JPH0575100B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material with improved slip properties and adhesion resistance, and more specifically, a silver halide photographic material with improved surface physical properties using a specific organopolysiloxane. This invention relates to silver oxide photographic materials. [Background of the Invention] Silver halide photographic materials generally consist of at least one silver halide emulsion layer and at least one non-photosensitive layer on a support such as paper, glass, cellulose acetate film, or polyester film. It has a photographic constituent layer,
Hydrophilic colloids, especially gelatin, are usually used as binders for photographic constituent layers. This coated film made of gelatin has a high coefficient of friction against other metal surfaces or gelatin surfaces, and for this reason, silver halide photographic materials that generally use hydrophilic colloids, especially gelatin, as a binder have a high coefficient of friction when the surface is exposed to contact, friction, etc. It has a serious drawback of being easily scratched. In particular, silver halide photographic materials are sensitive to pressure because the silver halide used as a photosensitive substance is sensitive to pressure.
Scratches caused by contact, friction, etc. sometimes cause pressure fogging, desensitization due to pressure, etc., and have a fatal effect on photographic images. Furthermore, since gelatin is used as a binder, the surface is sticky under high humidity conditions, and the photosensitive materials tend to adhere to each other. For this reason, in silver halide photographic materials, a non-light-sensitive protective layer is usually provided outside the light-sensitive silver halide emulsion layer, and silica, glass, synthetic resin, etc. are present in the protective layer. Methods such as roughening the surface and reducing the contact area to control the coefficient of friction, prevent the occurrence of fog due to adhesion and pressure between photosensitive materials, or protect silver halide photographic photosensitive materials from scratches. is being carried out.
Furthermore, in recent years, a method of dispersing high-boiling point solvents, solid paraffin, whale oil, etc. in an aqueous gelatin solution and applying it to silver halide photographic materials has been proposed, for example in the US Patent No.
It is described in specification No. 3121060 or Japanese Patent Application Laid-open No. 49-5017. Although these methods are effective and each has excellent features, they also have the following drawbacks. For example, silica, glass, synthetic resin, etc. are inferior in terms of preventing scratches, and especially when applied to the back side, they have the disadvantage of being easily scratched. Moreover, when these materials are used in large amounts, the transparency of the photosensitive material is reduced, resulting in a disadvantage that the sharpness of the image is deteriorated. Also, if a high boiling point solvent, which is also used as a solvent for protected couplers, is used as a slipping agent,
Under conditions of high temperature and high humidity, high boiling point solvents migrate from the layer to the surface, causing the films to adhere to each other. Furthermore, the stability of a colloidal dispersion of a high-boiling solvent greatly depends on the viscosity of the liquid, the concentration of the activator, etc., and therefore there are drawbacks such as difficulty in preparing the dispersion. Furthermore, solid paraffin has poor dispersibility, and in particular, dispersibility strongly depends on temperature, making it difficult to create a stable and uniform dispersion of fine particles. There are disadvantages such as the need to keep the entire container or pipe warm in order to remove the heat. Furthermore, a method of controlling the slipperiness of silver halide photographic light-sensitive materials using a surfactant is also known, but the surfactant is eluted into the processing solution during processing, resulting in foaming of the processing solution, etc. There are drawbacks such as the amount of use is limited due to the inconvenience caused. A method is also known in which organopolysiloxane is contained in a silver halide emulsion layer, a protective layer or a back coating layer to improve the slipperiness of the surface of a photosensitive material. For example, a method using dimethyl silicone and a specific surfactant simultaneously as described in U.S. Pat. No. 3,042,522, a mixture of dimethyl silicone and diphenyl silicone as described in U.S. Pat. No. 3,080,317, etc. Methods using triphenyl-terminated methylphenyl silicones as described in UK Patent No. 1,143,118, di-lower alkyl silicones and certain surfactants as described in U.S. Pat. No. 3,489,567. Method, Special Publication 53-292
A method using an organopolysiloxane having a long-chain alkyl group in the side chain as described in No.
There is a method using an organopolysiloxane having a polyoxyethylene group in the side chain as described in Japanese Patent Publication No. 55-92843. Although these organopolysiloxane compounds slightly improve the slipperiness of photosensitive materials,
There is no one that can provide sufficient performance, and it is not possible to completely eliminate the stickiness of the film surface.In addition, in the case of silver halide color photographic materials, high boiling point organic solvents are used as solvents for protected couplers. However, under high temperature and high humidity conditions, the film migrates to the top layer, causing the films to adhere to each other, but it has not been of any use in improving this phenomenon. [Object of the Invention] The first object of the present invention is to provide a silver halide photographic material with good slip properties. A second object is to provide a silver halide photographic material that is prevented from adhering to each other when stored at high temperatures and high humidity. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide photographic light-sensitive material provided on the support is At least one of the constituent photographic constituent layers contains a structural unit represented by the following general formula [] and/or the following general formula []
This was achieved by containing an organopolysiloxane having a group represented by: General formula []

[In the formula, R ₁ represents a hydrogen atom, an alkyl group, or an aryl group. R ₂ represents an alkyl group having 4 or more carbon atoms. A represents an alkylene group,
m represents 0 or 1. Also, B is -O-,-
COO−, −OCO−, −NHCO−, −CONH−, −S
−, −SO ₂ −, −SO ₂ NH− or −NHSO ₂ −. ] General formula []

[In the formula, R ₂ , A, B and m are the general formula [ ]
It has the same meaning as R ₂ , A, B, and m in . _R3 and _R4 each represent a hydrogen atom, an alkyl group, an aryl group, or (-A- _n --B- _R2 .) [Specific structure of the invention] In the following general formula [] used in the present invention: An organopolysiloxane (hereinafter referred to as the organopolysiloxane of the present invention unless otherwise specified) having a structural unit represented by the following general formula [] and/or a group represented by the following general formula [] will be explained.General formula []

In the general formula [], R ₁ represents a hydrogen atom, an alkyl group or an aryl group. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, and t-butyl group. Further, specific examples of the aryl group for R ₁ include phenyl group, tolyl group, xylyl group, and the like. Preferred as R ₁ is a methyl group or a phenyl group. R ₂ represents an alkyl group having 4 or more carbon atoms.
Preferred R ₂ is an alkyl group having 5 to 18 carbon atoms, specifically a pentyl group, a hexyl group,
Examples include octyl group, decyl group, dodecyl group, pentadecyl group, heptadecyl group, and octadecyl group. A represents an alkylene group. Preferred as A are alkylene groups having 2 to 6 carbon atoms, and specific examples include dimethylene, trimethylene, tetramethylene, and hexamethylene groups. Further, m represents 0 or 1. B is -O-, -COO-, -OCO-, -NHCO-,
-CONH-, -S-, _-SO2- , _-SO2NH- or _-NHSO2- . General formula []

[Chemical formula] In the general formula [], R ₂ , A, B and m
is synonymous with R ₂ , A, B, and m in the general formula []. R ₃ and R ₄ may be the same or different groups, and each represents a hydrogen atom, an alkyl group, an aryl group, or (-A- _n --B-R _2. R ₃ and R Specifically, the alkyl group represented by ₄ includes methyl group, ethyl group, propyl group, i
-propyl group, butyl group, t-butyl group, etc., and specific examples of the aryl group include phenyl group, tolyl group, xylyl group, etc.
The alkyl group represented by R ₃ and R ₄ is a substituent,
For example, those substituted with an aryl group (eg, phenyl group, etc.) are also included. Preferred as R ₃ and R ₄ are methyl or phenyl groups. When the organopolysiloxane of the present invention has a group represented by the general formula [], even if one of the ends is a group represented by the general formula [] and the other is not a group represented by the general formula [], both ends are the group represented by the general formula []. Although it may be a group represented by the formula [], it is preferable that both ends are groups represented by the general formula []. When the organopolysiloxane of the present invention has a group represented by the general formula [] at both ends, even if R ₂ , R ₃ , R ₄ , A, B, and m are the same as each other in the two groups at both ends. They may be different, but preferably the same. Further, the organopolysiloxane of the present invention may have a structural unit represented by the following general formula [] in addition to the structural unit represented by the general formula []. Furthermore, when the organopolysiloxane of the present invention has a group represented by the general formula [], it may have only the structural unit represented by the general formula []. General formula []

embedded image In the general formula [], R ₅ and R ₆ may be the same or different, and each represents a hydrogen atom, an alkyl group, or an aryl group. Preferred alkyl groups represented by R ₅ and R ₆ are alkyl groups having 1 to 12 carbon atoms,
Specifically, methyl group, ethyl group, butyl group, i-
Examples include hexyl group, octyl group, and dodecyl group. As the aryl group represented by R ₅ and R ₆ ,
Specific examples include phenyl group, tolyl group, and hexyl group. Further, the alkyl groups represented by R ₆ and R ₇ include those substituted with an aryl group (eg, phenyl group, etc.). When the organopolysiloxane of the present invention has a structural unit represented by the general formula [],
It may have a group represented by the following general formula []. General formula []

In the general formula [], R ₇ , R ₈ and R ₉ may be the same or different groups, and each represents a hydrogen atom, an alkyl group or an aryl group. Specific examples of the _alkyl group for R ₇ , R ₈ and R ₉ include methyl group, ethyl group, propyl group, _i -propyl group, butyl group, t-butyl group, etc. Specific examples of the aryl group include phenyl group, tolyl group, xylyl group, and the like. Further, the alkyl group includes those substituted with a substituent, for example, an aryl group (eg, phenyl group, etc.). Preferred as R ₇ and R ₉ are methyl group or phenyl group, and preferred as R ₈ are:
A hydrogen atom, a methyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, or a phenethyl group. When the organopolysiloxane of the present invention has a group represented by the general formula [ ] at both ends, R ₇ , R ₈ and R ₉ in the two groups at both ends may be the same or different. Yes, but it is preferable if they are the same. Typical specific examples of the organopolysiloxane of the present invention are listed below, but the present invention is not limited to these compounds.

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[C] The method for producing the organopolysiloxane of the present invention is described, for example, in E.G. Rochou, "Chemistry of the Silicone (Chapman and Hall, 1951 edition)", pp. 66-70, "Processing and Applications of Silicone". ” (Kansai Plastics Technology Research Group
1954) p. 26, F.G.A. Stone (F.
GAStone) and WAG Graham, “Inorganic Polymers” (Academic Press 1962), 230.
In addition to being described on pages 231 and 288-295,
A method by co-hydrolysis of each component organoflorosilane as shown in Japanese Patent Publication No. 36-22361,
Special Publication No. 35-10771, No. 43-28694, No. 45-
14898, etc., or the dehydrogenation reaction of alcohols to siloxane containing ≡SiH using a metal salt catalyst. or a method in which hydroxy groups, carboxy groups, thiol groups, amino groups, epoxy groups, etc. bonded to carbon atoms that are not directly bonded to silicon atoms are modified by ordinary organic reactions. can be synthesized by Some of the organopolysiloxanes and raw materials of the present invention are also commercially available from Petrarch Systems, Inc. of the United States. The weight average molecular weight of the organopolysiloxane of the present invention is preferably 1,000 to 100,000. In order to incorporate the organopolysiloxane of the present invention into a photographic constituent layer, there are two methods: adding it to the coating solution in advance, and overcoating or permeating the organopolysiloxane of the present invention. The former is preferable. The method of adding the organopolysiloxane of the present invention to the coating solution is to disperse the organopolysiloxane of the present invention in water or a hydrophilic colloid solution, such as a gelatin solution, in the presence of a dispersion solution.
Further, there is a method of adding it to a desired photographic coating solution, or a method of dispersing it in a photographic gelatin solution in the presence of a dispersant and applying it as it is. As the dispersant, surfactants commonly used for photography can be used, for example,
Anionic surfactant, nonionic surfactant,
An amphoteric surfactant or a cationic surfactant appropriately selected can be used, and the dispersion can be carried out using an ultrasonic homogenizer, a bulb homogenizer, or the like. The preferred particle size of the organopolysiloxane of the present invention in a dispersed state is 0.1 to 10μ.
If the particle size is too small, the effect of the present invention, especially the slipperiness, will deteriorate, and if the particle size is too large, devitrification will occur, making it undesirable as a photosensitive material. In addition, during dispersion, in order to facilitate dispersion and control particle size, low boiling point organic solvents such as ethyl acetate, methanol, acetone, etc., and commonly used high boiling point solvents such as tricresyl phosphate are used. An organic solvent may also be used. The amount of organopolysiloxane used in the present invention is:
0.3 to the binder of the photographic constituent layer contained
A range of 30% by weight is preferred, and a range of 1 to 10% by weight is particularly preferred. Further, in the present invention, two or more types of organopolysiloxanes of the present invention can be used in combination as appropriate. In the present invention, the photographic constituent layers constituting the silver halide photographic light-sensitive material refer to non-photosensitive layers such as a silver halide emulsion layer, a protective layer, an intermediate layer, an antihalation layer and a back coat layer. Although the organopolysiloxane of the present invention may be used in any of the photographic constituent layers, it is particularly preferable to use it in a protective layer or a back coat layer because the effects of the present invention are significant. Further, when the organopolysiloxane of the present invention is used in a layer having a release surface of a release type diffusion transfer type silver halide photosensitive material, excellent performance can be exhibited. Hydrophilic colloids that can be advantageously used in the present invention include, in addition to gelatin, derivative gelatin, colloidal albumin, agar, gum arabic, alginic acid, and cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26%. , acrylamide, imidized polyacrylamide, casein, e.g. vinyl alcohol-
Urethanes such as vinyl cyanoacetate copolymers, vinyl alcohol polymers containing carboxylic acid groups or cyanoacetyl groups, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, obtained by polymerization of proteins or saturated acylated proteins with monomers having vinyl groups. Polymers and the like are included. In the present invention, it is desirable to use various film property improving agents, such as hardening agents, as necessary, for the purpose of improving the physical properties of the coating film made of the hydrophilic colloid. For example, if a hardening agent is used in combination, not only will a synergistic effect be obtained in preventing abrasions as referred to in the present invention, but also the mechanical strength of the coating and the dissolution resistance against processing liquids will be further improved. When gelatin is used as a hydrophilic colloid, typical hardening agents include aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate,
Examples of hardening agents include sulfonic acid ester hardeners, carbodiimide hardeners, mucochloric acid hardeners, acyloyl hardeners, pyridium salt hardeners, and polymer hardeners. The amount of hardening agent used at this time may be within any range that does not impair the effects of the present invention, depending on the type of gelatin film desired, the required physical properties, and photographic properties. The hydrophilic colloid used in the present invention may optionally contain photographic additives other than the hardening agent, such as gelatin plasticizers, surfactants, ultraviolet absorbers, antifoggants, antistain agents, and PH regulators. , antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. may be used within the range that does not impair the effects of the present invention. can. As the matting agent that can be used in the present invention, for example, compounds described in British Patent No. 1221980, US Patent No. 2992101, and US Patent No. 2956884, particularly those with a particle size of 0.5 to 20 μm are used. silica, a polymer of polymethyl methacrylate having a particle size of 0.5 to 20 μm, and an alkali-soluble matting agent described in JP-A-60-126644. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention) includes silver bromide, silver halide,
Any of those commonly used in silver halide emulsions can be used, such as silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, benzoxozal nucleus, naphthooxozal nucleus, benzothiazole nucleus, naphthothiazole nucleus,
benzoselenazole nucleus, benzimidazole nucleus,
Such as quinoline nucleus. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929080;
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 2945763 and British Patent No. 505979. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2454629, No. 2776280, and the like. Furthermore, U.S. Patent No. 2213995,
Cyanine dyes, merocyanine dyes, or composite cyanine dyes such as those described in No. 2493748, No. 2519001, and West German Patent No. 929080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publication No. 43-4932,
−4933, No. 43-4936, No. 44-32753, No. 45
-25831, 45-26747, 46-11627, 45-26747, 46-11627,
46-18107, 47-8741, 47-11114, 47-11114, 47-8741, 47-11114,
No. 47-25379, No. 47-37443, No. 48-28293,
No. 48-38406, No. 48-38407, No. 48-38408,
No. 48-41203, No. 48-41204, No. 49-6207,
No. 50-40662, No. 53-12375, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 50-33828
No. 50-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 51-151527, No. 115820, No. 51-135528, No. 51-151527, No.
No. 52-23931, No. 52-51932, No. 52-104916,
No. 52-104917, No. 52-109925, No. 52-110618
No. 54-80118, No. 56-25728, No. 57-1483
No. 58-10753, No. 58-91445, No. 58-
No. 153926, No. 59-114533, No. 59-116645, No. 153926, No. 59-114533, No. 59-116645, No.
59-116647, U.S. Patent No. 2688545, U.S. Patent No. 2977229
No. 3397060, No. 3506443, No. 3578447,
3672898, 3679428, 3769301, 3672898, 3679428, 3769301,
It is described in No. 3814609 and No. 3837862. The silver halide photographic light-sensitive material of the present invention may be either a black-and-white light-sensitive material or a color light-sensitive material, but in the case of a color light-sensitive material, an aromatic primary amine developer is used in the emulsion layer in the color development process. A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments can be included, such as spectral sensitizers, spectral sensitizers, and desensitizers. Colored couplers that have a color correction effect on these dye-forming couplers, or DIR that releases a development inhibitor during development and improves image sharpness and image graininess.
A coupler may also be used in combination. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor. The DIR couplers and DIR compounds used include:
one in which an inhibitor is directly bound to the coupling position;
The inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded in such a way that it is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. Although a coupling reaction is carried out with the oxidized product of the aromatic primary amine developer, a colorless coupler that does not form a dye can also be used in combination with a dye-forming coupler. Supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate,
polyamide film, polypropylene film,
Typical examples include polycarbonate film, polystyrene film, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic material. Various methods can be used for developing the silver halide photosensitive material of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. The black and white development process includes a development process, a fixing process, and a water washing process. If a stop treatment step is performed after the development treatment step or a stabilization treatment step is performed after the fixation treatment step, the water washing treatment step may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material, and the developing process may be carried out using only an alkaline solution. A development process using a lithium developer as a developer may be performed. As a color development process, a color development process, a bleaching process, a fixing process, a water washing process and/or a stabilizing process are performed as necessary,
Instead of the processing step using a bleaching solution and the processing step using a fixing solution, a bleach-fixing processing step can be performed using a one-bath bleach-fixing solution, and color development,
It is also possible to carry out a monobath processing step using a one-bath development, bleach-fixing treatment solution that allows bleaching and fixing to be carried out in one bath. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the color development treatment step, or an activator treatment step may be performed in place of the monobath treatment. Beta treatment, bleaching and fixing treatments may be carried out simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as the final step, which is either a water washing process, a stabilization process, a water washing process, or a stabilization process.) - Color development process - bleaching process - fixing process - color development process Process - Bleach-fixing process - Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleach process - Fixing process - Washing process - Post-hardening process - Color development process - Water washing process - Supplementary color development process - Stop process - Bleaching process -
Fixing process, monobath process, activator process - bleach-fixing process, activator process - bleaching process - fixing process The present invention can be applied to various photographic materials having a hydrophilic colloid layer. , typically uses silver halide as a photosensitive component, such as general negative photosensitive materials, general reversal photosensitive materials, general positive photosensitive materials, direct positive photosensitive materials, special purpose (e.g. printing, It can be used in silver halide photographic materials (for rays, high resolution, infrared, ultraviolet, etc.). [Effects of the Invention] By using the organopolysiloxane of the present invention in a photographic constituent layer, a silver halide that has good slip properties and prevents adhesion of photosensitive materials to each other even when stored under high temperature and high humidity conditions. A photographic material was obtained. [Examples] Specific examples of the present invention will be described below, but the aspects of the present invention are not limited thereto. [Example] In all the following examples, the amount added in the silver halide photographic material was 1 m ² unless otherwise specified.
Show the winning one. In addition, silver halide and colloidal silver are shown in terms of silver. On a triacetylcellulose film support,
A multilayer silver halide color photographic light-sensitive material was prepared by sequentially forming each layer having the composition shown below from the support side. First layer; antihalation layer Gelatin layer containing black colloidal silver. Second layer; intermediate layer gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone. 3rd layer; low sensitivity red-sensitive silver halide emulsion layer average grain size (r) 0.30 μm, containing 6 mol% AgI
Monodisperse emulsion (emulsion) consisting of AgBrI...silver coating amount 1.8 g/ ^m2 Sensitizing dye...6 x 10 ^-5 mol per mol of silver Sensitizing dye...1.0 x 10 ^-5 mol per mol of silver Lucian coupler (C-1)...for 1 mole of silver
0.06 mol Colored cyan coupler (CC-1)...0.003 mol for 1 mol of silver DIR compound (D-1)...for 1 mol of silver
0.0015 mol DIR compound (D-2)...for 1 mol of silver
0.002 mol 4th layer; high sensitivity red-sensitive silver halide emulsion layer average grain size (r) 0.5 μm, containing 7.0 mol% AgI
Monodispersed emulsion (emulsion) consisting of AgBrI...silver coating amount 1.3 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per mol of silver Sensitizing dye...1.0 x 10 ^-5 mol per mol of silver Lucian coupler (C-1)...for 1 mole of silver
0.02 mol Colored cyan coupler (CC-1)...0.0015 mol for 1 mol of silver DIR compound (D-2)...for 1 mol of silver
0.001 mol 5th layer; middle layer Same as the 2nd layer, gelatin layer. 6th layer: Low-sensitivity green-sensitive silver halide emulsion layer Emulsion - Coated silver amount: 1.5 g/m ² Sensitizing dye: 2.5 x 10 -5 mol per 1 mol of silver Sensitizing dye: 2.5 x 10 ^-5 mol per 1 mol of silver 1.2×10 ^-5 mole magenta coupler (M-1)...0.050 mole per mole of silver Colored magenta coupler (CM-1)...1 silver
0.009 mol per mole DIR compound (D-1)... per 1 mol of silver
0.0010 mol DIR compound (D-3)...for 1 mol of silver
0.0030 mol 7th layer: High sensitivity green-sensitive silver halide emulsion layer Emulsion - Coated silver amount 1.4 g/m ² Sensitizing dye... 1.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... 1 mol of silver 1.0×10 ^-5 mol magenta coupler (M-1)...0.020 mol colored magenta coupler (CM-1)...silver 1 mol relative to 1 mol silver
0.002 mol per mole DIR compound (D-3)... per 1 mole of silver
0.0010 mol 8th layer: Yellow filter layer Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone. 9th layer: Low sensitivity blue-sensitive silver halide emulsion layer A monodispersed emulsion (emulsion) consisting of AgBrI with an average grain size of 0.48 μm and containing 6 mol% of AgI...Silver coating amount 0.9 g/ ^m2 Sensitizing dye...1 mole of silver Yellow coupler (Y-1): 0.29 mol per mol of silver ^10th layer: High-sensitivity blue-sensitive emulsion layer average grain size 0.8 μm, monodisperse consisting of AgBrI containing 15 mol% AgI Emulsion (emulsion)... Silver coating amount 0.5 g/m ² Sensitizing dye... 1.0 x 10 ^-5 mol per 1 mol of silver Yellow coupler (Y-1)... 0.08 mol DIR compound (D- 2)...for 1 mole of silver
0.0015 mol 11th layer; UV absorber-containing layer Silver iodobromide (AgI 1 mol % Average particle size 0.07 μm) Silver coating amount 0.5 g/m ² Ultraviolet absorber UV-1, UV-2 and formalin scavenger HS-1 gelatin layer containing. 12th layer: The protective layer coating solution for the second and subsequent protective layers was coated at a gelatin concentration of 0.6 g/m ² . [Preparation of organopolysiloxane dispersion] Solution A Organopolysiloxane (exemplary compound OS
-1) 2.0g Ethyl acetate 1.5g Solution B 5% gelatin aqueous solution 20ml Sodium triisopropylnaphthalene sulfonate 2.0g Solution C 7% gelatin solution 50ml Mix solutions A and B and use a valve-type homogenizer manufactured by Mantogorin. The particle size of the dispersion is
A dispersion liquid was obtained by controlling the particle size to be about 0.8μ. Solution C was added to the obtained dispersion, and water was added to make up the volume to 80 ml to obtain an organopolysiloxane dispersion. [Protective layer coating solution] Organopolysiloxane dispersion 70ml Gelatin 40g Sodium-amyl-decyl sulfosuccinate
1.0g Copolymer particles of 30 mol% ethyl methacrylate, 30 mol% methyl methacrylate, and 40 mol% methacrylic acid (*average particle size 2.2 μm) 4.0 g 1,2-bisvinylsulfonylethane 2.0 g Finish with water to 1000 ml. *Average particle size is determined by Horiba automatic particle size distribution measuring machine.
CAPA-500 was used. In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each layer. The compounds contained in each layer are as follows. Sensitizing dye; anhydro 5,5'-dichloro-9-
Ethyl-3,3'-di-(3-sulfopropyl)
Thiacarbocyanine hydroxide sensitizing dye; anhydro9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-
Dibenzothiacarbocyanine hydroxide sensitizing dye; anhydro 5,5'-diphenyl-9
-Ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye; anhydro9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5' ,6′−
Dibenzothiacarbocyanine hydroxide sensitizing dye; anhydro 3,3'-di-(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine

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[C] The sample thus obtained is referred to as Sample A. Also
Samples B to H, which were the same as sample A, were prepared except that organopolysiloxane as shown in Table 1 was used instead of OS-1. For comparison, samples using organopolysiloxanes having the following structures are designated as Samples A and B.

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[Chemical formula] Regarding these samples, the friction coefficient of the emulsion layer side surface and the adhesion resistance between the emulsion surface and the triacetate back surface under high temperature and high humidity conditions were investigated using the following methods. The results are shown in Table-1. [Friction coefficient] - Measurement sample was measured at 23℃ 55% RH (relative humidity) 23℃ 80% according to the method of US ASTMD-1814
RH was measured after 24 hours of humidity control.・ Expressed as the coefficient of dynamic friction against light-shielding paper for photographic film [Adhesion resistance test method] Cut the sample into 5 x 5 cm pieces, make a set of 2 pieces, and test in an atmosphere of 23°C and 80% RH (relative humidity).
After conditioning the humidity for 24 hours, the protective layer and back layer of the same sample were brought into contact with each other and a load of 800g was applied to the sample at 40℃ 80%.
After storage for 24 hours under RH, the load was removed, the sample was peeled off, and the area of the adhesive part was measured to evaluate the adhesive resistance. The evaluation criteria were based on the method shown below. Rank A Adhesive area 0-20% B Adhesive area 21-40% C Adhesive area 41-60% D Adhesive area 61-80% E Adhesive area 81% or more

[Table] As is clear from Table 1, the samples of the present invention have good slip properties and little adhesion to the back surface of the film base, and have excellent surface properties. Example 2 98.5 mo% silver bromide and silver iodide were applied to both sides of a subbed polyethylene terephthalate support.
A silver halide emulsion layer containing highly sensitive silver halide grains of 1.5 mo% and an average grain size of 1.2 μm and a protective layer were coated to obtain a silver halide photographic material for X-rays. The following additives were added to the silver halide emulsion per mole of silver halide. 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene 1.2 g Diethylene glycol 11.0 g Cryoxal 1.2 g Sodium diethylhexyl succinate sulfonate 1.5 g Para-nitrophenyl triphenyl phosphate chloride 0.2 g The coating solution thus prepared was coated with 4 g/m ² of silver and 1.7 g of gelatin. It was applied so that it became g/ ^m2 . For the protective layer, a coating solution having the following composition was applied so that the amount of gelatin was 1.2 g/m ² . [Protective layer composition] Gelatin 80g Sodium diethylhexyl succinate sulfonate 1g Mucochloric acid 1g Polymethyl methacrylate with an average particle size of 3 to 4μ 2g Paranonyl phenyloxyethylene ether
Formaldehyde polycondensate: 4 g Sodium polyoxyethylene-di-nonylphenol ether sulfate: 2 g Organopolysiloxane OS-1 dispersion prepared by the method of Example 1: 120 ml The sample thus obtained is used as a sample. In addition, samples J to M were made the same as the sample except that organopolysiloxane as shown in Table 2 was used instead of OS-1. Regarding these samples, as in Example 1, the friction coefficient of the emulsion layer side surface and the adhesion resistance between the emulsion surfaces under high temperature and high humidity were examined. The results are shown in Table-2.

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[Table] As is clear from Table 2, even for black-and-white light-sensitive materials, the samples of the present invention have surface physical properties with good slip properties and excellent adhesion resistance between emulsion surfaces under high temperature and high humidity. are doing.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, a photographic constituent layer constituting the silver halide photographic material provided on the support. A silver halide photographic light-sensitive material characterized in that at least one layer thereof contains an organopolysiloxane having a structural unit represented by the following general formula [] and/or a group represented by the following general formula []. General formula [ ] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, or an aryl group. R ₂ represents an alkyl group having 4 or more carbon atoms. A represents an alkylene group,
m represents 0 or 1. Also, B is -O-,-
COO−, −OCO−, −NHCO−, −CONH−, −S
−, −SO ₂ −, −SO ₂ NH− or −NHSO ₂ −. ] General formula [] [In the formula, R ₂ , A, B and m are the general formula [ ]
It has the same meaning as R ₂ , A, B, and m in . R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or (-A) _n --BR ₂ . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the organopolysiloxane is contained in at least one of the outermost layers of the photographic constituent layers.