JPH07261307A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic characteristic extremely high in contrast and difficult to be stripped with an adhesive tape and the like by incorporating a polymer latex in the lowest layer nearest a support and a fluorinated surfactant in the uppermost layer. CONSTITUTION:The photographic sensitive material has at least 3 gelatin- containing layers on one side of the support and at least one of them is a photosensitive silver halide emulsion layer containing a hydrazine derivative, and it contains the polymer latex in the lowest layer nearest the support and the fluorinated surfactant in the uppermost layer farthest from the lowest layer. The hydrazine derivative to be used are hydrazine sulfate, hydrazine chloride, and the like, and its is preferred to use the polymer latex derived from an ethylenically unsaturated monomer comprising vinyl polymer particles, especially, vinyl copolymers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material used in a photoengraving process and capable of stably forming a negative image with high sensitivity and ultra-high contrast. It is about.

[0002]

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,
No. 727 (Developer combining ascorbic acid and hydrazine), No. 3,227,552 (Use hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831. No. 2 (containing β-monophenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975, and "The Theory of Photographic process" by Mees.
It is known in the third edition (1966), page 281 etc.

Among these, especially US Pat. No. 2,41
No. 9,975, it is disclosed that a high contrast negative image is obtained by adding a hydrazine compound. That is, when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developer having a high pH such as 12.8, it is possible to obtain extremely hard photographic characteristics with a gamma (γ) of more than 10.
Have been described.

However, a strong alkaline developer having a pH close to 13 is easily oxidized by air, is unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value of more than 10 are extremely useful for the photographic reproduction of continuous tone images with dot images, which are useful for printing plate making, or the reproduction of line drawings, whether it is a negative image or a positive image. It is useful.

For such a purpose, conventionally, a silver chlorobromide emulsion having a silver chloride content of more than 50 mol%, preferably 75 mol% was used, and the effective concentration of sulfite ion was extremely low (usually). A method of developing with a hydroquinone developer (0.1 mol / l or less) was generally used (lith development).

However, according to this method, the developing solution is extremely unstable and cannot endure storage for more than 3 days because the sulfite ion in the developing solution is low. Further, since none of these methods requires the use of a silver chlorobromide emulsion having a relatively high silver chloride content, high sensitivity cannot be obtained.

Therefore, there has been a strong demand for obtaining super-high contrast photographic characteristics useful for reproducing halftone images and line drawings by using a high-sensitivity emulsion and a stable developing solution.

To this end, US Pat. No. 4,168,
No. 977, No. 4,224,401, No. 4,243,7
No. 39, No. 4,269,929, No. 4,272,61
No. 4, 4,323,643 and the like, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added at a pH of 11.0 to 12.3 and a sulfurous acid preservative is added at a pH of 0. A system has been proposed which forms a very high tone negative image by processing with a developer containing 15 mol / l or more and having good storage stability. This new image forming system is characterized in that it is possible to use silver iodobromide and silver chloroiodobromide, whereas only conventional silver chlorobromide having a high silver chloride content can be used in lith development.

On the other hand, most of the printed materials around us today are not only line drawings and characters, but also photographic images. Moreover, not only black-and-white or monochromatic prints of specific colors but also full-color prints are increasing. In the photoengraving process, a photo original is converted to a halftone original with a scanner (in the case of color printing, color separation is performed for each color) and the line drawing original is combined and exposed on a single contact film photosensitive material. Then, make a manuscript for printing these. In the case of a color printed matter, four color (or at least two or more) originals (plates) are produced.

The photographic original is stuck on a transparent film by using a scotch tape so that the position of the photograph is not shifted and the color is not shifted in each plate. In addition, even after being exposed and developed on a light-sensitive adhesive film, it is often pasted with cellophane tape by various plate-making techniques. However, when the cellophane tape was peeled off, if the adhesion between the support and the hydrophilic colloid layer on the support was weak, the hydrophilic colloid layer was peeled off together.

[0011]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining extremely hard photographic characteristics in which γ exceeds 10 by using a stable developing solution. That is.

Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is hard to be peeled off with a cellophane tape or the like.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photosensitive halogenated having on one side of a support at least three gelatin-containing layers, at least one of which contains a hydrazine derivative. A silver halide photographic light-sensitive material, which is a silver emulsion layer, characterized in that it contains a polymer latex in the lowermost layer closest to the support and a fluorine-containing surfactant in the uppermost layer farthest from the lowermost layer. Was achieved with a silver halide photographic light-sensitive material.

The hydrazine derivative used in the present invention includes hydrazine sulfate, hydrazine hydrochloride and the like, and US Pat. Nos. 4,224,401 and 4,243,734,
No. 4,272,614, No. 4,385,108
No. 4,169,929, 4,323,64
3 and JP-A-56-106244 and 61-26.
No. 7759, No. 61-230145, No. 62-270.
No. 953, No. 62-178246, No. 62-1803.
No. 61, No. 62-275247, No. 63-25335.
No. 7, 63-265239, Japanese Patent Application No. 1-92356.
And hydrazine derivatives described in the specification such as JP-A-1-99822 and the like, which can be used in the present invention.

Typical examples of the hydrazine derivative are shown below, but the scope of the present invention is not limited to these.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

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[Chemical 3]

[0019]

[Chemical 4]

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[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

[0039]

[Chemical formula 24]

[0040]

[Chemical 25]

[0041]

[Chemical formula 26]

[0042]

[Chemical 27]

[0043]

[Chemical 28]

[0044]

[Chemical 29]

[0045]

[Chemical 30]

[0046]

[Chemical 31]

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[Chemical 32]

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[Chemical 33]

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[Chemical 34]

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[Chemical 35]

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[Chemical 36]

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[Chemical 37]

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[Chemical 38]

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[Chemical Formula 39]

[0055]

[Chemical 40]

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[Chemical 41]

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[Chemical 42]

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[Chemical 43]

[0059]

[Chemical 44]

[0060]

[Chemical formula 45]

[0061]

[Chemical formula 46]

In the light-sensitive material of the present invention, the above hydrazine derivative is contained in the silver halide emulsion layer. Since the content of the hydrazine derivative in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can be varied over a wide range, but in the silver halide emulsion About 10 ^-6 per 1 mol of silver
To 5 × 10 ^-2 mol per mol of silver a utility practice, more preferably, it is 10 ^-5 ~2 × 10 ^-2 mols.

A wide variety of polymer latices can be used as the polymer latices used in the present invention. A latex composed of ethylenically unsaturated monomers, so-called vinyl polymer particles, is preferable, and a copolymer of vinyl monomers is particularly preferable.

Suitable vinyl monomers include acrylic acid esters (methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, etc.), α-substituted acrylates (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl hexyl methacrylate, etc.),
Acrylamide (butylacrylamide, hexylacrylamide, etc.), vinyl ester (vinyl acetate, etc.), vinyl halide (vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene,
Examples thereof include ethylene, butadiene and acrylonitrile.

Especially preferred are alkyl acrylates and alkyl methacrylates. Alkyl acrylate or alkyl methacrylate copolymers containing vinyl monomers having acrylic acid, methacrylic acid, itaconic acid, or sulfonic acid groups, preferably in a proportion of up to 30 mol%, are particularly useful. Specific examples of these are disclosed in JP-B-46-22506, JP-A-56-56227 and JP-A-51.
Reference can be made to the specification such as -59942. The synthetic polymer latices disclosed in the above patent specifications can be used particularly advantageously. For example, preferred synthetic polymer latices include (butyl acrylate-acrylic acid) copolymers, (methyl acrylate-acrylic acid) copolymers, (ethyl acrylate-acrylic acid) copolymers,
(Butyl acrylate-itaconic acid) copolymer, (ethyl acrylate-methacrylic acid) copolymer, (propyl acrylate-acrylic acid) copolymer, (butyl acrylate-styrene sulfonic acid) copolymer, (ethyl acrylate-styrene sulfonic acid) copolymer,
(Methyl acrylate-sulfopropyl acrylate)
Copolymer, (ethyl acrylate-acrylic acid-2-
Acetoacetoxy-ethyl methacrylate) copolymer, (methyl methacrylate-acrylic acid) copolymer, (methyl methacrylate-itaconic acid) copolymer and the like.

The polymer latex is used together with a binder constituting a photographic layer such as gelatin, and in order to bring out the effect of the present invention, the polymer latex is contained in the lowermost gelatin-containing layer closest to the support, It is preferred that the photosensitive silver halide emulsion layer above the lowermost gelatin-containing layer contains substantially no polymer latex. It is considered that this is because the contrast enhancement by the hydrazine derivative is inhibited, and the hydrazine derivative is incorporated by the latex polymer. Further, the lowermost gelatin-containing layer may contain a photosensitive silver halide emulsion, but for the above reason, it is preferably 20% by weight or less based on the total silver amount of the silver halide emulsion. The polymer latex content of the gelatin-containing lowermost layer is 1 g or less per square meter in terms of solid content, and 5% by weight or more of the gelatin amount contained in the lowermost layer is preferable. Here, the fact that the emulsion layer contains substantially no polymer latex means that
It means that it does not contain polymer latex in an amount that affects the physical properties of the film and photographic characteristics. Specifically, the amount of polymer latex in the emulsion layer is less than 1% by weight of the amount of gelatin contained in the emulsion layer. Represent The polymer latex content defines the amount contained in the lowermost layer on the side of the photosensitive layer when viewed from the support, and the content in layers other than the emulsion layer and the lowermost layer is not affected by these. A necessary amount can be contained for the purpose of improving dimensional stability.

Techniques for incorporating a polymer latex into a silver halide photographic light-sensitive material containing a hydrazine derivative are described in JP-A-2-41, 2-18134 and 4-10.
6542. These are examples in which a polymer latex is added as a means for preventing black spots peculiar to a light-sensitive material containing a hydrazine derivative, and even in the examples, since all the polymer latex is added in the emulsion layer, this effect is maximized. It is clear that it is better to add the polymer latex into the emulsion layer in order to achieve the above expression. Further, JP-A-4-51142 discloses an example in which a matting property is improved by combining a polymer latex and a matting agent. Also in this case, the polymer latex is added to the emulsion layer in the examples.

On the other hand, the present inventors have found that in the silver halide light-sensitive material containing a hydrazine derivative, the main silver halide emulsion layer contains substantially no polymer latex, and the polymer in the lowermost layer closest to the support is used. By containing a latex and a fluorosurfactant in the uppermost layer farthest from the lowermost layer, film peeling due to use of cellophane tape, etc., without impairing the contrast due to the hydrazine derivative and other effects Found to suppress

Typical examples of the fluorine-containing surfactant used in the present invention are shown below, but the scope of the present invention is not limited thereto.

[0070]

[Chemical 47]

[0071]

[Chemical 48]

[0072]

[Chemical 49]

[0073]

[Chemical 50]

[0074]

[Chemical 51]

[0075]

[Chemical 52]

[0076]

[Chemical 53]

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[Chemical 54]

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[Chemical 55]

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[Chemical 56]

[0080]

[Chemical 57]

[0081]

[Chemical 58]

[0082]

[Chemical 59]

[0083]

[Chemical 60]

The fluorosurfactant used in the present invention may be an anion, cation or betaine, but betaine is most effective. The addition amount of the fluorine-based surfactant is usefully in the range of 0.1 to 100 mg per square meter, and more preferably in the range of 1 to 50 mg. The fluorinated surfactant may be used alone or in combination with other surfactants.

The silver halide emulsion used in the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, silver chloride and the like can be used. When silver bromide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less.

The form, crystal habit, size distribution, etc. of the silver halide grains used in the present invention are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable. It is preferable that 90% or more of all the particles have a particle diameter within the range of ± 10% of the average particle diameter. The preparation method of silver halide emulsion is forward mixing, reverse mixing,
Any known method such as simultaneous mixing may be used.

The emulsion that had been physically ripened was desalted and then
It is preferable that the necessary additives are added before coating, but the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine and rhodanine, U.S. Pat. Nos. 1,574,944, 2,278,947 and 2,410,689. Sulfur-containing compounds as described in Nos. 2,440,206, 3,187,458, 3,415,649, 3,501,313 and the like can be used. In addition to sulfur sensitization, US Patents 2,448,060 and 2,540,086
No. 2,556,245 and No. 2,566,263, the sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium and ruthenium can be used in combination. Further, a sensitizing method using various gold compounds such as potassium chloroaurate and auric trichloride and palladium compounds such as palladium chloride can be used in combination.

The silver halide emulsion of the present invention can be spectrally sensitized with a dye known as a sensitizing dye in the photographic industry. These dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholer cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes. These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

In the light-sensitive material of the present invention, a hydrophilic colloid layer such as a back coat layer can be provided in addition to the gelatin-containing layer of the present invention. A matting agent may be contained in these layers.

As the binder or protective colloid that can be used in the emulsion layer, intermediate layer, back coat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids are also used in combination. You can do it. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, Various synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, etc., such as single or copolymers, can be used in combination. . As for gelatin,
Other than lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sc
Oxygen-treated gelatin as described in i.Phot.Japan, No. 16, P30 (1966) may be used, or a hydrolyzed product or an oxygen-decomposed product of gelatin may be used.

The photographic emulsions used in the present invention include known stabilizers such as mercaptotetrazole, mercaptotriazole, benzotriazole and benzimidazole, antifoggants, polyalkylene oxides, thioether compounds and quaternary ammonium salt compounds. Various development accelerators can be contained.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-). 6-
Hydroxy-S-triazine, etc.) or the like can be used alone or in combination.

The photographic emulsion to be used in the present invention includes an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing the image quality due to irradiation, halation and the like, the character removal performance and other performances required in the printing plate making industry. Other hydrophilic colloid layers can contain filter dyes known to those skilled in the art.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement of slipperiness, an emulsion dispersion, an adhesion prevention and an improvement of photographic characteristics (eg, , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surface active agent containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group, such as an alkylcarboxylic acid salt, an alkyl sulfuric acid ester, an alkyl phosphoric acid ester, etc. Agents: amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium What cationic surfactant can be used.

The photographic light-sensitive material used in the present invention contains a water-insoluble or sparingly-soluble synthetic polymer decomposition product in the hydrophilic layer other than the emulsion layer and the lowermost layer for the purpose of improving dimensional stability. be able to. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α A polymer having a monomer component of a combination of β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, and styrenesulfonic acid can be used.

For the photographic light-sensitive material used in the present invention, any support known in the art can be used. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, metal plate such as aluminum, and the like. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method.

In order to obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10.5-1
With the developer of 2.3, a super-high contrast negative image can be sufficiently obtained. The developing agent is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. In addition to the above, the developing solution also includes pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably,
Development inhibitors or antifoggants such as nitroindazoles or benzotriazoles). Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a silver stain preventing agent for the film (for example, 2-mercaptobenzimidazole acids), etc. May be included. Specific examples of these additives are described in Research Disclosure No. 176-1.
7643 and the like.

In particular, in order to obtain super-high contrast photographic characteristics, the developing solution is described in JP-A-56-106244 and 61-26775.
9, the above-mentioned 61-230145, the above-mentioned 62-211647, and the amine compounds described in JP-A Nos. 2-50150 and 2-208652 can be added. The representative ones are listed below.

A-1) Nn-butyldiethanolamine A-2) 3-Diethylamino-1,2-propanediol A-3) 2-Diethylamino-1-ethanol A-4) 2-Diethylamino-1-butanol A -5) 3-Diethylamino-1,2-propanediol A-6) 3-Diethylamino-1-propanol A-7) Triethanolamine A-8) 3-Dipropylamino-1,2-propanediol A-9 ) 2-Dioctylamino-1-ethanol A-10) 3-amino-1,2-propanediol A-11) 1-diethylamino-2-propanol A-12) n-propyldiethanolamine A-13) 2- Di-isopropylaminoethanol A-14) N, N-di-n-butylethanolamine A-15) 3-Dip Pyramino-1,2-propanediol A-16) 2-Methylamino-1-ethanol A-17) 3-Diethylamino-1,2-propanediol A-18) 4-Diethylamino-1-butanol A-19) 1 -Diethylamino-2-butanol A-20) 1-diethylamino-2-hexanol A-21) 5-diethylamino-1-pentanol A-22) 6-diethylamino-1-hexanol A-23) 1-diethylamino-2- Octanol A-24) 6-diethylamino-1,2-hexanediol

The amount added may be any amount as long as it enhances the contrast.
Generally, an amount of 0.005-1.0 mol / l can be added.

In the present invention, a system may be adopted in which a developing agent is incorporated in a light-sensitive material and processing is carried out with an alkaline activator solution. (JP-A-57-129436, 57-129433, 57-129434, 5)
7-129435, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic processor for photographic processing. In the present invention, even when the total processing time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 60 seconds to 120 seconds, a sufficiently high-hardness negative tone gradation photographic characteristic can be obtained.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the description.

Example 1 <Preparation of Undercoat (Bottom) Layer> As an undercoat (bottom) layer, 0.8 g / m ^{2 of} gelatin, a surfactant of formula 61, a hardener, and the following A to G were used. Seven kinds of polymer latex 0.2
A coating liquid containing g / m ² was applied. As a comparative example, a coating liquid containing no polymer latex was also applied. A: (Ethyl acrylate-acrylic acid) copolymer (acrylic acid 5 mol%) B: (Butyl acrylate-acrylic acid) copolymer (acrylic acid 10 mol%) C: (Ethyl acrylate-styrene sulfonic acid) copolymer (styrene sulfonic acid 4 Mol%) D: (butyl acrylate-itaconic acid) copolymer (itaconic acid 5 mol%) E: (ethyl acrylate-methacrylic acid) copolymer (methacrylic acid 3 mol%) F: (methyl methacrylate-acrylic acid) copolymer (acrylic acid 10 mol%) G: (methyl methacrylate-butyl acrylate-acrylic acid) copolymer (acrylic acid 10 mol%)

<Preparation of Silver Halide Emulsion> Average particle size of 0.25 by pAg controlled double jet method.
A micron cubic monodisperse silver iodobromide emulsion was prepared, desalted, washed with water and redissolved by the flocculation method. The silver iodide content was set to 1.5 mol% so that the silver iodide was distributed evenly throughout the grains. After sulfur sensitizing this emulsion by a conventional method, 1-phenyl-5-mercaptotetrazole was added, and anhydro-5,5'-dichloro-sensitizing dye was added.
2. Add 9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt to 2.
5 × 10 ⁻⁵ mol / mol Ag was added, the hydrazine compound in Table 1 was added at 5 × 10 ⁻⁴ mol / mol Ag, and 5-methylbenzotriazole and 2-hydroxy-4,6-dichloro-1,3,5 were added. -Triazine sodium salt and
5g / m ^{2 of} silver nitrate and 3g / m of gelatin on the polyethylene terephthalate film after adding the surfactant of
^It was coated on the undercoat layer so that it would be ² .

<Protective (uppermost) layer> Furthermore, as a protective (uppermost) layer, 1 g / m ^{2 of} gelatin, the surfactant of Table 1 and Comparative Example, a matting agent and a hardener were added and coated. The surfactants of the comparative examples are shown below.

[0107]

[Chemical formula 61]

[0108]

[Chemical formula 62]

[0109]

[Chemical formula 63]

[0110]

[Chemical 64]

Each of the samples thus obtained was exposed and developed to measure gamma. A tungsten lamp was used for the exposure, and gamma was determined by tan θ of the linear portion having an optical density of 1.0 to 2.5. Develop with the developer of the following composition
Development was performed at 30 ° C. for 30 seconds, fixing, washing with water and drying were performed.

Further, as a test of film peeling by a tape, each unexposed sample was developed with the same developing solution, fixed, washed with water and dried, and immediately, a polyester tape for Nitto platemaking was attached to the edge portion of the sample for 2 hours and 20 hours. After the time has passed, peel it off strongly. The rate at which the film surface was peeled off together with the tape was evaluated in three grades of ◯, Δ, and ×. O indicates that the peeling probability is less than 5%, Δ indicates 5 to 20%, and X indicates 20% or more. The results are shown in Table 1.

<Developer> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA / 2Na 1 0.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzene imidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 g N-n-butyldiethanolamine 12.0 g sodium toluenesulfonate 8.0 g Water was added and adjusted to pH 11.8 with 1 l potassium hydroxide.

[0114]

[Table 1]

From the results shown in Table 1, the photographic light-sensitive material of the present invention gave a harder image than the photographic light-sensitive material of Comparative Example.
Furthermore, it can be seen that the film peeling by the tape is also improved. It can be seen that in the sample in which the polymer latex was added to the silver halide emulsion layer, not to the bottom layer, hard photographic characteristics were not obtained, and the film peeling by the tape was not improved.

[0116]

According to the present invention, a silver halide photographic light-sensitive material having extremely high contrast and having improved film peeling by a tape can be obtained by rapid development processing using a stable developer having a high sulfite ion concentration.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least three gelatin-containing layers on one side of a support, at least one of which is a light-sensitive silver halide emulsion layer containing a hydrazine derivative. 2. A silver halide photographic light-sensitive material characterized in that the lowermost layer closest to the support contains a polymer latex, and the uppermost layer farthest from the lowermost layer contains a fluorine-containing surfactant.