JPH0239038A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the physical property of a film and the pressure durability of the title material by specifying the jelly strength of a gelatin which is one of the measure of the physical property of the gelatin and the ratio of the each amounts of silver and a binder composed of the gelatin, respectively. CONSTITUTION:The hydrophilic colloid contd. in the emulsion layer of the photosensitive material contains at least 50% or more of the gelatin having the jelly strength of >=240, and the wt. ratio of the each amounts of the silver and the gelatin which are applied on the side having the emulsion layer against a supporting body is specified to 1.0-1.8. The emulsion particle is physically aged in the presence of the gelatin having the jelly strength of >=240. And, the photosensitive material contains a tetrazolium compd. shown by formula I. In the formula, R1, R2 and R3 are each hydrogen atom or a substituent, X<-> is an anion. Thus, the generation of the crack and the sticking of the gelatin layer does not occur even at the time of reducing the amount of gelatin, and the shelf-life property for a long period and the pressure durability of the photosensitive material are improved.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with high contrast. [Background of the Invention] In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time. The above trend can also be seen in the printing plate making field. In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to perform printing plate-making work in a short delivery time and in larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly. Generally, when ultra-rapid processing is performed, the fixing time and washing time are shortened, which increases the concentration of sulfur-containing groups remaining in the processed film, causing the problem that the processed film turns yellow during storage. arise. Another problem is that since the development time is short, the density decreases even if the initial sensitivity is adjusted by increasing the development activity of the developer or the temperature of the developer. Furthermore, the problem of insufficient drying also occurs. In this specification, ultra-quick processing means that the leading edge of the film is inserted into an automatic developing machine, passes through a developing tank, a transition area, a fixing tank, a transition area, a washing tank, a transition area, and a drying area. [In other words, the total length of the processing line (+a) is the line conveyance speed (m/
The quotient (see, )) divided by see, ) is 20 seconds to 60
It refers to a process that takes seconds. The reason why the time for the crossing portion should be included here is that it is well known in the industry,
This is because the liquid from the previous process is swollen in the gelatin film even at the transition part, so it can be considered that the processing step is actually progressing. Japanese Patent Publication No. 51-47045 describes the importance of the amount of gelatin in rapid processing, but the total processing time including the crossing portion is 60-120 seconds. However, this amount of time cannot meet the recent demands for ultra-quick processing. Reducing the amount of gelatin is an effective means. Reducing the amount of gelatin improves the diffusivity of the processing solution into the photosensitive material, and is effective in preventing density loss, which also occurs especially when the film is stored at high temperature and high humidity. This can reduce the sticking of films due to contact with each other, but on the other hand, reducing the amount of gelatin makes the film more likely to crack, and also increases the risk of scratches and pressure.
Fogging is more likely to occur. Therefore, in the case of a photosensitive material for printing, halftone dots or image quality are deteriorated. [Object of the Invention] In order to solve the above-mentioned problems, the object of the present invention is to reduce the amount of gelatin without causing cracks or sticking.
It is an object of the present invention to provide a silver halide photographic material which is excellent in long-term storage, has improved pressure resistance, and has high sensitivity and high contrast. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, in which the hydrophilic colloid in the emulsion layer has a jelly strength of 240 or more. containing at least 50% gelatin, and the weight ratio of the amount of silver to the amount of gelatin coated on the side containing the emulsion layer relative to the support is 1.0 to 1.8. This is achieved by a silver halide photographic material characterized by the following. In addition, in the present invention, silver halide crystals in at least one layer of the emulsion layer are used during physical ripening in the presence of gelatin having a jelly strength of 240 or more,
[In the formula, R+, R3, and Ri each represent a hydrogen atom or a substituent, and X represents an anion. ] The details of the present invention will be explained below. In the present invention, it is necessary that gelatin having a jelly strength of 240 or more be contained in an amount of 50% or more, preferably 60% or more of the total amount of gelatin in the emulsion layer side. Also, the jelly strength is preferably 265 or higher. The ratio of silver to gelatin is preferably 1.1-1.7. There are two methods for producing gelatin: an acidic method and an alkaline method; the former mainly uses pig skin as a raw material, and the latter uses cow bones or skin. For photography, insoluble collagen called ossein, which is mainly produced from bovine bones, is immersed in a suspension of slaked lime and treated with alkali. Changes in the structure and chemical composition of collagen during this alkaline treatment greatly influence the speed and properties of gelatin dissolution into the next warm water. The physical properties of gelatin are influenced by the raw material ossein and the liming conditions, but the extraction conditions into the hot water, such as temperature and pH,
It is most affected by 1 hour etc. In other words, gelatin in the early stage of extraction, called the first extraction, has excellent physical properties. It goes without saying that the physical properties of the film as a silver halide photographic light-sensitive material are greatly influenced by gelatin as a binder. The present invention uses jelly strength, which is one measure of gelatin physical properties,
In addition, by regulating the ratio of the amount of silver to the amount of binder gelatin, the film properties of the silver halide photographic light-sensitive material are improved, and the resistance to scratches and pressure is improved. Here, the jelly strength was measured using the value measured by the PAGI method. In addition, recently, rapid access processing, which can be processed quickly and has good stability, is often used for photosensitive materials for printing instead of the conventional lithographic processing. A technique using a tetrazolium compound as a material is disclosed. For example, Tokuko Sho 5
No. 9-17825, No. 59-17818, No. 59-1
No. 7819, No. 59-17820, No. 59-1782
No. 1, No. 59-17826, and No. 59-17822. In the present invention, the effects of the present invention are exerted by controlling the physical properties of gelatin and also using a tetrazolium compound shown in general formula CI). Below is the general formula (
1) will be explained. Preferred examples of the substituents represented by R1 to R1 in the general formula CI) include an alkyl group, an amino group, an acylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group, and a carboxyl group. Examples include groups such as acyl, cyano, nitro, mercapto, sulfoxy, and aminosulfoxy groups. Examples of the anion represented by x0 include halogen ions, acid groups of inorganic acids, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically lower alkylbenzene sulfonic acid anions, higher alkylbenzene sulfones, etc. Examples include polymers with acid groups such as acid anions, higher alkyl sulfate anions, borate anions, dialkyl sulfofosuccinate anions, polyether alcohol sulfate anions, higher fatty acid anions, and polyacrylate anions. . Specific examples of the compound represented by the general formula CI) used in the present invention are listed below, but the compound of the present invention and the tetrazolium compound used in the present invention are, for example,
-(C1)6@1cal Reviews) Vol. 55, pp. 335-483. The tetrazolium compound represented by the general formula CI) of the present invention may be used in an amount of about 1 to 10 g, preferably about 10 mg to about 29 g, per mole of silver halide contained in the silver halide photographic material of the present invention. It is preferable to use it within the range of . The silver halide photographic light-sensitive material of the present invention comprises a support and at least one silver halide emulsion layer on the support, containing at least 50% of gelatin having a jelly strength of 240 or more.
The silver halide emulsion layer is coated directly on the support, or coated via a gelatin layer that does not contain the silver halide emulsion. A gelatin layer may be further coated on the silver emulsion layer as a protective layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. A gelatin intermediate layer may be provided between the silver halide emulsion layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. The layer containing the tetrasyriam compound represented by the general formula [■] of the present invention is preferably a silver halide emulsion layer and/or a gelatin layer adjacent to the silver halide emulsion layer. In order to contain the tetrazolium compound represented by the general formula [I] of the present invention in the gelatin layer,
Examples include a method in which both are dissolved in appropriate water and/or an organic solvent and added, a method in which a solution dissolved in an organic solvent is dispersed in gelatin and then added, or a method in which the solution is added after being dispersed in latex. . The present invention may use any of these methods. The tetrazolium compounds represented by the general formula [I] used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound outside the present invention may be used in combination in an appropriate ratio. In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically p-)luenesulfonic acid anions, etc. Lower alkylbenzenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acid anions, lauryl sulfate anions, tetraphenylporones, di-2-
Dialkyl sulfate anions such as ethylhexyl sulfosuccinate anions, polyether alcohols such as cetyl polyethenoquine sulfate anions [M ester anions, stearic acid anions, polyacrylic acid anions, etc. can be mentioned. Such anions may be added to the gelatin layer after being mixed in advance with the tetrazolium compound of the present invention, or they may be added alone to the silver halide emulsion layer or gelatin layer containing or not containing the tetrazolium of the present invention. I can do something. The binder other than gelatin having a jelly strength of 240 or more described in the present invention is not particularly specified, and may include gelatin derivatives, gelatin and other polymeric polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers. Hydrophilic colloid layers can also be used, such as synthetic hydrophilic polymeric materials such as. The silver halide used in the silver halide photographic material of the present invention is not particularly limited, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is AgCC/AgBr
-10010-2/98, but preferably ^gC (1/AgBr = 10010-50150
The molar ratio of The average grain size of the silver halide grains is 0.
It is preferably 10 μm to 0.40 μm, and more preferably has a narrow particle size distribution with a coefficient of variation expressed by (standard deviation of particle size) average particle size)×100 of 15% or less. As the silver halide used in the present invention, various sensitizers, sensitizing dye stabilizers, etc. known in the photosensitive material industry can be used. As the support used in the present invention, various supports known in the photosensitive material industry, such as polyester films, can be used. The light-sensitive material according to the present invention has an appropriate film thickness on the side of the silver halide emulsion layer.
Preferably, a gelatin protective layer of 10 .mu.m, particularly preferably 0.8 to 2 .mu.m, is applied. The gelatin layer, which is the hydrophilic colloid layer used in the present invention, may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, and antistaining agents. , pH adjuster, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant,
Brighteners, development speed regulators, matting agents, and the like can be used within the range that does not impair the effects of the present invention. The silver halide photographic material containing the tetrazolium compound of the present invention is preferably developed in the presence of a compound represented by the following general formula [11]. General formula [ff) In formula C, R6 represents a 5- or 6-position nitro group, and R5 represents a hydrogen atom or a 01-C6 lower alkyl group. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] Specific examples of the compound represented by the general formula (I[) include 5-nitroindazole and 6-nitrointasole, but the present invention is not limited thereto in any way. The compound represented by the general formula (n) is an organic solvent such as diethylene glycol, triethylene glycol, ethanol, jetanolamine and triethanolamine,
It may be added to the developer after being dissolved in an alkali such as sodium hydroxide or an acid such as acetic acid, or it may be added as is. General formula [11] is preferably included in a concentration range of about 119 to 1.0ooIIg, more preferably about 50mg to 3001g. The developing agent used in developing the silver halide photographic material of the present invention is described in The Theory by T. H. James.
Of the Photographic Process 4th Edition (The
Theory of the Photography
ic Process, Fourth Editio
n) pp. 291-334 and Journal of the
American Chemical Society (Journa)
l or The American Che
l1lical 5oiety) No. 73, No. 3,
Developers such as those described on page 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 one of the effects of the invention will be improved. This can be mentioned as a characteristic. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid. metal ion scavengers such as, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide,
Addition of surfactants such as sodium alkyla 1'-rusulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, and glyoxal, and ionic strength regulators such as sodium sulfate. What you do is optional. The developer used for developing the photosensitive material of the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the above-mentioned alkanolamine include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The preferred amount of these alkanolamines used is 5 to 500 g, more preferably 20 to 200 g, per 112 g of the developer. In addition, the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
-bentanediol and the like, but jetting glycol is preferably used. The amount of these glycols used is 5 to 500 g, more preferably 20 to 200 g, per 112 g of the developer. 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 above-mentioned ffi developer is 9 to 12, but from the viewpoint of stability and photographic properties, the pH value is lθ to 11.
A range of is preferred. The silver halide photographic material of the present invention can be processed under various conditions. The processing conditions are, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 1 minute, but particularly preferably within 30 seconds often brings about good results. 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】

Examples will be specifically shown below. [Method for Preparing Emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B, and C. <Solution A> Ossein gelatin-1139 Polyethylene propylene-polyethylene oxydisuccinic acid ester sodium salt 2110% ethanol solution Distilled water 1000cc <Solution B> Silver nitrate 170g Distilled water
400ml12〈Solution C〉 Sodium chloride 45.9g Potassium bromide 27.49 Rhodium tribromide trihydrate 20. Oog polyisopropylene oxydifusuccinate sodium salt lO% ethanol solution 1.5raQ ossein gelatin-1119 Distilled water 407raQ After keeping solution A at 40°C, sodium chloride was added so that the EAg value was 160 V. . Next, solutions B and C were added by a double jet method using the mixing agitator described in JP-A-57-92523 and JP-A-57-92524. As shown in Table 1, the addition flow rate was gradually increased over a total addition time of 75 minutes, and addition was carried out while keeping EAg constant. The EAg value was 3 mol/Q 5 minutes after the start of addition from 160 V.
EAg (1120 V
This value was then maintained until the completion of mixing. In order to keep the EAg value constant, 3 mol/a of sodium chloride Table 1 For the measurement of EAg, a metal electrode and a double junction saturated Ag/AgCQ reference electrode were used (the electrode configuration was based on JP-A-57-197534). (using the double junction disclosed in the issue). Further, a variable flow rate roller tube metering pump was used to add solutions B and C. Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system. Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution. After the addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water using a conventional method.After that, an aqueous solution of ossein gelatin-■ was added, and the emulsion was aged at 55°03.
After being dispersed by stirring for 0 minutes, the volume was adjusted to 750cc and E
i-1 was obtained. The average particle size of the obtained particles was 0.29 μm
1 monodispersity was IO. Similarly, using ossein gelatin-2 and ossein gelatin-3 instead of ossein gelatin-1, Em-
2. EOI-3 was prepared. The grain size and monodispersity of these emulsion grains were the same as Em-1. The jelly strength of each ossein gelatin is as follows. Ossein gelatin Jelly strength l 220 Example 1 Each of the above emulsions was subjected to total sulfur sensitization, and 6
-Ig of methyl-4-hydroxy-1,3,3a,7-chitrazaindene was added per mole of silver halide, and the following compound (a) was added as a sensitizing dye at 370ra9 per mole of silver halide contained in the emulsion. (b) 90-
9 were added. Next, 700,119 gram of Exemplified Compound I-6 of general formula (1) was added per mole of silver halide, and 400 rag of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer, and styrene-butyl acrylate-acrylic acid copolymer were added. Polymer latex (average particle size approximately 0.2
A coating solution for emulsion layer was prepared by adding 15 g of 5 μm). Next, in another ossein gelatin aqueous solution, ■-decyl-2-(3-impentyl)succinate-2-sodium sulfonate 301119/II" was added as a spreading agent, formalin 251119/II" was added as a hardening agent, and A coating solution for the protective layer was prepared by adding 20 mg/m'' of Noarica with an average particle size of 3.5 μm as a matting agent. The example of JP-A No. 59-19941 (
On the polyethylene terephthalate film base coated with the undercoating described in 1), the silver amount was 4.19/IQ" and the total gelatin amount was 2.95 g/m", and the gelatin amount was coated on the opposite side. A normal backing layer was coated with a coating amount of 3.5 g/m" to obtain a sample as shown in Table 2. On the other side, gelatin was coated with a coating amount of 3.5 g/m". A backing layer was applied. These samples were exposed using an optical wedge. The above test sample was processed in an automatic processor using a developing solution and a fixing solution according to the following formulation. [Development processing conditions] (Process) (Temperature) (Time) Development
Fix at 28°C for 30 seconds
Wash and dry at 28°C for about 20 seconds. Composition of drying developer (composition A) Pure water (ion-exchanged water) 150 g of alpha-technical ethylene diamine tetraacetic acid disodium salt diethylene glycol 509 potassium sulfite (55% W aqueous solution) 100D112 carbonic acid Potassium 509 Hydroquinone
15g 5-methylbenzotriazole 200m @ l-phenyl-5-mercaptotetrazole 0 tag Potassium hydroxide Adjust the pH of the working solution to 10.4 Potassium monobromide 4.5g (composition) Pure water (ion exchange water) 31 (2 diethylene glycol) 50g Ethylenediaminetetraacetic acid disodium salt Room temperature approximately 20 seconds 50℃ 15 seconds 25 rtry Acetic acid (90% aqueous solution) 0.3 m (1
5-Nitroindazole 110191-
7enyl-3-pyrazolidone When using 700m+9 developer, it was dissolved in 500+ml of water in the order of composition 1 above and finished to IQ. [Fixer formulation] (Composition A) Ammonium thiosulfate (72.5% Wha aqueous solution) 240
Otori Q Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90% v/w aqueous solution)
13.6mQ (composition) Pure water (ion exchange water) L7vaQ sulfuric acid (50% v/v aqueous solution) 4.79 Aluminum sulfate (aqueous solution with Ai2203 equivalent content of 8.1% v/v) 2
6.5g When using a fixer, it was dissolved in 500t+2 of water in the order of composition 1 above, finished to IQ, and used. The pH of this fixer was about 4.3. A photographic characteristic curve was drawn for the developed sample, and the sensitivity fog density and the break in the leg of the characteristic curve were measured. The sensitivity was calculated from the reciprocal of the exposure amount required to form an optical density of 2.5, and was expressed as relative sensitivity with Sample No. 2 as lOO. Contrast is expressed as a gamma value for the exposure amount that gives optical densities of 0.2 and 1.5. For cracks, place 100g of completely dried silica gel together with the sample in a sealed desiccator.
It was left at 40° C. for one day, and the degree of cracking in the Em layer was visually determined. The judgment criteria are 5 levels, with 5 being no occurrence at all. 3 is the lower limit where the occurrence is practical, l is the level where the occurrence is significant and cannot be put to practical use, and 4.2 is the middle of each. Regarding sticking, after leaving the sample at 23°C and 48% for 2 hours, seal the sample in an airtight bag with the BC side opposite to the emulsion layer side in close contact, and after leaving it at 55°C for 1 day, take out the sample and remove the emulsion layer. When the layer surface and the BC surface were peeled off, the degree of adhesion was visually evaluated on a five-point scale in the same manner as in the case of cracks. As for pressure resistance, the sample was immersed in the developer at 28°C for 30 seconds, and the sample was scratched with the tip of a needle with a different load of 200 g, and the degree of scratching was evaluated by visually evaluating it in 5 stages as in the case of cracks.As is clear from the results in Table 2. Samples 1 and 2, which used gelatin with low jelly strength, had cracks and poor pressure resistance, and samples 3 and 4 had a silver-gelatin ratio lower than 1.0, so the sensitivity was low and the tone was soft, and the sticking properties were also deteriorated. are doing. Further, when the silver-gelatin ratio is greater than 1.8 as in sample 5, although high sensitivity and high contrast are obtained, cracking and pressure resistance are poor. Also, like Sample 6, those with a jelly strength of 240 or more and a low amount of gelatin crack and have poor pressure resistance. On the other hand, Samples 7 to 7, which use 50% or more of gelatin with high jelly strength and have a silver-gelatin ratio of 1.0 to 1.8
Regarding No. 11, it has high sensitivity and high contrast, and is also excellent in crack and pressure resistance. In particular, as in samples MIO and 11, the jelly strength is 265 or higher and the silver-gelatin ratio is 1.1-
1.7, and those containing 60% or more of gelatin with a jelly strength of 240 or more have excellent effects. [Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material that exhibits excellent long-term storage without cracking even when the amount of gelatin is reduced, has improved pressure resistance, and has high sensitivity and high contrast. .

Claims (3)

[Claims] (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, the hydrophilic colloid in the emulsion layer contains at least 50% or more of gelatin having a jelly strength of 240 or more. 1. A silver halide photographic light-sensitive material, wherein the weight ratio of the amount of silver and the amount of gelatin coated on the side of the support containing the emulsion layer is 1.0 to 1.8. (2) In the silver halide photographic material of claim 1,
A silver halide photographic material characterized in that emulsion grains are physically ripened in the presence of gelatin having a jelly strength of 240 or more. (3) The silver halide photographic material according to claim 1 or 2, which contains a tetrazolium compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, and R_3 each represent a hydrogen atom or a substituent, and X^■ represents an anion. ]