JP2857738B2 - Silver halide photographic light-sensitive material capable of obtaining high-contrast images - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material capable of obtaining a high-contrast photographic image. [0002] Silver halide photographic light-sensitive materials have hitherto been widely used in photolithography processes. The photoengraving process includes a step of converting a continuous tone original into a halftone image, that is, a step of converting a continuous tone density change of the original into a set of halftone dots having an area proportional to this density. Have been. In this conversion step, an original is photographed through a crossing screen or a contact screen using a silver halide photographic light-sensitive material having a high contrasting photographic characteristic, and is developed to obtain a halftone image. Was formed. In order to impart a high contrast characteristic to an image, a so-called high contrast silver halide photographic material has conventionally been used as disclosed in JP-A-56-106244 and US Pat. No. 4,686,167. A compound such as hydrazine is contained as an agent, and further, silver halide grains that effectively exhibit the high contrast characteristics of the compound are used, or other photographic additives are appropriately combined to obtain a desired photographic light-sensitive material. Had been adjusted. The silver halide photographic light-sensitive material thus obtained is certainly stable as a light-sensitive material, and a high-contrast photographic image can be obtained even by processing with a developer that can be rapidly processed. . However, in such a silver halide photographic light-sensitive material, when a continuous tone original is converted into a halftone image, sand-like pin-like fog appears in the halftone dots. However, there is a problem that a so-called black pin is generated and the quality of a dot image is impaired. Therefore, in order to solve this problem, conventionally, various stabilizers having a hetero atom,
In some cases, measures such as addition of an inhibitor were taken, but they were not always effective. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a high contrasting photographic characteristic by suppressing fog generated in a halftone dot image while having a high contrasting photographic characteristic. The present invention provides a silver halide photographic light-sensitive material that can be used. The silver halide photographic light-sensitive material according to the present invention contains, in this material, the following general formula (I): ## STR1 ## A compound containing the compound represented by the formula (1), which has high contrast characteristics and high-contrast photographic characteristics in which pin-like fog is suppressed in a halftone dot image. Can be. In the above general formula [I], R ₁ and R ₂ are a hydrogen atom, an alkyl group which may be substituted (for example, a methyl group,
Ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group),
Optionally substituted phenyl, naphthyl, cyclohexyl, pyridyl, pyrrolidyl (for example, phenyl, p-methylphenyl, naphthyl, α-hydroxynaphthyl, cyclohexyl, p-methylcyclohexyl, pyridyl) , 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group), and R ₃ represents a hydrogen atom or a benzyl group, an alkoxy group or an alkyl group which may be substituted (for example, a benzyl group, p -Methylbenzyl, methoxy, ethoxy,
R ₄ and R ₅ represent a divalent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group. (e.g. _{-SO 2 CH 2 CH 2 NH,} -SO 2 NH, -OCH 2 CH
_{2 CONH -, - OCH 2 SO} 2 NH -, -O -, -CH = N -) represents, X represents a -NR ₆ R ₇ or -OR _8, R _6, R ₇ and R ₈ are hydrogen atoms An optionally substituted alkyl group (eg, a methyl group, an ethyl group, a dodecyl group), a phenyl group (eg, a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group) or a naphthyl group (eg, an α-naphthyl group,
β-naphthyl group), and n represents 0 or 1. When X represents -OR _8, Y is preferably a sulfur atom. In formula (I), H of --NHNH, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, etc.), an oxalyl group ( For example, the compound represented by the general formula [I] may be substituted with a substituent such as ethoxalyl). Typical compounds represented by the above general formula [I] include the following. However, needless to say, specific compounds of the general formula [I] that can be used in the present invention are not limited to these compounds. [0013] Embedded image Embedded image Embedded image Next, a method of synthesizing the above-mentioned specific compounds will be described taking compounds 1 and 3 as examples. Synthesis of Compound 1: The synthesis scheme is as follows. Embedded image That is, 4-nitrophenylhydrazine 153
g and 500 ml of diethyl oxalate and reflux for 1 hour. Ethanol is removed while proceeding the reaction,
Finally, it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 g of the obtained crystal (A) was dissolved under heating with 1000 ml of methanol, and reduced under a pressurized H ₂ atmosphere of 50 Psi under a Pd / C (palladium / carbon) catalyst to give compound (B). obtain. 22 g of this compound (B) was mixed with acetonitrile 2
Dissolved in a solution of 00 ml and 16 g of pyridine,
(C) 24 g of acetonitrile solution was added dropwise. After filtering off insolubles, the filtrate was concentrated and purified by recrystallization to obtain 31 g of compound (D).
I got 30 g of compound (D) was hydrogenated in the same manner as above to obtain 20 g of compound (E). 10 g of compound (E) is added to 100 ml of acetonitrile
, And 3.0 g of ethyl isothiocyanate was added.
Refluxed for hours. After evaporating the solvent, the residue was purified by recrystallization to obtain 7.0 g of compound (F). 5.0 g of compound (F)
After dissolving in 50 ml, methylamine (8 ml of 40% aqueous solution) was added and stirred. After slightly concentrating the methanol, the precipitated solid was taken out and purified by recrystallization to obtain Compound 1. Synthesis of Compound 3: The synthesis scheme is as follows. Embedded image 22 g of p-nitrobenzenesulfonyl chloride was added to a solution of 22 g of the compound (B) in 200 ml of pyridine and stirring. After draining the reaction mixture, the precipitated solid was taken out to obtain compound (C '). This compound
Compound (C ′) was reacted in the same manner as Compound 1 according to the synthetic scheme to give Compound 3. The silver halide photographic light-sensitive material of the present invention contains the compound represented by the above general formula [I]. The amount is preferably from 5 × 10 ^-7 mol to 5 × 10 ^-1 mol per mol of silver halide contained in the photographic light-sensitive material of the present invention. It is particularly preferred that the content be in the range of 5 × 10 ^-5 mol to 1 × 10 ^-2 mol. The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one surface of the support, or at least one silver halide emulsion layer may be provided on both surfaces of the support. The silver halide emulsion can be coated directly on the support or can be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be provided on the emulsion layer. Further, the silver halide emulsion layer may be separately applied to silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer made of a hydrophilic colloid may be provided between the silver halide emulsion layers. Further, an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. That is, if necessary, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided. In order to incorporate the compound represented by the general formula [I] into the silver halide photographic light-sensitive material of the present invention, it is preferable that the compound is contained in a hydrophilic colloid layer in the material, and particularly preferable is a silver halide emulsion. And / or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. However, the compound of the above general formula [I] may be contained not in the silver halide emulsion layer but in another layer.
For example, it is a matter of course that another hydrophilic colloid layer coated on the emulsion layer may be contained. In the most preferred embodiment of the present invention, the compound of the formula [I] is contained in a silver halide emulsion layer, and the hydrophilic colloid comprises gelatin or a gelatin derivative. Next, a method for incorporating the compound of the general formula [I] into the hydrophilic colloid layer will be described. This method includes, for example, dissolving the compound in an appropriate water and / or organic solvent and adding the compound, or dispersing a solution dissolved in an organic solvent in a hydrophilic colloid matrix such as gelatin or a gelatin derivative and then adding the compound. Or a method of dispersing and adding in latex. In practicing the present invention, any of these methods may be used. And when adding, the above-mentioned general formula [I]
The compound (1) can provide preferable image characteristics even when used alone, but it has been confirmed that two or more compounds may be used in combination at an appropriate ratio. As another method of addition, the compound of the above general formula [I] is dissolved in a suitable organic solvent, for example, alcohols such as water, methanol and ethanol, ethers, esters and the like, and overcoated. It may be applied directly to the portion of the silver halide photographic material which will be the outermost layer of the silver halide emulsion layer by a method or the like so that the silver halide photographic material contains the silver halide emulsion. As described above, in a preferred embodiment of the present invention, a compound of the general formula [I] is added to a silver halide emulsion layer. In another preferred embodiment, a silver halide emulsion layer is added. Is added to the hydrophilic colloid layer immediately adjacent to the hydrophilic colloid layer containing, or to the hydrophilic colloid layer adjacent via the intermediate layer. Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. Any composition can be used as the silver halide. Examples include silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide or silver chloroiodobromide. The average diameter of the silver halide grains is 0.05 to 0.
Those having a range of 5 μm are preferably used.
Those having a diameter of 0.10 to 0.40 μm are preferred. The particle size distribution of the silver halide grains used in the present invention is arbitrary, but the value of the monodispersity defined below is 1 to 30.
Is preferably adjusted, and more preferably in the range of 5 to 20. Here, the degree of monodispersity is defined by the following equation. [Formula 1] That is, the monodispersity is defined as a value obtained by multiplying the standard deviation of the particle size by the average particle size by 100 times. The grain size of silver halide grains is represented by the ridge length of cubic grains for convenience. In practicing the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver chloride in the core and odor in the shell. Silver chloride, or conversely, silver chlorobromide particles having a core portion of silver bromide and a shell portion of silver chloride can be used. At this time, iodine can be contained in any layer, but it is preferable that iodine be within 5 mol%. Further, when preparing a silver halide emulsion, a rhodium salt can be added to control the sensitivity or gradation. Generally, the rhodium salt is preferably added at the time of grain formation, but may be added at the time of chemical ripening or at the time of preparing an emulsion coating solution. The rhodium salt may be a simple salt or a double salt, and typical examples thereof include rhodium chloride, rhodium trichloride, and rhodium ammonium chloride. The amount of rhodium salt added depends on the required sensitivity,
It may be arbitrarily changed depending on the gradation, but 10 ^-9 per mol of silver
A range from moles to 10 ^-4 moles is particularly effective. When a rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt, gold salt and the like may be used in combination. In particular, iridium salts are often used for imparting high illuminance characteristics, and are preferably used in the range of 10 ^-9 mol to 10 ^-4 mol per mol of silver. Further, the silver halide can be sensitized by various chemical sensitizers. Examples of the sensitizer include active gelatin, a sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), a selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.). ), Reduction sensitizers (triethylenetetramine, stannous chloride, etc.) such as potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinum Various noble metal sensitizers such as catenate and sodium chloroparadite can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent. The present invention is suitably applied when surface latent image type grains are contained as silver halide grains. Here, the surface latent image type particles refer to particles which are prepared so that the sensitivity when processed with a surface developer in the art is higher than the sensitivity when processed with an internal developer. The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole) and benzotriazoles (5-bromobenzotriazole,
Stabilization or fog suppression can be performed using methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), or the like. The silver halide emulsion used in the present invention may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like. When the compound of the general formula [I] according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but it is also possible to use a hydrophilic colloid other than gelatin. it can. Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material. For the development processing of the silver halide photographic material of the present invention, for example, the following developing agents are used. Representative HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol and pyrogallol. As the HO- (CHCHCH) n-NH ₂ type developer, ortho- and para-aminophenols or aminopyrazolones are typical, and N-methyl-p-aminophenol, N-β -Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like. Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-.
Examples thereof include 3-pyrazolidones such as hydroxymethyl-3-pyrazolidone. In addition, T.I. H. James The Theory of the Photographic Process 4th Edition (Th
e Theory of the Photographic Process, Fourth Editi
on) Pages 291-334 and Journal of the American Chemical Society (Journal of the Americ
An Chemical Society), vol. 73, p. 3, 100 (1951), is a developer which can be effectively used in the present invention. These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination. Hydroquinone alone or hydroquinone in combination is 1-phenyl-3-
Pyrazolidone or hydroquinone and N-methyl = p
-Aminophenol combinations are preferred. The effect of the present invention is not impaired even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention. Also, hydroxylamine and hydrazide compounds may be used as preservatives. Others: pH adjustment with a caustic alkali, an alkali carbonate, an amine, or the like as used in general black-and-white developing solutions and a buffer function; an inorganic development inhibitor such as bromocali; an organic development inhibitor such as benzotriazole; Metal ion scavengers such as acetic acid, methanol, ethanol, benzyl alcohol, development accelerators such as polyalkylene oxide, sodium alkylaryl sulfonate,
It is optional to add surfactants such as natural saponins, sugars or alkyl esters of the above compounds, hardeners such as glutaraldehyde, formalin, glyoxal, etc., and ionic strength modifiers such as sodium sulfate. The developer used in the present invention may contain an alkanolamine or a glycol as an organic solvent. Embodiments of the present invention will be described below. Needless to say, the present invention is not limited to the following embodiments. Example 1 Illustrative compounds represented by the general formula [I] and comparative compounds (the types of which are shown in Table 1 below) were added to a silver halide emulsion layer of a photographic light-sensitive material in the following manner. A sample was prepared by addition. (Preparation of silver halide photographic light-sensitive material) A 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both surfaces was coated on one undercoat layer of the following formula (1) 1.5g of gelatin in silver emulsion layer
/ M ² , and the amount of silver is 3.3 g / m ^2, and a protective layer having the following formulation (2) is further coated thereon with a gelatin amount of 1.0 g / m ^2.
m ^2, and on the other undercoat layer on the opposite side, a backing layer was coated according to the following formula (3) so that the gelatin amount was 3.5 g / m ² , and Sample Nos. 1, ² , 21 to 23 were obtained by coating a protective layer having the following formulation (4) so that the amount of gelatin became 1 g / m ² . Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image The obtained samples were subjected to a dot quality test by the following method. (Dot Quality Test Method) A half-tone screen (150 lines / inch) having a halftone dot area of 50% was partially attached to the step wedge, and the sample was brought into close contact with the screen, and the step was measured with a xenon light source.
Exposure for 2 seconds, this sample was developed with the following developer and the following fixer in a rapid processing automatic developing machine under the following conditions, and the dot quality of the sample was observed with a 100X magnifier.
Those with high dot quality are ranked "5", and the following "4",
Five ranks of "3", "2", and "1" were set. Note that the ranks “1” and “2” are levels that are not preferable for practical use. Fog in a halftone dot was evaluated in the same manner, and a dot having no black pin in the halftone dot was assigned the highest rank "5", and was determined according to the degree of occurrence of a black pin in the halftone dot. The ranks "4", "3", "2", and "1" were sequentially reduced and evaluated. In addition, in the ranks "1" and "2", the black pins are too large, which is not a practically preferable level. (Formulation of developer) At the time of use of the developing solution, the above-mentioned composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. (Fixing solution formulation) At the time of use of the fixing solution, the composition A and the composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. The pH of the fixing solution was about 4.3. (Development processing conditions) (Process) (Temperature) (Time) Current image 38 ° C 30 seconds Fixed 28 ° C 20 seconds Rinse at normal temperature 20 seconds [0073] The halogenation in formula (1) The following compounds (a) to (c) were used as comparative compounds added to the silver emulsion layer. Embedded image (Test Results) Table 1 shows the sample No. of the present invention.
Sample Nos. 21 to 21 prepared using the above-mentioned comparative compounds and the above-mentioned comparative compounds
For No. 23, the compounds added to the silver halide emulsion layer and the amounts added were shown. In addition, the compound of the general formula [I] in Table 1 is shown by the number of the exemplified compound. Table 2 shows the results of the dot quality test by ranking the above samples. As is clear from Table 2, the dot quality of the samples Nos. 1 and 2 according to the present invention is all excellent in rank "4" or higher. Comparative Sample Nos. 21 to 23 all showed the result of rank "3". If the ranks "1" and "2" indicate that they are not practical levels, none of the samples Nos. 21 to 23 can be said to have poor dot quality, but the sample Nos. It was found that .1 and 2 all had extremely high dot quality and were excellent. Further, with respect to the degree of occurrence of black pins as an index of fog, all of the samples Nos. 1 and 2 according to the present invention were evaluated as rank "4", and showed extremely good results without fog. On the other hand, it was found that Comparative Samples 21 to 23 each had a rank of “2” or less, indicating results that were hardly practical. [Table 1] [Table 2] As described above, according to the present invention, a silver halide photographic light-sensitive material contains a compound represented by the general formula [I] to obtain a photographic image having a high contrast characteristic and a halftone dot quality. And an excellent photosensitive material having a high image quality.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Hanyu 1 Sakuracho, Hino-shi, Tokyo Konica Corporation (72) Inventor Yutaka Uesawa 1 Sakuracho, Hino-shi, Tokyo Konica Corporation (56) References JP-A-2-37 (JP, A) JP-B 8-33604 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/06 501

Claims (1)

(57) [Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, comprising at least one compound represented by the following general formula [I]. Embedded image However, in the above general formula [I], R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group or a pyrrolidyl group, and R ₃ is a hydrogen atom or a substituted A benzyl group, an alkoxy group or an alkyl group; R ₄ and R ₅ are divalent aromatic groups; X is —NR ₆ R ₇ or OR ₈ ; R _6, R _{7 and} R ₈ are hydrogen atoms; An alkyl group, a phenyl group, a naphthyl group, Y represents a sulfur atom or an oxygen atom, L represents a divalent linking group, and n represents 0 or 1. The compound represented by the general formula [I] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.