-dichloro-1,
Prepared by adding 3,5-triazine sodium salt. <Preparation of protective solution> The protective solution was converted into an aqueous gelatin solution.
Surfactant, matting agent, 2-hydroxy-4,6-
Add dichloro-1,3,5-triazine sodium salt
Prepared. <Preparation of undercoat liquid and intermediate liquid>
Surfactant of formula 18, 2-hydroxy in aqueous gelatin solution
-4,6-dichloro-1,3,5-triazine sodium
It was prepared by adding salt. The mercapto compound was added to each of the above coating solutions as shown in Table 1.
As shown, each 3 × 10^-3Mol / mol Ag, also
20 mg / m of organic siloxane compound^TwoAnd added to Table 1
With the layer configuration shown, a polyethylene terephthalate film
On top, the emulsion layer was 5 g / m 2 of silver nitrate.^Two, Gelatin 3g /
m^TwoSo that the protective layer, undercoat layer, and intermediate layer
1 g / m^TwoIt was applied so that [0077] Embedded image [0078] Embedded image The samples shown in Table 1 were subjected to an interference filter of 670 nm.
Xenon through a sensitometric wedge
After exposure with flash light, a developer 1 having the following composition
Develop at 35 ° C for 30 seconds using a fixer having the composition described above.
Wear, wash and dry. This processing also includes an automatic processor
(LD-221Q manufactured by Dainippon Screen Mfg. Co., Ltd.
T) was used. Sensitivity value is required to obtain transmission density of 3.0
Table 1 shows the mercapto compounds and organic
Feeling of sample (No1) containing no siloxane compound
The values are shown as relative values when the degree value is set to 100. Table of results
It is shown in FIG. In order to test the physical development fog,
Automatic development of 61cm sample length without exposure
Developing process for 5 sheets continuously. Fifth developed image
Visually inspect physical development fog at the tip and end of the sample.
It was evaluated on a scale. 1 indicates the worst, 5 indicates the best
And 1 and 2 are severely fogged and are not practically usable.
Le. No. 3 is slightly usable, but barely usable
bell. 4 and 5 are usable levels with almost no gabble
is there. Table 1 shows the results. [0081]   <Developer 1>   Hydroquinone 50.0g   N-methyl-p-aminophenol 1 / 2H_TwoSO_Four                    0.3g   Sodium hydroxide 18.0g   55.0 g of 5-sulfosalicylic acid   Potassium sulfite 110.0g   EDTA ・ 2Na 1.0g   Potassium bromide 10.0g   0.4 g of 5-methylbenzotriazole   0.2 g of 2-mercaphate sodium imidazole-5-sulfonic acid   Sodium 3- (5-mercaptotetrasole) benzenesulfonate 0.2g   N-n-butyldiethanolamine 12.0 g   8.0 g of sodium toluenesulfonate   1 liter with water   Adjust to pH 11.8 with potassium hydroxide. [0082]   <Fixer>   Ammonium thiosulfate 124.0 g   Sodium sulfite 22.0g   Sodium tartrate 2H_TwoO 5.0g   Na_TwoB_TwoO_Four・ 8H_TwoO 15.3g   9.5 g of aluminum sulfate   1 liter with water   Adjust to pH 4.7 with acetic acid. [0083] [Table 1] From the results shown in Table 1, the mercapto compound and the white
Xanth compound added to protective layer, intermediate layer and undercoat layer
Photographic light-sensitive material of the present invention (samples Nos. 3 to 8, 13
To 17) are photographs of comparative examples containing no mercapto compound.
Greater sensitivity compared to photosensitive materials (No. 1, 9, 19)
Without reducing physical development fog.
Understand. In addition, the emulsion layer was added with a mercapto compound.
True photosensitive material (No.2, 10-12) and No.18 white
Photosensitive materials that do not contain xanse compounds are
Blistering is suppressed, but a large decrease in sensitivity is seen.
It is. In addition, mercapto compounds and siloxane compounds
A photographic light-sensitive material contained in the same hydrophilic colloid layer (No.
4, 6 to 8) are photographic light-sensitive materials (N
o3, 7), physical development fog is not increased.
And the decrease in sensitivity is small. Embodiment 2 In the emulsion of Example 1, 2 × 1 hydrazine compound of H-6 was added.
0^-FourSame as Example 1 except that mol / mol Ag was added
The samples shown in Table 2 were prepared. For these samples
Exposure and development are performed in the same manner as in Example 1, gamma is determined, and
Physical development fog was tested as in Example 1. Gamma is optical
It measured by tan (theta) of the linear part whose density | concentration was 1.0-2.5.
Table 2 shows the results. [0086] [Table 2] From the results shown in Table 2, the mercapto compound and the white
The photographic light-sensitive material of the present invention in which a xanse compound is added to the protective layer
(Sample Nos. 22 to 27 and 32 to 36) are Mercap
Photographic light-sensitive material of Comparative Example containing no compound (No. 20,
28, 38), while suppressing physical development fog,
It can be seen that a good image is obtained. Also, the emulsion layer
Photosensitive materials to which a capto compound is added (Nos. 21 and 29)
-31) and no siloxane compound of No37
Photosensitive materials with reduced physical development fog
However, hydrazine development was also greatly suppressed, and high-contrast images were obtained.
I can't. Furthermore, the mercapto compound and the siloxane compound
Photosensitive material containing a substance in the same hydrophilic colloid layer
(No23, 25, 27) are photographs not contained in the same layer
Physical development fog compared to photosensitive materials (Nos. 22 and 26)
Higher contrast images without increasing image quality
I understand. Embodiment 3 <Preparation of emulsion> pAg controlled double jet method
Gives a cubic monodispersion with an average particle size of 0.13 microns
And rhodium dichloride in 6.4 × 10^-6Mol / mol
A silver chloride emulsion containing Ag was prepared and subjected to flocculation.
5-chlorobenzene was added to the emulsion that had been desalted, washed with water and re-dissolved.
Nzotriazole 1 × 10^-3Mol / mol Ag is added,
This is divided into hydrazine compounds shown in Table 3 respectively.
Is 1 × 10^-3Mol / mol Ag and the nucleation accelerator shown in Table 3.
Is 2 × 10^-3Mol / mol Ag, and then 2-hydroxy
C-4,6-dichloro-1,3,5-triazine
It was prepared by adding a sodium salt and a surfactant of the formula (18). <Preparation of protective solution>
2 x 10 capto compounds^-3Mol / mol Ag, organic
Loxane compound at 20 mg / m^TwoAddition and surface activity
It was prepared by adding a curing agent, a matting agent, and a hardening agent. The coating solution prepared as described above is
On the lentephthalate film, the emulsion layer was
g / m^Two 3g / m gelatin^Two To be a protective layer
Is 1g / m of gelatin^Two It was applied so that The samples shown in Table 3 were used for sensitometry.
Light room printer through the edge (made by Dainippon Screen
After exposing with P-627FM manufactured by Zou Co., Ltd.,
The same procedure as in Example 2 was carried out except that development was carried out with developer 2 having the composition.
Test was carried out. Also, the same physical development fog test as in Example 1
Was done. Table 3 shows the results. [0091]   <Developer 2>   2.3 g of 1-phenyl-4-human-peroxymethyl-4-methyl-3-perazodritone   Hydroquinone 85.0g   Sodium hydroxide 26.0 g   Sodium carbonate 50.0g   Potassium sulfite 220.0 g   9.1 g of diethylenetriaminepentaacetic acid   Potassium bromide 12.5g   Benzotriazole 0.6g   110.0 g of diethylene glycol   1 liter with water The concentrate was diluted at a ratio of 1 part concentrate to 2 parts water.
Thus, a developer having a working strength of pH 10.5 is adjusted. [0092] [Table 3] From the results shown in Table 3, occurrence of physical development fog
Even in silver chloride emulsions, mercapto compounds
The photographic light-sensitive material of the present invention in which a xanse compound is added to the protective layer
(Sample Nos. 39 to 46) are the mercapto of No. 47
Comparative photographic material containing no compound or siloxane compound
Of the comparative example not containing the siloxane compound of No.
Compared to photographic light-sensitive materials, p
High-contrast images can be obtained even when processed with a developing solution of less than H11.0.
It is understood that it is possible. Embodiment 4 Using the emulsion prepared in Example 3, hydrazine of H-9
Compound 1 × 10^-3Mol / mol Ag and nucleation of A-15
2 × 10 accelerator^-3Mol / mol Ag added and protected
A mercapto compound and a comparative compound represented by the formula
Is 2 × 10^-3Mol / mol Ag and siloxane compound in 20
mg / m^TwoAdd and make a sample in the same manner as in Example 3.
After exposure and development, gamma was determined. In addition, automatic development
(Made by Dainippon Screen Mfg. Co., Ltd., LD-221Q
Using T), the developer is 300 ml / m^Two, Fixer is 5
00, 300, 200 ml / m^TwoReplenish at the rate of
Equivalent to 60 sheets per day in terms of Daizen (20 x 24 inches)
1 month with the amount of photosensitive material after exposure (blackening rate 50%)
After running for a while, the same as
Various fogging tests were performed and evaluated. The developer is
Using the developing solution 2 used in Example 3, the fixing solution was also used in Example 1.
The fixing solutions used in Nos. 1 to 3 were used. Table 4 shows the results. [0095] Embedded image [0096] [Table 4]From the results shown in Table 4, the photographic light-sensitive material of the present invention was obtained.
(Samples Nos. 50-53) are the substitutes for mercapto compounds.
Instead, the photographic feeling of the comparative example to which the comparative compound of Chemical Formula 19 was added
Physical development fog compared to optical materials (No. 54-56)
Even when processed with a developer having a pH of less than 11.0,
It can be seen that a good image is obtained. In addition, 300, 2
00ml / m^TwoRunning at a fixed replenishment rate
It can be seen that the development fog does not increase. [0098] According to the present invention, sensitivity, tone, etc.
Continuously develops a large amount without deteriorating photographic characteristics
Negative silver halide that does not cause physical development fog
A photographic light-sensitive material is obtained. In addition, the automatic processing machine
Replenishing amount of liquid is 1m^Two300ml or less per
Maintain photographic characteristics even when processing while replenishing at a ratio
While preventing physical development fog
Provided is a method for processing a silver photographic light-sensitive material.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/06 501 G03C 1/34 G03C 1/43 G03C 5/38 G03C 5/395

Claims (1)

(57) [Claim 1] At least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer of an undercoat layer, an intermediate layer and a protective layer on a film support a silver halide photographic material having at least includes one of the nitrogen-containing heterocyclic compound having at least one layer mercapto group of said hydrophilic colloid layer, and at least one emulsion layer or said hydrophilic colloid layer Silver halide copy for plate making containing at least one organosiloxane compound in the layer
The amount of fixer replenished with a true photosensitive material is fixed by an automatic processor.
Fixing while replenishing at a rate of 300ml or less per 1m2
Silver halide photographic exposure for plate making characterized by processing
Material treatment method .