JPH02103532A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obviate the deterioration in safe light character and the degradation of density and to improve dropout character quality, by incorporating a specific compd. into at least one layer of hydrophilic colloidal layers on the side of an emulsion layer. CONSTITUTION:At least one layer of photosensitive silver halide emulsion layers are provided on a base and are subjected to a development processing to form the silver halide photographic sensitive material having >=6 gamma (at 0.3 to 3.0 concn.). At least one kind selected from the groups of the formula I and the formula II are incorporated into at least one layer of hydrophilic colloidal layers on the side of the photosensitive silver halide emulsion layers. In the formula II, X denotes a hydrogen atom, alkaline metal, aryl group, alkyl group, thioether group, sulfo group or carboxyl group. The dropout character quality is improved in this way without deteriorating the safe light characteristic and degrading the densities.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material.

[Background of the invention]

In recent years, in the printing plate-making field, in order to save labor, streamline the work environment, and improve the work environment, there has been a demand for technology that allows the so-called turning process, which was traditionally done in a dark room, to be performed in a bright room, and this has led to the need for technology that allows photosensitive materials, printers, etc. Improvements are being 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, and halogen lamps.

And these silver halide photographic light-sensitive materials are 100~
It can be handled under a general fluorescent light with a brightness of 400 lux or a dedicated fluorescent light with a low amount of ultraviolet rays.

By the way, for printing materials that have a high-contrast image with a γ value of 6 or more (at a density of 0.3 to 3.0), special emphasis is placed on the quality of blank characters, and they can be handled in a bright room as described above. Although it is known to increase the amount of filter dye to fIji as a means of improving the quality of printed characters in light-sensitive materials, implementation of this improving means has the disadvantage of causing deterioration of safelight properties and reduction of density.

[Disclosure of the Invention] The object of the present invention is that the amount of filter dye used is, for example, 5X.
We have developed a silver halide photographic light-sensitive material that can improve the quality of blank characters without causing deterioration of safelight properties or decrease in density even in the normal case of 10-' to 5X10-' mol/1. This is what we provide.

, the above object is to provide at least one photosensitive silver halide emulsion layer on a support and develop it to obtain γ (density 0).
．． 3 to 3.0) is 6 or more, wherein at least one hydrophilic colloid layer on the side of the photosensitive silver halide emulsion layer contains the following [I] and (■). This can be achieved by a silver halide photographic material containing at least one selected from the group.

(1) (II) However, X: hydrogen atom, alkali metal, aryl group (including those with a substituent), alkyl group (including those with JAM), thioether group, sulfone group, or carboxyl group. Among these, X is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

, Next, specific examples of the compound represented by the general formula (2) are listed below, but the present invention is not limited thereto.

Moreover, it is more preferable to use both the compounds (1) and (If) in the silver halide photographic emulsion layer.

The amount of these compounds added is lXl0-'~1x10
-t mol/Ag 1 mol is sufficient, and more preferably 5X10-' to 5X10-3 mol/Ag 1 mol.

Furthermore, in the above silver halide photographic light-sensitive material, at least one of the hydrophilic colloid layers on the side containing at least one selected from compounds [I] and [II] contains a hydrazine compound and/or a tetrazolium compound. Those that do are particularly preferred.

The hydrazine compound used is preferably a compound represented by the following general formula (Ill-a).

General formula (I[[-a) In the formula, R1 represents a monovalent organic residue, R represents a hydrogen atom or a monovalent organic residue, and Q and Q are a hydrogen atom and an alkylsulfonyl group. (!Including those with a substituent), represents an arylsulfonyl group (including G having a substituent), and X represents an oxygen atom or a sulfur atom.

Among the compounds represented by formula -a (ml-a), compounds in which xl is an oxygen atom and Rt is a hydrogen atom are particularly preferred.

The above-mentioned monovalent organic residues 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, carboxyl groups, nitro groups, alkylthio groups, and hydroxy groups). , a sulfonyl group, a carbamoyl group, a halogen atom, an acylamino group, a sulfonamide group, a thiourea group, etc.). group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2methylphenyl group, 4 -(3-ethylthioureido)phenyl group, 4- (2-(2,4-dit
Examples include ert-butylphenoxy)butylamide]phenyl group, 4-(2-(2,4-di-tert-butylphenoxy)butylamide)phenyl group, and the like.

The heterocyclic residue is a pure or six-membered monocyclic or fused ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, which may have a substituent, specifically, for example, Pyrroline ring, pyridine ring, quinoline ring,
Residues such as indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, etc. I can list some basics.

These heterocycles include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 1B carbon atoms, a halogen atom, an alkoxycarbonyl group, a cyano group,
It may be substituted with an amide group or the like.

Aliphatic residues include straight-chain and branched alkyl groups, cycloalkyl groups and those with an 'l1ttA group attached, as well as alkenyl and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably 1 to 8 alkyl groups, and specific examples include methyl group, ethyl group, isobutyl group, and 1-octyl group.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclohexyl group, and an adamantyl group. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amido groups, acyloxy groups, cyano groups, sulfonyl groups, halogen atoms, aryl groups (e.g. phenyl groups, halogen (substituted phenyl group, alkyl-substituted phenyl group), etc. Specific examples of substituted groups include 3-methoxypropyl group, ethoxycarbonylmethyl group, 4-chlorocyclohexyl group, benzyl group, ρ-
Examples include methylbenzyl group and p-chlorobenzyl group.

Examples of alkenyl groups include allyl (a-yl) groups, and examples of alkynyl include propargyl groups.

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

(1114) 1-formyl-2-(4-(2-(2,
4-di-tert-butylphenoxy)butyramide]
phenyl)hydrazine (m-2) 1-formyl~2- 14- (2-(
2,4-diter[~butylphenoxy)butylureido)phenyl)hydrazine (III-3) 1-formyl-2-(4-diethylaminophenyl)hydrazine (III-4) 1-formyl-2-(p-tolyl ) hydrazine (I[[-5) l-formyl-2-(4-ethylphenyl)hydrazine (Ill-6) 1-formyl-2-(4-acetamido-2-methylphenyl)hydrazine (Ill-7) 1 -Formyl-2-(4-oxyethylphenyl)hydrazine (I[[-8) I-formyl-2-(4-N, N-
dihydroxyethylaminophenyl)hydrazine (Ill-9) 1-,hlumi-2-(4-(3-1
-5-ruthio')L4do)phenyl)hydrazine(I[l-10)1-thioformyl-2-(4-(2-
(2,4-di-tart-butylphenoxy)butylamidophenyl)hydrazine (t[l-11)1-formyl-2-(4-benzylaminophenyl)hydrazine (DI-12)1-formyl-2-(4 -octylaminophenyl)hydrazine(III-13)1-formyl-2-(4-dodecylphenyl)hydrazine(I[l-14)l-acetyl-2-[4-(2-(2
, 4-diterLbutylphenoxy)butylamidophenyl)hydrazine (■~15) 4-carboxyphenylhydrazine (■~
16) 1-acetyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine Cm-17-ethoxycarbonyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine (II
[-18) l-formyl-2-(4-hydroxyphenyl)-2-(4-methylphenylsulfonyl)-hydrazine (I[l-19)1-(4-acetoxyphenyl)-2
-Formyl~1-(4-methylphenylsulfonyl)-
Hydrazine (III-20) 1-formyl-2-(4-hexanoxyphenyl)-2-(4-methylphenylsulfonyl)
-Hydrazine (Ill-21) 1-formyl-2-(4-(tetrahydro-211-pyran-2-yloxy)-phenyl)
-2-(4-methylphenylsulfonyl)-hydrazine(III-22) 1-;hlumi-2-(4-(3
-hexylureidophenyl) -2-(4-methylphenylsulfonyl)-hydrazine (Ill-23) I-formyl-2-(4-methylphenylsulfonyl)-2-(4-(phenoxythiocarbonylamino)-phenyl )-hydrazine (m-24)
l-(4-ethoxythiocarbonylaminophenyl)-
2-formyl-1-(4-methylphenylsulfonyl)
-Hydrazine (1-25)! -formyl-2-(4-methylphenylsulfonyl)-2-(4-(3-methyl-3-phenyl-2-thioureido)-phenyl]-hydrazine (L26) 1-1 (4-+3- (4-( 2,4-bis-1-amylphenoxy)-butyl)ureido)phenyl11-2-formyl-■-(4-methylphenylsulfonyl)-hydrazine (Ill-27) (m-28) (III ) (Ill -30) (Ill Ill -32) (III-33) (III-34) CSH port (L) (I[I -35) ([[I -36) (■ (■ (II[-39 ) (Ill -40) (ill CI[l-42) (III-43) <m-44) ([[I (■ (■ Note that the addition position of the hydrazine compound is the silver halide emulsion layer and/or the support It is a non-photosensitive layer (hydrophilic colloid layer) located on the side of the upper silver halide emulsion layer, and is preferably the silver halide emulsion layer and/or its lower layer.

The amount added is preferably 10-' to 10'' mole/im1 mole, and more preferably 10-4 to 10-1 mole/im1 mole.

or, Tetrazolium compounds will be explained.

Preferred examples of this tetrazolium compound include: The following general formula (m-b), [■～C] or [■ =d).

General formula (m b] General formula [■ C] General formula (ill-d) In the formula, R1゜ Rtsu.

R4+ Rs.

R1゜R9゜R1 and R0 each represent an alkyl group (for example, a methyl group, an ethyl group,
propyl group, dodecyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, propenyl group, etc.), aryl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, α - a group selected from a naphthyl group, a β-naphthyl group, a hydroxynaphthyl group, a carboxynaphthyl group, an aminonaphthyl group, etc.), and a heterocyclic group (e.g., a thiazolyl group, a benzothiazolyl group, an oxacylyl group, a pyrimidinyl group, a pyridyl group, etc.) Each of these may be a group that forms a metal chelate or a complex.

Rx, R& and R1 each represent an allyl group, a phenyl group which may have a substituent, a naphthyl group which may have an ia group, a heterocyclic group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group). , butyl group, mercaptomethyl group, methylcaptoethyl group, etc.), hydroxyl group, carboxyl group or its salt, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), amino group (
D represents a divalent aromatic group, and E represents an alkylene group, an arylene group, an aralkylene group. represents a group selected from
X- represents an anion, i represents an integer of 1 or 2, provided that n is 1 when the compound forms an inner salt.

Next, the general formula (m-b), (In-c) or (II
Specific examples of the tetrazolium compound represented by I-d) are shown below, but the present invention is not limited thereto.

(II-61) 2-(Benz'thiazol-2-yln-3-phenyl-5-dodecyl-211-tetrazolium (III-62) 2.3-diphenyl-5~(
4-1-octyloxyphenyl)-2■-tetrazolium (nl-63) 2,3.5-)'j7E=ru28
-tetra7''J'7mu(III-64) 2.3.5- 68) (Ill-72) (III-73) 2-(benzothiazol-2-yl)-3-phenyl-
5-(o-chlorophenyl)-28-tetrazolium 2.3-diphenyl-2H-tetrazolium 2.3-diphenyl-5-methyl-2H-tetrazolium 3-(p-hydroxyphenyl)-5-methyl-2-phenyl- 211-tetrazolium 2,3-diphenyl-
5-ethyl-2 former tetrazolium 2.3-diphenyl-5-n-hexyl-2H-tetrazolium 5-cyano-2,3-diphenyl-2■-tetrazolium 2-(benzothiazol-2-yl)-5- phenyl
3-(4-)lyl)-2H-tetrazolium 2-(benzothiazol-2-yl)-5-(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium(III-74) ( ml-75) (III-76) (I[[-78) (I[[-79) (III-80) (Ill-81) 5-ethoxycarbonyl-2,3-di(3-nitrophenyl)- 2H-tetrazolium 5-acetyl-2,3-
Di(p-ethoxyphenyl)-2■-tetrazolium 2.5-diphenyl-3-(p-tolyl)-2H-tetrazolium 2.5-diphenyl-3-(ρ-iodophenyl)-2
H-tetrazolium 2.3-diphenyl-5-(p-diphenyl)-2H-
Tetrazolium 5-(p-7'romophenyl)-2-phenyl-3-(
2,4,6-Dolichlorophenyl)-2totitrazolium 3-(p-hydroxyphenyl)-5-(ρ-nitrophenyl)-2-phenyl-2totitrazolium 5- (3,4-dimethoxyphenyl)-3- (2-ethoxyphenyl)-2-(4-methoxyphenyl)-2
■-Tetrazolium 5-(4-cyanophenyl)-2,3-dipheny(II)
I-83) (Ill-85) ([86) (I[l-89) (III-90) (III-91) 2H-tetrazolium 3-(p-acetamidophenyl)-2,5-diphenyl-21 Totitrazolium 5-acetyl-2,3-diphenyl-2■-tetrazolium 5-(furan-2-yl)-2,3-diphenyl-2H
-tetrazolium 5-(thiophen-2-yl)-2,3-diphenyl-
2■-Tetrazolium 2.3-diphenyl-5-(pyrid-4-yl)-2 Totitrazolium 2.3-diphenyl-5-(quinol-2-yl)-2
H-tetrazolium 2,3-diphenyl-5-(benzoxazole-2-
yl)-2-tetrazolium 2.3.5-)(p
-ethylphenyl)-28-tetrazolium2.3.5-tri(p-allylphenyl)-2daytetrazolium2.3.5-tri(p-hydroxyethyloxyethoxyphenyl)-2H-tetrazolium (II-93) 2.3.5-)Su(p-dodecylphenyl)-2H-tetrazolium (III-94) 2,3.5-)Su(p-benzylphenyl)-2H-tetrazolium The above general formula (fit-b) Examples of the anion represented by X- in 11l-c) include halogen ions, such as Cl-.

The tetrazolium compounds used in the present invention can be used alone or in combination of two or more 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 present invention, it is added to a non-photosensitive hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a non-photosensitive hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable W1-containing solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and used in an overcoating method or the like. It may be incorporated into the light-sensitive material by directly coating the outermost layer on the side of the silver halide emulsion layer.

Further, the tetrazolium compound according to the present invention has an amount of 1X10 per 111 moles of halogen contained in the photosensitive material of the present invention.
It is preferred to use a range from -' mol to 1O mol, in particular from 2X10-' mol to 2X10-' mol.

(Hereinafter, blank space) In the present invention, on one side of the support, the average particle size is 0.
．． An emulsion layer of photosensitive silver halide grains of 05/7 to 0.3μ is provided.

In the case of spherical particles, the average particle size refers to the diameter thereof, and in the case of particles having a shape other than spherical, the average particle diameter refers to the diameter when the projected image is converted into a circular image of the same area.

It is preferable that 60% or more of the total number of particles have a particle size within ±10% of the average particle size.

The silver halide emulsion (hereinafter referred to as silver halide emulsion or simply emulsion) used in the present invention includes silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, Any silver halide emulsion used in ordinary silver halide emulsions such as silver halide and silver chloride can be used, but preferably silver chlorobromide containing 60 mol% or more of silver chloride as a negative silver halide emulsion, and silver chloride containing 60 mol% or more of silver chloride, Type silver halide emulsions include silver chlorobromide, silver bromide, and silver iodobromide containing 60 mol % or more of silver bromide.

Silver halide grains used in silver halide emulsions contain cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt ( Metal ions can be added using at least one selected from iron salts (complex salts containing) and iron salts (complex salts containing iron salts) to contain these metal elements inside the particles and/or on the particle surfaces. In particular, water-soluble rhodium Preferably, it contains salt. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. When adding a water-soluble rhodium salt, the amount added is lXl0-'~1xl0-4 mol/Ag
Preferably it is X1 mole.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It may be something with

As the silver halide emulsion, two or more types of silver halide emulsions formed separately may be mixed and used.

Silver halide emulsions are used, for example, in British Patent Box 618,061.
No. 1,315,755, No. 1,396.696, Japanese Patent Publication No. 15748/1974, U.S. Patent No. 1,574,
No. 944, No. 1,623゜499, No. 1,673.5
No. 22, No. 2,278,947, No. 2゜399.08
No. 3, No. 2,410,689, No. 2,419,974
No. 2,448,060, No. 2,487,850, No. 2,518,698, No. 2,521,926,
No. 2,642,361, No. 2,694゜637, No. 2,728.668, No. 2,739,060, No. 2
゜743.182, 2.743.183, 2,
No. 983.609, No. 2,983,610, No. 3.0
No. 21,215, No. 3,026.203, No. 3,29
No. 7,446, No. 3,297,447, No. 3,361
No. 564, No. 3,411,914, No. 3, 554
, No. 757, No. 3゜565.631, No. 3,565
．． No. 633, No. 3,591,385, No. 3,656.
No. 955, No. 3,761,267, No. 3,772.0
No. 31, No. 3,857.711, No. 3,891,44
No. 6, No. 3,901714, No. 3,904,415, No. 3,930.867, No. 3984.249,
No. 4,054.451, No. 4,067.740, Research Disclosure
Closure) No. 12008, No. 13452, No. 13654, The Theory of the Photographic Process (written by T, H, Ja+ses)
Theory of the Photographer
aphicProcess, 4th, Ed, Ma
It is preferable to carry out sensitization using a chemical sensitizer or sensitization method described in Cmillan, 1977) I) P67-76.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. A supersensitizer that enhances the sensitizing effect of the enhancing dye may be included in the emulsion.

The silver halide emulsion used in the present invention may be used during chemical ripening or at the end of chemical ripening for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to maintain stable photographic performance. and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers may be added.

Furthermore, all the hydrophilic colloid layers of the photosensitive material used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, and antistaining agents, as necessary. agent, pH adjuster, antioxidant,
Antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, and the like can be used within the range that does not impair the effects of the present invention.

Filter dyes or dyes used for irradiation prevention and other purposes include oxanol dyes,
Contains myoxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among these, oxanol dyes, hemioxanol dyes, and merocyanine dyes are useful.

In particular, it is suitable to use these dyes in light-sensitive materials that have a sensitivity to 400 nm light of 3.
It is particularly preferable to use it so that the sensitivity to 60n- light is 30 times or more.

Specific examples of the dyes used are West German Patent No. 616.007, British Patent No. 584,609, German Patent No. 1,177.429,
Special Publication No. 26-7777, No. 39-22069, No. 5
No. 4-38129, JP-A-48-85130, JP-A No. 49
-99620, 49-114420, 49-1
No. 29537, No. 50-28827, No. 52-108
No. 115, No. 57-185038, U.S. Patent No. 1,8
No. 78,961, No. 1゜884.035, No. 1,91
No. 2,797, No. 2,098,891, No. 2,150
, No. 695, No. 2,214.182, No. 2,298.
No. 731, No. 2,409,612, No. 2,461,4
No. 84, No. 2,527゜583, No. 2,533,47
No. 2, No. 2.865.752, No. 2.956.879
No. 3,094,438, No. 3.125.448, No. 3.148.187, No. 3.177, 078,
3,247.127, 3,260.601, 3.282.699, 3,409゜433, 3
, 540.887, 3,575.704, 3゜653.905, 3,718.472, 3,8
No. 65.817, No. 4,070,352, No. 4,07
1.312, PB Report No. 74175, each specification, Photographic Abstract (Photo, Ab
str, ll 28 ('21), etc.

It is also possible to use a technique in which a polymer latex is contained in a silver halide emulsion layer or a backing layer to improve dimensional stability.

Gelatin is used as a binder for the photosensitive material used in the present invention, but gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, #M derivatives, cellulose derivatives, single or copolymers may also be used. Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as these can also be used in combination.

The support used in the photosensitive material of the present invention includes an α-olefin polymer (for example, polyethylene/butene copolymer).
Flexible reflective supports such as paper laminated with synthetic paper, etc.
Includes films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, metals, etc. It will be done.

Among them, polyethylene terephthalate is particularly preferred.

As the undercoat layer that can be used in the present invention,
9-3972, etc., undercoating layer in an aqueous solvent system containing polyhydroxybenzenes, JP-A-49-11
No. 118, No. 52-104913, No. 59-1994
No. 1, No. 59-19940, No. 59-18945,
No. 51-112326, No. 51-117617, No. 51-58469, No. 51-114120, No. 51
-121323, 51-123129, 51-
No. 114121, No. 52-139320, No. 52-6
No. 5422, No. 52-109923, No. 52-119
No. 919, No. 55-65949, No. 57-12833
Examples include water-based latex subbing layers described in Japanese Patent Publications No. 2 and No. 59-18945.

Furthermore, when carrying out the present invention, Japanese Patent Application Laid-Open No. 61-26041
The positive l of the polarograph described in the issue etc.! It is also possible to use an organic quenching agent in which the sum of Fl potential and cathode potential is positive.

The light-sensitive material of the present invention can be exposed using electromagnetic waves having a spectrum gradient to which the emulsion layer constituting the 400-450n+* light-sensitive material has sensitivity.

The present invention is applicable to photosensitive materials for printing which require extremely high dimensional stability before and after processing, especially when handled in a bright room (a substantially bright room such as a tactile light lamp or a white fluorescent lamp that cuts ultraviolet light). Particularly remarkable effects can be obtained when applied to photosensitive materials that can be used.

Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following.

IO-(CI-C1l) Typical n-OH type developing agents include hydroquinone, as well as catechol, hyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2.3- dibromohydroquinone, 2,5-diethylhydroquinone, catechol,
4-chlorocatechol, 4-phenylcatechol, 3
-methoxy-catechol, 4-acetyl-pyrogallol, sodium ascorbate, and the like.

, HO-(CH-CM) n-NHx type developers are typically ortho- and para-aminophenols, and others such as 4-aminophenol, 2-amino-
6-phenylphenol, 2-amino-4-chloro-6
-phenylphenol, N-methyl-p-aminophenol, etc.

Further, HtN-(CH-CIl)n-NHx type developers include, for example, 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-( Examples include 4-amino-3-methylphenyl)-morpholine and p-phenylenediamine.

Examples of the heterocyclic visual developer include 3-pyrazolidone such as 1-phenyl, 3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. pyrazolidones,
Examples include 1-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ry of The Photographic Pro
cess Fourth Edl Lion) No. 291
~334 pages and Journal of the American Chemical Society
+5erlcan Chemical 5ociety
), Vol. 73, No. 3, 100 Kai (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 diminished. As a preservative, hydroxylamine or a hydrazide compound can be used, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g per 12 of the developer.

Further, the developer may contain glycols as an organic solvent, and examples of such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 19.4-butanediol, and 1.5-bentanediol. etc., but diethylene glycol is preferably used. The preferred amount of these glycols used is 5 to 500 per li of the developer.
g, more preferably 20 to 200 g. These organic solvents can be used alone or in combination.

By developing the silver halide photographic light-sensitive material according to the present invention using a developer containing a development inhibitor, an extremely excellent light-sensitive material can be obtained.

The silver halide photographic material according to the present invention can be processed under various conditions. As for the processing temperature, for example, the development temperature is preferably 50°C or lower, particularly preferably around 25°C to 45°C, and the developing time is 9 to 50 seconds, but ultra-quick processing of less than 20 seconds, for example 19 seconds or less, is preferable. It is effective even if it is done.

Furthermore, it is optional to employ processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate.

Further, the present invention exhibits its advantages to a great extent even when ultra-quick processing with a processing time of 20 to 60 seconds is applied.

In this specification, ultra-quick processing means that the leading edge of the film is inserted into an automatic developing machine, passes through a developing tank, a transition area, a fixing tank, a transition area, a washing tank, a transition area, and a drying area. The total time it takes for the product to emerge from the drying section (in other words, the quotient of the total length of the processing line divided by the line conveyance speed is
This refers to a process that lasts from 20 seconds to 60 seconds.The reason why the transition period should be included here is that it is well known in the industry that even in the transition period, the liquid from the previous process is absorbed into the gelatin film. This is because it can be considered that the treatment process is actually progressing because the inside of the container is swollen.

〔Example〕

Specific examples of the present invention will be described below. However, the present invention is not limited to the same extent by this.

Example 1 (1) Preparation of emulsion A silver nitrate aqueous solution and a sodium chloride aqueous solution containing a rhodium trichloride complex were simultaneously mixed in a gelatin solution, and 4-hydroxy-6-methyl-1,3°38-7 was added as a stabilizer. −
After adding citrazaindene, the mixture was desalted in a conventional manner, and gelatin was added again and dispersed to obtain a conventional silver halide emulsion (hereinafter simply referred to as an emulsion). The rhodium content in this emulsion is 1.2XIO-'mol/A
g1 mole.

5-methylbenzotriazole, sodium dodecylbenzenesulfonate, saponin, polymer latex, and styrene-sodium maleate copolymer as a thickener were added to this emulsion to obtain a coating liquid (A).

Further, the following compound (a), (bL gallic acid propyl ester, matting agent (amorphous silica) dispersed in an aqueous solution of compound (b), and citric acid were added to the gelatin aqueous solution to form a protective film coating solution (B). was prepared.

Tetrazolium compound (C) and compounds (1) and (n-13 of the present invention) were added to emulsion coating solution (A) as shown in Table 1 to prepare emulsion coating solutions A-1 to A-4. .

Table 1 In addition, compounds of the present invention [■], (n
) as shown in Table 2 to protect II! i! Coating liquid B
-1-B-4 was prepared.

Table 2 The amount added per unit area at the time of application is A-1.
~A-4 was added in the same amount as A-4.

Emulsion coating solutions A-1 to A-4 and protective film coating solution B-1-8-
Samples S-1 to S-5-16 were prepared by simultaneously coating and drying the samples S-1 to S-5-16 in combinations shown in Table 3. At this time, the amount of coated silver was 3.9g/■3. The amount of applied gelatin is 2゜5g/+
It was "s".

These samples were placed in close contact with the emulsion side of the film and the original, as shown in Figure 1 (in the figure, 1 is a PE film with a thickness of 100μ).
The film was exposed using Dainippon Screen's Akishiro printer P-627FM as shown in (T base). This was carried out using a developer (Part 1) and a fixer (Part 1) with the following formulations, and an automatic developing machine as shown in Figure 2 (in the figure, 5 is a developer tank, 6 is a fixer tank, 7 is a fixer tank, and 7 is a developer tank). is a washing tank, 8 is a squeeze roller,
9 is a drying section) under the following processing conditions.

The evaluation is that the area of 48% of the halftone dots in the manuscript is 1:1 (5
2%) was evaluated using a 100x louver. Note that the line width of the positive image in the blank text original is 105μ. A halftone dot densitometer DT-101 manufactured by Dainippon Screen Co., Ltd. was used to measure the halftone dots.

Each sample was also exposed through a glass wedge using the same printer and processed under similar conditions using a Konica densitometer PDA-65.
T was measured using

[Developer prescription (Part 1)] (Composition A) Pure water (ion-exchanged water) 150ml 1 g Diethylene glycol 50g Potassium sulfite (55% aqueous solution) 100mj! Potassium carbonate 50g Hydroquinone 1585o methylbenztriazole 200mg, -Phenyl-5-mercaptotetrazole 0g Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5g (composition) Pure Water (ion-exchanged water) 3ml! Diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25s + g acetic acid (90%
Aqueous solution) 0.3-1 5-nitroindazole 110mg1
-Phenyl-3-pyrazolidone 500mg When using developer, 50011i of water! , the above composition A in
Dissolve composition B in order, II! , and used it.

[Fixer formulation (Part 1)] (Composition A) Ammonium thiosulfate (72.5%-/V aqueous solution) 30
ml Sodium sulfite 9.5g Sodium acetate trihydrate 15.9g Boric acid
6.7g, sodium citrate dihydrate 2g acetic acid (90%-/-aqueous solution)8. (Composition) Pure water (ion-exchanged water) 17 mA sulfuric acid (50% - aqueous solution) 5.8 g aluminum sulfate (Aj!*Aqueous solution with an Os conversion content of 8.1%) 26
．． When using 5 g of fixer, the above composition A was dissolved in 500 ml of water in the order of composition A and composition 12 was used. The pn of this fixer was about 4.3.

[Processing conditions (Part 1)] Development: 35°C, 15 seconds fixation, 35°C, 15 seconds washing, drying at room temperature, 10 seconds.
45°C 9 seconds Dry to Dry 49 seconds Runsbee F 2433+ms/a+in Each process also includes so-called workpiece conveyance time.

Compound (a) Compound (b) CH Coo (CHz) wcHs Tetrazolium compound (c) From the results in Table 3, compound [! ] and/or (II), it can be seen that the inside of blank characters is significantly improved. Moreover, from the comparison of S-2 to 4 and S-5 to 16, the compound (
It can be seen that it is more effective to contain 1) and/or (If-13 in the emulsion layer).

Example 2 The same procedure as in Example 1 was carried out except that the self-developing mode was changed to GR-27 manufactured by Konica Corporation and the development was carried out at 28°C for 30 seconds, and the same results as in Example 1 were obtained. Obtained.

Example 3 Emulsion coating solution (A) of Example 1 except that chemical sensitization was not performed.
An emulsion coating solution (C) was prepared in the same manner as above. Then, a hydrazine compound (d) was added to the emulsion coating solution (C) (the amount was 3.
5 Xl0-' mol/Ag 1 mol) and 1-phenyl-
A UV absorber is added to 5-mercaptotetrazole and the compound [I] and/or (n-1) of the present invention.
were added as shown in Table 4 to prepare emulsion coating solutions C1 to C4.

Table 4 In addition, the protective film has the protection l! of Example 1! Coating liquid B-1 to B-
Samples T-1 to T-16 as shown in Table 5 were prepared using T-4.

The processing was carried out under the following conditions (Part 2) using the developer shown below (Part 2) and the fixer shown in Example 1 (Part 1). Further, the same automatic developing machine as in Example 1 was used. The evaluation was also the same as in Example 1. The results are shown in Table-5.

[Developer prescription (part 2)] Hydroquinone 45.0g N-methyl p-aminophenol 1/2 sulfate 0.8g, sodium hydroxide 15.0g potassium hydroxide 55.0g5, sulfosalicylic acid 45.0g boric acid
35.0g potassium sulfite
110.0g Ethylenediaminetetraacetic acid disodium salt 1.0g Potassium bromide 6.0g 5-methylbenzotriazole 0.6gn-Butyl jetanolamine 15.0g Add water
1N (pH-11,6) Hydrazine compound (d) [Processing conditions (Part 2)] Development 38' CI 5 seconds fixation 35°C 15 seconds Washing at room temperature 9 seconds (Less than margin) Add hydrazine as shown in Table 5. It can be seen that even in the films to which the compound (1) and [■] were added, the reproducibility in blank characters was excellent.

Also, from the comparison between T-2~4 and T-5~■6, the compound [
I] and/or (n) are found to be more effective when added to the emulsion layer.

Example 4 In Example 3, an experiment was conducted in exactly the same manner as in Example 3, except that the automatic developing machine was changed to FC-660F manufactured by Fuji Photo Film Co., Ltd., and the developing temperature was 38° C. for 20 seconds. The same results as in Example 3 were obtained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a document for evaluating blank characters, and FIG. 2 is an explanatory diagram of an automatic developing machine. 5...Developer tank, 6...Fixer tank, 7...Washing tank, 8
... Squeeze roller, 9... Drying section. Patent applicant Konica Corporation

Claims (3)

[Claims] (1) At least one photosensitive silver halide emulsion layer is provided on a support, and developed to give γ (density 0.3 to 3.
0) is 6 or more, in which at least one hydrophilic colloid layer on the side of the photosensitive silver halide emulsion layer contains a compound selected from the following groups [I] and [II]. A silver halide photographic material containing at least one selected from the group consisting of at least one selected from the group consisting of: [I] [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ However, X: hydrogen atom, alkali metal, aryl group (including those with substituents), alkyl group (including those with substituents), thioether group, sulfone group, or carboxyl group (2) In the silver halide photographic light-sensitive material according to claim 1, at least one of the hydrophilic colloid layers on the side containing at least one selected from the group of compounds [I] and [II] containing a tetrazolium compound. (3) In the silver halide photographic light-sensitive material according to claim 1, at least one of the hydrophilic colloid layers on the side containing at least one selected from the group of compounds [I] and [II]. containing hydrazine compounds.