JPS63306436A - Negative type silver halide photographic sensitive material handleable in daylight room and having satisfactory return characteristic - Google Patents

Abstract

PURPOSE:To enable handling in a daylight room and to obtain satisfactory return characteristics by forming at least one of silver halide emulsion layers with a specified emulsion and incorporating a desensitizing dye and org. polymer latex into at least one of hydrophilic colloidal layers. CONSTITUTION:At least one of silver halide emulsion layers is formed with an emulsion contg. silver halide particles of <=0.095mum average particle size, having >=50mol.% silver chloride content and further contg. a rhodium salt by 10<-4>-10<-8>mol. per 1mol. silver halide. At least one of hydrophilic colloidal layers adjacent to the emulsion layers is formed with an emulsion contg. a desensitizing dye and org. polymer latex. Handling in a daylight room is enabled and the quality of white-on-black letters related to return characteristics is improved.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a negative-working silver halide photographic light-sensitive material, and in particular a material that can be handled in an environment that can be called a bright room and has good return characteristics. This invention relates to the resulting silver halide photographic material.

[Background of the invention]

In recent years, in order to save labor, rationalize, and improve the working environment in the printing and plate-making field, there has been a demand for technology that allows film making, or the so-called turning process, which was traditionally done in a dark room, to be carried out in a bright room. , improvements have been made to photosensitive materials and equipment such as printers.

Such photosensitive 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.

These silver halide photographic materials have a molecular weight of 100 to 300
It can be handled under a bright general fluorescent light called Lux or a special fluorescent light with a low amount of ultraviolet rays.

As a method for producing silver halide photosensitive materials that can be handled in a bright room, a method is known in which rhodium salts or bismuth salts are added as inorganic desensitizers to emulsions mainly composed of silver chloride (for example, in Japanese Patent Application Laid-Open No. 56-125734). Furthermore, a method of adding an organic desensitizer to an emulsion containing silver chloride as a main component is well known (for example, in the case of photographic science and engineering).
ic 5science & Engineering),
Vol 1B, N115 (1974) P475~4
85, Japanese Patent Publication No. 45-17273). Further 0.1~
A method is known in which an inorganic desensitizer and an organic desensitizer are used in combination in an emulsion that is mainly composed of silver chloride with an average grain size of 0.3 μm and is not subjected to chemical ripening (for example, Japanese Patent Application Laid-open No. 59-157633
Publication No.).

However, such conventional photosensitive materials that can be handled in a bright room have a lower processing speed compared to photosensitive materials that can be handled in a dark room.
It is known that the following performance is inferior. In other words, the line drawing performance (cutting character performance) is poor when a halftone image and a line image are overlapped and exposed as a return original, and when a line drawing original or a halftone original is pasted and fixed on the base with transparent plate-making tape. However, there was a problem in that this tape left a mark (adhered tape mark), impairing the finished image quality, and improvements in this respect were desired.

[Purpose of the invention]

The purpose of the present invention is to enable handling in a bright room and to provide good performance.
In particular, it is an object of the present invention to provide a negative silver halide photographic light-sensitive material which has good photographic performance in terms of cut-out character quality in return characteristics and which does not leave any traces of tape pasting.

[Structure of the invention]

The above object is to provide a negative silver halide photographic material comprising at least one silver halide emulsion layer coated on a support, in which at least one of the silver halide emulsion layers has an average grain size of 0. Formed from an emulsion containing silver halide grains of .095 μm or less, a silver chloride content of 50 mol% or more, and containing 10-4 to 10-'' mol of rhodium salt per mol of silver halide, and is formed from an emulsion containing a desensitizing dye and an organic polymer latex in at least II'I of this emulsion layer and/or a hydrophilic colloid layer that can be provided adjacent to this emulsion layer, and this emulsion layer and/or Alternatively, this can be achieved by a negative-working silver halide photographic material characterized in that at least one hydrophilic colloid layer that can be provided adjacent to this emulsion layer contains a desensitizing dye and an organic polymer latex.

In other words, the negative-working silver halide photographic light-sensitive material having the above structure can be handled in a bright room, and has good photographic properties such as good cutout character quality and no tape pasting marks. .

Such effects are greatly enhanced by containing at least one type of tetrazolium compound in the silver halide emulsion layer used in the negative-working silver halide photographic light-sensitive material.

The hydrophilic colloid layer that can be provided adjacent to the emulsion layer is formed as necessary, and may be a negative silver halide photographic emulsion layer or a non-photosensitive layer. It's okay. Examples of the non-photosensitive layer include a base layer, an intermediate layer, and a protective layer.

The invention will be explained in more detail below.

The composition of the silver halide used in the emulsion for forming at least one layer of the negative silver halide photographic material of the present invention contains at least 50 mol % of silver chloride. In particular, the composition is preferably silver chloride or silver chlorobromide. In addition, the emulsion has an average grain size of 0.095 μm.
It is essential to contain the following silver halide.

These are so-called Lippmann type silver halide grains. Various methods are known for producing such ultrafine silver halide grains, and any method may be used, but it is more preferable to maintain the silver potential at a constant value near the value where the grain solubility is the lowest, for example, 120 mV or more. One example is the so-called function addition control double jet method in which the supply amount of silver nitrate and halide is varied in proportion to the growth speed of silver halide grains produced in a reaction vessel at a relatively low temperature while maintaining the voltage at 210 mV. Further, the pH in the reactor during silver halide production may be any pH, but an acidic method with a pH of 1 to 4 is more preferred. Further, silver halide particles such as nucleic acid decomposition products such as adenine, benzyladenine, adenosine, tetrazaindene compounds, or mercapto compounds are adsorbed in the reaction vessel to reduce the solubility of the silver halide particles. The method of preparation is also a preferred embodiment for particle formation according to the present invention.

In this specification, the grain size of silver halide grains is conveniently expressed in terms of the size of cubic grains having the same volume.

The above emulsion has lo-4 to l0 per mole of silver halide.
- Contains 8 moles of rhodium salt.

In order to contain a rhodium salt in the emulsion, various rhodium salts may be added. For example, as the water-soluble rhodium salt used in the present invention, any conventionally known water-soluble rhodium salt may be used, and representative (Na3RhlJ6), (Kz
RbBr, :l, rhodium chloride ammine complex, rhodium trichloride, etc. are used.

The amount of rhodium salt to be contained is 10-4 to 10-8 mol per mol of silver halide, but more preferably 1
It is 0-5 to 10-7 mol.

The water-soluble rhodium salt used is generally particularly preferably used during the production of silver halide, but it can also be used at any time thereafter, or it can be used in portions.

In addition to being contained in the above-mentioned emulsion, rhodium salts can also be contained in layers other than the emulsion layer formed by this emulsion, for example, in any hydrophilic colloid layer that is involved in coating the silver halide emulsion layer. Alternatively, it may be divided and added to two or more layers.

Furthermore, when using rhodium salts, other inorganic compounds such as iridium salts, platinum salts, thallium salts, cobalt salts, gold salts, etc. may be used in combination.

The monodispersity of the silver halide grains in the emulsion is arbitrary, but gA is preferably made to be 5 to 60, more preferably 8 to 30.

Here, the monodispersity is expressed as a value obtained by dividing the standard deviation of the particle size defined above by the average particle size, multiplied by 100.

As the silver halide in the emulsion, grains having a multilayer structure of at least two layers can be used.

For example, the core part is silver chloride and the shell part is silver bromide,
Conversely, silver chlorobromide particles having a core portion of silver bromide and a shell portion of silver chloride can be used. In either case, it is essential that the silver chloride content in the emulsion is 50 mol% or more. In this case, any layer may contain iodine, but each layer preferably contains iodine in an amount of 5 mol % or less.

The light-sensitive material of the present invention includes an emulsion layer formed from an emulsion having the above-mentioned average grain size and silver chloride content and containing a rhodium salt, and/or a hydrophilic colloid layer that can be provided adjacent to this emulsion layer. At least one layer contains a desensitizing dye and an organic polymer latex.

That is, in the present invention, a hydrophilic colloid layer may be formed adjacent to the emulsion layer (or may be adjacent via another layer) if necessary, but the emulsion layer and/or this hydrophilic colloid layer At least one of the sexual colloid layers contains a desensitizing dye and an organic polymer latex.

The organic polymer latex is generally an aqueous solution of a compound having the effect of stabilizing the surface of the hydrophobic vinyl-coated particles, with a water-soluble layer serving as a continuous layer and a dispersion layer serving as a dispersion layer. As the raw material monomer constituting the hydrophobic vinyl addition polymer, any monomer known in the art may be used, and various monomers may be used alone or synthesized in any combination. A preferred general formula of the raw material monomer is the following (I-1).

(1-2), (I-3), and (I-4).

(wherein R is hydrogen, halogen, or vinyl, and R
, is an ethene type monomer having hydrogen, halogen, alkoxy group or methyl or cyano group when R is hydrogen, specific examples being isoprene, chlorobrene, 1,3-butadiene, propene nitrile,
Vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, ethylene, propylene, etc. (I-2) (wherein Rz is hydrogen or methyl, and R3, R4 and R6 are hydrogen or 1 to 5 is a lower anoC-kyl group having 4 carbon atoms, R1 together with hydrogen or R4 forms the atomic group necessary to complete the fused benzene ring, and Rs
and one of R6 is halomethyl), specific examples are styrene, 0-vinyltoluene, p-vinyltoluene, p-chloromethylstyrene, m-chloromethylstyrene, α-methylstyrene, 2 - ethylstyrene, 4-butylstyrene, 4-pentylstyrene, 2-vinylmethylstyrene and 1-vinylnaphthalene, (I-3) (wherein R6 is hydrogen or has 1 to 5 carbon atoms) is a lower alkyl group, R8 is hydrogen, chlorine or a lower alkyl group having 1 to 5 carbon atoms, R9
is an alkyl or halogenalkyl group having from 1 to 20 carbon atoms), in a preferred form R1 is hydrogen and R, is hydrogen or methyl; is formed from acrylic acid or methacrylic acid, in such preferred forms the ester has 1 to 5 carbon atoms, in such preferred forms R9 has 1 to 5 carbon atoms, preferred 2-alkenoic acid esters is an acrylic or methacrylic acid lower alkyl ester, such as acrylic or methacrylic acid methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl ester, etc., and other as specifically indicated. It is also possible to use 2-alkenoic acid esters, and in addition to acrylic acid or methacrylic acid esters, α-ethyl acrylic acid, α-propylacrylic acid, α-propylacrylic acid,
α-Butylacrylic acid, α-Pentylacrylic acid, 2-
Butanoic acid, 2-methyl-2-butanoic acid, 2-hexanoic acid, 2-octanoic acid, 2-methyl-2-octanoic acid ester can also be used, and in addition to lower alkyl esters, hexyl, heptyl, octyl, Undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl esters and branched isomers of the above-mentioned 2-alkanoic acids can be used, (wherein RIG is hydrogen or a methyl group, R8 is hydrogen or Alkenoic acid type monomers, which are lower alkyl groups having 1 to 5 carbon atoms, examples of which include acrylic acid, methacrylic acid, etc.).

The organic polymer latex used in the present invention preferably has an average particle size of 0.01 to 1 μm. Further, since the organic polymer latex used in the present invention is not intended for modifying the physical properties of silver halide photographic materials, it may have any glass transition temperature.

The organic polymer latex used in the present invention can be synthesized using various commonly known methods. The most typical method is the method. An example of a free radical polymerization method is U.S. Pat.
No. 99, No. 3.033,833, No. 3,574,
No. 899 and Canadian Patent No. 704,778. Specific examples of organic polymer latexes useful in carrying out the present invention are listed below. The numerical values indicate the weight ratios of raw material monomers, and the numerical permutations in parentheses correspond to the monomer permutations.

G-1 Polystyrene (100) G-2 (
styrene)-(butyl acrylate)-(acrylic acid)
Copolymer (60/38.5/1.5) G-3 (butyl acrylate)-(vinylidene chloride) copolymer
(50150)G-4 (butyl acrylate)-
(vinyl acetate) copolymer (50
150) G-5 polybutyl acrylate (100
) G-6 polyethyl acrylate (100) G-7 (butadiene)-(styrene)-(methyl acrylate) copolymer (40150/10) G-8 (ethyl acrylate)-(methacrylic acid) copolymer
(95,6/4.4)G-9 polymethyl methacrylic acid
(100) The desensitizing dye used to achieve the object of the present invention is preferably a compound in which the sum of the polarographic anodic potential and cathodic potential is positive, and such compounds are described in numerous patents and literature. Although any desensitizing dye can be used, in particular, desensitizing dyes represented by the following general formulas (II) to (Vl) can be preferably used.

These compounds are described in U.S. Pat. No. 3,567.456, U.S. Pat.
, No. 615,608, No. 3.598,596, No. 3,
No. 598.955, No. 3,592.653, No. 3.5
No. 82.343, Special Publication No. 40-26751, No. 40-
No. 27332, No. 43-13167, No. 45-883
It can be synthesized with reference to specifications such as No. 3 and No. 47-8746.

General formula (n) l R4R4Xe General formula (I[l) p.

s In the general formulas (II) and (III), R9 is hydrogen, a halogen atom, a cyano group, or a nitro group, and R1 and R2 may form an aromatic ring.

R1 and R4 each represent an alkyl group, a lower alkenyl group, a phenyl group, or a lower hydroxyalkyl group, and R1
and R may be an aryl group when other than a hydrogen atom, n is a positive number of 1 to 4, R1 represents a lower alkyl group or a sulfonated lower alkyl group, and X represents an acid anion.

General formula (IV) In the general formula (IV), R5 and R2 are each a hydrogen atom or a nitro group, R3 and R4 are a lower alkyl group, an allyl group, or a phenyl group, Z is a nitrobenzothiazole nucleus, a nitrobenzoxazole nucleus, Nitrobenzoselenazole core, imidazo[4.5-b]quinoxaline core, 3,
3-dimethyl-3H-pyrrolo[2,3-b]pyridine nucleus, 3,3-dialkyl-3H-nitroindole nucleus, thiazolo[4,5-b]quinoline nucleus, nitroquinoline nucleus,
Atom group necessary to form a nitrothiazole nucleus, a nitronaphthothiazole nucleus, a nitrooxazole nucleus, a nitronaphthoxazole nucleus, a nitrone-jizole nucleus, a nitronaphthoselenazole nucleus or a nitropyridine nucleus, X is an anion, m and n are Each represents 1 or 2. However, when the compound forms an inner salt, n represents 1.

General Formula (V) In General Formula (V), R+, Rz, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a nitro group, and R2 is a hydrogen atom, an alkyl group, or Represents a nitro group, Z is unsubstituted or each lower alkyl group, phenyl group, chenyl group, halogen atom, alkoxy group, hydroxy group, cyano group, alkylsulfonyl group, alkoxycarbonyl group, ponylsulfonyl group, trifluoromethyl group Thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus substituted with
Naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, 3,3-dialkyl-3H-indole nucleus, imidazole nucleus, benzimidazole nucleus or naphthimidazole nucleus represents an atomic group necessary to form, L and L2 each represent an unsubstituted or lower alkyl group or a methine chain substituted with an aryl group, R6 and R7 each represent an unsubstituted or substituted alkyl group, an alkenyl group, an aryl group, a sulfoalkyl group, or an aralkyl group; X represents an anion; m and n each represent 1 or 2; However, when the compound forms an inner salt, n represents 1.

General Formula (Vl) In General Formula (Vl), R and R1 each represent an alkyl group, and R2 represents an aryl group. LI and Lt each represent a methine chain that is unsubstituted or substituted with a lower alkyl group or an aryl group, and 2 is a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Thiazoline nucleus, pyridine nucleus, quinoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, imidazo [4
-5-b] An atomic group necessary to form a quinoxaline nucleus, where X represents an anion, m represents a positive integer of 1 to 3, and n represents a positive integer of 1 to 2.

Next, specific examples of the compounds represented by the above general formulas (n) to (Vl) are shown below. It goes without saying that the present invention is not limited to these compounds. Moreover, in the following exemplified compounds, Pt5e represents para-toluenesulfonic acid anion.

(Exemplary Compounds) CHzcHzOHCH2CHzOH tHs NH Shisushi H3 The amount of desensitizing dye used in the present invention is preferably 1 to 1000, particularly preferably 5 to 1000, per mole of silver halide.
Selected within the range of 300■. The addition time may be at the time of silver halide production, physical ripening, chemical ripening, after ripening, or during preparation of the coating solution.

The silver halide emulsion used in the present invention is a negative silver halide emulsion, not a positive silver halide emulsion. The difference between negative-tone emulsions and positive-tone emulsions is that silver halide grains in the latter have been fogged in advance compared to the former.The effect of the present invention is promoted by chemical ripening, but The ripening may be carried out by any method within the scope of producing the above-mentioned negative emulsion.

urea, allyl isothiocyanate, etc.), selenium sensitizers (N, N-
dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride, ammonium Various noble metal sensitizers represented by chloroparadate, potassium chlorooleate, sodium chloroparadite, etc. 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. Particularly preferred is a sulfur sensitizer, and the preferred amount of the sulfur sensitizer to be used is 15 to 150 cm per mole of halogenated tB.

In the silver halide emulsion layer used in the present invention, for example, JP-A Nos. 52-18317, 53-17719,
Particularly preferable results are obtained by using tetrazolium compounds as shown in Japanese Patent Nos. 3-17720 and 61-149946. For example, the following general formula [■-1], [
These are tetrazolium compounds represented by [■-2] and [■-3].

[■-1] [■-2] [■-3] [In the formula, R, ノ, R7・, Rs, R9, R+z
, R13.

RI4 and RI5 each represent an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group, a phenyl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group) group, methoxyphenyl group, etc.),
naphthyl group (e.g. α-naphthyl group, β-naphthyl group,
hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (e.g. thiazolyl group,
benzothiazolyl group, oxacylyl group, pyrimidinyl group, pyridyl group, etc.), and any of these may be a group that forms a metal chelate or a complex. Rh"-'RIG and RI 1 each represent an allyl group, a phenyl group, a naphthyl group, a heterocyclic group, an alkyl group (for example, a methyl group, an ethyl group, a pyl group, a butyl group, a mercapto group, a mercaptoethyl group, etc.) ), hydroxyl group, alkylphenyl group, alkoxyphenyl group, carboxyl group or its salt, carboxyalkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), amino group (e.g. amino group, ethylamino group, anilino group, etc.), mercapto group , represents a group selected from a nitro group and a hydrogen atom, D represents a divalent aromatic group,
E represents a group selected from an alkylene group, an arylene group, and an aralalkylene group, (e represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1.) Next, specific examples of the cation moiety of the tetrazolium compound used in the present invention will be shown, but the cation moiety of the compound that can be used in the present invention is not necessarily limited to these.

(T-1) 2-(benzothiazol-2-yl)-
3-phenyl-5-dodecyl-2H-tetrazolium (T-1) 2.3-diphenyl-5-(4-t-
octyloxyphenyl)-2H-tetrazolium (T-3) 2.3.5-triphenyl-2H-
Tetrazolium (T-4) 2,3.5-tri(p-carboxyethyl phenyl)-2H-tetrazolium (T-5) 2-(benzothiazol-2-yl)-
3-phenyl-5-(0-chlorphenyl)-2H-tetrazolium (T-6) 2.3-diphenyl-2H-tetrazolium (T-7) 2.3-diphenyl-5-methyl-2
H-tetrazolium (T-8) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium (T-9) 2.3-diphenyl-5-ethyl-2
H-tetrazolium (T-10) 2. 3-Schiff 5---Lou 5-n
-hexyl-2H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-2H-tetrazolium (T-12) 2-(benzothiazol-2-yl)-5-phenyl-3-(4- )Ryl)-2H-tetrazolium (T-13) 2-(benzothiazol-2-yl)-5-(4-chlorophenyl)-3 -(4-nitrophenyl)-2H-tetrazolium (T-14) 5 -ethoxycarbonyl-2,3-
Di(3-nitrophenyl)-2H-tetrazolium (T-15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium (T-16) 2,5-diphenyl-3-(p −
triyl)-2H-tetrazolium (T-17) 2,5-diphenyl-3-(p
-iodophenyl)-2H-tetrazolium (T-18) 2,3-diphenyl-5-(p-
diphenyl)-2H-tetrazolium (T-19) 5-(P-bromophenyl)-2
= phenyl-3-(2,4,6-dolychlorophenyl)-2H-tetrazolium (T-20) 3-(p-hydroxyphenyl)-5-(p-nitrophenyl)-2-phenyl-2H- Tetrazolium (T-21) 5- (3,4-dimethoxyphenyl)-3-(2-ethoxyphenyl)-2-(4-
methoxyphenyl)-2H-tetrazolium (T-22) 5-(4-cyanophenyl)-2
゜3-diphenyl-2H-tetrazolium (T-23) 3-(p-acetamidophenyl)-2,5-diphenyl-2H-tetrazolium (T-24) 5-acetyl-2,3-diphenyl-2H-tetrazolium ( T-25) 5-(fluor-2yl)-2,3-diphenyl-2H-tetrazolium (T-26) 5-(cheno-2yl)-2,3-
Diphenyl-2H-tetrazolium (T-27) 2.3-diphenyl-5-(pyrid-4yl)-2H-tetrazolium (T-28) 2.3-diphenyl-5-(quinol-2yl)-2H- Tetrazolium (T-29) 2.3-diphenyl-5-(benzoxazol-2yl)-2H-tetrazolium (T-30) 2.3-diphenyl-5-nitro-2H-tetrazolium (T-31) 2. 2',3.3'-tetraphenyl-5,5'-1,4-butylene-di(2H-tetrazolium) (T-32) 2.2',3.3'-tetraphenyl-5,5' -p-phenylene-di(2H-tetrazolium) (T-33) 2-(4,5-dimethylthiazol-2yl)-3,5-diphenyl- 2H-tetrazolium (T-34) 3,5-diphenyl- 2-(triazin-2yl-2H-tetrazolium (T-35) 2-(benzothiazol-2yl)
-3-(4-methoxyphenyl)-5-phenyl-2H-tetrazolium (T-36) 2.3-dimethoxyphenyl-5
-Phenyl-2H-tetrazolium (T-37) 2.3.5-) Lis(methoxyphenyl)-2H-tetrazolium (T-38) 2.3-dimethylphenyl-5-
Phenyl-2H-tetrazolium (T-39) 2.3-hydroxyethyl-5-phenyl-2H-tetrazolium (T-40) 2.3-hydroxymethyl-5-phenyl-2H-tetrazolium (T-41) 2. 3-cyanohydroxyphenyl-5-phenyl-2H-tetrazolium (T-42) 2.3-di(p-chlorophenyl)-
5-phenyl-2H-tetrazolium (T-43) 2.3-di(hydroxyethoxyphenyl)-5-phenyl-2H- tetrazolium (T-44) 2.3-di(2-pyridyl)- 5-phenyl-2H-tetrazolium (T-45) 2.3.5-tris(2-pyridyl)-2H-tetrazolium (T-46) 2,3.5-)lis(4-pyridyl)-2H-tetrazolium When a tetrazolium compound is used as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation moiety and an anion moiety is used.

Examples of the anion moiety of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid, and perchloric acid, sulfonic acid,
Acid groups of organic acids such as carboxylic acids, lower alkylbenzenesulfonic acid anions such as p-)toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfate esters such as lauryl sulfate anions. anion, dialkylsulfosuccinate anion such as di-2-ethylhexylsulfosuccinate anion, polyether alcohol sulfate ester anion such as cetyl polyethenoxysulfate anion, higher fatty acid anion such as stearate anion, polyacrylate anion Examples include polymers with acid groups attached.

By appropriately selecting the anion moiety and the cation moiety, the non-diffusible tetrazolium compound according to the present invention can be synthesized. The compounds according to the present invention synthesized in this way include, for example, 2°3.5-triphenyl-2H-tetrazolium-dioctylsuccinate sulfonate, and these are as described in detail in the examples below, respectively. In some cases, a soluble salt of the oxidizing agent is dispersed in gelatin, and then the two are mixed and dispersed in the gelatin matrix. In other cases, crystals of the oxidizing agent are synthesized pure and then dissolved in a suitable solvent (e.g. dimethyl sulfoxide). may be dispersed in a gelatin matrix. If it is difficult to achieve uniform dispersion, emulsification and dispersion using an appropriate homogenizer such as ultrasonic waves or a Manton-Gorlin homogenizer may give good results. It is also possible to microdisperse it in a high boiling point solvent such as dioctyl phthalate, protect it, and then disperse it in a hydrophilic colloid layer.

The light source for exposing the silver halide photographic light-sensitive material of the present invention is preferably a light source having a maximum specific energy in the range of 390 to 430 nm, and any light source that meets this condition may be used, with or without a filament, or with or without a filament. The presence or absence of electric bridges is not limited, and the luminescent gas contained in the luminescent electrode tube may also be a halogen gas, a rare gas, or a mixture. Further, a light-emitting metal may be contained at the same time as the gas.

In general, preferred light sources suitable for this purpose include ultra-high pressure mercury lamps, metal halide lamps, and an electrodeless discharge tube with a bulb-type emission spectrum described later. This type of luminescent discharge tube is available from Fusion and other light source manufacturers, and is specifically described in U.S. Pat.
No. 3,993.379, No. 3,950゜670, No. 3,873.884, No. 3,790.852,
3゜787.705, 3,786.308, 3,645.629, 4,536,675, 4
, No. 422,017, No. 4,415.838, No. 4,
No. 390.813, No. 4,383.203, No. 4,3
59゜668, 3,911,318, 3,87
No. 2,349, No. 3983.039, No. 4,042
, No. 850, No. 4,208.587, No. 4,313,
No. 969, No. 4,269,581, and the like.

In addition, in order to obtain the above-mentioned sphere-type emission spectrum, a 390 nm
Absorption filter that cuts short waves of 430nm or less
It is also possible to obtain the effects of the present invention by installing a device that may or may not cut the long waves above. This filter can be attached by using absorption filter glass for the glass plate near the light source or above the printer (<the glass plate shown in the diagram v, z). Examples of this filter include Dialite P-1001 manufactured by Mitsubishi Rayon Co., Ltd. and Dialite A manufactured by Mitsubishi Rayon Co., Ltd.
R-1001, FR100I, Acrylite 549
, Eastman Kodak Color Printing Nα
Commercially available products such as 2B, PE11400 manufactured by Sumitomo Bakelite Co., Ltd., and -1505 manufactured by Toyobo Co., Ltd. can be used.

Various dyes can be used in the silver halide photosensitive material of the present invention. As a dye, for example, the following general formula [■
There are compounds represented by -a], [■-b], [■-C] and [■-d].

In the general formula [■-a], there is an atomic group Represents a good alkyl group or its sodium/potassium salt, R1″ and R1″ are hydrogen atoms,
represents a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the above 10X group, and Q represents at least one halogen atom, a carboxy group, a sulfo group, a sulfoalkyl group, or L represents a phenyl group, a sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group substituted with a sodium/potassium salt, and L represents an optionally substituted methine group. R4// is an alkyl group, a carboxy group,
0m representing an alkyloxycarbonyl group or an acyl-substituted or unsubstituted amino group represents an integer of 1 or 2, and n represents an integer of 0 or 1, respectively.

General formula [■-b] In the formula, R5" * R6", Rs, R"' and RIG
represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group, a sulfone group, or a sodium or potassium salt thereof, and R? represents an alkyl group or a carboxyl group.

General formula [■-C] In the formula, R0'' and R,;r represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R13' and R3:' are a sulfonic acid group or a carboxyl group. It represents a substituted alkyl group, a sulfonic acid group, a carboxyl group, an aryl group substituted with a sulfonic acid group, or a sodium/potassium salt thereof, and L represents a substituted or unsubstituted methine chain.

M represents sodium, potassium or hydrogen atom, l represents O or 1.

General formula [■-d] In the formula, Rl" + R!"'L R2"'+ R-
represents an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group and a sulfoalkyl group.

R3 and Rh represent a sulfonic acid group or an alkylsulfonic acid group.

Compounds according to the following general formulas [■-a] to [■-d] and silver halide photosensitive materials used in the present invention include JP-A-60-1
Mordants such as those described in No. 40338 may also be used.

Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Patent No. 2.444,607, U.S. Pat.
No. 2, No. 3.512.982, West German Application Publication No. 1
．． No. 189゜380, No. 2,058,626, No. 2.118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3.342.596, Japanese Patent Publication No. 4417-1987, West German Application Public Notice No. 2.149.789, Special Publication No. 1977
-2825, Special Publication No. 49-13566, Special Publication No. 1977
-40665, JP-A-61-198147 and other specifications or publications, preferably 5.6-)limethyl-7-hydroxy-3-triazolo(1,5-a)pyrimidine, 5. 6-Titramethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-3-)riazolo(1,5-a)pyrimidine, 7-hydroxy-3-)
Riazolo(1,5-a)pyrimidine, 5-methyl-6-
Pro-1--7-hydroxy-3-triazolo(1,5
-a) Pyrimidines, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (l-phenyl-
5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nidrobenzimidazole),
It can be stabilized using a quaternary salt compound of phosphorous disulfides.

The hydrophilic colloid 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. No. 2,614,928;
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in each specification of U.S. Pat. No. 25.753, 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 Colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, 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.

The following developing agents can be used for developing the silver halide photographic material of the present invention.

Typical examples of 80- (CH=CH), -OH type developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone,
Methylhydroquinone, 2.3-dibromohydroquinone, 2.5-diethylhydroquinone, catechol, 4
-chlorocatechol, 4-phenyl-catechol, 3-
Methoxy-catechol, 4-acetyl-pyrogallol,
Examples include sodium ascorbic acid.

In addition, HO(CH-C)l)-Nlh type developing agents are typically ortho- and para-aminophenols or aminopyrazolones, such as 4-aminophenol, 2-
Examples include amino-6-phenylphenol and 2-amino-4-chloro-6-phenylphenol.

Furthermore, HJ-(CH=CH), -NHt type developer, for example, 4-amino-2-methyl-N,N-
Diethylaniline, 2,4-diamino-N, N-diethylaniline, N-(4-amino-3-methylphenyl)
-morpholine, p-phenylenediamine, etc.

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

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocessFourth Bdition) No. 29
pp. 1-334 and Journal of the American
Chemical Society (Journal of t
he American Chemical Soc
iety) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention, and it is preferable to use them 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 of the invention, the effects of the invention will not be impaired, and the present invention will not be impaired. This can be mentioned as one of the characteristics. In addition, using hydroxylamine and hydrazide compounds as preservatives,
-500g is good, more preferably 20-200g.

Also ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-
Glycols such as butanediol and 1,5-bentanediol can be used, and diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g per 12 of the developer. These organic solvents can be used alone or in combination. The pH value of the developing solution is 9 to 12, but from the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably, within 2 minutes often brings about good effects. Processing steps other than development, such as washing, stopping, stabilizing,
It is optional to adopt steps such as fixation, preduration, and neutralization if necessary, and these steps 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 using Examples.

It should be noted that, as a matter of course, the present invention is not limited to the examples.

Example-1 Preparation of sample In an acidic atmosphere with nitric acid at pH 3.0, while maintaining the silver potential (EAg) at 170 mV, [solution B] was added to the following [solution A].
] at the addition flow rate shown in Table 5 below to add EAg IN.
At the same time, [Solution C] was added at the same reaction temperature and addition flow rate as [Solution B] until the addition time was 2 minutes, and then the EAg of [Solution B] was mixed using the controlled double jet method. The silver halide emulsions a and b of the present invention and C1 comparative silver halide emulsion d in Table 2 were added at a flow rate of 0.99 times the addition flow rate while controlling with NaC1 of IN.
e was prepared.

[Solution A]

[Solution B] [Solution C] [Solution D] , no.

Margin Table 5 Below, the average silver halide grain size of each silver halide emulsion obtained is shown in the table. Each silver halide grain had a silver chloride content of 90 mol %, a rhodium content of 2×10 −' mol per mol of silver halide, and a monodispersity of 8 to 15%.

A metal silver electrode and a double junction type saturated ^g/AgC1 reference electrode were used to measure the EAg value.

(The double junction structure disclosed in JP-A-57-197534 was used for the electrode structure.) In addition, a variable flow rate roller tube metering pump was used to add [Solution B] and [Solution C]. .

During the addition, the emulsion was sampled and observed using an electron microscope to ensure that no new grains were generated, thereby confirming that the amount added did not exceed the critical growth rate in the system.

6-methyl-4-hydroxy-1,3,3a was added to each of the emulsions a to e thus prepared.

7-thitrazaindene at 20% per mole of silver halide
The pH was adjusted to 5.7 with sodium carbonate, and then [Solution D] was added. Thereafter, each silver halide emulsion was washed with water and desalted according to a conventional method, and then the halogenated fi1
58 μm of 6-methyl-4-hydroxy-1 per mole,
After adding 3,3a,7-chitrazaindene and 150 μm of potassium bromide, the sulfur worsened. 6-methyl-4-hydroxy-1,3,3a as a stabilizer after sulfur sensitization
, 7-chitrazaindene per mole of silver halide
70 and 25g of gelatin were added. Furthermore, the following additives were added to prepare a coating solution for emulsion layer, and
Samples N111 to 19 in Table 3 were coated on a polyethylene terephthalate film with a thickness of 1100 a, which was subjected to latex subbing treatment according to Example 1 of No.
I got it. All silver devices were 3.5 g/po.

[Coating liquid additive for emulsion layer]

(Synthesis example of organic polymer latex (exemplified compound-G-2)) Add 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Awa-Nori Sangyo to water 402 and 0.05 kg of ammonium persulfate to a liquid at a temperature of 81°C. ``i?N-butyl acrylate-1-4,5 under nitrogen atmosphere with stirring
1 temple, 5.49 kg of styrene and 0.1 kg of acrylic acid
was added over a period of 1 hour, then 0.005 kg of ammonium persulfate was added, and after further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 with aqueous ammonia. The obtained latex liquid was treated with Whoman product GF/D Fill (L
)It was created.

(Emulsion protective layer composition) Compound (M) Compound (s)
Compound (K) [Backing layer] [Backing protective layer] The sample thus obtained was placed under a glass plate using an electrodeless discharge tube light source manufactured by Fusion (FUSIoN), USA, which has the spectrum shown in Figure 1. The original and the photosensitive material were overlapped and exposed so that the pasting marks shown in FIG. 2 and quality of cut-out characters could be evaluated on the glass surface.

Subsequently, development processing was carried out using the developer and fixer shown below.

[Developer prescription]

(Composition A) (Composition) When using a developer, the above composition A and the composition were dissolved in 500 d of water in that order, and the developer was finished to lβ.

[Fixer prescription]

(Composition A) (Composition) When using a fixer, the above composition A was dissolved in 500 d of water in that order, and the composition was finished to 12 before use. The p of this fixer was approximately 4.3.

[Development processing conditions]

(Process) (Temperature) (Time) Development 38
℃ 20 seconds fixation 28℃ 20 seconds water washing Room temperature 20 seconds It was fixed with Scotch tape for plate making, and after exposure and development processing, there was no tape mark (pasting mark), and a rating of 5 was made, with 15 being the most noticeable mark and 1 being the worst.

(2) Cutout character quality The cutout character quality is 50% of the mesh film 2 in Figure 2.
It refers to the image quality in which the line width of 50 μm on the line drawing film 4 in FIG. 2 is reproduced when the part with the halftone dot area is properly exposed to the return exposure material l so that the halftone dot area is 50%. A five-level evaluation was made, with a very good cutout character image quality being rated ``5'' and the worst level being ``1''. The evaluation results are shown in Table-3.

(4,,,';-,+ The results of the sliding IL dispersion measurement are shown in Table 3.Sample of the present invention Nα1゜2.
6-11. 17-20 has a cutout character performance of 3.5-4.5
The pasting mark performance was also good at 3.5-5, and the comparative samples Nα3-5. 3.5
It was found that there is no product that has both good performance.

〔Effect of the invention〕

The present invention solves problems such as poor cut-out character surface and remaining pasting marks in light room photosensitive materials, and has good return characteristics while taking advantage of the characteristics of light room photosensitive materials that are excellent in operability. We were able to provide an excellent bright room photosensitive material.

[Brief explanation of the drawing]

FIG. 1 shows the spectrum of the light source, which is an electrodeless discharge tube manufactured by Fusion, USA. FIG. 2 shows the positional relationship between the document and the photosensitive material during cutout and turning operations. 1.----Reversing photosensitive material, 2.--------Ichitsuna dot image film, 3, 5------Passing base, 4--------- Line drawing positive image film, 6
−−−−−−−・Cut mask film. Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative patent attorney: Toru Takatsuki! nm Shujono λ earth character (prefectural electric pyo ni electric 1 meeting Figure 1...[LQ'1. shoulder to TPX the call 2.
...halftone dot 11kV<tshil. 3.5...One stroke on the paste 4° Boring picture positive 4 The sword of love l → 6... No L Mazukufi U4 Fig. 2

Claims (1)

[Claims] 1. A negative-working silver halide photographic material comprising at least one silver halide emulsion layer coated on a support,
At least one of the silver halide emulsion layers contains silver halide grains with an average grain size of 0.095 μm or less, and has a silver chloride content of 50 mol % or more and 10 ^ per mol of silver halide. - formed from an emulsion containing 4 to 10 8 moles of rhodium salt and reduced to at least one hydrophilic colloid layer which may be provided in this emulsion layer and/or adjacent to this emulsion layer. A negative silver halide photographic material characterized by containing a dye-sensitive dye and an organic polymer latex. 2. The negative according to claim 1, wherein the emulsion layer and/or at least one hydrophilic colloid layer that can be provided adjacent to the emulsion layer contains a tetrazolium compound. type silver halide photographic material.