JPH07295136A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce occurrence of stains during fixing processing and occurrence of insufficient fixing by satisfying specified conditions in the addition ratio of surfactants to be incorporated in a photosensitive material containing the surfactant. CONSTITUTION:This photosensitive material contains at least each one or more of the surfactants represented by formulae I and II in an addition ratio X2/X1>=P, where each of X1 and X2 is the sums of the addition amounts of the surfactants of the formula I and formula II to be added to the photosensitive material, and P is the staining restraint ratio, and when the surfactants of the formula II exist in the fixing solution to that of the formula I in a ratio more than this P, occurrence of the stains attaching to the photosensitive material and occurrence of insufficient fixing are restrained. In the formulae I and II, M is H or an cation; and each of R1-R4 is an alkyl, aryl, aralkyl, or an alkenyl.

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 is increasing more and more, such as having rapid processing stability.

In most cases, an automatic processor is used for the development processing of photographic materials, and in order to satisfy the above-mentioned demand for rapid processing, 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.

The contamination of the light-sensitive material in the developing tank attracts attention because it causes uneven development and causes a serious quality problem, and many improvement methods have been proposed. It hasn't been a problem so much.

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 surfactants represented by the chemical formulas 1 and 2 are ones which have been most often used as extremely excellent coating aids.

However, when the silver halide photographic light-sensitive material coated with the surfactants represented by Chemical Formulas 1 and 2 alone is subjected to high-speed rapid processing by the automatic processor as described above, the fixing process is performed. It was found that a large amount of dirt adhered to the light-sensitive material and uneven fixing were generated, and a solution thereof has been 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.
On the support, at least one photosensitive layer composed of a silver halide emulsion and at least one non-photosensitive layer are contained, and at least one of the surfactants represented by Chemical formulas 1 and 2 is used.
It has been found that in a silver halide photographic light-sensitive material containing more than one kind, the ratio of the added amount of the surfactant can be achieved with a silver halide photographic light-sensitive material characterized by satisfying the following conditions. X2 / X1 ≧ P Here, X1 and X2 are the total amounts of the surfactants represented by Chemical Formulas 1 and 2 added to the photosensitive material. P is a stain suppression ratio, and when the surfactant represented by Chemical formula 2 is present in the fixing solution in a ratio of at least this ratio with respect to the surfactant represented by Chemical formula 1, adhesion of stain to the photosensitive material during the fixing process. The ratio is set so that the occurrence of defective fixing and fixing is suppressed.

In the formula, M represents hydrogen or a cation. R
₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents hydrogen, a cation, an unsubstituted or substituted alkyl group, an aryl group, an aralkyl group or an alkenyl group. However, the case where R ₁ and R ₂ , and R ₃ and R ₄ are simultaneously hydrogen or a cation is excluded. In addition, R ₁ , R ₂ , R
₃ , R ₄ each have a linking group (k, l is 0 or a positive integer) such as — (CH ₂ CH ₂ O) _k — or — (CH ₂ CH ₂ CH ₂ O) ₁ —. Good. Further, in R ₁ and R ₂ , the number of carbon atoms in the linear portion excluding the carbon atom having a branched chain is 5 or less,
At least one of R ₃ and R ₄ has a portion having 6 or more carbon atoms.

Here, the unsubstituted straight chain portion which is not linked to the branched chain refers to the structure-(CH ₂ ) _m CH ₃ or-(CH ₂ ) _n- shown below, and in R ₁ and R ₂ m ≦ 4, n ≦ 5, and R
_{For 3} and R ₄ , m ≧ 5 and n ≧ 6.

The present invention will be described in more detail below. Specific examples of the chemical formula 1 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]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

Next, specific 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.

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

The addition amount of the surfactants represented by Chemical Formulas 1 and 2 is such that the coating liquid containing the surfactant can be uniformly and evenly coated on RC paper or film base without any coating failure. 10 mg to 100 per liter
It is added in the range of 0 mg.

The total addition amount of the surfactants used in the present invention is an amount satisfying the above conditions, and the ratio of the addition amount is determined according to the value of P.

A method of obtaining the value of P will be briefly described below.
First, gelatin is added to the fixing solution in the automatic processor at Tmg / L, and one of the surfactants shown in Chemical formula 1 is added to X1mg.
/ L is added, and the automatic developing machine is used in the state that the photosensitive material is not processed.
Run idle for about a minute. Then, it is assumed that when the unexposed light-sensitive material is processed, adhesion of stains on gelatin and improper fixing are caused. When any one of the surfactants shown in Chemical formula 2 was added little by little to this fixing solution, when the amount of addition became X2 mg / L, adhesion of gelatin stains and fixing failure due to it Suppose the outbreak has started to decrease. At this time, P = X2 / X1. The value of P depends on the combination of the surfactants shown in Chemical formulas 1 and 2, and can be experimentally obtained. 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 includes at least the steps of developing, fixing and washing with water or stabilizing treatment.

The developing solution used in the present invention is not particularly limited and may have a publicly known and commonly used 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 usually preferably used 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 sulfites used as preservatives in the developer used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. can give. The concentration of sulfite is preferably 0.4 mol / L or more, particularly 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 developer, 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 be composed of 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 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 process 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 of gelatinizing 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 the materials 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.

[0048]

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 A cubic silver iodobromide emulsion containing 1 mol% of iodine having an average grain size of 0.25 micrometer was prepared by the controlled double jet method. This emulsion was subjected to gold-sulfur sensitization by a conventional method, and a sensitizing dye, a stabilizer, a hardener and a surfactant of Chemical formula 3 were added to obtain a finished emulsion.
Also, as a coating liquid for the backing and the over layer,
An acrylic latex, an acrylic resin matting agent having an average particle size of 4 micrometers, a hardener and a surfactant of Chemical Formula 3 were added to an ordinary aqueous solution of alkali-treated ossein gelatin. These were applied to a polyethylene terephthalate film having a thickness of 100 μm, with 3 g of gelatin per square meter in the backing layer, 3.8 g of silver per square meter in the emulsion layer, and 2 g of gelatin.
g, and the overlayer was coated such that 1.1 g of gelatin was applied. 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 6-liter developing tank and a fixing tank 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 surfactant represented by Chemical formula 1 were added. When this automatic processor was idle for 10 minutes and then passed through the film A, adhesion of gelatin stains and defective 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 6.5 g Add water to make 1000 ml.

A fixed amount of the surfactant represented by Chemical formula 2 was added to the fixing solution in such a state, and the film A was passed through the film A after 10 minutes of idle operation. Was observed. If the adhesion of gelatin stains and improper fixing are not alleviated, the above-mentioned surfactant is added and the idle operation is repeated again to clearly reduce the adhesion of gelatin stains and improper fixing. The value of the addition amount X2 of the above-mentioned surfactant at the start was determined. From these results, it is possible to suppress the adhesion of stains to the photosensitive material and the poor fixing when one of the surfactants represented by Chemical Formula 1 is used alone by using the surfactants represented by Chemical Formulas 1 and 2. The stain inhibition ratio P as a measure of the effect to be obtained was obtained.

The values of the stain inhibition ratio P obtained by the combination of the surfactants represented by Chemical formulas 1 and 2 are shown in Table 1.
Summarized in.

[0055]

[Table 1]

Example 2 In the emulsion, backing and over coating solutions prepared in the same manner as in Example 1, the total amount of the surfactants represented by Chemical Formulas 1 and 2 to each layer is shown in the table below. Was added so that Further, the addition amounts of the respective surfactants represented by Chemical Formulas 1 and 2 to the emulsion and the overlayer were 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 13 was also prepared.

[0058]

[Chemical 13]

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.

[0062]

[Table 2]

[0063]

[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 which is free from stains and fixing defects in the fixing tank.

[0065]

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 support comprising at least one photosensitive layer comprising a silver halide emulsion and at least one non-photosensitive layer on a support, and at least one or more surfactants represented by Chemical formulas 1 and 2 respectively. In the silver halide photographic light-sensitive material containing, the ratio of the addition amount of the surfactant satisfies the following condition. X2 / X1 ≧ P Here, X1 and X2 are the total amounts of the surfactants represented by Chemical Formulas 1 and 2 added to the photosensitive material. P is a stain suppression ratio, and the surfactant of Chemical formula 2 is converted into the fixing liquid.
When it is present in this ratio or more with respect to the surface-active agent, the ratio is such that the adhesion of stains to the photosensitive material during fixing processing and the occurrence of defective fixing are suppressed. [Chemical 1] [Chemical 2] In the formula, M represents hydrogen or a cation. R ₁ , R ₂ , R
₃ and R ₄ may be the same or different and each is hydrogen, cation, an unsubstituted or substituted alkyl group,
It represents an aryl group, an aralkyl group or an alkenyl group. However, the case where R ₁ and R ₂ , and R ₃ and R ₄ are simultaneously hydrogen or a cation is excluded. R ₁ , R ₂ , R ₃ , and R ₄ may each have a linking group. Further R ₁ and R ₂
Has a carbon number of 5 or less in a straight chain portion excluding a carbon atom having a branched chain, and at least one of R ₃ and R ₄ has a portion having 6 or more carbon atoms.