JPH0327100B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photographic light-sensitive material"), and in particular improves antistatic properties and decreases in photographic sensitivity. The dependence on changes in processing conditions (hereinafter referred to as ``processing dependence'') ensures that good photographic properties can be obtained even when processing with a fatigued developer with a reduced hydroquinone concentration or when the developer temperature fluctuates. ) is related to a photographic material with a reduced amount. (Prior art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so they are subject to contact friction or peeling with surfaces of the same or different materials during the manufacturing process and during use. This often results in the accumulation of electrostatic charges. This accumulated electrostatic charge causes many problems, but
The most serious problem is that the photosensitive emulsion layer becomes sensitized due to the discharge of electrostatic charges accumulated before processing, resulting in dot-like spots or dendritic or feather-like line spots when the photographic film is processed. It is something that happens. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it. For example, if it appears in medical or industrial X-ray film, it will be easily recognized that it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Further, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or uneven coating. As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials. This occurs due to separation of the support surface and emulsion surface, etc. Alternatively, the problem may be caused by contact separation between the mechanical part of the X-ray film or the fluorescent intensifying screen in an automatic photographing machine. It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such electrostatic charge accumulation become more noticeable as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, static marks are more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. There is. On the other hand, X-ray films are often processed using a variety of automatic processors. Automatic processors are designed to automatically replenish developer when processing photographic materials in order to keep the developer composition constant (to compensate for deterioration due to oxidation and changes due to development reactions). . However, when the number of sheets to be processed within a certain period is very small, even with the above-mentioned replenishment, it may not be possible to catch up with the oxidative deterioration, and processing may be performed using a solution with extremely low developer activity. In such cases, the concentration of hydroquinone in the developer is abnormally low, making it impossible to obtain sufficient developer activity, resulting in a decrease in the maximum density and gradation of the photographic material, resulting in images with low diagnostic ability. This will cause inconvenience. (This is expressed as poor processing dependence.) In order to eliminate problems caused by static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive material. British patent No. 1 shows that surfactants with oxyethylene groups are particularly effective among antistatic agents.
861134 and German Patent No. 1422809. As nonionic surfactants having an oxyethylene group, compounds represented by the following general formulas [-1] and [-2] are disclosed in U.S. Patent No. 2982651 and the same.
No. 3428456, No. 3457076, No. 3454625, No. 3454625, No. 3457076, No. 3454625, No.
It is disclosed in Japanese Patent Publications No. 3552972, No. 3655387, Japanese Patent Publication No. 51-9610, Japanese Patent Application Publication No. 53-29715, Japanese Patent Application Publication No. 54-89626, etc. General formula [-1] R ₇ -A-(CH ₂ CH ₂ O)- _o1 H General formula [-2] In the formula, _R7 is a substituted or unsubstituted alkyl group, alkenyl group, or aryl group having 1 to 30 carbon atoms, and A is -O- group, -S- group, -COO- group,

【formula】

【formula】

[Formula] (where R ₁₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group).
R ₈ and R ₉ represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.
R ₁₀ and R ₁₁ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. _R10 and _R11
may be linked to each other to form a substituted or unsubstituted ring. n ₁ and n ₂ are numbers from 2 to 50. When the compound of general formula [-1] is applied to a photographic light-sensitive material, it exhibits excellent antistatic properties, but the following disadvantages occur. Significantly reduces sensitivity.
Even if it has good antistatic properties immediately after production,
Since the properties deteriorate over time, the antistatic properties deteriorate by the time the product is used. When the compound of general formula [-2] is applied to photographic light-sensitive materials, there is an advantage that there is little decrease in sensitivity, but sufficient antistatic properties etc. cannot be obtained and processing dependence is worsened. (Objective of the Invention) The first object of the present invention is to provide a photographic light-sensitive material which is prevented from charging and which does not adversely affect photographic properties such as desensitization. A second object of the present invention is to provide an antistatic photographic material whose antistatic properties do not change over time after manufacture. A third object of the present invention is to provide a photographic material with good processing dependence. (Structure of the Invention) In order to achieve the above object, as a result of intensive development research, we have discovered that the support has at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer as the outermost layer. In the silver halide photographic light-sensitive material, a nonionic surfactant represented by the following general formula [] in the non-photosensitive hydrophilic colloid layer;
A silver halide photographic light-sensitive material, characterized in that the non-photosensitive hydrophilic colloid layer and/or the photosensitive silver halide emulsion layer contains a vinyl sulfone type gelatin hardener represented by the following general formula [] or []. The above objectives were achieved. General formula [] In the formula, R ₁ and R ₃ are an alkyl group substituted with a group selected from a halogen atom and a phenyl group, an unsubstituted alkyl group, an aryl group substituted with a halogen atom, an unsubstituted aryl group, and an unsubstituted alkoxy group. Represents a group or a halogen atom. R ₂ and R ₄ are a hydrogen atom, an alkyl group substituted with a group selected from a halogen atom and a phenyl group, an unsubstituted alkyl group, an aryl group substituted with a halogen atom, an unsubstituted aryl group, an unsubstituted alkoxy The group represents a halogen atom. The substituents on the phenyl ring may be symmetrical. R ₅ and R ₆ are a hydrogen atom, an alkyl group substituted with a halogen atom, an unsubstituted alkyl group, a halogen atom,
It represents an aryl group substituted with a group selected from a methoxy group and a nitro group, an unsubstituted aryl group, or an α-furyl group. R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be linked to each other to form a ring. m and n represent the average degree of polymerization of ethylene oxide, and are numbers from 2 to 50. General formula [] In the formula, A represents a divalent group, but may be omitted; R represents a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms; however, two R's in one molecule are not necessarily the same. General formula [] ( _CH2 =CH- _SO2 ) _-2B In the formula, B represents any of the following divalent groups.

【formula】

【formula】

【formula】

[Formula] −CH ₂ −, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ − Next, the general formula [] will be explained. In the general formula [], R ₁ and R ₃ are preferably an alkyl group or a halogen atom, and particularly preferably a bulky tertiary alkyl group such as a t-butyl group, a t-amyl group, or a t-octyl group. R ₂ and R ₄ are particularly preferably hydrogen atoms. R ₅ and R ₆ are preferably hydrogen atom, methyl group, ethyl group, n-propyl group, i
-propyl group, n-heptyl group, 1-ethylamyl group, n-undecyl group, trichloromethyl group,
Substituted or unsubstituted alkyl groups such as tribromomethyl group, substituted or unsubstituted aryl groups such as α-furyl group, phenyl group, naphthyl group, p-chlorophenyl group, p-methoxyphenyl group, m-nitrophenyl group, etc. It is. Furthermore, R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be linked to each other to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, R ₅ and R ₆ are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a furyl group. m and n are particularly preferably numbers from 5 to 30.
m and n may be the same or different. Next, specific examples of nonionic surfactants preferably used in the present invention will be shown. The amount of nonionic surfactant used in the present invention can be arbitrarily selected depending on the purpose. Generally, the amount used may be 5 to 500 mg per m ² of the photographic material, preferably 20 to 200 mg. The nonionic surfactant represented by the general formula [] is applied to the layer of a photographic material after being dissolved in water, an organic solvent such as methanol, ethanol, acetone, or a mixed solvent of water and the organic solvent. It may be incorporated into a layer, spray coated on the surface of the photographic material, or immersed in the solution and dried. At this time, two or more types of nonionic surfactants of the present invention may be mixed. It is a compound having an active vinyl group represented by the following general formula [] or []. General formula [] In the formula, A represents a divalent group, but may be omitted; R represents a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms; however, two R's in one molecule are not necessarily the same. General formula [] ( _CH2 =CH- _SO2 ) _-2B In the formula, B represents any of the following divalent groups.

【formula】

【formula】

【formula】

[Formula] -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - Specific examples of compounds represented by the general formula [] or [] are shown below.

【table】

[Table] The amount of gelatin hardening agent used in the present invention is
It can be selected arbitrarily depending on the purpose. Typically, it can be used in proportions ranging from 0.01 to 20 percent by weight of dry gelatin. Particular preference is given to using proportions ranging from 0.1 to 10% by weight. The light-sensitive material according to the present invention includes ordinary black-and-white silver halide light-sensitive materials (for example, black-and-white light-sensitive materials for photography,
Examples include various photosensitive materials such as black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color reversal films, color negative films, color positive films, etc.). can. It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-abundance silver halide light-sensitive materials. Below, the photographic layer of the silver halide photosensitive material according to the present invention will be briefly described. As a binder for the photographic layer, proteins such as gelatin and casein; carboxymethyl cellulose,
Cellulose compounds such as hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylporolidone, polyacrylic acid copolymers, polyacrylamide or derivatives and moieties thereof A hydrolyzate or the like can also be used in combination. Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. In addition to replacing part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e., functional groups contained in the molecule such as amino, imino, hydroxy, or carboxyl groups, can be replaced with groups that can react with them. It may be used instead of a reagent treated or improved with a single reagent, or a graft polymer to which molecular chains of a polymeric substance are bonded. The silver halide emulsion layer of the photographic light-sensitive material of the present invention,
Types of silver halide used in surface protective layers, manufacturing methods, chemical sensitization methods, antifoggants, stabilizers,
There are no particular restrictions on antistatic agents, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color couplers, etc. For example, Product Licensing Magazine
Volume 92, pages 107-110 (December 1971) and Research Disclosure.
You can refer to the description in Vol. 176, pages 22-31 (December 1978). In particular, antifoggants and stabilizers include 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene-3-methyl-benzothiazole,
A very large number of compounds can be mentioned, including 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. A known surfactant may be further added to the photographic constituent layer of the present invention. Surfactants that can be used include natural surfactants such as saponin, nonionic surfactants such as glycerin and glycidol,
Cationic surfactants such as higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphoniums or sulfoniums; carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters,
Examples include anionic surfactants containing acidic groups such as phosphate esters, and amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino acids, aminosulfonic acids, and amino alcohols. Moreover, each fluorine surfactant can also be used in combination. In addition, the photographic light-sensitive material of the present invention has a photographic constituent layer containing U.S. Pat.
The alkyl acrylate latex described in No. 5331 and the like can be included. (Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto. (1) Method for determining antistatic ability: Antistatic ability was determined by measuring the occurrence of static marks. In the static mark generation test, static marks are generated by placing an unexposed photosensitive material on a rubber sheet with the antistatic agent-containing surface facing downward, pressing the material with a rubber roller, and then peeling it off. . The measurements were carried out at 26°C and 25% RH, and the humidity of the sample test piece was kept under the above conditions all day and night. Each sample was developed to evaluate the extent of static mark development. RD- as a developer
(manufactured by Fuji Photo Film Co., Ltd.) using an automatic developing machine
It was developed for 90 seconds using Fuji RN (manufactured by Fuji Photo Film Co., Ltd.). The evaluation of static marks was based on the following five-level criteria. A: No static marks were observed. B: Some static marks occur. C: Significant static marks occur. D: Significant static marks occur. E: Static marks appear on the entire surface. (2) Aging test method: After conditioning the sample and white high-quality paper at 25°C and 70% RH for 1 hour, test two sheets of each sample so that the surface on the emulsion layer side is in contact with both sides of the high-quality paper. A piece of high-quality paper was sandwiched between them, and these were placed in a polyethylene laminate bag and sealed. These samples were aged at room temperature for one week under a load of 40 g/cm ² . Thereafter, the antistatic ability was measured according to the above-mentioned method for determining antistatic ability, and compared with that before aging. (3) Photographic property testing method: After exposing the sample to tungsten lamp light through a filter SP-14 manufactured by Fuji Film Co., Ltd., using RD- (manufactured by Fuji Photo Film Co., Ltd.) as a developer, an automatic developing machine was used.・Fuji RN (Fuji Photo Film)
Co., Ltd.) for 90 seconds, and the photographic properties were examined. (4) Processing dependency test method: How to make a fatigued developer Using RD- (manufactured by Fuji Photo Film Co., Ltd.), an automatic developing machine Fuji RN (manufactured by Fuji Photo Film Co., Ltd.) was operated from 9 a.m. to 5 p.m. Until then, it has been operating (on standby) every day, processing five X-ray films of four-cut size (10 inches x 12 inches). The above operation was continued for 30 days to obtain a fatigued developer. Using the above fatigued developer, replenish Fuji RN at a ratio of 45 ml/4 cuts of developer and 60 ml/4 cuts of fixer, and transfer the sample to Fuji Film Filter SP-14.
After exposure to tungsten lamp light through
Developed for 90 seconds. Photographic properties of processed samples (maximum density, gradation,
relative sensitivity). Example 1 A silver halide emulsion layer having the composition shown below was coated on both sides of a polyethylene terephthalate film support having a thickness of 180 μm which had been undercoated, and then a protective layer having the composition shown below was further coated on top of the silver halide emulsion layer, which was then dried to form a black and white halogenated layer. A silver photosensitive material was prepared. (Emulsion layer) Thickness: Approximately 5μ Composition A silver iodobromide gelatin emulsion containing 1.5 mol% silver iodide (average size of silver halide grains 1.3μ) was mixed with 0.6 mg of chloroauric acid per mole of silver halide and 3.4mg
of sodium thiosulfate was added and heated at 60°C for 50 minutes to perform ripening. 4-hydroxy-6-methyl-1,3,3a,7 was added to the resulting emulsion as a stabilizer.
- Added tetrazaindene. (Protective layer) Thickness: Approximately 1μ Composition and coating amount are shown in Table 1.

【table】

[Table] Table 2 shows the test results of (1-1) to (1-6) above.

[Table] It can be seen that the present invention is good in all performances. Example 2 Emulsion layers similar to those in Example 1 were applied to a thickness of approximately 5 μm on both sides of an undercoated polyethylene terephthalate film support having a thickness of 180 μm, and on top of this, a protective layer having the following composition was applied to a thickness of approximately 1 μm. A sample was obtained.

[Table] The test results of (2-1) to (2-6) above are shown in Table-4.

[Table] It can be seen that the present invention is good in all performances.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer as the outermost layer on a support, the non-light-sensitive hydrophilic colloid layer is A nonionic surfactant represented by the following general formula [] and a vinyl sulfone type gelatin hardener represented by the following general formula [] or [] for the non-photosensitive hydrophilic colloid layer and/or the photosensitive silver halide emulsion layer. A silver halide photographic material characterized by containing. General formula [] In the formula, R ₁ and R ₃ are an alkyl group substituted with a group selected from a halogen atom and a phenyl group, an unsubstituted alkyl group, an aryl group substituted with a halogen atom, an unsubstituted aryl group, and an unsubstituted alkoxy group. Represents a group or a halogen atom. R ₂ and R ₄ are a hydrogen atom, an alkyl group substituted with a group selected from a halogen atom and a phenyl group, an unsubstituted alkyl group, an aryl group substituted with a halogen atom, an unsubstituted aryl group, an unsubstituted alkoxy Represents a group or a halogen atom. The substituents on the phenyl ring may be symmetrical. R ₅ and R ₆ are a hydrogen atom, an alkyl group substituted with a halogen atom, an unsubstituted alkyl group, a halogen atom,
It represents an aryl group substituted with a group selected from a methoxy group and a nitro group, an unsubstituted aryl group, or an α-furyl group. R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be linked to each other to form a ring. m and n represent the average degree of polymerization of ethylene oxide, and are numbers from 2 to 50. General formula [] In the formula, A represents a divalent group, but may be omitted; R represents a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms; however, two R's in one molecule are not necessarily the same. General formula [] ( _CH2 =CH- _SO2 ) _-2B In the formula, B represents any of the following divalent groups. [Formula] [Formula] [Formula] [Formula] −CH ₂ −, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −.