JPS638736A - Silver halide photographic sensitive material high in contrast - Google Patents

Abstract

PURPOSE:To obtain a high-contrast sharp image high in sensitivity without causing pinholes by forming a backing layer having a dye concentration enhanced to >=40% in average transmittance of sensitive wavelength light, and incorporating a specified matting agent in the outermost layer of the backing layer in an amount of 1-15wt% of a binder. CONSTITUTION:The dye concentration of the backing layer is set so as to enhance the average transmittance of the sensitive wavelength light to >=40%, and a proper dye is selected from various kinds of dyes in accordance with the spectral sensitivity characteristics on the side of emulsion layers. The matting agent contained in the uppermost layer of the backing layer has an average particle diameter of <=10mum, a monodispersion degree of 5-50, and a refractive index of <=2, and natural silica, synthetic silica, starch, a synthetic resin, such as polymethyl methacrylate, and the like are used for it. This agent is used in an amount of 1-15wt% of the hydrophilic collid matrix binder for dispersing and carrying it, nd if too much, the pinholes due to aggregation of the matting agent occur, and if too small, vacuum contact performance is deteriorated at the time of printing operation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a high contrast silver halide photographic material. The present invention can be suitably used, for example, as a so-called silver halide photographic light-sensitive material for reverse photography, which is exposed from the backing layer side.

[Conventional technology]

Among conventional techniques of this type, for example, silver halide photographic materials for plate making, silver halide photographic materials used for camera photography involve coating a support with a high-contrast light-sensitive silver halide emulsion. A silver halide photographic light-sensitive material is used in which a non-photosensitive backing layer is coated on the opposite side of the support.

When photographing with a camera, the original is exposed as a mirror image with the left and right sides reversed when the photograph is taken through an optical lens system.

To avoid this when printing plates for letterpress printing,
A normal image is obtained by exposing from the buffing layer side rather than from the silver halide emulsion layer side.

However, ordinary silver halide photographic materials are designed to be exposed from the emulsion layer side, and when exposed from the backing layer side, the amount of transmitted light decreases due to the light absorption of the dye on the backing layer side, resulting in a lower intensity. Sometimes. In addition, problems such as minute holes called pinholes are likely to occur on the photographic image due to the influence of the surface condition of the backing layer, which has been a hindrance.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art and provide a silver halide photographic material that is highly sensitive, free from pinholes, and capable of producing sharp images with high contrast.

[Structure of the invention]

The present invention has a backing layer having a dye concentration with an average transmittance of light of a photosensitive wavelength of 40% or more, and has an average particle size of 10 μm or less and a monodispersity of 5 on the outermost layer of the backing layer. The object of the present invention is to provide a silver halide photographic material containing a mantle agent having a refractive index of 1 to 50 and a refractive index of 2 or less in an amount of 1 to 15% by weight per binder, and the above object of the present invention is achieved by this configuration.

The average transmittance referred to in the present invention is the dose concentration at which the sensitivity decreases by half when exposed from the backing layer side, and the average transmittance is 50%, and is calculated using this calculation method. It refers to the transmittance of

In addition, the outermost layer of the backing layer is the outermost surface layer on the side of the banking layer (usually a protective layer, but not limited to a protective layer), but this does not exclude the case where an additional coating is applied. , which essentially functions as the outermost layer.

Furthermore, the binder refers to a hydrophilic colloid matrix that is dispersed and supported.

In the present invention, the average transmittance of light at the sensitive wavelength is 4.
The dye concentration of the backing layer is set to be 0% or more, but such a dye concentration can be obtained by appropriately selecting various dyes depending on the spectral sensitivity characteristics of the light-sensitive silver halide emulsion layer side. .

For example, as a common means, an orthochromatic type sensitizing dye is used on the side of the light-sensitive silver halide emulsion layer. In this case, the absorption maximum wavelength λmax is 500n
Preferably, the wavelength is in the range of m to 600 nm. To obtain such spectral characteristics, Japanese Patent Publication No. 46-18105,
No. 46-18108, No. 46-18106, No. 48
It is preferable to use the aggravating dye disclosed in Japanese Patent No. 41204 and the like.

For example, by using a dye required for backing of a silver halide photographic light-sensitive material as described above, selecting the dye as appropriate and adjusting the amount used so that the average transmittance of light at the sensitive wavelength is 40% or more, A desired backing density can be achieved.

In a preferred embodiment of the present invention, the banking layer is exposed to light by being exposed to light from the side thereof. In such an embodiment, the higher the transmittance of the backing layer, the higher the sensitivity can be obtained. However, in terms of photographic properties, it is required that the average transmittance of light at the sensitive wavelength be 40% or more.

If the average transmittance is outside this range, the sensitivity, sharpness, pinhole defects, and other characteristics will deteriorate. The average transmittance is preferably 40% to 90%, more preferably 50%.
% to 80%.

Any light source can be used to expose the silver halide photographic material of the present invention, and various light sources such as tungsten lamps, metal halide lamps, xenon lamps, mercury lamps, and electrodeless microwave electrodes may be used depending on the sensitivity. be able to.

Next, the capping agent used in the backing layer in the present invention will be explained. In the photosensitive material of the present invention, the capping agent contained on the outermost layer of the backing layer has an average particle size of 10 μm or less, a monodispersity of 5 to 50, and a refractive index of 2 or less.

Examples of capping agents having a refractive index of 2 or less include natural silica, synthetic silica, starch, synthetic resins such as polymers of acrylic acid or methacrylic acid esters (for example, polymethylmethacrylate), polyvinyl resins (for example, polyvinyl acetate, (polyvinyl alcohol), polyvinyl resin bodies, styrene homopolymers or copolymers, hardened gelatin particles, and the like.

In the present invention, the matting agent used preferably has a monodisperse particle size. The degree of monodispersity is defined by the following formula (1), and in the present invention, a value of 7 to 50 is used.

More preferably, it is adjusted to 8-40. Preparation of such monodispersity is important in practicing the present invention.

Otsu n1 (However, in (2) (1), r represents the particle size of the first particle, n represents the first particle, and 7 represents the average particle size.) In addition, the mantle agent used in the present invention The average particle size is 10 μm or less, and more preferably the average particle size is 6.0 μm.
This is the case when the following are used.

The mantle agent according to the present invention is contained on the outermost layer of the backing layer of the silver halide photographic light-sensitive material. It is preferable to include it in the colloid layer. In this way, the outermost layer includes not only the literally outermost layer (usually the 3i layer) but also the layer that functions as the outermost layer.

Although it is preferable for the present invention to use the above-mentioned matting agent according to the present invention as a mantle agent in the protective layer on the photosensitive emulsion layer, it is preferable for the present invention to use a generally known mantle agent on the emulsion layer side. It can be used arbitrarily.

Various methods can be arbitrarily employed to disperse the matting agent in the hydrophilic colloid layer. For example, it may be dispersed in a hydrophilic colloid matrix such as gelatin in advance and then added to the desired layer, and dispersed using a homomixer, ball mill, or ultrasonic vibration in the presence of a dispersion aid such as an activator or thickener. You can also use it after letting it.

The amount of the matting agent on the puffing side used in the present invention is 1 to 15% by weight based on the hydrophilic colloid matrix (binder) to be dispersed and supported. If the amount is too large, pinholes will occur due to agglomeration of the capping agent, and if it is too small, the vacuum adhesion during printing will deteriorate, making it impossible to obtain high-quality properties, especially back-shooting properties.

When applying a protective layer containing a matting agent to the upper surface of the backing layer, it is preferable that the time required for the application to dry is within 1 to 15 minutes, and the temperature difference between the soft bulb and wet bulb is 20 minutes in the decreasing rate part during drying. It is preferably less than 15°, more preferably 15°
or less, and the wet bulb temperature is preferably 106 to 206.

As mentioned above, the dye used in the backing layer of the light-sensitive material of the present invention can be arbitrarily selected depending on the spectral characteristics of the photosensitive silver halide. Dyes preferably used in carrying out the present invention include U.S. Pat. No. 3,540,887 and U.S. Pat.
Dyes disclosed in Japanese Patent Application Publication No. 615546, Japanese Patent Application Laid-Open No. 57-185038, Japanese Patent Publication No. 56-49953, and the like can be mentioned. Specifically, (1) to (1) are illustrated below.
The effect of the invention can be enhanced by using the backing dye of 6). It goes without saying that the dyes used in the present invention are not limited to the specific exemplified compounds below.

OJa 03Na SO, Na 5O3Na SO3Na 03Na C1I□CII□CII□SO3■ CHzCOO1! Silver halide of any composition can be used in the silver halide photographic light-sensitive material of the present invention. For example, silver chlorobromide or silver chloroiodobromide containing at least 50 mol % of silver chloride can be preferably used. The average particle diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, more preferably 0.10 to 0.40 μm.

The monodispersity of the silver halide grains used in the present invention is as follows (
When defined in 1), the value is preferably 5-25, more preferably 8-20. Note that this equation (1) is the same as the equation (1) that defines the monodispersity of the mantle agent.

In other words, the grain size of silver halide grains can be measured using an optical microscope or a coal counter, but for convenience it is expressed in terms of the principal grain size, and the monodispersity is expressed as the particle size as shown in equation (1) below. It is expressed as a value obtained by dividing the standard deviation by the average particle diameter (7) and multiplying it by 100.

(However, in formula (1), r represents the grain size of the first grain, n represents the first grain, and 7 represents the average grain size.) Also, silver halide that can be used in the present invention For example, silver chloride particles and silver chlorobromide particles having a multilayer structure of at least two layers may be used. At this time, iodine can be contained in any layer within 5 mol%.

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

The rhodium salt used in the present invention may be a double salt as well as a simple salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt to be added can be freely changed depending on the required sensitivity and frequency, but a range of 10 -9 mol to 10 -4 mol per mol of silver is particularly useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used for the purpose of imparting high-intensity characteristics, and can preferably be used in a range of 10-9 to 10-4 mol per mol of silver.

The silver halide used in the present invention can be degraded by various chemical aggravators.

Examples of aggravating agents include activated gelatin, sulfur sensitizers (sodium oxosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.) , reducing aggravating agents (triethylenetetramine, stannous chloride, etc.), such as potassium chlorooolite, potassium aurithiocyanate,
Various noble metal aggravating agents represented by potassium chloroaurate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroaurate, sodium chlorovaladite, etc., each alone or in combination of two or more. It can be used as When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat. Nos. 2,444,607 and 2,716,06
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. 4417-47, West Germany Application Publication No. 2,149,789, Special Publication No. 1973
-2825 and Japanese Patent Publication No. 49-13566 are preferably used, preferably for example 5,6
-drimethylene-7-hydroxy-s-triazolo(1
, 5-a) Pyrimidine, 5.6-titramethylene-7-
Hydroxy-S-) triazolo (1,5-a) pyrimidine, 5-methyl-7-hydroxy-8-triazolo (
15-a) Pyrimidine, 7-hydroxy-S-triazolo(1,5-a) pyrimidine, 5-methyl-6-promorph-hydroxy-S-triazolo(1,5-a)
Pyrimidines, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (e.g. 1-phenyl-
5-mercaptotetrazole, 2-mercaptohentthiazole), benzotriazoles (e.g. 5-bromobenztriazole, 5-methylbenztriazole)
, benzimidazoles (for example, 6-nidrohenzimidazole), and the like.

The silver halide used in the present invention is generally added to a hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in carrying out the present invention is gelatin.

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. Nos. 2.614.928 and 2,525,75
phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Patent No. 3, or for example, U.S. Pat.
, 83L767, styrene acrylate, acrylic ester, methacrylic acid,
Examples include gelatin graft-polymerized with a polymerizable nA polymer having an ethylene group such as methacrylic acid ester, and these hydrophilic colloids can be used in layers that do not contain silver halide, such as antihalation layers and protective layers. , it can also be applied to intermediate layers, etc.

The photographic light-sensitive material of the present invention can be embodied by coating a silver halide emulsion layer or a backing layer on a support. Examples of supports that can be used in this case include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, Typical examples include glass plates, 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.

A preferred embodiment of the photographic material of the present invention has at least one hydrophilic colloid layer containing silver halide on a support, and a hydrophilic colloid layer constituting a banking layer on the opposite side of the support. A protective layer having an appropriate thickness on the buffing layer side, that is, preferably 0.1 to 10 μm.
Particularly preferably, a gelatin protective layer of 0.8 to 2 μm is coated. It goes without saying that the present invention can also be applied to photosensitive materials other than those used for rear edge printing.

The hydrophilic colloid used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners,
Surfactant, image stabilizer, ultraviolet absorber, antistain agent, pH adjuster, antioxidant, antistatic agent, thickener,
Graininess improvers, dyes, mordants, brighteners, development speed regulators, etc. can be used within the range that does not impair the effects of the present invention.

Among the various additives mentioned above, those that can be particularly preferably used in carrying out the present invention include thickeners or plasticizers,
For example, US Pat. No. 2,960,404, Japanese Patent Publication No. 43-4939, West German Application Publication No.
, Specification No. 604, JP-A-48-63715, JP-A-45-15462, Belgian Patent No. 762,
833, U.S. Patent No. 3,767.410, and Hergi Patent No. 558.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc., as a hardening agent. Various hardeners and ultraviolet absorbers such as aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl are used. For example, US Patent No. 3,253°921, British Patent No. 1,30
Compounds described in the specifications of No. 9,349, especially 2-(2-hydroxy-5-tertiary butylphenyl)pendutriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl)hencytriazole, 2-(
2-hydroxy-3-tertiary butyl-5-butylphenyl)-5-chlorohencytriazole, 1(2-hydroxy-3,5-di-tertiary butylphenyl)-5-chlorobenzo I-riazole, etc. The dyes include U.S. Patent No. 2.072.908, German Patent No. 107,990, and U.S. Patent No. 3,048. ．． No. 187, U.S. Patent No. 515,988, etc., can be used, and these compounds can be used to form a protective layer,
It may be contained in an emulsion layer or an intermediate layer. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 5.
48.532, U.S. Patent No. L216,389, U.S. Patent No. 3,026,202, U.S. Patent No. 3,514,293, Japanese Patent Publication No. 44-26580, U.S. Patent Publication No. 43-1792
No. 2, No. 43-17926, No. 43-13166,
18-20785, French Painting Patent No. 202,
Anionic, cationic, nonionic, or amphoteric compounds described in specifications such as No. 588, Belgian Patent No. 773.459, and JP-A-48-101118 can be used. However, among these, anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are particularly preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
Japanese Patent Application Laid-open No. 48-89979, U.S. Patent Nos. 2 and 8
Specifications of 82゜157 and 2,972,535, JP-A-48-20785, JP-A-48-43130,
No. 48-90391, Japanese Patent Publication No. 46-24159, No. 46-39312, No. 48-43809, Japanese Patent Publication No. 48-43809
Examples include compounds described in various publications such as No. 7-33627.

As the developing agent used in developing the silver halide photographic window optical material of the present invention, various arbitrary ones can be mentioned depending on the specifically manufactured photographic material. Examples include:

110- (C1l = C11) A typical example of an n-OH type developing agent is hydroquinone,
In addition, catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2
．． 3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone,
2.5-di-p-phenethylhydroquinone, 2.5-
Dihenzoylaminohydroquinone, catechol, 4-
Examples include chlorocatechol, 3-phenylcatechol, 4-phenylcatechol, 3-methoxycatechol, 4-acetyl-pyrogallol, 4-(2-hydroxybenzoyl)pyrogallol, and sodium ascorbate.

Typical 110 (CH=CI) n N) 12 type developers are ortho and para aminophenols or aminopyrazolones, 4-aminephenol, 2-amino-6-phenylphenol, 2-aminophenol, 2-amino-6-phenylphenol,
Amitsu~4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2
．． 4-cyamylsorcinol, 2.4.6-1-riaminophenol, N-methyl-p-aminophenol, N
-β-hydroxyethyl-p-aminephenol, p-
Examples include hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Furthermore, HJ (C)I = C)I) n NH2
Examples of mold development developers include 4-amino-2-methyl-N,
N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N, N-dimethyl-3- Hydroxyaniline, N
, N, N, N-tetramethylparaphenylenediamine,
4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-
N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl=(β-methoxyethyl)-3-methyl-
Aniline, 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)-aniline, 4-
amino-N-butyl-N-r-sulfobutylaniline,
■-(4-aminophenyl)-pyrrolidine, etc.

Examples of the hetero prototype developer include 1-phenyl-3-virapritone, 1-phenyl-4,4-dimethyl-3-virapritone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. 4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, ■-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-
Examples include 2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, and 5-aminouracil.

Others, T, 1. The Theory of James
The Photographic Ink Process 4th Edition (The Th
theory of the Photographic
Process.

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
Developers such as those described on page 3, 100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material 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.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, it is necessary to adjust the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers, and provide a buffer function, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid, etc. Metal ion scavenger, methanol, ethanol, benzyl alcohol, development accelerator such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponin,
It is optional to add surfactants such as saccharides or alkyl esters of the aforementioned compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, and ionic strength regulators such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include triethanolamine jetanolamine ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-diethylamino-1-propanediol 3-diethylamino-1-propatool 5- Amino-1-Pentanol Diethylamine Methylamine Triethylamine Dipropylamine Di-isopropylamine 3.3'-Diaminodipropylamine 3-Dimethylamino-1-propatolhydantoic acid Allylamine Ethylamine Dimethylamine Ethylene diamine 2-Dimethylaminoethanol 2-ethyl Aminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminoco-
ethanolaminoguanidine sulfate 6-aminohexanoic acid 3-amino-1-propatol 1-dimethylamino-2-propatol 2-hydroxy-4-thiadodecyltrimethylammonium (pta
) Pyridine Glycine 0-Amine Benzoic Acid Polyethyleneimine L-(+) -Cystine Hydrochloride Benzylamine 2-Amino-1-ethanol 4-Amino-1-Butanol 3-(dimethylamino) -L 2-Propanediol 3-morpholino -1,2-propanediol 1,4-piperazinebis(ethanesulfonic acid)3-piperidino-
Examples include 1,2-propanediol, N-piperidine ethanol, and the like.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, ■, 1-butanediol, 1,
Among them, diethylene glycol is preferably used. The amount of these alkanolamines and glycols used is 5% per 11 parts of the developer.
-500g is preferred, more preferably 20-200g
It is.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1.4-7"tanediol, 1,
Among them, diethylene glycol is preferably used. The preferred amount of these glycols used is 5 to 500 g per 1z of developer.
More preferably, it is 20 to 200 g. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material of the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The pH value of the developer having the above composition is preferably 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
0"C or less is preferable, especially around 30°C,
Further, the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which often brings about good effects. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, 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〕

The present invention will be explained below with reference to examples, but it goes without saying that the present invention is not limited to the examples.

Example 1 Using solutions A-E with the composition shown below, an average particle size of 0.2
A silver chlorobromide emulsion having a diameter of 4 μm and a composition of 65 mol % silver chloride and 35 mol % silver bromide was prepared.

(Solution A) (Solution B) "., IN nitric acid aqueous solution 1.15 n
u (solution C) (?Each method D) (containing solution E) Solution A was kept warm at 40'C and stirred using the mixer described in JP-A-57-92523 and JP-A-57-92524. Solution B, solution C1 solution and solution E were added using a double jet method. The addition method at this time is as follows.
Shown in the table.

That is, the addition flow rate of solutions B-E was varied incrementally over 80 minutes as shown in Table 1 to form silver halide grains. Solution B2C was added for the first 10 minutes of mixing.

After 10 minutes, the solution was dissolved and E was added. The EAg of the emulsion was maintained at 160 mV for 5 minutes from the start of mixing, and after 5 minutes from the start of mixing, it was adjusted to 123 ± 5 mV using a 1.8 mol/β aqueous sodium chloride solution, and thereafter this value was adjusted using the aqueous sodium chloride solution. held. Furthermore, p during mixing
H is 0. 3.0±0.1 by adding IN nitric acid
was maintained within the range.

After adding solution B-E, add 20 cc of IJum aqueous solution to return the pH to 5.8 = 0.1, and after Ostwald ripening the emulsion for 10 minutes, desalt by the usual method. After washing with water, 132.4 ml of an aqueous solution of ossein gelatin (containing 10 g of ossein gelatin) was added and dispersed by stirring at 55°C for 30 minutes.
The volume was adjusted to 250ml.

The average particle size of the obtained particles was 0.24 μm, and the monodispersity was 1.
It was 0.

To measure the EAg value, a metal silver electrode and a double-junction type saturated A g / A g C (l comparison snow plow) were used. ) Also, a variable flow rate roller tube metering pump was used to add solution B-E.

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 n-field growth rate in the system.

Next, warm this emulsion to 60°C and add 5 cc of 1% citric acid.
and 15 cc of 1% potassium bromide aqueous solution were added and aged for 20 minutes, followed by 2 cc of 0.1% tetrachloroauric acid aqueous solution and 0.1% aqueous tetrachloroauric acid solution.
Gold sulfur aggregation was performed for 70 minutes by adding 4 cc of 1% sodium thiosulfate aqueous solution, and 1% 6-methyl-4 was added as a stabilizer.
-Hydroxy-1,3,3a,',-tetrazaindene (50 cc) was added. As sensitizing dyes, the following compounds (Δ) and (13) were added in an amount of 50 mg and 35 mg, respectively, and optically sensitized.

Next, 265 mg of 2,3.54-liftonyltetrazolium chloride as a contrast enhancer, 100 mg of sodium p-dodecylbenzenesulfonate, 109 mg/m of Merck saponin as a coating aid, and 2% aqueous sodium hydroxide solution were added to adjust the pH to 5.8. After stirring, 0.2 g/rf of styrene-butyl acrylate copolymer and 0.48 g/A of styrene-maleic acid copolymer were added.
emulsion was added to the base so that A g ff was 4.5 g/m and gelatin ffi was 1.9 g/m (g/lem represents grams per 1β emulsion).

At that time, 1.5 mg/d of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate was used as a spreading agent so that the gelatin ff was 11.1 g/m, and the average particle size was 3.0 ptn as a capping agent. of silica (S i O
z) at 5Qmg/rr? A protective layer containing 5.3 mg/m of citric acid to adjust the pH of the silver halide emulsion layer and 25 mg/m of formalin as a hardening agent was simultaneously coated in multiple layers.

A banking coating solution used to then apply the backing underlayer was prepared as follows.

(Banking coating made at night 8 laps) 36 kg of gelatin was swollen in water, heated and dissolved, and the following compound (C-1) was added as a dye, 6 kg, second
The above exemplary dye shown in the table was then added to the following compound (C-2).
1.9 kg of saponin was added as an aqueous solution, and then 2 kg of saponin was added.
0% aqueous solution was mixed with 11β, and the following compound (C
-3) was added, and 800 g of styrene-maleic acid copolymer water-soluble polymer was added as a thickener to this liquid.
Add to adjust the viscosity, and then use a citric acid aqueous solution to adjust the pH to 5.4.
Finally, 144 g of glyoxal was added and finished to 9601 with water to prepare BC coating material B-1.

Compound (C-1) CH□SO,I+ Compound (C-2) S(hK SO:lK Compound (C~3) -(CH2-cH), and (CI+2-Ch
Copoli CO□CqHq Cj! Maratex (m:n=1:1) Next, a protective film coating liquid P-2 was prepared as follows for coating the protective film layer of the hashing layer.

(Preparation of protective film coating solution P-2) Swell 50 kg of gelatin in water, dissolve it by heating, add 340 g of 2-sulfonate succinic acid bis(2-ethylhexyl) ester sodium salt, and use it as a matting agent as shown in Table 2. Add the ingredients shown in the amounts shown in Table 2, add 3.4 kg of sodium chloride, and add 1.1 kg of glyoxal.
kg, add 540g of mucochloric acid, add 1000g of water
A protective film coating liquid P-2 was prepared.

(Preparation of evaluation sample) The above-mentioned coating liquids were combined as shown in Table 2 and prepared as follows:
Example 1 of -09941 was coated on both sides of a polyethylene terephthalate film (FE 100 μm) provided with an undercoat layer to prepare evaluation samples shown in Table 2. At that time, a backing lower layer was coated on one side of the support coated with an undercoat layer so that the gelatin dry weight was 1.5 g/=, and at the same time, a backing protective film layer was applied on top of the backing layer with a gelatin dry weight of 1.5 g/=. The coating was applied so that the weight was 1 g/M, and evaluation samples 1 to 22 in Table 2 were prepared.

・+7. − The created evaluation sample (test sample) was brought into contact with the emulsion side on the board of a plate-making camera, and the line drawing manuscript was turned into liquid form by back-photographing, and then processed according to the following processing steps and processing contents,
The resulting images were evaluated. The sensitivity was determined from the exposure amount that gave the best reproducibility of thin lines on the original, and was expressed as relative sensitivity with the sensitivity of evaluation sample Kan 10 as 100. Pinholes were evaluated visually on a high-volatility light table on a sample that had been uniformly exposed at the exposure amount at this time, and evaluated on a five-point scale. The best level is rlJ, and it is also the worst level.
The evaluation was made as ``5''. For practical purposes, it is considered that a rating of 3j or higher is sufficient.The obtained results are shown in Table 3.The results in Table 3 show the composition of the dye and the effect of the capping agent, and show the composition of the dye and the effect of the mantle agent. Sensitivity is good, especially
Surprisingly, the behind-the-scenes characteristics, especially the pinhole, were unexpectedly improved, clearly showing the remarkable effect on this.

<Development processing conditions> (Process) (Temperature) (Time) Development 2
8°C 30 seconds fixation 28°C 2
Wash with water for 0 seconds 20 seconds at room temperature Developer formulation> (Mi composition A) Pure water (ion exchange water) 150 mA ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50 g Potassium sulfite (55% W/V aqueous solution) 100 m1
Potassium carbonate 50 gHydroquinone 15 g5-methylbenzotriazole 200 mgl-Phenyl-5-mercaptotetrazole 0 mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5 g (composition) Pure water (ion Exchange water) 3m7! Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 m
A3-nitroindazole 110 mg
When using 500 mg of 1-phenyl-3-pyrazolidone as a developer, it was dissolved in 500 mE of water in the order of composition A and then finished to 1β.

Fixer formulation> (Composition A) Ammonium 1000 sulfate (72.5% stored water solution 24O
n+j! Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90% aqueous solution)
13.6ml (contains N) Pure water (ion exchange water) 17mf sulfuric acid (50% W/H) water? 8i'lI) 4.
7 g Aluminum sulfate (aqueous solution with content of 8.1% A/h in terms of Al 203) 26.5
When using the β fixer, it was dissolved in 500 ml of water in the order of composition A and composition 11. The pH of this fixer was about 4.3.

Table 3 [Effects of the Invention] As described above, according to the present invention, it is possible to obtain a silver halide photographic material that has a high degree of excitation, does not generate pinholes, and can provide sharp images with high contrast.

Claims (1)

[Claims] 1. A backing layer having a dye concentration with an average transmittance of light at a photosensitive wavelength of 40% or more, and a dye having an average particle size of 10 μm or less and a monodispersity of 5 on the outermost layer of the backing layer.
50, a silver halide photographic material containing 1 to 15% by weight of a matting agent having a refractive index of 2 or less per binder.