JPH0621924B2 - Silver halide photographic light-sensitive material with improved adhesion resistance and sliding property - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having improved adhesion resistance and sliding property, and more specifically to a surface of a silver halide photographic light-sensitive material using a modified organopolysiloxane. The present invention relates to a silver halide photographic light-sensitive material having improved properties.

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials are generally composed of at least one silver halide emulsion layer and at least one light-insensitive layer on a support such as paper, glass, cellulose acetate film, polyester film and the like. A hydrophilic colloid, especially gelatin, is often used as a binder for the photographic constituent layer.

A coating film made of this gelatin has a high friction coefficient with respect to other metal surfaces or gelatin surfaces. Therefore, a silver halide photographic light-sensitive material using a hydrophilic colloid as a binder, especially gelatin, is liable to come into contact with the surface due to contact or friction. It has the serious drawback of being easily scratched. In particular, in silver halide photographic light-sensitive materials, since the silver halide used as a light-sensitive substance is sensitive to pressure,
The scratches due to contact, friction, etc. sometimes cause pressure fog and desensitization due to pressure, which has a fatal effect on photographic images. Also,
Since gelatin is used as a binder, it has a drawback that it has a sticky surface under high humidity, which makes it easy for the photosensitive materials to adhere to each other. Therefore, in a normal silver halide photographic light-sensitive material, a non-light-sensitive protective layer is provided outside the light-sensitive silver halide emulsion layer, and further silica, glass, synthetic resin, etc. are present in the protective layer to form a film. A method has been carried out in which the surface is roughened and the contact area is reduced to control the friction coefficient to prevent the occurrence of fog due to pressure or to protect the silver halide photographic light-sensitive material from scratches. Furthermore, in recent years, a method of dispersing a high boiling point solvent, solid paraffin, whale oil, etc. in an aqueous gelatin solution and applying it to a silver halide photographic light-sensitive material is described in, for example, U.S. Pat. No. 3,121,060 or JP-A-49-5017. Has been done.

Although these are effective methods and have excellent characteristics, they have the following drawbacks. For example, silica, glass, synthetic resin, etc. are inferior in terms of preventing scratches, and particularly when applied to the back surface, they tend to be scratched. Further, if a large amount of these materials is used, the transparency of the light-sensitive material is lowered, and as a result, the sharpness of the image is deteriorated.

Further, when a high boiling point solvent which is also used as a solvent for a protect type coupler is used as a slip agent, the high boiling point solvent is transferred from the layer to the surface under the condition of high temperature and high humidity, and the film members cause adhesion. Further, since the stability of the colloidal dispersion of the high boiling point solvent depends largely on the viscosity of the solution, the concentration of the activator, etc., it is difficult to prepare the dispersion.

Furthermore, since solid paraffin has poor dispersibility, and particularly the dispersibility strongly depends on temperature, it is difficult to form a stable and uniform fine particle dispersion liquid, and solid paraffin easily adheres to the wall of a container or piping. However, there is a drawback in that the container or the entire pipe must be kept warm in order to remove

Furthermore, a method of controlling the slip property of a silver halide photographic light-sensitive material using a surfactant is also known, but the surfactant is eluted into the processing solution during processing, and as a result, the processing solution foams. Therefore, there is a drawback that the amount of use is limited because of the inconvenience.

Also known is a method of improving the slipperiness of the surface of a light-sensitive material by incorporating an organopolysiloxane in a silver halide emulsion layer, a protective layer or a back coating layer. For example,
A method of simultaneously using dimethyl silicone and a specific surfactant as described in U.S. Pat.No. 3,042,522, as described in U.S. Pat.No. 3,080,317,
A method using a mixture of dimethyl silicone and diphenyl silicone, a method using a triphenyl-terminated methylphenyl silicone as described in British Patent 1,143,118, a lower alkyl silicone as described in U.S. Pat. And a method using a specific surfactant, a method using an organopolysiloxane having a long-chain alkyl group in the side chain as described in JP-B-53-292, and JP-B-55-92843. As such, there is a method of using an organopolysiloxane having a polyoxyethylene group in its side chain.

Although these organopolysiloxane compounds slightly improve the slipperiness of the light-sensitive material, none of them have sufficient performance, and the tackiness of the film surface cannot be completely removed. In the case of photographic light-sensitive materials, the high boiling point organic solvent used as a solvent for protect type couplers migrates to the uppermost layer under high temperature and high humidity, and there is a phenomenon that the films stick to each other. , No use.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material having good sliding property and preventing adhesion between silver halide photographic light-sensitive materials when stored at high temperature and high humidity. That is.

[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, the silver halide photographic light-sensitive material being provided on the support. Organo having a structural unit represented by the following general formula [I] and / or the following general formula [III] in at least one of the photographic constituent layers, and having a group represented by the general formula [II] at both ends. It is achieved by a silver halide photographic light-sensitive material containing polysiloxane.

[Specific Structure of the Invention] The fluorine-modified organopolysiloxane, vinyl-modified organopolysiloxane, and cyano-modified organopolysiloxane used in the present invention (hereinafter, unless otherwise specified, these are generically referred to as the organopolysiloxane of the present invention). Means that the organic groups bonded to the silicon atom forming the organopolysiloxane skeleton each have a fluorine atom, a vinyl group or a cyano group, or the above silicon atom has a fluorine atom or a vinyl group. Alternatively, each cyano group is directly bonded.

Among the organopolysiloxanes used in the present invention, useful ones include those having a structural unit represented by the following general formula [I].

General formula [I] Here, R ₁ is a hydrogen atom, an alkyl group, an aryl group, or R ₂ represents a divalent linking group, and A represents a fluorine-substituted alkyl group, a vinyl group or a cyano group. n represents 0 or 1. However, when A is a vinyl group, n
Represents 0.

Examples of the alkyl group represented by R ₁ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. R ₁ is preferably a methyl group or a phenyl group, and most preferably a methyl group.

The divalent linking group represented by R ₂ is specifically an alkylene group (eg, dimethylene group, trimethylene group, etc.)
Alternatively, an arylene group (for example, a phenylene group) is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, and a dimethylene group or a trimethylene group is most preferable. Examples of the fluorine-substituted alkyl group represented by A include a trifluoromethyl group and a perfluorohexyl group.

In the general formula [I], n is preferably 1 when A is a fluorine-substituted alkyl group or a cyano group, and n is preferably 0 when A is a vinyl group.

Further, the organopolysiloxane of the present invention preferably has an unterminated group represented by the following general formula [II] at both ends.

General formula [II] Here, R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group, an aryl group or (R ₂ , A and n are each R in the general formula [I].
₂ , synonymous with A and n. ), R ₃ , R ₄ and R ₅ may be the same or different. Examples of the alkyl group represented by R ₃ , R ₄ and R ₅ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group.
The alkyl group represented by R ₃ , R ₄ and R ₅ includes those substituted with a single or a plurality of aryl groups (eg, phenyl group etc.), and the aryl represented by R ₃ , R ₄ and R _5. The group also includes those substituted with a single or plural alkyl groups (eg methyl group etc.).
R ₃ , R ₄ and R ₅ are preferably an alkyl group or an aryl group, and particularly preferably a methyl group. Further, the organopolysiloxane of the present invention may have a structural unit represented by the following general formula [III].

General formula [III] Here, R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₆ and R ₇ may be the same or different.

The alkyl group represented by R ₆ and R ₇ is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group and a hexyl group, and examples of the aryl group include a phenyl group. The alkyl group represented by R ₆ and R ₇ includes those substituted with a single or multiple aryl group (eg, phenyl group etc.), and the aryl group represented by R ₆ and R ₇ is single or plural. And those substituted with an alkyl group (eg, a methyl group) and the like. R ₆ and R ₇ are preferably a methyl group or a phenyl group.

The organopolysiloxane of the present invention has the structural unit represented by the general formula [I] and / or the structural unit represented by the general formula [III], and further has a terminal group represented by the general formula [II]. Those having are preferred. The terminal groups at both ends may be the same or different from each other, but preferably the same. However,
When the main chain is formed only from the structural unit represented by the general formula [III], at least one of R ₃ , R ₄ and R _{5 in} the terminal group represented by the general formula [II] is used. One is Is.

Typical specific examples of the organopolysiloxane of the present invention are shown below, but the present invention is not limited thereto.
Note that n is the viscosity measured by a rotational viscometer at 25 ° C., and the unit is centistokes (CS).

SF-1 SF-2 SF-3 SF-4 SF-5 SF-6 SF-7 SF-8 SF-9 SF-10 SV-1 SV-2 SV-3 SV-4 SV-5 SV-6 SV-7 SV-8 SV-9 SV-10 SV-11 SC-1 SC-2 SC-3 SC-4 SC-5 SC-6 The method for producing the organopolysiloxane of the present invention is described in, for example, "E.G. Rochou""Chemistry.
Of The Silicone (Chapman & Hall
1951 edition), pp. 66-70, "Silicone processing and applications" (Kansai Plastics Research Group, 1954), p. 26, FG A Stone and BG G.・ Graham (WAG Graha
m) "In Organic Polymers" (Academic Press 1962), pages 230-231, pages 288-295, etc., and Japanese Patent Publications 35-10771, 43-28694, 45.
-S with a metal catalyst as shown in No. 14898
It can be synthesized by applying a method by addition reaction of olefins to siloxane containing iH, or a method by co-hydrolysis of each component organofluorosilane as shown in JP-B-36-22361.

Some of the organopolysiloxanes of this invention are also commercially available from Petrarch Systems, Inc., USA.

The viscosity of the organopolysiloxane of the present invention is about 10-100,000 when measured with a rotational viscometer at 25 ° C.
Those exhibiting centistokes are preferred.

In order to include the organopolysiloxane of the present invention in the photographic constituent layer, there are a method of previously adding to the coating solution and a method of overcoating or permeating the organopolysiloxane of the present invention, but in terms of production cost, The former is preferable. As a method of adding to the coating liquid, the organopolysiloxane of the present invention is dispersed in water or a hydrophilic colloid solution, for example, a gelatin solution in the presence of a dispersant,
Further, there are a method of adding to a desired photographic coating solution, a method of dispersing in a gelatin solution for photography in the presence of a dispersant, and coating as it is.

As the dispersant, a surfactant commonly used for photography can be used. For example, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant or a cationic surfactant is appropriately selected. It can be dispersed by using an ultrasonic homogenizer or a valve homogenizer. The preferred particle size of the organopolysiloxane of the present invention in a dispersed state is 0.
If the particle size is 1 to 10 μm and the particle size is too small, the effects of the present invention, particularly the slipperiness are deteriorated. In addition, at the time of dispersion, in order to facilitate the dispersion and to control the particle size, a low boiling point organic solvent such as ethyl acetate, methanol, or acetone, or a commonly used high boiling point organic solvent such as tricresyl phosphate. You may use a solvent.

The use amount of the organopolysiloxane of the present invention is preferably 0.3 to 30% by weight, and particularly preferably 1 to 10% by weight, based on the binder of the photographic constituent layer.

Further, in the present invention, two or more kinds of the organopolysiloxane of the present invention can be appropriately used in combination.

In the present invention, the photographic constituent layers constituting the silver halide photographic light-sensitive material refer to silver halide emulsion layers and non-photosensitive layers such as protective layers, intermediate layers, antihalation layers and backcoat layers.

The organopolysiloxane of the present invention may be used in any of the photographic constituent layers, but it is particularly preferably used in the protective layer or the back coat layer because the effect of the present invention is remarkable. Further, when the organopolysiloxane of the present invention is used in a layer having a peeling surface of a peeling type diffusion transfer type silver halide photosensitive material, excellent performance can be exhibited.

As the hydrophilic colloid advantageously used in the present invention, in addition to gelatin, derivative gelatin, colloidal albumin,
Agar, acacia, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26%, acrylamide, imidized polyacrylamide, casein, urethane such as vinyl alcohol-vinyl cyanoacetate copolymer, carboxylic acid. A vinyl alcohol polymer containing a group or a cyanoacetyl group, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group, and the like are included.

In the present invention, it is desirable to use various film property-improving agents such as a film-forming agent, if necessary, for the purpose of improving the property of the coating film comprising the hydrophilic colloid.
For example, when a hardener is used in combination, not only synergistic effect for preventing scratches in the present invention can be obtained, but also the mechanical strength of the coating and the dissolution resistance to the treatment liquid are further improved.

When gelatin is used as the hydrophilic colloid, typical hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, sulfonate-based, carbodiimide-based. Examples thereof include various hardeners such as mucochloric acid-based, acyloyl-based, pyridium salt-based, and polymer-based hardeners.

The amount of the hardener used at this time may be any range depending on the type of the intended gelatin film, the required physical properties, and the photographic characteristics so as not to impair the effects of the present invention.

In the hydrophilic colloid used in the present invention, if necessary, as a photographic additive other than the hardener, for example, gelatin plasticizer, surfactant, ultraviolet absorber, antifoggant, antistaining agent, pH adjusting agent. It is possible to use an antioxidant, an antistatic agent, a thickener, a graininess improver, a dye, a moldant, a whitening agent, a developing speed adjusting agent, a matting agent, etc. within a range in which the effect of the present invention is not impaired. it can.

Examples of the matting agent that can be used in the present invention include compounds described in, for example, British Patent No. 1,221,980, U.S. Patent No. 2,992,101, and No. 2,956,884, particularly having a particle size of 0.5 to 20 μm. Holding silica, 0.5 to 20
Examples thereof include a polymer of polymethylmethacrylate having a particle size of 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).
As the silver halide, any silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride used in ordinary silver halide emulsions can be used.

The silver halide emulsion of the present invention can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized in a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone,
You may use it in combination of 2 or more type. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a strong dye sensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus having an aromatic hydrocarbon ring fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxozar nucleus, a naphthoxozar nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benz nucleus. Examples include imidazole nucleus and quinoline nucleus. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

Examples of useful sensitizing dyes used in a blue-sensitive silver halide emulsion layer include West German Patent 929,080 and U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, No. 52-24844 and the like. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, and 2,
Representative examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 739,149, 2,945,763 and British Patent 505,979. Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 234, No. 2,270,378, No. 2,442,710, No. 2,454,629
Nos. 2,776,280 and the like, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical ones. Furthermore, U.S. Pat.Nos. 2,213,995, 2,493,748, 2,519,001, and cyanine dyes as described in West German Patent 929,080 and the like,
A merocyanine dye or a complex cyanine dye can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive halogen emulsion.

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 Japanese Examined Japanese Patent Publication No. 43-4932, No. 43-4933, No. 43-4936, No. 4
4-32753, 45-25831, 45-26747, 46-11627
No. 46, No. 46-18107, No. 47-8741, No. 47-11114, No. 47-
No. 25379, No. 47-37443, No. 48-28293, No. 48-38406
No. 48, No. 48-38407, No. 48-38408, No. 48-41203, No. 48
-41204, 49-6207, 50-40662, 53-12375
No. 54-34535, No. 55-1569, JP-A No. 50-33220,
50-33828, 50-38526, 51-107127, 51-11
No. 5820, No. 51-135528, No. 51-151527, No. 52-23931
No. 52-51932, No. 52-104916, No. 52-104917, No. 52-104917
52-109925, 52-110618, 54-80118, 56-257
No. 28, No. 57-1483, No. 58-10753, No. 58-91445, No. 5
8-153926, 59-114533, 59-116645, 59-116
647, U.S. Pat.Nos. 2,688,545, 2,977,229, and 3,3
97,060, 3,506,443, 3,578,447, 3,672,89
No. 8, No. 3,679,428, No. 3,769,301, No. 3,814,609,
No. 3,837,862.

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. In the case of a color light-sensitive material, the emulsion layer contains an aromatic primary amine developer during color development processing. A dye-forming coupler that forms a dye by a coupling reaction with an oxidant of a p-phenylenediamine derivative or an aminophenol derivative is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each 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, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers are required to reduce four silver ions in order to form one molecule of dye. Even if they are four equivalents, only two silver ions need to be reduced. Either equivalence may be used. Dye-forming couplers include development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, fog agents, antifoggants, and chemical sensitizers by coupling with an oxidized product of a developing agent. , Spectral sensitizers, and compounds that release photographically useful fragments such as desensitizers. A colored coupler which has a color correction effect on these dye-forming couplers, or a development inhibitor which is released upon development to improve image sharpness and image graininess.
An R coupler may be used in combination. At this time, it is preferable that the DIR coupler is of the same type as that of the dye formed from the dye-forming coupler used in the same emulsion layer, if the color turbidity is not noticeable. It may form a dye. Instead of the DIR coupler, a DIR compound which, in combination with or in combination with the coupler, reacts with an oxidized product of a developing agent to form a colorless compound and simultaneously releases a development inhibitor may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position and those in which the inhibitor is 2
Those linked to the coupling position via a valent group so that the inhibitor is released by an intramolecular nucleophilic reaction in the group that has left due to the coupling reaction or an intramolecular electron transfer reaction ( Timing DIR couplers, and timing DIR compounds). Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A colorless coupler which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Typical examples include glass plates, cellulose acetate, and cellulose nitrate, for example, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, and the like. It is appropriately selected depending on the purpose of use of the material.

Various methods can be used for the development processing of the silver halide light-sensitive material of the present invention. This developing process may be either a process for forming a silver image (black and white developing process) or a developing process for forming a color image depending on the purpose.

The black and white development processing includes a development processing step, a fixing processing step,
A water washing process step is performed. When the stop processing step is performed after the development processing step or the stabilization processing step is performed after the fixing processing step, the water washing processing step may be omitted. Further, the developing agent or its precursor may be incorporated in the light-sensitive material, and the developing treatment step may be carried out only with the alkaline solution. A development process using a lith developer as a developer may be performed.

As a color developing process, a color developing process, a bleaching process, a fixing process, a washing process if necessary, and /
Alternatively, a stabilizing treatment step is carried out, but instead of the treatment step using a bleaching solution and the treatment step using a fixing solution, a bleach-fixing treatment step can be carried out using a one-bath bleach-fixing solution, and color development is performed. It is also possible to carry out a monobath processing step using a one-bath development bleach-fix processing solution capable of bleaching and fixing in one bath.

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these treatments, instead of the color development processing step, a color developing agent or its precursor may be contained in the material and the development processing may be performed by an activator solution, or an activator processing step may be performed instead of the monobath processing. It may be performed at the same time as the beta treatment and the bleaching and fixing treatments. A typical process is shown among these processes. (These steps are the final step, a washing step,
Any of a stabilization treatment process, a water washing treatment process, and a stabilization treatment process is performed. ) -Color development processing step-bleaching processing step-fixing processing step-Color development processing step-bleach fixing processing step-Pre-hardening processing step-neutralization processing step-color development processing step-
Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplementary color development process-Stopping process-Bleaching process- Fixing processing step-Mono bath processing step-Activator processing step-bleach-fixing processing step-Activator processing step-bleaching processing step-fixing processing step The present invention can be applied to various photographic light-sensitive materials having a hydrophilic colloid layer. , Typically, a photographic light-sensitive material of a type using silver halide as a light-sensitive component, such as a general negative light-sensitive material, a general reversal light-sensitive material, a general positive light-sensitive material, a direct positive light-sensitive material, a special (for printing, X Rays, high resolution, infrared, ultraviolet, etc.) silver halide photographic light-sensitive materials.

[Advantages of the Invention] Since the silver halide photographic light-sensitive material of the present invention has improved adhesion resistance and sliding property, it prevents the light-sensitive materials from adhering to each other and prevents fogging due to pressure. Can be protected.

[Examples] Examples of the present invention are described in detail below, but the present invention is not limited to these embodiments.

[Example 1] In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

On the triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer silver halide color photographic light-sensitive material.

First layer: antihalation layer A gelatin layer containing black colloidal silver.

Second layer: intermediate layer A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer AgB containing average grain size () 0.30 μm, AgI 6 mol%
Monodisperse emulsion consisting of rI (Emulsion I): Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ⁻⁵ mol Cyan coupler (C-1) …… 0.06 mol for 1 mol of silver Colored cyan coupler (CC-1)… 0.003 mol for 1 mol of silver DIR compound (D-1) …… Silver 0.0015 mol to 1 mol DIR compound (D-2) ... 0.002 mol to 1 mol of silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer Average grain size () 0.5 μm, AgI 7.0 mol% Including A
Monodisperse emulsion consisting of gBrI (Emulsion II): Silver coating amount 1.3 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ⁻⁵ mol Cyan coupler (C-1) ... 0.02 mol per mol of silver Colored cyan coupler (CC-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... silver 0.001 mol per mol 5th layer; intermediate layer Gelatin layer, same as 2nd layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer Emulsion-I ... coating amount of silver 1.5 g / m ² sensitizing dye III ... 2.5 × 10 ^-5 mol sensitizing dye IV per 1 mol of silver 1.2 × 10 ⁻⁵ moles to 1 mole of silver Magenta coupler (M-1) ... 0.050 moles to 1 mole of silver Colored magenta coupler (CM-1) ... 0.009 moles to 1 mole of silver DIR compound (D -1) ... 0.0010 mol per mol of silver DIR compound (D-3) ... 0.0030 mol per mol of silver Seventh layer; high-sensitivity green-sensitive silver halide emulsion layer Emulsion-II ... coated silver Amount: 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per mol of silver Magenta coupler (M-1) ... 0.020 mol per 1 mol of silver Colored magenta coupler (CM-1) ... 0.002 mol per 1 mol of silver DIR compound (D- ) 0.0010 mol eighth layer against ...... silver mole; emulsified dispersion and the gelatin layer containing yellow filter layer Yellow colloidal silver and 2,5-di -t- octylhydroquinone.

Layer 9: Low-sensitivity blue-sensitive silver halide emulsion layer Monodisperse emulsion consisting of AgBrI containing 0.48 μm of average grain size and 6 mol% of AgI (Emulsion III) ... Silver coating amount 0.9 g / m ² sensitizing dye V .. 1.3 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1) ... 0.29 mol per 1 mol of silver 10th layer; high-sensitivity blue-sensitive emulsion layer 0.8 μm average grain size, containing 15 mol% AgI AgBrI
Monodisperse emulsion (Emulsion IV): Silver coating amount: 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1): 1 mol of silver On the other hand, 0.08 mol DIR compound (D-2) ... 0.0015 mol per 1 mol of silver 11th layer: UV absorbing layer Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.5 g / m ² A gelatin layer containing the UV absorbers UV-1, UV-2 and the formalin scavenger HS-1.

12th layer: Protective layer The following coating solution for protective layer was applied so as to give gelatin of 0.6 g / m ² .

[Preparation of Organopolysilochylline Dispersion] Liquid A Organopolysiloxane (Exemplified Compound SF-2) 2.0 g Ethyl acetate 1.5 g Liquid B gelatin aqueous solution 5% 20 m Triisopropylnaphthalene sodium sulfonate 2.0 g Liquid C gelatin aqueous solution 7% 50 m The liquids A and B were mixed, and a valve homogenizer manufactured by Manton Gorin Co. was used to control the particle size of the dispersion to be about 0.8 μm to obtain a dispersion. Liquid C is added to the obtained dispersion liquid, and water is added to make 80 m,
This was an organopolysiloxane dispersion.

[Protective layer coating liquid] Organopolysiloxane dispersion liquid 70 m Gelatin 40 g Sodium-amyl-decyl sulfosuccinate 1.0 g Ethyl methacrylate 30 mol%, Methyl methacrylate 30 mol%, Methacrylic acid 40 mol% Copolymer particles 4.0 g 1,2- Bisvinylsulfonylethane 2.0g Water 1000m
To finish.

* Average particle size is HORIBA automatic particle size analyzer CAPA-500
Was used.

In addition to the above composition, each layer contains a gelatin hardening agent (H-
1) and a surfactant were added.

The compounds contained in each layer are as follows.

Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'- The-
(3-Sulfopropyl) -4,5,4'5 ', dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing Dye IV; Anhydro 9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5'6 ', dibenzothiacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiacyanine C-1 CC-1 D-1 D-2 D-3 M-1 CM-1 Y-1 UV-1 UV-2 HS-1 H-1 The sample thus obtained is referred to as sample A. Further, instead of SF-2, the compounds shown in Table 1 were used to prepare samples B to N, respectively.

For comparison, samples using organopolysiloxanes I and II having the following structures will be referred to as comparative samples a and b.

Comparative compound I Comparative compound II For these samples, the friction coefficient of the surface on the emulsion layer side and the adhesion resistance between the emulsion surface and the triacetate back surface under high temperature and high humidity were examined by the following methods. The results are shown in Table-1
Shown in.

[Friction Coefficient] ・ The measurement sample is 2 according to the method of American ASTM D-1814.
3 degreeC55% RH (relative humidity) 23 degreeC80% RH Each 24 hours after humidity control, it measured.

・ Displayed by dynamic friction coefficient for light-shielding paper for photographic film [Adhesion resistance test method] Cut the sample into a size of 5 × 5 cm, and make two sheets into one set.
After conditioning the humidity in an atmosphere of 3 ° C. and 80% RH (relative humidity) for 24 hours, the protective layer and the back surface layer of the same sample were brought into contact with each other,
After applying a load of 800 g and storing it at 40 ° C. and 80% RH for 24 hours, the load was removed, the sample was peeled off, the area of the contact portion was measured, and the adhesion resistance was evaluated. The evaluation criteria were the following methods.

Rank AA Adhesive area 0-5% A 〃 0-20% B 〃 21-40% C 〃 41-60% D 〃 61-80% E 〃 81% or more As is clear from Table 1, the sample of the present invention has good slip properties as compared with the comparative sample, and also has surface properties that are excellent in adhesion resistance to the back surface of the film base under high temperature and high humidity. In particular, there was almost no area of the adhesion part using the fluorine-modified organopolysiloxane of Samples A to E, and the adhesion resistance was particularly excellent. Further, the samples using vinyl-modified organopolysiloxanes of Samples F to L were particularly excellent in slipperiness.

Example 2 A silver halide emulsion layer containing high-sensitivity silver halide grains consisting of 98.5 mol% silver bromide and 1.5 mol% silver iodide and having an average grain size of 1.2 μ, was formed on both sides of a polyethylene terephthalate support having an undercoat. And a protective layer were coated to obtain a silver halide photographic light-sensitive material for X-ray.

The following additives were added to the silver halide emulsion per mol of silver halide.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.2g Diethylene glycol 11.0g Glyoxal 1.2g Diethylhexyl succinate sodium sulfonate 1.5g Paranitrophenyl triphenyl phosphide chloride 0.2g Prepared coating liquid 4g / m ² silver, 1.7g gelatin
It was applied so as to be / m ² .

The protective layer was coated with a coating solution having the following composition so that the amount of gelatin was 1.2 g / m ² .

[Protective layer composition] Gelatin 80 g Diethylhexyl succinate potassium sulfonate 1 g Mucochloric acid Polymethylmethacrylate having an average particle size of 3 to 4 µg 2 Paranonylphenyloxyethylene eral / formaldehyde polycondensate 4 g Polyethylene-di-nonylphenol ether sulfate sodium 2 g Organopolysiloxane (S-1) dispersion liquid 120 m prepared by the method of Example 1 The sample thus obtained is designated as sample O. Further, instead of SF-2, the compounds shown in Table 2 were used to prepare samples P to S.
It was created.

For comparison, the comparative compounds I and II shown in Example 1 were used.
Samples C and D were prepared using.

For these samples, 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 in the same manner as in Example 1. The results are shown in Table-2.

As is clear from Table-2, the black and white photosensitive materials also
Samples O to S of the present invention have good slipperiness and surface physical properties with excellent adhesion resistance between emulsion surfaces under high temperature and high humidity.

Further, the samples O and P had almost no area of the bonded portion, and were particularly excellent in adhesion resistance. The samples of samples Q and R are
The sliding property was particularly excellent.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one of the photographic constituent layers constituting the silver halide photographic light-sensitive material provided on the support has a structural unit represented by the following general formula [I] and / or the following general formula [III], A silver halide photographic light-sensitive material having improved adhesion resistance and sliding property, which contains an organopolysiloxane having groups represented by the general formula [II] at both ends. General formula [I] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group,
Or R ₂ represents a divalent linking group, and A represents a fluorine-substituted alkyl group, a vinyl group or a cyano group. n represents 0 or 1. However, when A is a vinyl group, n represents 0. ] General formula [II] [Wherein R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group, an aryl group or Represents R ₂ , A and n have the same meaning as in formula [I]. ] General formula [III] [In the formula, R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₆ and R ₇ may be the same or different. ] 2. The improved adhesion resistance and sliding property according to claim 1, characterized in that the organopolysiloxane is contained in at least one of the outermost layers of the photographic constituent layers. Silver halide photographic light-sensitive material.