JP2681629B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material. The photographic light-sensitive material of the present invention can be used as, for example, a silver halide photographic light-sensitive material for an argon laser scanner that can be handled under a yellow safety light. [Prior Art] In recent years, the platemaking process has been made brighter, and silver halide photographic light-sensitive materials that can be handled under a white fluorescent lamp or a yellow safety lamp have been widely used. The performance required for a light-sensitive material used in such a bright room has a high density and a sufficient maximum density, and can be handled for a long time in a bright room (under a white fluorescent lamp or a yellow safety lamp). In addition, it has high sensitivity to printers and scanner light sources. On the other hand, the use of scanners has become common practice. Scanners are used for color separation of color originals and layout of printed originals. Laser light is generally used as the light source of the scanner, and particularly an argon laser is often used. Even in the process using such a scanner, a bright room is required. However, in this case, the light-sensitive material that can be safely handled in the bright room has not been fully developed yet. [Object of the Invention] An object of the present invention is to provide a scanner system using an argon laser as a light source, which has a long safety time under a yellow safety light, has a high sensitivity to the argon laser light source, and has a strong halogenation. It is to provide a silver photographic light-sensitive material. [Structure of the Invention] The above-mentioned object of the present invention is a photograph in which at least one silver halide emulsion layer is provided on one surface of a hydrophobic support, and a hydrophilic colloid layer is coated on the opposite support surface. In a silver halide photographic light-sensitive material comprising constituent layers, the silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0.05 to 0.5 μm, a monodispersity of 20 or less, and a silver halide content of at least 50 mol%. The silver halide containing silver chlorobromide or silver chloroiodobromide containing silver chloride, containing at least one compound selected from the compounds represented by the following general formula (I) in the photographic constituent layers, Achieved by a silver halide photographic light-sensitive material for an argon laser scanner containing at least one compound selected from the compounds represented by the following general formula (II) in the hydrophilic colloid layer opposite to the emulsion layer. It is. General formula (I) [Wherein, Z is a group of non-metal atoms necessary for forming 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, Examples thereof include a benzoselenazole ring, a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, and a quinoline ring. Further, these heterocycles may have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, etc.), for example, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group), halogenated alkyl group ( For example, a trifluoromethyl group, etc.), an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, etoxy group). Group, n- propyl group, etc.),
Examples thereof include a hydroxy group and an aryl group (eg phenyl group). Q represents a group of non-metal atoms necessary for forming a 5-membered heterocycle, provided that at least one of the 5-membered rings is C—S. Examples of the heterocyclic ring include a rhodanine ring, a thiohydantoin ring, a thiooxazolidinedione ring, and a thioselenazolidinedione ring, and these heterocyclic rings may have a substituent. Preferably, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl 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-butyl group etc.), aryl group (eg phenyl group, p-sulfophenyl group etc.) or pyridyl group (eg 2- Pyridyl group, 3
-Pyridyl group, methyl-2-pyridyl group and the like). R is an alkyl group, and specifically, has, for example, 1 to 1 carbon atoms.
8 alkyl groups such as methyl group, ethyl group, 2-hydroxyethyl 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, vinylmethyl group, benzyl group, phenethyl group, n-propyl group, isopropyl group, n-butyl group and the like are preferable. General formula (II) [Wherein R ₂ represents an alkyl group, a carboxyl group, an alkoxycarbonyl group, a carbamide group, a nitrile group, a trifluoromethyl group or an acylamino group, and R ₃ represents an aryl group substituted with one or more sulfone groups. Represent. R ₄ ,
R ₅ represents an alkyl group which may be different from each other or an alkyl group having a substituent, and n is 1 or 2. Next, specific examples of the compound represented by the general formula (I) used in the silver halide photographic light-sensitive material of the present invention will be shown. However, needless to say, the compounds used in the present invention are not limited to these. Examples of compounds represented by the above general formula (I) In addition, the compound represented by the above general formula (I) used in the present invention is obtained from US Pat. No. 2,161,331 and West German patent 936071.
It can be easily synthesized based on the method described in the specification and the like. To use the compound represented by the above general formula (I) in a silver halide emulsion, it is added and dissolved in a coating solution, or water or an organic solvent such as methanol, ethanol, acetone or the like or a mixed solvent thereof is dissolved. Then, it may be added to the coating solution. However, if necessary, it can be added to a layer adjacent to the silver halide emulsion layer, for example, a protective layer or an intermediate layer as long as it does not affect the photographic performance. The amount of the compound represented by the general formula (I) contained in the silver halide photographic light-sensitive material of the present invention to be added to the silver halide emulsion depends on the kind of the silver halide emulsion and the kind of the compound. However, the range is usually 5 mg to 1000 mg per mol of silver halide. The compound represented by the general formula (I) according to the present invention may be added to the silver halide emulsion at any time, but it is usually at any time during ripening or after ripening and immediately before coating. It is preferable to add it at a time. Next, specific examples of the compound represented by the general formula (II) used in the present invention will be shown. The compound represented by the general formula (II) is added to the surface of the hydrophobic support on which the silver halide photographic material is not provided, that is, the backing layer. Water is used as the solvent and the addition amount is 10 to 500 mg /
and cm ^2. The backing layer has a structure in which the compound represented by the general formula (II) is dispersed in a hydrophilic colloid such as gelatin, and a hardener usually used in silver halide photographic light-sensitive materials.
A surfactant, a thickener, a matting agent, a polymer latex, and other stabilizers, antifoggants, development inhibitors, dyes, heavy metals, and ultraviolet absorbers may be added if necessary. The layer structure of this photographic light-sensitive material may be a single layer or a multilayer having an intermediate layer and a protective layer. When the silver halide photographic light-sensitive material of the present invention is handled indoors, a yellow light can be used as a safety light. Examples of the yellow lamp include a yellow fluorescent lamp, a white fluorescent lamp wrapped with a yellow film, and a sodium lamp. And the safety light can be used with any illuminance, but preferably 1 to
It is 150 looks. The silver halide in the emulsion layer in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide containing substantially no silver iodide. The presence of silver iodide is not preferable because it does not improve the safelight property. The term "substantially free from" means that the present invention includes a small amount of such an amount that the undesirable effect on the safelight property cannot be exhibited. The grain size of silver halide in the silver halide photographic light-sensitive material of the present invention is 0.05 to 0.5 μm. If the particle size is smaller than 0.05 μm, the sensitivity as a photosensitive material for argon laser cannot be obtained, and if it is larger than 0.5 μm, the required image density cannot be obtained, which is not preferable. The silver halide grains to be used may be used as they are, or may be prepared by blending two or more kinds having different average grain sizes at any time after grain formation to obtain a predetermined gradation. May be. The monodispersity of silver halide grains of the light-sensitive material of the present invention can be defined by the following formula. In the present invention, the grain size of the silver halide grains is represented by the ridge length of cubic grains and the diameter of the projected area converted into a circle in the case of other than cubic grains for convenience, and the average value is defined as the average grain size (). . The monodispersity is expressed as a value obtained by dividing the standard deviation of particle diameter by the average particle diameter by () and multiplying the value by 100. Here, if the degree of monodispersion is expressed by an equation, Becomes In the present invention, it is important to prepare the silver halide grains so that this value is 20 or less, and if the monodispersity exceeds 20, the contrast is deteriorated and the sharpness deteriorates, which is not preferable. The silver halide photographic emulsion of the present invention is, for example,
P.Glafkides "Shemie e Fijique Photography" published by Paul Montel (Chim
ie etphysique Photographique; published by Paul Montel) 1967
GF Duffin, "Photographic Emulsion Chemistry," published by The Focal Press (Photographic Emulsion Chemistry;
Published by The Focal Press) 1966, V.L. Zelikman, et al. (VLZelikman, et.al.) "Making and Coating Photographic Emulsion"
The Focal Press (Making and Coating Photo
grap-hic Emulsion; published by The Focal Press) 1964, etc. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided synthesis method, a double jet method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. PA in the liquid phase where silver halide is formed as a form of the double jet method.
A method of keeping g constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Two or more silver halide emulsions formed separately may be used as a mixture. In the process of silver halide grain formation or physical ripening,
A compound containing a metal belonging to Group 8 can coexist. These compounds are preferably used in the form of an aqueous solution, generally during the grain formation of the silver halide emulsion, during the physical ripening or during the chemical ripening, or thereafter, in an amount of 10 ^-8 to 10 per mol of silver halide.
It may be added in an amount of 10 ^-6 mol. However, when desensitization or reversal is likely to occur due to the kind of metal of the compound used, the method of preparing the emulsion or the developing method, it is 10 ^-8 mol per mol of silver halide.
It is preferred to use 10 ^-7 mol before the end of physical ripening. In order to remove the soluble salts from the emulsion after the precipitation or after the physical ripening, the Nudel washing method in which gelatin is gelled may be used, and inorganic salts, anionic surfactants, anionic polymers (for example, polystyrene) may be used. Alternatively, a precipitation method (flocculation method) using a sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. The silver halide emulsion of the light-sensitive material of the present invention may be chemically sensitized before use. For the chemical sensitization, for example, H. Frieser edited by “Die Grundlagen der Photographischen Protez Mitz Gilber Halogeneden”, Academiash Fairlarks Gesellschaft (Die Grundlagen) d
er Photographischen Prozesse mit Silberhalogenide
n; (Akademische Veralags Gesellschaft) 1968, 675 ~
The method described on page 734 can be used. Gelatin is advantageously used as the binder or protective colloid of this photographic emulsion and the hydrophilic colloid of the backing layer, but other hydrophilic colloids can also be used. This gelatin includes lime-processed gelatin, acid-processed gelatin, and Burtin of Society of
Enzyme-treated gelatin as described in Science of Photography of Japan (Bull.Soc.Sci.Rhot.Japan), No.16, p.30 (1966) may be used, or water of gelatin may be added. Degradation products and enzymatic degradation products can also be used. As the gelatin derivative, for example, various compounds such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are reacted with gelatin. What is obtained is used. The silver halide photographic emulsion and the backing layer of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heteromercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, and 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 such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy substitution (1 , 3,3a,
7) Tetraazaindenes), benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added. The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex may be contained in the silver halide photographic emulsion of the present invention and the backing layer. Methyl acrylate as polymer latex,
Aqueous dispersions of homo- or copolymers of methyl methacrylate, acrylic acid, methacrylic acid, chrysidyl acrylate, styrene, vinyl chloride, vinylidene chloride and the like are used. As the support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass , Metals and the like. These supports are subjected to a base treatment as required. The silver halide photographic light-sensitive material according to the present invention is a photographic light-sensitive material for various uses such as general black and white, X ray, color, infrared, micro, silver dye bleaching, reversal and diffusion transfer. It can be effectively applied to materials. The silver halide photographic light-sensitive material according to the present invention can be developed after exposure by various methods, for example, a commonly used method. The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols and aminobenzenes, and further contains sulfites, carbonates, bisulfites, bromides and iodides of other alkali metal salts. be able to. [Examples] Next, the present invention will be specifically described with reference to Examples. However, it goes without saying that the present invention is not limited thereto. Example 1 A hydrophilic colloid coating solution having the following composition was applied to both sides of a polyethylene terephthalate film which is a hydrophobic support. (Preparation of backing layer) Polymethyl methacrylate having an average particle size of 5μ was used as a matting agent in 50 g of inert gelatin dissolved in 1000 ml of water.
2 g, 20 ml of a 20% saponin aqueous solution as a spreading agent, 10 ml of a 3% formalin aqueous solution as a hardening agent, and sodium 2,6-dichloro-1,3,5-triazine-4-as a hardening agent.
Olate (1.0 g) was added, and ethyl acrylate polymer latex polymer (40 g) was further added. This was divided into 10 equal parts, and the compound belonging to the general formula (II) was added so that the kind and coating amount shown in Table 1 were included, and each was coated on the film support so that gelatin was 4.5 g / m ² . . (Preparation of Emulsion Layer) A silver chlorobromide gelatin emulsion containing 35 mol% of silver bromide was prepared by the simultaneous mixing method at 45 ° C. for 35 minutes. The emulsion thus prepared was desalted and redispersed to obtain a monodisperse emulsion having an average particle size of 0.2 μm. To this emulsion, 8 mg of sodium thiosulfate and 10 mg of chloroauric acid were added in 1 mol of AgX and chemically ripened at 60 ° C for 70 minutes. To this chemically aged emulsion, the compound of the above-mentioned I-9 belonging to the above-mentioned general formula (I) was added.
The amount added was 0 mg / m ² . Furthermore, 6 ml of a 0.5% solution of 1-phenyl-5-mercaptotetrazole as an antifoggant and 6-
130 ml of a 1% solution of methyl-4-hydroxy-1,3,3a, 7-tetrazaindene, 15 ml of a 20% saponin aqueous solution as a spreading agent, and 5 m of a 3% formalin aqueous solution as a hardening agent.
l, and as a hardening agent, sodium-2,6-dichloro-
0.6 g of 1,3,5-triazine-4-olate was added, and 30 ml of a high molecular weight latex polymer of ethyl acrylate was added.
g was added. This emulsion was prepared on a film support having a backing layer so that the amount of silver would be 3.5 g / m ² , and as a protective film, 80 g of 5% formalin was added to an aqueous solution of 500 g of inert gelatin with an average grain size of Amorphous silica with a diameter of 2 μm
The emulsion layer and this protective layer were coated simultaneously so that the amount of 15 g added was adjusted to 1.1 g / m ^{2 of} gelatin. Each of the 10 kinds of films thus obtained was exposed with an argon laser and developed for 20 seconds at 33 ° C. using a Sakura automatic developing machine GR-27 with the following developing solution and fixing solution. The unexposed samples of the 10 samples of film were placed at a distance of 2 m under a yellow lamp in which a yellow filter film was wrapped around a 40 W fluorescent lamp, left for 0 minutes and 5 minutes, and the fog density was measured by a conventional method. (Developer formulation) Add pure water (ion-exchanged water) to make 1.000 ml. The developer pH was about 10.8. <Fixer formulation> At the time of use of the fixer, the composition A and the composition B were dissolved in 500 ml of water in this order in order, and finished to 1 before use. The pH of the fixing solution was about 4.3. Table 2 shows the measurement results. The sensitivity is represented by the reciprocal of the exposure amount at the fog density + 3.0. Sample No. 2 containing both the compounds belonging to the general formulas (I) and (II) according to the present invention
In Nos. 10 to 10, the sensitivity was 246 to 250, and the fog under the yellow safety light was 0.01 to 0.02 when left for 0 minutes, and 0.04 to 0.12 when left for 5 minutes. On the contrary, the sample No. 1 containing only the compound belonging to the general formula (I) had a sensitivity of 250 and was 0 under the yellow safety light.
Fog after standing for 5 minutes was as good as 0.01, but fog after standing for 5 minutes was inferior at 0.23. Example-2 The compound I-9 in Example 1 and Table 1 was replaced with I-7,
The compound II-3 in Table 1 is II-1, the compound II-4 in Table 1 is II-5, and the compound II-8 in Table 1 is II.
Samples were prepared in the same manner as in Example 1 except that the sample was changed to -7.
No. 11 to No. 20 are prepared and shown in Table 3. The sensitivity and the fog were measured for these in the same manner as in Example 1 and Example 1. The measurement results are shown in Table 4. As is apparent from Table 4, samples No. 12 to No. 20 containing the compounds belonging to the general formulas (I) and (II) according to the present invention.
The sensitivity was 305 to 309, and the fog under the yellow safety light was 0.02 to 0.03 when left for 0 minutes, and 0.06 to 0.17 when left for 5 minutes.
On the other hand, Sample No. 11 containing only the compound belonging to the general formula (I) had a sensitivity of 310 and had a good fog of 0.02 when left in a yellow safety light for 0 minutes, but had a fog after standing for 5 minutes. 0.30
Was inferior. Example-3 An emulsion prepared in the same manner as in Example 1 was divided into 10 equal parts, and as shown in Table 5, compounds II-6, II-4 represented by the general formula (II),
Regarding II-1 and II-2, the presence or absence in the backing layer and the compounds I-16 and II- represented by the general formula (I) in the emulsion layer.
5, I-17, and I-19 were combined and coated on a film support in the same manner as in Example 1. The 10 kinds of films shown in Table 5 thus obtained were exposed with an argon laser, respectively, and then the cherry blossom automatic developing machine was used.
Using GR-27, the following developing solution and the fixing solution used in Example 1 were developed at 28 ° C. for 30 seconds, fixed, washed with water and dried. <Developer formulation> When the developer was used, the above composition A and composition B were dissolved in this order in 500 ml of water and finished to 1 before use. The measurement results are shown in Table 6. Sample No. 22, N containing both the compounds belonging to the general formulas (I) and (II) according to the present invention
o, 24, No, 26, No, 27, No, 28, No.30 has a sensitivity of 206-232, fog of 0.02 to 0.03 for 0 minutes left under a yellow safety light, and 0.07 to 0.14 for 5 minutes. It was good. On the contrary, the samples No. 21, No. 23, N containing only the compounds belonging to the general formula (I)
Nos. 25 and 29 had a sensitivity of 208 to 235 and fog under a yellow safety light was 0.01 to 0.02 when left for 0 minutes, but was fogged to 0.23 to 0.31 for 5 minutes. Example-4 The sample prepared in Example 1 was exposed by forming halftone dots with an argon laser. When treated in the same manner as in Example 1 and observing the shape of the halftone dot with a magnifying glass of 100 times, the general formula (II)
With a backing layer containing a compound belonging to
It can be seen that o.2 to No. 10) are superior in sharpness and have a higher contrast than the sample (No. 1) not containing. [Effects of the Invention] As described above, according to the present invention, a silver halide photographic light-sensitive material which is safe to handle under a yellow safety light, has high sensitivity to an argon laser light source, and has high contrast. Is obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/83 G03C 1/83

Claims (1)

(57) [Claims] A silver halide photographic light-sensitive material comprising a photographic constituent layer having at least one silver halide emulsion layer on one surface of a hydrophobic support and coating a hydrophilic colloid layer on the opposite surface of the support. The silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0.05.
~ 0.5μm, monodispersity of 20 or less, at least 50mol%
Of silver chlorobromide or silver chloroiodobromide containing at least one compound selected from the compounds represented by the following general formula (I) in the photographic constituent layer,
A silver halide photograph for an argon laser scanner, characterized in that the hydrophilic colloid layer on the opposite side of the silver halide emulsion layer contains at least one compound selected from the compounds represented by the following general formula (II): Photosensitive material. General formula (I) [Wherein, R is an alkyl group, Z is a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle, and Q is a non-metal atom necessary for forming a 5-membered heterocycle. A group, provided that at least one of the 5-membered rings is C-S. General formula (II) [Wherein R ₂ represents an alkyl group, a carboxyl group, an alkoxycarbonyl group, a carbamide group, a nitrile group, a trifluoromethyl group or an acylamino group, and R ₃ represents an aryl group substituted with one or more sulfone groups. Represent. R ₄ , R ₅
Represents an alkyl group which may be different from each other. n is 1 or 2. ]