JPH06138576A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material excellent in coating uniformity and little in the sticking of the stain at a fixing tank and in the occurrence of fixing fault. CONSTITUTION:In the silver halide photographic sensitive material containing the compd. expressed by the formula and a fluorines surfactant, the added amounts of the compd. and the surfactant satisfy the following conditions. A2/A1>=P. Here, A1 and A2 is the sum of the added amounts of the formula compd. and the surfactant into the photographic material respectively, P is stain-control ratio, that is, when the fluorinated surfactant presents at more than this ratio to the formula compd. in the fixing liq., P is the suppressed ratio of the sticking of stain and the causing of fixing fault to the photographic material during fixing treatment. In the formula, M is hydrogen or metal ion, R1 and R2 is alkyl or phenyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a black-and-white photographic light-sensitive material which is excellent in coating uniformity and which is free from stains and poor fixing during fixing processing.

[0002]

BACKGROUND OF THE INVENTION Black-and-white silver halide photographic light-sensitive materials are widely used in the plate making field, medical field and the like. In recent years, technological advances in these fields have been remarkable, and accordingly, photographic light-sensitive materials have also been required to have a high level of quality. For example, not only is it required to have appropriate photographic characteristics to reproduce images faithfully, they must be uniformly coated without coating failure, and short-time processing and constant results can be obtained at any time. The demand for quality, such as the rapid processing stability required, is increasing more and more.

In most cases, an automatic processor is used for the development processing of photographic materials, and in order to meet the demand for rapid processing mentioned above, the processing temperature has been increasing. When the processing temperature rises, the amount of gelatin and other chemicals eluted from the photosensitive material into the processing solution increases, and the concentration of the processing solution evaporates further, resulting in the development, fixing, and washing tanks and transportation. Roller stains tend to adhere, and the influence of the stains on the photosensitive material on quality has become a problem.

Since the contamination of the light-sensitive material in the developing tank causes unevenness of development and causes a serious quality problem, many improvements have been noted and proposed. However, the contamination during the fixing process has not been so much until now. It hasn't been a problem.

Regarding the coating of silver halide photographic light-sensitive materials, many techniques have been developed for a long time with respect to coating methods, coating aids and the like. In particular, with regard to coating aids, there are restrictions such that the silver halide photographic light-sensitive material is thin-layer high-speed coating, sometimes simultaneous multi-layer coating, and the emulsion characteristics of the silver halide photographic emulsion must not be adversely affected. There were many conditions and it was very difficult to find a suitable one. Among them, the compound represented by Chemical formula 1 is one of the most widely used as an extremely excellent coating aid.

However, when the silver halide photographic light-sensitive material coated by using the chemical formula 1 is subjected to the high temperature and rapid automatic developing machine processing as described above, adhesion of stains and fixing to the sensitive material during fixing processing. It was found that unevenness was very high, and a solution for it was desired.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a black and white photographic light-sensitive material which is excellent in coating uniformity and causes less stains or improper fixing during fixing processing.

[0008]

The above objects of the present invention are as follows.
A silver halide photographic light-sensitive material containing the following general formula 2 and a fluorine-containing surfactant, wherein the addition amount of the compound 2 and the fluorine-containing surfactant satisfies the following conditions. It turns out that the material can achieve. A2 / A1 ≧ P where A1 and A2 are chemical formulas 2, respectively, the total amount of the fluorine-based surfactant added to the photosensitive material, and P is a stain suppression ratio,
When the fluorine-containing surfactant is present in the fixing solution in a ratio of not less than that of the chemical formula 2, the ratio is such that the adhesion of stains to the photosensitive material during fixing processing and the occurrence of defective fixing are suppressed.

[0009]

[Chemical 2]

Wherein M is hydrogen or a metal ion, R ₁ ,
R ₂ represents an alkyl group or a phenyl group.

The present invention will be described in more detail below. Examples of the chemical formula 2 used in the present invention are shown below, but of course the present invention is not limited to these examples.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

The amount of the compound of Chemical formula 2 added is such that the coating solution containing the compound can be applied evenly and uniformly on RC paper or film base without any coating failure, and is generally in the range of 10 mg to 1000 mg per liter of the coating solution. Is added in.

Examples of the fluorine-containing surfactant used in the present invention are shown below, but needless to say, these are not limited to this example.

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

[0031]

[Chemical 20]

The fluorosurfactant used in the present invention may be any of anion, cation and betaine, but betaine is most effective. The addition amount of this fluorine-based surfactant is determined according to the value of P in relation to the addition amount of Chemical formula 2.

A method of obtaining the value of P will be briefly described below.
First, Tmg / l of gelatin and X1 mg / l of chemical formula 2 were added to the fixing solution in the automatic developing machine, and idle operation was performed for about 10 minutes. afterwards,
It is assumed that when the unexposed light-sensitive material is passed through, adhesion of gelatin stains and improper fixing are caused. It is assumed that when a fluorine-based surfactant is added little by little to this fixing solution, when the amount of addition becomes X2, the adhesion of stains on gelatin and the occurrence of improper fixing due to this start to decrease. At this time, P = X2 / X1. The value of P varies depending on the chemical formula 2 and the type of the fluorosurfactant and can be experimentally determined. In addition, the value of P is obtained using the fixing liquid described in Example 1 described later.

The processing method of the present invention comprises at least the steps of development, fixing, washing with water or stabilization.

The developing solution used in the present invention is not particularly limited and may have a publicly known and publicly known composition. The developing agent used in the developer used in the developing step of the present invention is not particularly limited, but preferably contains dihydroxybenzenes, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or dihydroxybenzenes. In some cases, a combination of and p-aminophenols is used. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,
Although there are 5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferable.

Further, as a developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Examples include tolyl-4,4-dimethyl-3-pyrazolidone. Further, as p-aminophenol-based developing agents, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2
-Methyl-p-aminophenol, p-benzylaminophenol and the like.

The developing agent is preferably used usually in an amount of 0.05 mol to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p
When the combination with -amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.0 mol / l.
It is preferably used in an amount of 6 mol / l or less.

Examples of the sulfite used as a preservative in the developer used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. can give. The concentration of sulfite is preferably 0.4 mol / l or more, more preferably 0.5 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

As the alkaline agent used for setting the pH of the developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate,
A pH adjuster or buffer such as potassium triphosphate can be included. In addition to the above components, as additives used in the developer, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide , Organic solvents such as methyl cellosolve, hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and indazoles such as 5-nitroindazole Examples include antifoggants such as benzotriazole-based compounds such as 5-based compounds and 5-methylbenzotriazole. Further, if necessary, a toning agent, a surfactant, a defoaming agent, a water softener, a hardener, etc. may be added.

The fixing solution used in the present invention is not particularly limited and may be a publicly known and publicly known composition. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, and fixing agents such as thiourea, as well as hard films such as aluminum chloride, aluminum sulfate and potassium alum. Agent,
Preservatives such as sodium sulfite, sodium bisulfite,
Organic acids such as acetic acid, citric acid, tartaric acid, malic acid, succinic acid, and chelating agents may be included.

The silver halide photographic emulsion used in the present invention can be prepared by various known methods.

The silver halide grains in the photographic emulsion may have a regular crystal such as a cube, an octahedron, a tetrahedron and an orthorhombic dodecahedron, and may have an irregular shape such as a sphere or a plate. It may have a crystal system, or may have a composite form of these crystal forms. It may also consist of a mixture of grains of various crystal forms.

The silver halide grains may have different phases in the inside and the surface layer, or may have a uniform phase.

Further, for example, a composite type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, or an epitaxially grown silver halide crystal (for example, It is also possible to epitaxially grow silver chloride, silver iodobromide, silver iodide, etc. on silver bromide).

The aspect ratio is 3 or more, preferably 5
It is also possible to use tabular silver halide grains of -20. More specifically, U.S. Pat. Nos. 4,434,226 and 44
No. 39520, JP-A-59-99433, "Research Disclosure" Vol. 225, No. 22534 (1
January 983) and the like.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but it may be monodisperse. Here, monodisperse refers to a dispersion system in which 95% of particles are within ± 60% of the number average particle size, preferably within 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

The photographic emulsion used in the present invention is Photographic by GDFuffin.
Emulsion Chemistry (Photographic EmulsionC
hemistry), The Focal Pres
s) (1966), VLZelikman et al, Making and Coating Photographic Emulsion (Making and
Coating Photo-graphic Emulsion), published by The Focal Press (1964) and the like. 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 halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good.

As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, two or more kinds of silver halide emulsions formed separately may be mixed.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, and the like may coexist.

As a method for removing the soluble salts from the emulsion after the formation of the precipitate or after the physical formation, the noodle method for gelling gelatin, inorganic salts, anionic surfactants, anionic polymers or modified gelatin are used. The precipitation method (flocculation method) or the like is used.

The silver halide emulsion can be chemically sensitized by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine, and rhodanine, and US Pat.
No. 278947, No. 2410689, No. 244020
No. 6, No. 3187458, No. 3415649, No. 3
Sulfur-containing compounds such as those described in No. 501313 can be used. Also, US Pat.
No. 2,597,915, No. 2,399,083 and the like can be used for gold sensitization.
Also, US Patent Nos. 2448060 and 2540036.
No. 2556245 and No. 2566263, the sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium and ruthenium can be used in combination. And these sensitization methods can be used not only in combination but also in combination.

In the present invention, polyalkylene oxide,
Various development accelerators such as thioether compounds and quaternary ammonium salt compounds can be used.

The silver halide photographic emulsion used in the present invention may optionally contain other sensitizing dyes such as cyanine,
Spectral sensitization may be carried out by using merocyanines in combination, and additives such as stabilizers, surfactants and hardeners can be added by known methods.

Examples of the hydrophilic colloid used in the present invention include proteins such as gelatin, colloidal albumin and casein, cellulose derivatives such as carboxymethyl cellulose, agar, sodium alginate, sugar derivatives such as starch, polyvinyl alcohol and polyacrylamide. These synthetic polymers and the like can be used alone or in admixture at an appropriate ratio.

In the light-sensitive material of the present invention, all those usually used as a support for a photographic light-sensitive material can be used. Examples thereof include a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butylate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film and other laminates thereof, and paper. Also suitable are supports such as baryta or α-olefin polymers, especially paper coated or laminated with a polymer of α-olefin having 1 to 10 carbon atoms such as polyethylene and polypropylene.

[0057]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the embodiments of the present invention are not limited thereto.

Example 1 An average particle size of 0 was obtained by the controlled double jet method.
A cubic silver iodobromide emulsion containing 25 moles of 1 mol% iodine was prepared. This emulsion was subjected to gold-sulfur sensitization by a conventional method to obtain a sensitizing dye, a stabilizer, a hardener and a chemical compound.
Was added to give a finished emulsion. Further, as a coating solution for the backing layer and the overlayer, an acrylic latex is added to an aqueous solution of normal alkali-treated ossein gelatin, a matting agent made of an acrylic resin having an average particle size of 4 micrometers, a hardener and a surface active agent of Chemical formula 3. The thing which added the agent was prepared. These were applied to a polyethylene terephthalate film having a thickness of 100 micrometers, with 3 g of gelatin per square meter of the backing layer, 3.8 g of silver per square meter of the emulsion layer, and 2 g of gelatin per square meter.
The overlayer was coated so that the amount of gelatin was 1.1 g. This was designated as film A. Film A contained the compound of Chemical formula 3 in a total amount of 60 mg / m ² .

Next, a developing tank and a fixing tank of 6 liters each of an automatic developing machine for processing a normal black and white silver halide photographic light-sensitive material are filled with the following developing solution and fixing solution, and the fixing solution is used for photography. 10 mg / l of alkali-treated ossein gelatin and 50 mg / l of the compound represented by Chemical formula 2 were added. This automatic processor is 10
When the film A was passed through after idling for a minute, adhesion of gelatin stains and improper fixing occurred on the entire surface.

(Developer) Hydroquinone 24 g 1-phenyl-3-pyrazolidone 0.75 g anhydrous sodium sulfite 60 g sodium metaborate 33 g sodium hydroxide 19 g potassium bromide 1 g 6-nitrobenzimidazole 0.5 g Water is added to make 1000 ml. .

(Fixer) Water (50 ° C.) 700 ml Ammonium thiosulfate (60 W / W%) 165 ml Anhydrous sodium sulfite 15 g 80% Acetic acid 20 ml Tartaric acid 4 g Caustic soda 7.5 g Aluminum sulfate 15 g 12N. Sulfuric acid 6.5g Add water 1000ml

A fixed amount of a fluorinated surfactant was added to the fixing solution in such a state, and after 10 minutes of idle operation, the state of occurrence of adhesion of gelatin stains and defective fixing was observed through the film A. . If the adhesion of dirt on gelatin and the occurrence of improper fixing are not alleviated, repeat the operation of adding a fluorosurfactant and idling again,
The value of the addition amount X2 of the fluorine-based surfactant at the time when the adhesion of dirt and the occurrence of improper fixing due to the compound represented by Chemical Formula 2 started to be clearly reduced was determined. From this result, the stain suppression ratio P was obtained.

The values of the stain inhibition ratio P thus obtained depending on the chemical formula 2 and the kind of the fluorine-containing surfactant are summarized in Table 1.

[0064]

[Table 1]

Example 2 In the emulsion, backing and over coating solutions prepared in the same manner as in Example 1, the total addition amount of Chemical formula 2 and the fluorine-containing surfactant to each layer is as shown in the table below. So added. The amount of the fluorine-based surfactant added to the emulsion and the overlayer was distributed so that the balance of the surface tension during the multi-layer coating of these was not disturbed.

For comparison, a film coated with a backing, an emulsion and an overlayer using only the surfactant represented by Chemical Formula 21 was also prepared.

[0067]

[Chemical 21]

In the same automatic processor as used in Example 1,
This was also filled with the same developer and fixer as used in Example 1, and the film prepared as described above was treated in an unexposed state in an amount of 2 square meters per 1 liter of treatment liquid, and then left empty for 10 minutes. I drove. After that, each film was passed through in an unexposed state, and the occurrence of stains and improper fixing on the film surface was examined.

The results are summarized in Tables 2 and 3. The degree of occurrence of dirt and fixing failure due to adhesion of dirt was evaluated by a numerical value from 1 to 5. No. 1 did not generate these stains at all,
No. 5 is a case where an extremely large amount of stains or improper fixing is generated on the entire surface, and the practically no problem level is up to 3.

Further, the coating uniformity of the coated film was evaluated on a scale of 1 to 5. 1 represents a very good state without any coating failure, and 5 represents a state in which there is no coating failure or coating unevenness and there is no part that can be put to practical use.

[0071]

[Table 2]

[0072]

[Table 3]

As described above, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which is excellent in coating uniformity and has less stains and improper fixing in the fixing tank.

[0074]

EFFECT OF THE INVENTION A silver halide photographic light-sensitive material having excellent coating uniformity and capable of rapid high-temperature processing without causing stains or improper fixing in the fixing tank can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing the following general formula 1 and a fluorine-containing surfactant, wherein the addition amounts of the chemical formula 1 and the fluorine-containing surfactant satisfy the following conditions. Silver halide photographic light-sensitive material. A2 / A1 ≧ P where A1 and A2 are chemical formulas 1 and 1, respectively, the total amount of the fluorine-based surfactant added to the photosensitive material, and P is a stain suppression ratio,
When the fluorine-based surfactant is present in the fixing solution in a ratio of 1 or more relative to the chemical formula 1, the ratio is such that the adhesion of stains to the photosensitive material and the occurrence of fixing failure during the fixing process are suppressed. [Chemical 1] In the formula, M represents hydrogen or a metal ion, and R ₁ and R ₂ represent an alkyl group or a phenyl group.