JPS61267752A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material operable for a long time without high fog under a yellow safelight F and high in sensitivity to Ar laser beams and contrast by controlling a silver halide emulsion layer contg. a specified compd. to specified pAg after the completion of physical ripening, and chemically ripening it. CONSTITUTION:The silver halide emulsion layer contains at least one of compds. represented by the formula shown on the right in which R1 is alkyl; Z is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; Q is a nonmetallic atomic group necessary to form a 5-membered hetero ring; and m is 1 or 2. It is controlled to a pAg of 7.0-10.0 at an optional time of the chemical ripening after the end of physical ripening, thus permitting the obtained emulsion to have a long safe time under the yellow safelight, and a photosensitive material high in sensitivity, especially to Ar laser beams, high in contrast to be obtained, and used as a silver halide photographic sensitive material for use in an Ar laser scanner used under the yellow safelight.

Description

[Detailed description of the invention] [Purpose of the invention] (Industrial application field) The present invention relates to a silver halide photographic material.

The photographic light-sensitive material of the present invention can be used, for example, as a silver halide photographic light-sensitive material for Ar laser scanners, which can be handled under a yellow safety light.

(Prior Art) In recent years, the use of bright rooms in plate-making processes has progressed, and silver halide photographic materials that can be handled under white fluorescent lamps or yellow safety lamps have come into widespread use.

The performance required of a photosensitive material used in such a bright room is that it has high contrast and sufficient maximum density, and can be handled for a long time in a bright room (under white fluorescent light or yellow safety light). It also has high sensitivity to printer and scanner light sources.

On the other hand, it has become common to use scanners. Scanners are used for color separation of color originals and layout of printed originals. Laser light is generally used as a light source for scanners, and Ar laser is particularly often used.

Even in processes using such scanners, a bright room is required. However, in this case, the reality is that a photosensitive material that is safe to handle in a bright room has not yet been sufficiently developed.

(Objects of the Invention) The objects of the present invention are, firstly, to provide a silver halide photographic material that can be handled for a long time with less fog under yellow safety lights, and secondly, to provide a silver halide photographic material that can be handled for a long time under a yellow safety light. The object of the present invention is to provide a silver halide photographic material that has high sensitivity and high contrast.

Other objects of the invention will become apparent from the description.

[Structure and operation of the invention]

A silver halide photographic light-sensitive material that satisfies the above object is prepared by preparing a silver halide emulsion containing at least one compound selected from the compounds represented by the following general formula, and adjusting its pAg at any point from the end of physical ripening to chemical ripening. 7.0-10.0
It is obtained by controlling the pAg and chemically ripening within the pAg range.

[However, in the general formula, R1 is an alkyl group, specifically an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group,
2-hydroxyethyl group, 2-methoxyethyl group, 2-
Acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl A phenethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and the like are preferred.

Zl is a nonmetallic atomic group necessary to form a 5-membered or 6-membered heterocycle, and examples of the heterocycle include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, Examples include a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, a quinoline ring, etc. Furthermore, these heterocycles may have a substituent, and these substituents include, for example, halogen. atoms (e.g. chlorine atom, bromine atom, etc.), e.g. alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, etc.), halogenated alkyl groups (e.g. trifluoromethyl group) etc.), an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group, an ethoxy group, an n-prooxy group, etc.), a hydroxy group, an aryl group (for example, a phenyl group, etc.). Q represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and these heterocycles include, for example, rhodanine ring, thiohydantoin ring, thioxazolidinedione ring,
These heterocycles may have a substituent, and these substituents include an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group). group, n-propyl group, 2-hydroxyethyl group, 2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group,
Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n -propyl group, n-butyl group), aryl group (e.g. phenyl group, p-sulfopropyl group, etc.), pyridyl group (e.g. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-methyl-2 -pyridyl group, etc.). Moreover, m represents 1 or 2. ] Examples of the compounds represented by -general include the following 1 to 25.

The compounds represented by the above general formula used in the present invention can be easily synthesized based on the methods described in, for example, U.S. Patent No. 2,161,331 and West German Patent No. 936,071. can do. In order to use the compound represented by the above general formula in a silver halide emulsion, it is added and dissolved in a coating solution, or dissolved in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof. It can be added to the coating solution at the appropriate time. Usually, it may be added at any time from the end of ripening to just before coating. It is preferably added to the silver halide emulsion layer. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance.

Furthermore, the amount of the compound represented by the above general formula used in the present invention when added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but is usually 5 to 5 mol per mole of silver halide. The optimum amount for obtaining appropriate effects can be arbitrarily selected over a wide range from 1 to 500 .

Furthermore, pAg can be controlled to 7.0 to 10.0 by methods known to those skilled in the art.

That is, by appropriately performing water washing and desalting after physical ripening, or by removing water-soluble halogen salts (e.g. potassium bromide,
The pAg can be controlled to any desired value by adding sodium chloride, potassium iodide, etc.) or silver nitrate. Control of pAg is carried out at any time from the end of physical ripening to before chemical ripening. Here, physical ripening refers to a process in which silver ions and halogen ions are reacted in a solution to form crystals in the process of producing a silver halide emulsion. For example, P.Gelafkiid (F.
, Glafkide S), “Chimie et P.
hysiquePhotographique; P
aul Monte 1, 1967), G.F. Duffin, "Photographic Emulsion Chemistry" (Photo)
graphic emulsion chemist
ry; The Focal Press, 1966), V. L. Zelikman et al.
``Making and...'' by Kman et al.
Coating/Photographic Emulsion J
(Making and Coating Photo
graphicEmulsion; The Foc
Al Press, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion is chemically ripened after #Al to the pAg of the present invention. Here, chemical ripening refers to a process in which a required amount of water, gelatin, etc. is added to a desalted emulsion, a sensitizer and an inhibitor are added, and the emulsion is heated and reacted for a certain period of time. For chemical ripening, for example Frieser mr.
Die Grundlagen der Photogr
aphischen prozesse wit Si
lberhalogeni-den (Akademi
Verlagsgesellschaft)
(1968) pp. 675-734) can be used.

The silver halide grains used in the present invention can be subjected to reduction sensitization at any point in the manufacturing process.

Reduction sensitization may be performed using a suitable reducing agent such as tin chloride, dimethylamine borane, hydrazine, or thiourea dioxide.

Note that a method of chemically ripening at a high pAg is known. That is, JP-A-48-60916 describes chemical ripening at pAg 8.9, and JP-A-54-9
No. 8236 states that the amount of water-soluble colloidal material is 1.0 g or less per 1 g of silver halide in terms of silver nitrate, and the total weight of the emulsion including silver halide, water-soluble colloidal material, water, etc. is 2 to 20 g. It is described that a silver halide emulsion of 2000 is chemically ripened at a pAg of 8 to 10.

However, by chemically ripening the silver halide emulsion containing the compound of the above general formula of the present invention at pAg of 7.0 to 10.0, yellow safety lamps can have a long safety time, high sensitivity, and It was completely unexpected that a silver halide emulsion with high contrast could be obtained.

In practicing the invention, a yellow light can be used as a safety light. Yellow lights include yellow fluorescent lights, white fluorescent lights wrapped in yellow film, and sodium lights.

The safety light can be used at any illuminance, but is preferably between 1 and 150 lux.

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

Silver halides that can be used in the present invention include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide, etc., which are commonly used in silver halide photographic emulsions. It is optional. Silver chloroiodobromide or silver chlorobromide having a silver chloride content of 50 mol % or more is preferred.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, etc. may be present together.

The grain size of the silver halide grains that can be used in the present invention is not particularly limited, and is preferably 0.1 to 3.0 μm.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelling gelatin, may be used. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

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; sugars such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol
A wide variety of synthetic hydrophilic polymeric materials can be used, such as monopolymers or copolymers of polyvinylpyrazole, polyvinylpyrazole, and the like.

In addition to lime-processed gelatin, acid-processed gelatin and Bulletin of Society of Scientific Photography Op.
l, 5acs 5ciSPhot, Japan)+m
16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanate a, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. Those obtained by reaction can be used.

In carrying out the present invention, the photographic emulsion may contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. . i.e. azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenz. Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds, e.g. Oxazolinthione; azaindenes such as tetraazaindene! [
(particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers. Can be done.

The hardening agent used in the present invention is not particularly limited, but it includes compounds containing reactive halogens such as aldehyde compounds, ketone compounds, and 2-hydroxy-4,6-dichloro-1°3.5-triazine. , compounds with reactive olefins (e.g. vinyl sulfone compounds), N-
Methylol compounds, aziridine compounds, carbodiimide compounds, etc. can be used.

A surfactant may be added to the silver halide emulsion layer of the present invention for purposes such as a coating aid and improvement of photographic properties.

As surfactants, natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxide type and cricidol type, carboxylic acids, sulfonic acids (for example, the surfactants described in U.S. Pat. No. 3,415.649), phosphoric acids,
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphoryl ester groups, amino acids, aminosulfonic acids,
Amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols are preferably used.

Further, the silver halide photographic emulsion used in the present invention can also contain a polymer latex. As the polymer latex, an aqueous dispersion of a homo or copolymer of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. is used.

The silver halide photographic emulsion used in the present invention also contains thickeners, plasticizers, slipping agents, development inhibitors, ultraviolet absorbers,
Anti-irradiation agents, dyes, heavy metals, matting agents, etc.
It can be further included in various ways.

Examples of the support in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass, metal, etc. used. These supports are subjected to surface treatment if necessary.

After exposure, the silver halide photographic material according to the present invention can be developed by a commonly used known method.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides, iodides, and the like.

The measurement of fog density according to the present invention is carried out by developing an unexposed sample under normal conditions and then measuring the density with a densitometer.

[Embodiments of the invention]

Next, the present invention will be specifically explained using examples. However, as a matter of course, the present invention is not limited thereto.

Example 1 - A silver chlorobromide gelatin emulsion containing 35 mol % of silver bromide was prepared by a simultaneous mixing method at 45° C. for 60 minutes. The emulsion thus prepared was desalted and redispersed, with an average grain size of 0.2.
A cubic monodisperse emulsion of μm was obtained.

This emulsion was divided into 10 equal parts, and the pAg was adjusted to a range of 6.0 to 9.0 as shown in Samples Hikari 1 to Arashi 10 in Table 1. , 20 μl of chloroauric acid were added, and chemical ripening was carried out at 60° C. for 70 minutes.

Compound 3 or 2 belonging to the above general formula was added to these samples.
2, the coating amount is 4.5 as shown in Table 1, magnetic 1 to 10.
6-methyl-4-hydroxy-1,3,3a as a stabilizer.
, 7-chitrazaindene were added, and in addition to these, saponin and formalin were added. Each of these samples was coated onto a support so that the amount of silver was 3.8 g/rd to prepare a film.

The 10 types of films thus obtained were each exposed to Ar laser and developed for 20 seconds at 38° C. using a Sakura automatic processor 0R-26 using a Succidol type 621 developer. In addition, an unexposed sample of the IO sample film was placed under a 40W fluorescent lamp with a yellow filter film wrapped around it.
The film was placed at a distance of m and left for 0 and 5 minutes, and the fog density was measured by the method described above.

The measurement results are shown in Table 1 and Table 2. From Table 2, sample sizes 1 to IV
kL10 had a sensitivity in the range of 98 to 112, and was highly sensitive to the Ar laser light source, but samples 11hl and lh2, whose pAg was 6.0, which was outside the range of the present invention, had a sensitivity when left for 5 minutes. Capri is 0.095.0.088, which is a practical problem, and pAg is 7.2 to 7.2, which is within the range of the present invention.
Sample lights 3 to 10 at 9.5 had a good fog of 0.044 to 1,061 when left for 5 minutes, demonstrating the effect of the present invention.

Table 2 Example 2 Sample lights 11 to 20 were prepared in the same manner as in Example 1, except that pAg, the type of compound belonging to the above general formula, and the coating amount were changed as shown in Table 3. Then, sensitivity and fog were measured in the same manner as in Example 1.

Table 4 shows the measurement results. From Table 4, sample lights 11 to 20 had sensitivities in the range of 115 to 127 and were highly sensitive to the Ar laser light source, but samples mll and N whose pAg was 6.0, which was outside the range of the present invention. [L12 has a fog of 0.093.0.090 when left for 5 minutes, which is a big practical problem, and p and Ag are 7.5 to 7.5 within the range of the present invention.
Sample light 13~ in 9.7! 1h20 had a good fog of 0.043 to 0.060 when left for 5 minutes, demonstrating the effects of the present invention.

Table 3 Table 4 Example 3 The sample of Example 2 was photographed using an Ar laser scanner.
The quality of the halftone dots was evaluated. Sample light 13-11h2 in Table 3
0 had high contrast and excellent sharpness.

However, Table 3 11h11. No. 12 had poor sharpness.

〔Effect of the invention〕

As described above, according to the present invention, a silver halide photographic material with a long safety time under a yellow safety light, high sensitivity to an Ar laser light source, and high contrast was obtained.

Claims (1)

[Scope of Claims] A silver halide emulsion containing at least one compound selected from the compounds represented by the following general formula is prepared to have a pAg of 7.0 to 1 at any point from the end of physical ripening to before chemical ripening.
1. A silver halide photographic light-sensitive material, characterized in that it is formed by controlling the pAg to 0.0 and chemically ripening within the pAg range. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the general formula, R_1 is an alkyl group, Z_1 is a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and Q
represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and m represents 1 or 2. ]