JPS6134658B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material.
More specifically, the present invention relates to a silver halide photographic material with improved charging characteristics. Silver halide photographic materials are generally films made of polyolefins such as polyethylene, polyesters such as polyethylene terephthalate, cellulose esters such as cellulose triacetate, etc.
Synthetic paper or a support made of paper coated with the above polymer substance is used, and the surface of the support is coated with a silver halide photographic emulsion layer, a subbing layer, an intermediate layer, a filter layer, a protective film layer, and an antihalation layer. , packing layers and other photographic constituent layers are coated in appropriate combinations. Since the support has high electrical insulating properties, static electricity is often accumulated during the manufacturing process of silver halide photographic materials and when subjected to contact with the same or different materials, friction, or peeling during use. . This accumulated static electricity causes many problems.
For example, in silver halide photographic light-sensitive materials with high sensitivity such as X-ray film, the silver halide emulsion layer is exposed to light or charged particles generated by electrostatic discharge, and when developed, the silver halide emulsion layer is exposed to light, which causes dots, clouds, etc. Dark spots such as so-called static marks occur. Furthermore, when handling a large version of silver halide photosensitive material, a worker may receive an electric shock when separating and peeling the material. Or the occurrence of spots due to dust floating in the environment adhering to the surface.
There are many problems such as non-uniform coating, etc., and it is required to prevent charging. Silver halide photographic materials are also required to have adhesion resistance. If the material is adhesive, static electricity is likely to be generated at low humidity when the materials are stacked or taken out from the stacked state, which causes static electricity damage, and at high humidity the silver halide emulsion layer is damaged due to adhesion, etc. cause problems. In silver halide photographic light-sensitive materials, adhesion on the surface is a problem, and the silver halide emulsion layer may peel off when one sheet is taken out from a stacked state, and static electricity may occur due to the adhesion of the polymerized state. This caused problems such as static electricity damage. Conventionally, many proposals have been made to improve these problems. As a method for preventing charging, for example, a hygroscopic substance made of various polymers, surfactants, boron-based substances, zinc oxide, semiconductors, colloidal silica, or water-soluble inorganic salts is applied to the surface of the photographic light-sensitive material. Electrical conductivity can be imparted by incorporating the material into the photographic component layer, or by including it in the photographic component layer along with a binder material such as gelatin or polyvinyl alcohol. However, the use of these hygroscopic substances cannot prevent charging when the humidity is low, whereas it can prevent charging when the humidity is high, but has the disadvantage that adhesiveness increases. If a large amount of antistatic agent is included in an attempt to improve the antistatic effect, it will have a negative effect on the photographic performance of the silver halide photographic material, such as sensitivity, fog, and storage stability, and may sometimes have the disadvantage of increasing adhesiveness. It exhibited excellent antistatic properties both in low humidity and high humidity, and it was difficult to maintain low adhesion. Conventionally, methods for preventing the adhesion of silver halide photographic materials include the use of fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium oxide, and calcium oxide, or of organic substances such as polymethyl acrylate and cellulose acetate propionate. A method of increasing roughness by incorporating it into a surface layer is known. However, according to this method, aggregates are formed in the coating solution, making it impossible to obtain a uniform coating layer,
Alternatively, the slippage may become poor, resulting in disadvantages such as damaging the silver halide photographic material or impairing transportability. Furthermore, there are drawbacks that include side effects such as lowering the transparency of the finished image, impairing the graininess of the image, and causing missing or missing halftone dots in halftone images. Recently, various surfactants have been proposed to improve adhesion resistance, but surfactants that improve adhesion resistance have poor antistatic properties, while surfactants that improve antistatic properties have poor adhesion resistance. have a tendency to worsen
At present, there is no surfactant that can improve both properties. As described above, excellent photographic properties cannot be obtained by using a conventional antistatic agent and an anti-adhesive agent in combination, and it has been difficult to achieve both of the above-mentioned properties by using a surfactant alone. The present invention has been made to solve these problems. A first object of the present invention is to provide a silver halide photographic material that exhibits excellent antistatic properties under both low and high humidity conditions. A second object of the present invention is to provide a silver halide photographic material that has antistatic properties and does not deteriorate adhesion resistance or photographic properties. It has been found that the above object can be achieved by containing a lanolin-based ethylene oxide adduct and an alkali metal salt and/or an alkaline earth metal salt in the outermost layer of a silver halide photographic light-sensitive material. . The present invention provides a support for a silver halide photographic light-sensitive material, an outermost layer of one or both of the photographic constituent layers coated on the support, and a layer adjacent to the outermost layer containing a lanolin-based ethylene oxide adduct and an alkali metal. A silver halide that is characterized by containing a salt and/or an alkaline earth metal salt, and has excellent adhesion resistance and antistatic performance without adversely affecting the photosensitivity of the silver halide. It provides photographic materials. The lanolin-based ethylene oxide adduct used in the present invention is obtained by adding and condensing ethylene oxide or polyethylene glycol to lanolin fatty acid or lanolin alcohol separated and purified from fatty secretions attached to wool in the presence of a catalyst. It was synthesized by Lanolin is mainly composed of esters of fatty acids and higher alcohols, which have a chemically complex structure, and also contains small amounts of fatty acids and alcohol. When it is hydrolyzed, it produces fatty acids (lanolin fatty acids) and alcohols (lanolin alcohol) is obtained. Lanolin added and condensed with polyhydric alcohols such as propylene glycol, grindol, and sorbitan can also be used in the present invention. These lanolin-based ethylene oxide adducts may be commercially available products, but they can also be synthesized as follows. Synthesis Example 2 parts of ethylene oxide was added to 1 part of lanolin alcohol by blowing it into 1 part of lanolin alcohol at 120°C under normal pressure using tin tetrachloride as a catalyst. The number of moles added was determined by increasing the weight of the reactant and measuring the hydroxyl value. The reaction catalyst was removed under reduced pressure. Furthermore, it was found that polyethylene glycol, which is expected to be a by-product, does not exist because the average number of moles of ethylene oxide added due to the weight increase of the product matches that determined by hydroxyl value measurement. Examples of lanolin-based ethylene oxide adducts used in the present invention are shown by constituent components and their molar ratios.

[Table] Among such lanolin-based ethylene oxide adducts, 5 to 50 ethylene oxide adducts have particularly preferable antistatic properties. In order to add the above-mentioned compounds to a photographic coating solution, they can be dissolved in water or an organic solvent that is miscible with water such as methanol, ethanol, acetone, etc., and the amount added to the coating solution is usually the same as that of gelatin. For photographic coating liquids containing
Added at a rate of 0.01 to 10g, generally 0.02 to 5g
is suitable. Note that the compound may be added usually just before coating. The alkali metal salts and alkaline earth metal salts used in the present invention include alkali metal salts such as lithium, sodium, potassium, magnesium, and calcium or alkaline earth metal cations, hydrochloric acid, hydrobromic acid, nitric acid, and sulfuric acid. Salts with acids such as , phosphoric acid, carbonic acid, bicarbonate, etc. can be used. Preferred examples of compounds in the present invention are illustrated below.

[Table] Among these metal salts, lithium chloride, sodium chloride, sodium carbonate, and potassium nitrate are particularly preferred. All of the above compounds can be commercially available. In order to incorporate these compounds into the uppermost layer of a silver halide photographic light-sensitive material, they can be added directly to the coating solution for forming those layers, or dissolved in water, methanol, ethanol, acetone, dioxane, methylcellosolve, etc. It may be added to the coating liquid after being dissolved in an organic solvent alone or in a mixed solvent. Furthermore, since these compounds have a relatively high diffusion rate, they may be added to a layer adjacent to or in a close proximity to the uppermost layer. Alternatively, the solution may be sprayed onto the surface of the silver halide photosensitive material, or the surface of the silver halide photosensitive material may be immersed in the solution and then dried. When this compound is applied to a silver halide photographic light-sensitive material, the amount varies depending on the type of compound and the location where it is added, but it is approximately 5 x 10 ^-1 to 1 x 10 ^-5 mol per square meter of the light-sensitive material. By allowing it to exist, an effective antistatic effect can be exhibited. However, the amount to be used is not limited to this range, and the optimum amount for obtaining appropriate effects can be arbitrarily selected. In the present invention, the amount of both the lanolin-based ethylene oxide adduct and the alkali metal salt and/or alkaline earth metal salt added is 5 mg to 1.
g/m ² Particularly preferably 10 mg/m 2 to 500 mg/m ² . It goes without saying that the amount and ratio used will vary depending on the structure of the photosensitive element, the composition of each layer in the photosensitive element, coating method, drying conditions, packaging form, and purpose of use. The photographic component layer to which both of these are added during the production of the silver halide photosensitive material may be any layer as described above.
Most preferably both are added together in the top layer and support layer in the photographic component. By using both in combination, a large amount of the lanolin-based ethylene oxide adduct concentrates on the surface, resulting in particularly excellent antistatic performance. When lanolin-based ethylene oxide adducts, alkali metal salts, etc. are used alone, there is not much effect, but when both are used in combination, more excellent effects are exhibited. Of course, both of these may be contained separately in the uppermost layer and the layer adjacent thereto. According to the present invention, the following excellent effects are achieved. (1) It has an antistatic effect in both high humidity and low humidity, and regardless of temperature changes.
This makes it possible to transport the photographic material at high speed, making it easy to handle large-sized or roll-shaped photographic materials, and preventing electrical shock from being applied to the operator. Furthermore, static marks do not occur, dust attracted by static electricity does not adhere, and pinhole-like defects are eliminated. (2) There is no deterioration in adhesion resistance and there is no adhesion failure at high humidity, which makes it possible to simplify the packaging of photographic materials. (3) In the case of high-contrast developers such as X-ray developers, fine particle developers such as D-72, and lithium-type developers, there is virtually no effect on sensitivity or fog, and there is no delay in development and deterioration of halftone dot quality. There is no coloration, and the fringes around the halftone dots are not colored. (4) In photographic light-sensitive materials for line drawings, the reproduction characteristics and exposure latitude of line drawings are improved. (5) Even if it spills into processing solutions such as developing solution and fixing solution, it does not cause foaming or oily sludge. (6) Since it retains its antistatic properties even after photographic processing,
Storage of film after photo processing such as line film,
It is extremely easy to take out the film, and it also becomes easy to perform operations such as printing a large-sized photographic film, thereby improving work efficiency. (7) By using both in combination, a smaller amount is required compared to when each is used alone. The silver halide photographic material of the present invention includes:
For example, it may be of any type, such as black and white photographic materials, color photographic materials, or false color photographic materials, and may include photographic materials for various purposes such as general use, printing, X-ray use, radiation use, etc. ,
Mechanistically, all kinds of photographic materials such as negative type, positive type, and diffusion transfer type can be mentioned. These silver halide photographic light-sensitive materials were produced in
-A photosensitive material containing a general silver halide emulsion described in Publication No. 17493, etc., and these emulsions include:
The present invention can be effectively applied even if commonly used photographic additives such as sensitizers, coating aids, and antistatic agents and binders are contained. As the support, commonly known photographic supports made of polyethylene terephthalate, polycarbonate, cellulose acetate, etc. can be used. Furthermore, when the silver halide photographic material of the present invention is applied to so-called lithography, it may be used as a development accelerator in order to improve the infectious development characteristics and increase the sensitivity.
Quaternary ammonium salts (U.S. Pat. No. 2,271,623,
Specification No. 2944898, JP-A-48-59827, No. 49
−123022 Publication, Special Publication No. 46-21186, No. 47−
11116) For example, 1-phenyl-2
-Mercaptotetrazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-
Phenyl-benzimidazole, benztriazole, 4-mercaptopyrimidine, 2,3-dihydroxy-5-mercaptopyrimidine, 5-nitrobenzimidazole, etc. can also be used. Furthermore, it is known that a polyethylene oxide compound is added to the photosensitive layer of a silver halide photographic light-sensitive material for squirrels in order to improve the quality of halftone dots.
For example, US Pat. No. 3,288,612, US Pat.
No. 3294540, Specification No. 3516830, etc., Special Publication No. 1973-
As described in Publication No. 13822, Japanese Patent Application No. 53-113822, etc., polyalkylene oxide, or polyethylene oxide and aliphatic alcohols, glycols, fatty acids, aliphatic amines,
Condensation products of phenols and hexitol derivatives with dehydrated cyclic compounds, HO (C ₂ H ₄ O) ₅₀ H, HO
(C ₂ H ₄ O) ₁₀₀ H, HO (C ₂ H ₄ O) ₁₀ (CH ₂ ) ₁₀ O
(C ₂ H ₄ O) ₁₀ H, C ₁₇ H ₃₅ O (C ₂ H ₄ O) ₂₆ H, HO (C ₂ H ₄ O) ₅₀ NHC ₂ H ₂₅ , HO (C ₂ H ₄ O) ₄₀ CO
(CH ₂ ) ₇ CH=CHC ₈ H ₁₇ , C ₄ H ₉ S
_{( C2H4O} ) _{50 COCH2CH2COOH ,} m=22 HO(C ₂ H ₄ O) _l (C ₄ H ₈ O) _n (C ₂ H ₄ O) _o Hl+n=
30m=15 m=17 HOCOCH ₂ CH ₂ CO ₂ (C ₂ H ₄ O) _l (C ₄ H ₈ O) _n
(C ₂ H ₄ O) _o COCH ₂ CH ₂ COOH l+n=23, m=
21 etc. The present invention can be applied to these photosensitive materials for squirrels. In addition, the silver halide photographic light-sensitive material of the present invention includes ethylenediaminetetraacetic acid and US Pat. No. 3,236,652, West German Pat. −
The sequestering agent described in JP 25218 may also be used. Example 1 Highly sensitive silver halide grains containing 98.5 mol% silver bromide and 1.5 mol% silver iodide and having an average grain size of 1.2 μm were prepared. Sufficient desalting was carried out by the flocculation method using poly[β-methylene-sodium naphthalene sulfonate]. Chemical ripening was performed using a gold sensitizer and a sulfur sensitizer, and the following photographic additives were added per mole of silver halide. 4-hydroxy-6-methyl-1,3,3a,7-
Tetrazaindene 1.2g Diethylene glycol 11.0g Glyoxal 1.2g Sodium diethylhexyl succinate sulfonate 1.5g Paranitrophenyl-triphenyl phosphate chloride 0.2g The coating solution thus prepared was mixed with silver 4g/m ² and gelatin.
The gelatin was coated on a polyethylene terephthalate support so that the gelatin concentration was 1.7 g/m ² , and then the exemplified compound was added to a solution with the composition shown below, and the sample was coated in layers so that the gelatin concentration was 1.2 g/m ² . . Gelatin 100 g Sodium diethylhexyl succinate sulfonate 1 g Mucochloric acid 1 g Polymethyl methacrylate (average particle size 3μ)
2.5g Sample name and details are shown in Table 1.

[Developer composition 1]

Sodium N-methyl-p-aminophenol sulfate 6g Hydroquinone 10g Anhydrous sodium sulfite 60g Sodium carbonate monohydrate 54g Potassium bromide 3g Ethylenediaminetetraacetic acid disodium salt 1g Add water to 1 and adjust the pH to 10.00. The results are shown in Table 2.

[Table] As shown in Table 2, the photosensitive materials of sample numbers 8 and 9 according to the present invention have good conductivity, almost no or no static marks, and are durable. Adhesion does not pose a practical problem, and the effect on relative sensitivity and fog is small. Therefore, it can be seen that the present invention has particularly excellent properties as a high-sensitivity photographic material that requires high-speed transportation. Although it is not clear what causes the combined effect in the present invention, lanolin-based ethylene oxide adducts, alkali metal salts, and alkaline earth metal salts are hydrophilic and highly compatible with gelatin; Although these compounds are highly dispersed in the solution, it is presumed that when used together, these compounds tend to migrate to the surface due to the salting out effect. This phenomenon can be inferred from the fact that when a solution of these compounds is added to the surface of a coated and dried silver halide photosensitive material by spray coating or supercoating, the effect is very large. Example 2 A silver chlorobromide emulsion containing 25 mol % of silver bromide and 0.5 mol % of silver iodide was prepared. The average particle size is 0.25μ, and 50% of all particles are in the range of 0.6 to 1.4 times the average particle size.
Moreover, 50% of all particles are substantially cubic. This emulsion was chemically ripened using a gold sensitizer and a sulfur sensitizer, and the following photographic additives were added per mole of silver halide.

[Backing layer composition 1]

Gelatin 100 g Diethylene glycol 2 g Acid fuchsin 2 g Silicon dioxide (average particle size 4μ) 1.5 g Sodium diethylhexyl succinate sulfonate 1.5 g Vinyl acetate/vinyl chloride copolymer latex
5 g Formalin 0.5 g Exemplified compound -4 5 g Exemplified compound -1 to 12 2 g [Backing layer composition 2] Gelatin 100 g Trimethylolpropane 2 g Tartrazine 3 g Saponin 2 g Polymethyl methacrylate (average particle size 5 μ)
1.5g Mucochloric acid 1.1g Exemplary compound -4 5 g Exemplary compound -5-9 2 g

【table】

[Developer composition 2]

Hydroquinone 15 g Formaldehyde acidic sodium sulfite 50 g Anhydrous sodium sulfite 2.5 g Sodium carbonate 74 g Potassium bromide 2.5 g Triethanolamine 8 g 5-nitroindazole 10 mg Add water to 1 and adjust the pH to 9.80. Example 3 A silver chlorobromide emulsion containing 65 mol % of silver chloride and 35 mol % of silver bromide was prepared. The average particle size is 0.3μ.
This emulsion was chemically ripened using a sulfur sensitizer, and the following photographic additives were added per mole of silver halide. 4-hydroxy-6-methyl-1,3,3a,7-
Tetrazaindene 1.1g 5-[(3-γ-sulfopropyl-2-benzoxazolinylidene)-ethylidene]-1(β-hydroxyethyl)-3-phenylthiohydantoin
100 mg 3-allyl-5-[1-methyl-2-(1H)-pyridylidene]-rhodanine 35 mg Polyethylene glycol (molecular weight 2000) oleate 0.5 g Saponin 1.2 g Mucochloric acid 0.5 g Bis-(methylene-vinyl sulfone) 0.5 g The coating solution prepared in this manner was adjusted to the sample number of Example-2 so that the silver content was 4.5 g/m ² and the gelatin content was 1.7 g/m ² .
36, 37, and 38, and then a protective layer having the composition shown below was coated at a gelatin concentration of 1.5 g/m ² to prepare samples. Gelatin 100 g Formalin 1.7 g Exemplified compound -4 5 g Exemplified compound -5 to 9 2 g Saponin 3 g Polymethyl methacrylate (average particle size 5μ)
7.5g The surface resistivity of the surface containing the silver halide emulsion of each sample was measured by the method of Example 2. Next, to check the adhesion resistance, two copies of each sample were prepared.
After conditioning the humidity at 80% RH for 20 hours and bringing the backing layer and silver halide emulsion layer into contact with each other, they were heat-sealed into a bag laminated with aluminum foil/polyethylene in the same manner as in Example 1, and a 1 kg bag was heated. Apply a load,
After keeping at 55°C for 6 hours, the adhesive area ratio was determined. Table 5 shows the sample breakdown and results.

[Color developer composition]

4-amino-3-methyl-N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5 g Potassium hydroxide 1.0 g Add water to make 1 and adjust the pH to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to bring the solution to 1 and adjust the pH to 6.0. [Fixer composition] Ammonium thiosulfate 50% aqueous solution 162 ml Anhydrous sodium sulfite 12.4 g Add water to bring the solution to 1 and adjust the pH to 6.5. [Stable bath composition] Formalin 37% aqueous solution 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Sensitometry was performed using blue light on the developed sample. These results are shown in Table-6. However, the sensitivity was expressed as a relative sensitivity, with the sensitivity of sample number 43, which was processed on the same day, taken as 100.

[Table] Table 6 shows that the samples according to the present invention have excellent conductivity and have no adverse effect on storage stability.

Claims (1)

[Claims] 1. A lanolin-based ethylene oxide adduct and an alkali metal salt and/or an alkaline earth metal in the outermost layer or the adjacent layer on one or both sides of a silver halide photographic light-sensitive material formed by coating a photographic constituent layer on a support. A silver halide photographic material characterized by containing a salt.