JPH02256049A - Silver halide photographic sensitive material nearly free from pinhole - Google Patents

Abstract

PURPOSE:To prevent the occurrence of pinholes and to improve reversal characteristics for a photomechanical process such as the quality of white-on- black letters by forming one or more layers each contg. a water soluble electrically conductive polymer having at least one kind of group such as hydroxy or amino on the rear side of a support with an emulsion layer on the front side and by hardening at lest one of the layers on the rear side with a peptide type hardening agent. CONSTITUTION:One or more layers each contg. a water soluble electrically conductive polymer having at least one kind of group selected among hydroxy, amino, epoxy, aziridine, active methylene, sulfinic acid, aldehyde and vinylsulfone are formed on the rear side of a support with a photosensitive emulsion layer on the front side and at least one of the layers on the rear side is hardened with a peptide type hardening agent. The occurrence of pinholes is prevented and reversal characteristics such as the quality of white-on-black letters are improved.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an image forming method for a silver halide photographic light-sensitive material. This invention relates to a silver halide photographic material that can be handled under the conditions in which it is obtained.

[Background of the invention]

In recent years, in order to save labor and improve the rational work environment in the printing and plate-making field, there has been a demand for technology that allows film making, the so-called film-returning process, which was traditionally done in a dark room, to be performed in a bright room. Improvements have been made to the equipment.

Examples of light-sensitive materials that can be handled in a bright room include silver halide photographic materials that are sensitive to light sources rich in ultraviolet light, such as ultra-high-pressure mercury lamps, metal halide light sources, xenon lamps, halogen lamps, and the like. These silver halide photographic materials can be handled under bright general fluorescent lamps of 100 to 300 lux or special fluorescent lamps with a low amount of ultraviolet rays.

Although it has these advantages, it also has the disadvantage that defects called pinholes are likely to occur in the blackened image obtained after development.

The pinhole referred to here is a phenomenon in which a white spot within about 30 μm appears in a blackened image.The shape is circular or irregular, and it is created because it looks like a hole punctured by a pin. be.

As a film for the process of returning minute halftone images, if the film itself has abnormal darkened areas, faithful image reproduction cannot be obtained. As a result, the resulting pinholes had to be dealt with by opening (filling holes and correcting images), which significantly reduced work efficiency.

Under these circumstances, there has been a strong desire for a film for use in bright rooms that is less prone to pinholes.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and its first object is to provide a silver halide photographic material that does not generate pinholes when exposed to light from a selected light source.

The second object is to provide a silver halide photographic light-sensitive material that has improved plate-making return characteristics such as cutout character quality.

[Structure of the invention]

The object of the present invention described above is to provide one of hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, and vinyl sulfone groups on the opposite side of the support provided with the photosensitive emulsion layer. A silver halide photographic light-sensitive material comprising at least one layer containing a water-soluble conductive polymer having at least one group, at least one of the layers being hardened with a peptide hardener. achieved.

The photosensitive emulsion layer preferably contains a hydrazine compound or a tetrazolium compound.

The details of the present invention will be explained below.

The water-soluble conductive polymer according to claim 1 of the present invention has at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Examples include polymers with Among these groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred.

The electrically conductive group is required to be present in an amount of 5% by weight or more per polymer molecule. Of the hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, and vinyl sulfone groups contained in water-soluble conductive polymers, hydroxy groups, amino groups, epoxy groups, and aziridine groups , aldehyde groups are preferred. These groups are required in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3,000 to 100,000, preferably 3,500 to 5oooo.

Examples of compounds of the water-soluble conductive polymer used in the present invention are listed below, but are not limited thereto. Scoop U, b Ka So, Na 5o, Na 01 Na SO, Na I2 M #10,000 Degree of dextran sulfate substitution 2.0 M = 100,000 So 3 Na M #50,000 x:y:z:w-40:30 :20:10M#50,003Na x:y:z=80=10:10Ma10,000In addition, in the above (1) to (50), X, 7. z.

W represents the mol% of the monomer components, and M represents the average molecular weight (in this specification, the average molecular weight refers to the number average molecular weight).
represents.

These polymers can be synthesized by polymerizing heptamers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01 g to 10 g/m', particularly preferably 0.1 g to 5 g/m'.

These compounds can be used alone or mixed with various hydrophilic binders or hydrophobic binders to form a layer. Particularly advantageously used as hydrophilic binders are gelatin or polyacrylamide, but others include colloidal albumin, cellulose acetate, cellulose nitrate, polyvinyl alcohol, hydrolyzed polyvinyl acetate, phthalated gelatin. can be mentioned. As a hydrophobic binder, the molecular weight is 2.
10,000 to 1,000,000 or more, examples include styrene-butyl acrylate-acrylic acid ternary copolymer, butyl acrylate-acrylonitrile-acrylic acid ternary copolymer, and methyl methacrylate-ethyl acrylate-acrylic acid ternary copolymer. It will be done.

Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex form that is substantially insoluble in water. This hydrophobic polymer can be any combination of styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. - obtained by polymerizing. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.

To make a hydrophobic polymer into a latex, emulsion polymerization is performed, and the solid polymer is dissolved in a low boiling point solvent.

There are two methods, in which the solvent is distilled off after fine dispersion, but emulsion polymerization is preferred because it produces particles with fine and uniform particle sizes.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive layer.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

7.

8.

12゜13゜C00CHs C00CzHaOHC00H14
゜CH.

15.Next, as the peptide hardener used in the present invention, a compound represented by the following formula (I[) is preferably used.

General formula (n) In the formula, R, , R, , R and R are an alkyl group, an alkenyl group, an aralkyl group, a hydroxyalkyl group, an acetyl group, a sulfamoyl group, a morpholyl group, a pyridyl group,
It represents a pyrrolisilyl group, a cyanoalkyl group, an alkoxyalkyl group, or an aryl group, and these may be the same or different from each other, and also include substituted ones.

Furthermore, any two of R, R, R, and R6 may be bonded to form a ring, or three or more may be bonded to each other to form a condensed ring. X is a group that can be separated when the compound represented by the general formula [■] reacts with a nucleophile.

Ye represents an anion, and any one of X, RIRx, Rs, or R4 (if two or more of Rl, R!, Rs, and R1 are combined to form a ring, it may be plural) may be combined with to form an inner salt.

More specifically, R, , R, , R, and R6 are preferably linear or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, butyl group, 2-ethylhexyl group). , dodecyl group, etc.), aralkyl group having 6 to 20 carbon atoms (e.g. benzyl group, 7enethyl group, 3-pyridylmethyl group, etc.), aryl group having 5 to 20 carbon atoms (e.g. phenyl group, naphthyl group, pyridyl group, etc.) ), which may be the same or different. Also, Rl+R! ,
Rs and R4 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and N,N-disubstituted carbamoyl. Examples include groups.

It is also preferable that any two of R□, R, , R, and R4 combine to form a ring. For example, R1 and R3,
Examples of R1 and R1 bonding together to form a ring with a nitrogen atom include a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring, a virol ring, and the like.

Examples of R1 and R3 or R1 and R4 bonding together to form a ring with two nitrogen atoms and a carbon atom sandwiched between them include an imidacilline ring, a tetrahydropyrimidine ring, a tetrahydroazepine ring, etc. can be mentioned.

Further, as an example of forming a condensed ring, A pyridinyramyl group is preferred.

YO represents an anion, examples of which are halide ion, sulfonate ion, sulfate ion, phosphonate ion, phosphate ion, BF, θG120aes P
Examples include F@e, particularly preferably CQe,
BF, e, Ci, e, PF, e and U sulfo*-ions.

Moreover, the compound represented by the formula (ff) is represented by the formula CI[a
) and (I[b), but depending on the three-dimensional structure of the molecule, the electronic effects of substituents, etc., this equilibrium is expressed as the equilibrium of the general formula (IIa) or (I[b). It may take a structure that leans towards It b).

General formula (n a) General formula (n b) [wherein, R1* Rx * Rs + R41X +
Y e) Same as definition bar formula (n). ] An example of the compound represented by this formula (I[) is T, Fujisawa et al., as an esterification reagent.
, Chemi-stry Letters, 1891 (
1982).

Examples of the compound represented by the general formula [11] used in the present invention are listed below, but the present invention is not limited thereto.

ff-1 It-5 F-2 ■ ■ ■ ■ =10 ■ ■ ■ ■ \-/ ■ ■ ■ ■ =19 ■ ■ ■ PF, e Q Qe ae ■ ■ ■ =25 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ IF-39 ■ -43 ■ -40 ■ -44 f-41 ShiU ■ -42 The hydrazine compound used in the present invention is preferably a compound represented by the following formula [I[1].

-Formula (III) R1-N-N-C-R.

In the formula, R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, Q and Q are a hydrogen atom,
Alkylsulfonyl group (including those with substituents),
It represents an arylsulfonyl group (including one having a substituent), and Xl represents an oxygen atom or a sulfur atom. -Among the compounds represented by the formula CI), compounds in which XI is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxy groups, nitro groups, alkylthio groups, and hydroxy groups). , sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group,
urea group, thiourea group, etc.). Specific examples of those with substituents include, for example, 4-) thi/L= phenyl group, 4-ethylphenyl group, 4-, t
xyethylphenyl group, 4-dodecylphenyl group, 4-
Carboxyphenyl group, 4-diethylamino 7enyl group, 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4-(3-ethylthioureido)phenyl group, 4 −[
2-(2,4-di-tert-butylphenoxy)butyramido]phenyl group, 4-[2-(2,4-tert-butylphenoxy)butyramido]phenyl group,
rt-butylphenoxy)butyramide] phenyl group, and the like.

The heterocyclic residue is a membered or six-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and a substituent may be attached thereto.

Specifically, for example, biroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
Alkyl group, methoxy group, ethoxy group, etc. having 1 to 4 carbon atoms
may be substituted with an alkoxy group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, an amino group, or the like.

Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, carbon atoms with 1-
18, preferably an alkyl group of 1 to 8, and specific examples include a methyl group, ethyl group, isobutyl group, l-octyl group, and the like.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as cyclopropyl, cyclohexyl, adamantyl, and the like. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkyl substituents, amide groups, acyloxy groups,
Cyano group, sulfonyl group, halogen atom (e.g. chlorine,
bromine, fluorine, iodine, etc.), aryl groups (e.g., phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group), etc. Specific examples of substituted groups include 3
-methoxypropyl group, ethoxycarbonylmethyl group,
Examples include 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group. In addition, examples of alkenyl groups include allyl (a
Examples of the alkynyl group and the alkynyl group include a propargyl group.

Preferred specific examples of the hydrazine compound of the present invention are shown below, but the present invention is not limited thereto in any way.

(I[r-1) (I[[-2) (m-3) (m - g) (I[[-4') CH.

(DI-9) (II-5) (m-10) (If[-6) (m-11) (I[ll-7 ) C-12) C, H.

(III -13) Cm -14) (Iff -15) (I[l -16) (■ (III-23) (I[[-24) (■ (III-26) Cm -18) (m -19 ) (III-20) (III -21) (III -22) (I[[-27) r (I[[-28) Hs (II[-29) (Ill-30) OC+aH2s (I[[-31 ) (I[[-32) (n[-33) (m-34) (I[l-35) (II -40) (III -41) (I[[-42) (I[r -36) (m-38) (m-39) (III-44) (m-45) (I[I-46) The hydrazine compound represented by the general formula (n[) is added to the silver halide emulsion layer and/or A non-photosensitive layer on the side of the silver halide emulsion layer on the support, preferably,
The silver halide emulsion layer and/or its lower layer. The amount added is preferably 101 to 1O-1 mol/silver 1 mol, more preferably 1O-4 to 1O-2 mol/silver 1 mol.

Next, the tetrazolium compound used in the present invention will be explained.

The tetrazolium compound can be represented by the following formula.

General formula (IM) In the present invention, substituent R1 of the phenyl group of the triphenyltetrazolium compound represented by the above-mentioned formula (IV)
, R2, and R1 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (σP) indicating the degree of electron attraction. In particular, negative ones are preferred.

Hammett's sigma value for phenyl substitution has been reported in many publications, e.g.
Tori (Journal of
Medical Che + * 1stry) 20th
Vol. 304, 1977, described by C. Hanks (c.

Particularly preferable groups having negative sigma values include, for example, methyl groups (σP--0.17 or less, all σP values), ethyl groups (
-0,15), cyclopropyl group (-0,21), n-
Propyl group (-0,13), isopropyl group (-0,
15), cyclobutyl group (-0,15), n-butyl group (-0,16), 1sO-butyl group (-0,20), n
-pentyl group (-0,15), cyclohexyl group (-0
, 22), amino group (-0,66), acetylamino group (-0,15), hydroxyl group (-0,37), methoxy group (-0,27), ethoxy group (-0,24), Propoxy group (-0,25), butoxy group (-0,32)
, pentoxy group (-0,34), and the like, all of which are useful as substituents for the compound of general formula (IV) of the present invention.

Specific examples of the compound of general formula (IV) used in the present invention are listed below, but the compound of the present invention is not limited thereto.

Below (lower margin (exemplary compounds)) ■-1 IV-5 IV-6 IV-7 IV-8 IV-4 IV-9 IV-13 IV-10 IV-14 ■-11 1V-15 IV-12 IV-16 ■-17 IV-18 The tetrazolium compound used in the present invention is, for example, Chemical Revi-L.
It can be easily synthesized according to the method described in EWS, Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention may be used in an amount of about 1 mg to about 10 g, preferably about 1 mg to about 2 g, per mole of silver halide contained in the silver halide photographic material of the present invention.
It is preferable to use a range up to g.

The tetrazolium compounds used in the present invention can provide preferable properties when used alone, but the preferable properties will not deteriorate even when a plurality of them are combined in any ratio.

One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the invention, it is added to a hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, esters, etc., and then applied to a silver halide photographic light-sensitive material by an overcoating method or the like. It may be incorporated into the silver halide photographic light-sensitive material by directly coating the outermost layer on the side of the silver halide emulsion layer.

The silver halide used in the silver halide photographic material according to the present invention preferably has an arbitrary composition of silver chloride, silver chlorobromide, silver chloroiodobromide, etc., and preferably contains at least 50 mol % of silver chloride. The average grain size of silver halide grains is 0.025 to 0.
．． Those in the range of 5 μm are preferably used, but 0.05
~0.30μ■ is more preferred.

The monodispersity of the silver halide grains according to the present invention is expressed by the following formula (
1), and its value is preferably adjusted to 5-60, more preferably 8-30.

The grain size of the silver halide grains according to the present invention is conveniently expressed by the edge length of the cubic grain, and the monodispersity is calculated by dividing the standard deviation of the grain size by the average grain size. represent.

Further, as the silver halide that can be used in the present invention, a type having a multilayer laminated structure of at least two layers can be preferably used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell. At this time, iodine can be contained in any layer within 5% by mole.

Furthermore, a mixture of at least two types of particles can also be used. For example, raw milk grains contain up to 10 mol% silver chloride and 5
Cubic, octahedral, or tabular silver chloroiodobromide grains containing iodine of mol% or less; subgrains are cubic, octahedral, or tabular grains containing iodine of 5 mol% or less and silver chloride of 50 mol% or more. The mixed grains may be made of silver chloroiodobromide grains. When using a mixture of particles in this way, chemical sensitization of the main and sub particles is optional, but the sensitivity of the sub particles can be increased by refraining from chemical sensitization (sulfur sensitization or gold sensitization) compared to the main particles. The sensitivity may be lowered, or the sensitivity may be lowered by adjusting the particle size or the amount of noble metal such as rhodium doped inside. Furthermore, the inside of the sub-particle may be covered with gold, or the core/particle may be covered with gold.
Foaming may also be achieved by changing the composition of the core and shell using the shell method. The smaller the main particles and sub-particles, the better, for example 0.
It can take any value from 0.025 μm to 1.0 μm.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution.

The rhodium salt added to the silver halide emulsion used in the present invention may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but from lo-9 mol to 1 mol per mol of silver.
A range of o-4 moles is particularly useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used to improve high-light properties, ranging from 101 to 1 mole per mole of silver.
It can be preferably used up to a range of 0.01 mol.

The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triple (ethylenetetramine, stannous chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazolemethyl chloride, ammonium chlorovaladate, potassium chlorooleate, sodium chloroparadite, etc. Various noble metal sensitizers represented by can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Further, the silver halide emulsion used in the present invention is, for example, US Pat. No. 3,567,456, US Pat.
, 3.579,345, 3,615,608, 3
,598,596, 3,598°955, 3,59
2,653, No. 3,582.343, Special Publication No. 1977-2
67511 40-27332, 43-13167,
Desensitizing dyes and/or ultraviolet absorbers described in specifications such as No. 45-8833 and No. 47-8746 can be used.

Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat. No. 2,444.607, U.S. Pat.
No. 62, No. 3,512.982, West German Application Publication No. 1,189.380, No. 2.058.626, No. 2.118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3.342.596, Special Publication No. 47-4417
No., West German Application Publication No. 2.149.789, Special Publication No. 3
Compounds described in Japanese Patent Publication No. 9-2825, Japanese Patent Publication No. 49-13566, etc., preferably, for example, 5,6-trimethylene-7-hydroxyne-S-triazolo (1,5-
a) Pyrimidine, 5,6-tetramethylene-7-hydroxy-s-triazolo (1,5-a) pyrimidine, 5
-Methyl-7-hydroxy-s-triazolo (1,5
-a) Pyrimidine, 5-methyl-7-hydroxy-S-
Triazolo (1,5-a) pyrimidine, 7-hydroxyn-S-triacylon (1,5-a) pyrimidine, 5
-Methyl-6-bromohydroxy-s-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (l-
Stabilization using phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nidropenzimidazole), etc. I can do it.

The silver halide photographic material and/or developer according to the present invention preferably contains an amino compound.

The amino compounds preferably used in the present invention are primary to
Includes all quaternary amines. Examples of preferred amino compounds include alkanolamines. below,
Preferred specific examples will be listed, but the invention is not limited thereto.

diethylaminoethanoldiethylaminobutanoldiethylaminopropane-1,2-dioldimethylaminoprobane-1,2-diolgetanolaminediethylamino-1-propanoltriethanolaminedipropylaminopropane-1,2-dioldioctylamino-1-ethanoldioctylamino Glopane-1,2-dioldodecylaminopropane-1,2-dioldecylamino-1
-Propaturdodecylamino-1-ethanolaminopropanol-1,2-dioldiethylamino-2-propanoldiglobanolamineglycinetriethylaminetriethylenediamine The amino compound is used in the coating layer on the photosensitive layer side of the silver halide photographic light-sensitive material (e.g. It may be contained in at least one layer (silver halide emulsion layer, protective layer, hydrophilic colloid layer of the subbing layer) and/or in the developer, and a preferred embodiment is a mode in which it is contained in the developer.

The content of the amino compound varies depending on the object to be included, the type of the amino compound, etc., but a contrast promoting amount is required.

Further, in order to improve the developability, a developing agent such as phenidone or hydroquinone or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer can contain a developing agent or an inhibitor.

The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include:
For example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat. Second
．． phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat. No. 525,753, or U.S. Pat.
Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in No. 831.767.
These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following. HO-(
Typical CI-CI (), -〇H type developing agents include hydroquinone, and others include catechol,
pyrogallol and its derivatives and ascorbic acid,
Chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, 2
．． Examples include 5-diethylhydroquinone, catechol, 4-chloro9-catechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, and sodium ascorbate.

In addition, typical IO-(CH-C)l)-NHz type developers include ortho and para aminophenols, such as 4-aminophenol, 2-amino-6-phenylphenol, and 2-aminophenol. -4-chloro-6-phenylphenol, N-methyl-p-aminophenyl and the like.

Furthermore, examples of the HzN (CH-CH)-N1m type developer include 4-amino-2-methyl-N, N-diethylaniline, 2.4-diamino-N, N-diethylaniline, N-(4-amino -3-methylphenylundiamine and the like.

Examples of the Petero ring type developer include 3-pyrazolidones such as -phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, and l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. ,
Examples include 1-7enyl-4-amino-5-pyrazolone and 5-aminolaucil.

Others, T. H. The Theory of the...
The Photographic Process 4th Edition (The Theo
ry of Photographic Processes
s Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal of the A++eri)
can Chemical Society), Vol. 73, p. 3, 100 (1951), can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination.

Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. Further, hydroxylamine or a hydrazide compound can be used as a preservative, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g, per developing solution iff.

The developer may also contain glycols as an organic solvent, such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-bentanediol, etc. However, diethylene glycol is preferably used. The preferred usage amount of these chemicals and recalls is 5 to 500 per developer IO.
g, more preferably 20 to 200 g. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, it is possible to obtain a photographic material with excellent storage stability.

The pH value of the developer having the above composition is preferably 9 to 13.
However, from the viewpoint of storage stability and photographic properties, the pH value is 1O~1
A range of 2 is more preferred. Regarding cations in the developer, it is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.

The silver halide photographic material according to the present invention can be processed under various conditions. Regarding the processing temperature, for example, the development temperature is preferably 50°C or less, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds. ~50 seconds often produces good results. In addition, processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening,
It is optional to employ steps such as neutralization, and these can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples.

Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of emulsion) Silver halide with an average grain size of 0.11/7 m containing 10-' mol of rhodium salt per 1 mol of silver was prepared by the Chondrold double-jet method in an acidic atmosphere at pH 3.0. Silver chlorobromide particles having a monodispersity of 15 and containing 5 mol % of silver bromide were prepared. Particle growth was carried out in a system containing 30 mg of benzyladenine per 11 1% aqueous gelatin solution. After mixing silver and halide, 6-methyl-4-hydroxy-1
, 3,3a, 7-tetrazaindene was added in an amount of 600 mg per mole of silver halide, followed by washing with water and desalting.

Then, 60 mg of 6methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide was added, followed by 15 mg of sodium thiosulfate per mole of silver halide, and the mixture was heated at 60°0. Sulfur sensitized. After the sensitization, 600 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added per mole of silver halide as a stabilizer.

Additives were added to the resulting emulsion in the amounts shown below, and one side of a 100 μm thick polyethylene terephthalate support was coated with latex on both sides according to Example 1 of JP-A-59-19941. applied on top.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0 g/■2 Tetraphenylphosphonium chloride 30 rag/ra” Saponin 200 B/m’ Polyethylene glycol 100 tag/la
“Hydroquinone 200 tag/
cm” Styrene-maleic acid copolymer 20 a+g
/■2 Hydrazine compound 5 shown in Table-1
-Methylbenzotriazole 30 mg/m” Desensitizing dye (M) 20 mg7c
m” alkali-treated gelatin (isoelectric point 4.9) 1.5 g
/ls” bis(vinylsulfonylmethyl)ether 15
mg/. 2 Silver amount 2゜8 g/yx”
(Emulsion layer protective film) An emulsion layer protective film was prepared in the following amount and coated simultaneously with the emulsion in a multilayer manner.

Fluorinated dioctyl sulfosuccinate ester 200ag/
m” Sodium dodecylbenzenesulfonate 10011g/
I11” Matting agent: Polymethyl methacrylate (average particle size 3° 5μ
m) 100 H7m” lithium nitrate salt 301 μmg/m2 gallic acid propyl ester 3001 g/II+22-mercaptobenzimidazole-5-sulfonate sodium
30 +*g/m” Alkali-treated gelatin (isoelectric point 4.9) 1.3 g/ln” Colloidal silica 30 rag/m” Styrene-maleic acid copolymer 100 mg/rs” Bis(vinylsulfonylmethyl) Ether 15 mg/
m2 Next, additives were prepared and applied in the amounts shown below on the support opposite to the emulsion layer.

(Backing layer) Latex polymer: Butyl acrylate-styrene copolymer 0.5 glla'' Polymer of the present invention Styrene-maleic acid copolymer shown in Table 1 100 g/s'' Citric acid (pH 5 after coating,
4) 40 Ui 9/11 Saponin
200 g/l1ffi Lithium nitrate salt 30 mg/m" Backing dye (a) (b) CH, So, H 5ojX 5OJ (c) osNa Alkali-treated gelatin 2.0 g/m" Hardener of the present invention Table-1 Shown below.

(Backing Layer Protective Film) Additives were prepared in the amounts shown below and simultaneously coated on top of the backing layer.

Dioctyl sulfosuccinate 200 mg 7m" Matting agent: Polymethyl methacrylate (average particle size 4.0 μm) 50 rag/m" Alkali-treated gelatin (isoelectric point 4.9) 1.0 g/m' Fluorinated dodecylbenzenesulfonic acid Sodium 50 mg/+” Bis(vinylsulfonylmethyl) ether 20 mg/m’
Note that the p)l of the above coating solution was adjusted in advance to 5.4 before coating. The samples thus obtained were exposed to light using the light source shown in Table I, and developed using the developer and fixer shown below.

(Exposure method) An electrodeless discharge light source made by American company Fusion, called "7 bulbs" which has a maximum specific energy in the range of 400 to 420 nm, or a conventional light source called "D bulb", which has a maximum specific energy in 350 to 380 nm. A light source was attached under the glass plate, and the original and photosensitive material were placed on the glass surface and exposed so that the quality of cut-out characters could be evaluated.

Developer formulation Hydroquinone 25 gl-7
Enyl 4.4dimethyl-3-pyrazolidone 0.4g Sodium Bromide 3g 5-Methylbenzotriazole 0.365-nitroindazole
0.05g 5g Diethylaminopropane-2-diol Potassium sulfite Sodium 5-sulfosalicylate 75 Sodium ethylenediaminetetraacetate Finished to 1Q with water.

The pH is 11.5 with caustic soda. Fixer formulation (Composition A) Ammonium thiosulfate (72.5w% did.

Aqueous solution) 240 Kena 7 g 6.5g g g 13.6mff Sodium sulfite Sodium acetate, trihydrate Borate Sodium citrate, dihydrate Acetic acid (90w% aqueous solution) (Composition B) Pure water (ion exchange water) Sulfuric acid ( 50w% aqueous solution) Aluminum sulfate (A (220s equivalent content: 7-a 4.7g 8.1v% aqueous solution) When using 26.5g fixer, dissolve in 500ml of water in the order of the above compositions, lI2 The pH of this fixer was approximately 4.3.

Development processing conditions> (Process) (Temperature) (Time) Development
Fixing at 40 DEG C. for 15 seconds, Washing with water at 35 DEG C. for 10 seconds, Room temperature, 10 seconds Evaluation was carried out as follows, and the results are shown in Table 1.

(Photographic performance evaluation method) (1) Pinhole improvement performance Place the mesh film on the pasting base, fix the periphery of the mesh film with transparent scotch tape for plate making, and after exposure and development process, pinhole improvement performance. A five-point evaluation was made, with "5" indicating no holes occurring and rlJ indicating the worst level with the greatest number of holes occurring.

(2) Cutout character quality Cutout character quality is defined as the line width of 50 μm on the line drawing film when the part with 50% halftone dot area is properly exposed to light so that the halftone dot area becomes 50% on the photosensitive material for return. The image quality that is reproduced was evaluated on a five-point scale, with "5" representing very good character image quality and rlJ representing the worst quality.

Table 1 shows that by providing a layer containing a hydrazine compound in the silver halide emulsion layer and a layer containing the polymer according to the present invention and a hardening agent in the backing layer, the generation of pinholes can be suppressed and cut-out characters can be suppressed. It can be seen that performance has also been improved.

Furthermore, it has been shown that when a light source having an energy maximum at 400 to 420 nm is used as an exposure light source, a photosensitive material with improved character extraction performance and less occurrence of pinholes can be obtained.

Example 2 In the same manner as in Example 1, rhodium salt was added in l/mol of silver.
Silver chlorobromide particles containing 2 mol % of silver bromide with an average particle diameter of 0.20 μm and a monodispersity of 20 were prepared.

This was treated in the same manner as in Example 1, washed with water, desalted, and then sulfur sensitized.

Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on the undercoated polyethylene terephthalate support used in Example 1.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer 1.0g/+”phenol
l rag/m”saponin
200mg/+m" Sodium dodecylbenzenesulfonate 50mg/m" Tetrazolium compound Compounds shown in Table 2 (N
) 40mg/m” Compound (0) 50B/m2 Styrene-maleic acid copolymer 20g/Ia 2 alkali-treated gelatin (isoelectric point 4.9) 2.0g/+n
”Silver amount 3.5g/■2
Formalin 10I110l1 Compound (0) The coating solution was adjusted to pH 6.5 with sodium hydroxide before coating. As an emulsion protective film, additives were prepared in the amounts shown below and were coated simultaneously with the emulsion coating solution.

Fluorinated dioctyl sulfosuccinate ester 1001g/1m”
Dioctylsulfosuccinate 100+ag/m
'Matting agent: Amorphous silica 50mg/m
'Compound (0) 30+mg
/m”5-methylbenzotriazole 20m
g/m” Compound (P) 5
00mg/m” gallic acid propyl ester 3
00B/m' styrene-maleic acid copolymer 1
00 g/+” alkali-treated gelatin (isoelectric point 4.9)
1.0g/+*” formalin
10+ag/m”.
It was coated after adjusting to H5.4.

/ Below (lower margin) Compound (P) Next, a backing layer was provided on the support opposite to the emulsion layer in exactly the same manner as in Example 1.The polymer and hardener used were are shown in Table-2.

The obtained sample was exposed and developed in the same manner as in Example-1.

However, the following developer was used. The results obtained are shown in Table-2.

(Composition A) Pure water (ion exchange water) 150+wf
f Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100ml12 Potassium carbonate 50ghydroquinone 15g1-phenyl-5-
Mercaptotetrazole 30mg Amount to adjust the pH of the potassium hydroxide solution to 10.4 Potassium bromide 4.5g (composition) Pure water (ion-exchanged water) 3mg diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25+mg acetic acid (90% aqueous solution) 0.3 mina l-phenyl-3-pyrazolidone 500+
When using a mg developer, the above-mentioned i-formation A1 composition was dissolved in 500 mα of water in the order described above, and the composition was finished to lα.

7'-1 As is clear from the results in Table 2, even when a tetrazolicum compound is used in the silver halide emulsion layer in the combination according to the present invention, the occurrence of bottle balls can be suppressed and the cutout character performance can be improved. It can be seen that it has improved.

Example 3 In Example 2, a sample was prepared having a layer containing the polymer of the present invention and a hardening agent as shown in Table 3 between the backing layer and the undercoated support.

Furthermore, samples were also prepared in which the backing layer and/or backing protective layer also contained the polymer of the present invention.

The obtained sample was exposed and developed in the same manner as in Example-2.

-As is clear from the results in Bottom Margin Table-3, in the combination according to the present invention, even when a polymer content is provided between the backing layer and the subbing method support, the generation of pinholes is suppressed, It can be seen that the performance of cut-out characters has been improved.

Furthermore, it has been found that when the polymer of the present invention is used in combination with the backing layer and/or the backing protective layer, pinholes can be further improved with a small amount.

〔Effect of the invention〕

As described above, according to the image forming method of the present invention, it is possible to form a silver halide photographic light-sensitive material and an image thereof, which suppress the occurrence of pinholes as a photographic property and have good cutout character quality.

Claims (2)

[Claims] (1) At least one group selected from the group consisting of a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group is provided on the opposite side of the support provided with the photosensitive emulsion layer. 1. A silver halide photographic light-sensitive material, comprising at least one layer containing a water-soluble conductive polymer, and at least one of the layers is hardened with a peptide hardener. (2) The silver halide photographic material according to claim 1, wherein the photosensitive emulsion layer contains a hydrazine compound or a tetrazolium compound.