JP2649968B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic material having a surface layer with improved physical properties. More specifically, the present invention relates to a silver halide photographic material (hereinafter simply referred to as a photographic material or a photographic material) having a surface layer provided with excellent slipperiness and scratch resistance.

[Prior Art] Photosensitive materials are generally cellulose triacetate,
Polyethylene terephthalate, silver halide photographic emulsion layer and optionally an intermediate layer on one or both sides of a support such as paper or paper coated on both sides with polyethylene terephthalate, or on both sides directly or through an undercoat layer, Various layers such as a protective layer, a filter layer, an antistatic layer and an antihalation layer are applied in various combinations. These layers generally contain a hydrophilic binder such as gelatin as a constituent. As a photographic material having a photographic emulsion layer on both sides of the support, for example, there is a direct x-ray film, but most photographic materials have a photographic emulsion layer on only one side of the support. . Therefore, in the latter case, the surface on which the photographic emulsion layer is not coated,
That is, there is a support surface, which is generally referred to in the art as the "back surface" of a photographic light-sensitive material. Usually, depending on the type of photosensitive material, an antihalation layer, an antistatic layer, an anti-adhesion layer, an anti-curl layer, an overcoat layer, etc. are provided on the back surface of the photographic material in order to enhance the photographic or physical quality of the photographic material. An auxiliary layer is provided.

By the way, since the photographic material has the above-described configuration, it can be used for handling such as winding, rewinding, or transporting in the manufacturing process such as coating, drying, and processing, as well as photographing, developing, printing, and projecting. Various equipment, machinery,
Between the adhesive parts of photosensitive materials such as cameras, or dust,
Adhesion friction between deposits such as fiber waste is often severely adversely affected. For example, generation of scratches or scratches on the surface or the back surface of the photographic emulsion layer side, deterioration of drivability of the photosensitive material in a camera or other machine, generation of a film layer, and the like. Of these, the back surface is likely to be particularly scratched because many machines directly contact various equipment. The occurrence of these abrasions is superimposed on the image surface at the time of printing or at the time of video, and is therefore a serious defect in practical use. In recent years, photosensitive materials have been used in the past due to expansion of use and processing methods for photosensitive materials such as high-speed coating, rapid photographing, and rapid processing, and diversification of use environments such as in a high-temperature and high-humidity atmosphere. As described above, the device is subjected to severe handling, and it is easy for scratches to occur and driveability to deteriorate. Therefore, a photosensitive material having a surface quality that can sufficiently withstand such severe conditions is desired.

Hitherto, as a means for improving the slipperiness and scratch resistance of the surface of a photographic light-sensitive material, a method of adding a slip agent to a surface layer has been used. For example, polyorganosiloxanes disclosed in JP-B-53-292, U.S. Pat.
Higher fatty acid amides disclosed in Japanese Patent Publication No. 58-33541, British Patent Nos. 1,320,564, and
Fatty acid esters as disclosed in U.S. Pat.Nos. 1,320,565 and 1,466,304; and U.S. Pat.
Higher fatty acid metal salts and the like as disclosed in the specification of 3,516 are known.

[Problems to be Solved by the Invention] However, although the slipperiness and scratch resistance of photographic light-sensitive materials can be certainly improved by using these known methods, severe conditions such as recent high-speed conveyance processes can be attained. Below, it is not satisfactory, and often involves the following obstacles. For example, when silicone is used as a slipping agent for a back layer (a layer formed on the back surface), the added silicone migrates to the support surface on the side where the photographic emulsion is coated, causing a bad condition when the photographic emulsion is coated. It exerts an effect and may significantly impair coating properties such as repelling and wetting. In addition, silicones, higher fatty acids, polyhydric alcohol esters of higher fatty acids, higher fatty acid amides, higher alcohol esters of higher fatty acids, higher fatty acid amides,
When used as a slipping agent for the back layer such as esters of higher alcohols, it shows considerable slipperiness and scratch resistance at the beginning of production, but it deteriorates with time (diffusion into the slipperiness), The bleeding has disadvantages such as the formation of white powder on the surface of the back layer, the elution or diffusion of the slipping agent during the development process, losing its effect, and the generation of contamination of the processing solution.

Further, in order to provide a back layer using a slipping agent, usually, a method of dissolving or dispersing it in an appropriate solvent alone or together with a binder to prepare a coating solution, and coating this on a support However, in this case, when the solvent swells the support, there is a problem that the slip agent diffuses inside and is hardly retained on the surface, so that good slip properties cannot be obtained. For this reason, the solid content of the slip agent is increased. However, the concentration of the slip agent in the coating solution is increased, so that the slip agent is likely to be precipitated, and the process is contaminated.

[Summary of the Invention] An object of the present invention is to provide a surface layer which retains sufficient lubricity and scratch resistance under high-speed transport conditions, does not have a flash over time, and retains sufficient lubricity and scratch resistance even after development processing. A photographic light-sensitive material having:

Another object of the present invention is to provide a photographic light-sensitive material having improved slipperiness and scratch resistance without impairing the coating properties during the production of the photographic light-sensitive material.

The present invention provides a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on one side of a support, wherein the support has a surface back layer opposite to the silver halide emulsion layer, The following general formula [I]: (In the above formula, R ¹¹ and R ¹² are each independently, one of them is composed of a branched aliphatic hydrocarbon group having 12 or more carbon atoms, and the total carbon number of R ¹¹ and R ¹² is 32-140. X represents an aliphatic hydrocarbon group having 12 to 70 carbon atoms;
Represents a divalent linking group. A) a silver halide photographic material comprising an aliphatic group-containing diester compound represented by the formula:

The photographic light-sensitive material of the present invention preferably has the following aspects.

(1) In the general formula [I], the total carbon number of R ¹¹ and R ¹² is 40
To 140.

(2) In the general formula [I], one of R ¹¹ and R ¹² is a branched aliphatic hydrocarbon group having 23 or more carbon atoms.

(3) All aliphatic groups contained in the aliphatic group-containing ester compound are branched aliphatic hydrocarbon groups having 12 or more carbon atoms.

(4) The aliphatic group-containing ester compound represented by the general formula [I] is added to the surface layer in an amount of from 0.02 to 0.05 to the solid weight of the layer.
300% by weight (more preferably 0.1 to 150% by weight.

[Effects of the present invention] The photographic light-sensitive material of the present invention containing a branched aliphatic hydrocarbon group-containing ester compound represented by the general formula [I] is compared with a conventionally known photographic light-sensitive material containing an ester compound. Has excellent slip and scratch resistance. Even after a lapse of time or after photographic processing, the deterioration of the slipperiness and scratch resistance hardly occurs.

This means that it can be used for various photographic materials for rapid processing that does not damage the photographic emulsion layer surface even under severe processing by automatic photographic processors under conditions of high pH, high temperature and high speed, or for repeated projection. This is particularly advantageous in the production of a photographic positive photosensitive material having a large mechanical strength on the film surface that can withstand.

In general, when the linear aliphatic hydrocarbon group has 20 or more carbon atoms, the total carbon number of the ester form is also
If it exceeds 40, the solubility will be extremely deteriorated, and it will be extremely difficult to adjust the coating solution. Further, such an ester compound has a high melting point and easily bleeds on the coated surface, which causes a white powder failure.

However, the branched aliphatic hydrocarbon group-containing ester compound represented by the general formula [I] used in the present invention has extremely excellent solubility in an organic solvent despite the fact that the aliphatic hydrocarbon group has a large carbon number. ing. Therefore, the coating solution containing the ester compound at the time of manufacturing the photographic light-sensitive material does not cause coating trouble due to cloudiness or the like, and can be coated in a good state. Further, the photographic light-sensitive material manufactured in this manner does not cause white powder failure due to bleeding as described above.
In particular, it is effective in forming the back layer. The reason for this is that the compound used in the present invention has a higher molecular weight than the conventional compounds described in each of the above publications, and the surface activity behavior and the dissolution behavior due to the branched aliphatic hydrocarbon group. It is presumed to be caused by this.

Further, when the ester compound used in the present invention is introduced into the back layer, it does not affect the coating characteristics of the emulsion layer, and has a photographically unfavorable effect on the photographic material (fog generation, sensitization, etc.) I do not give.

[Detailed description of initial extinction] The aliphatic group-containing ester compound used in the silver halide photographic light-sensitive material of the present invention will be described.

General formula [I]: In the above formula [I], R ¹¹ and R ¹² are each independent, one of them is a branched aliphatic hydrocarbon group having 12 or more (more preferably 24 or more) carbon atoms, and R ¹¹ and R 12 ^{12 having} a total carbon number of 32 to 140 (more preferably 40 to 40)
~ 140) which represents an aliphatic hydrocarbon group having 12 to 70 carbon atoms. X represents a bivalent coupling machine. This X may be a branched aliphatic hydrocarbon machine. R ¹¹ and R above
^It is preferable that any of ¹² is a branched aliphatic hydrocarbon group having 12 or more (more preferably 24 or more) carbon atoms.

Next, specific examples of alcohols and carboxylic acids which are the raw materials of the branched aliphatic hydrocarbon group contained in the branched aliphatic group-containing ester compound will be shown.

Branched aliphatic alcohol Next, specific examples of the divalent linking group represented by X are shown below.

CH _{2 j} (j = 2 to 20), (R ¹ = H or an alkyl group of C _{1 to} C ₆ , k = 1 to 20), —CH ₂ CH ₂ SCH ₂ CH ₂ —, Hereinafter, specific examples of the branched aliphatic hydrocarbon-containing ester compound used in the photographic light-sensitive material of the present invention will be described.

Specific examples of the compound of [I] (I-1) (iso) C 17 H 35 COO (CH 2) 14 OOCC 17 H 35 (iso) (I-2) (iso) C 17 H 35 COO (CH 2) ₂₀ OOCC ₁₇ H ₃₅ (iso) (I-6) (iso) C 17 H 35 COOCH 2 CH 2 SCH 2 CH 2 OOCC 27 H 53 (n) (I-9) (iso) C 23 H 47 COO (CH 2) 2 OOCC 23 H 47 (iso) (I-10) (iso) C 15 H 31 COO (CH 2) 6 OOCC 21 H 43 (n) (I-11) (iso) C ₃₁ H _{63 to} C ₃₅ H ₇₁ COO (CH ₂ ) ₄ OOCC ₃₁ H _{63 to} C ₃₅ H ₇₁
(Iso) The branched aliphatic hydrocarbon group-containing ester compound represented by the general formula [I] used in the present invention as described above can be easily synthesized by an ordinary method. That is, a dehydration reaction using an acid and an alcohol, or a dehydrochlorination reaction using an acid chloride and an alcohol. As the raw materials of the branched fatty acid and the branched aliphatic alcohol, synthetic products can be used.

The photographic light-sensitive material of the present invention contains the above branched aliphatic hydrocarbon group-containing ester compound in its surface layer. In the present invention, the surface layer means a layer formed on the outermost layer of the photosensitive material. For example, in a photographic material having a silver halide emulsion layer on only one of the supports,
It means a layer provided on the silver halide emulsion layer or on the surface opposite to the side on which the silver halide emulsion layer is provided (back surface). When a protective layer is provided on the silver halide emulsion layer and / or a back layer (including various functions) is provided on the back surface, the compound according to the present invention may be contained in the layer. Means that it is included.

The introduction of the ester compound according to the present invention into the above-mentioned surface layer is performed in order to form a hydrophilic colloid solution for forming a surface layer on the photosensitive photographic emulsion side and / or a back layer (a layer formed on the back surface). In various coating liquids, the ester compound used in the present invention was previously dissolved in water, an organic solvent or a mixed solvent thereof, and then added or prepared in advance in the presence of a suitable dispersant such as a surfactant. A method of adding an aqueous dispersion and coating it on a photographic emulsion layer or a support is used. Alternatively, a method of overcoating or penetrating after each photographic constituent layer is coated on a support is used. The hydrophilic colloid represented by gelatin will be described later.

In the present invention, a method in which the ester compound is contained in the back layer of the photographic light-sensitive material has a remarkable effect, and is more preferable.

As a method of applying or penetrating the layer containing the ester compound used in the present invention, for example, a dip method as described in U.S. Pat.No. 3,350,026, for example, as described in U.S. Pat. A method of applying or penetrating from the outside by an extrusion method, for example, a spray method as described in US Pat. No. 2,674,167 can be used.

The amount of the ester compound used in the present invention is not particularly limited. However, when used as a photographic constituent layer by adding to a coating solution before being coated on a support, 0.02 to 300% by weight, particularly preferably 0.1 to 150% by weight, based on the weight of solids in the coating composition. % By weight is used. 0.02% by weight
If the amount is less, it is difficult to obtain a desired effect.

In introducing the ester compound used in the present invention into the back layer, the ester compound is used together with a binder having a film-forming ability. Such polymers include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyalkylalkyl cellulose phthalate and cellulose long chain alkyl esters; formaldehyde and cresol;
Polycondensation polymers such as polycondensates with salicylic acid or oxyphenylacetic acid, or polycondensates with terephthalic acid or isophthalic acid and polyalkylene glycol; single polymers such as acrylic acid, methacrylic acid, styrene carboxylic acid or styrene sulfonic acid Copolymers or copolymers of these monomers or maleic anhydride with styrene derivatives, alkyl acrylates, alkyl methacrylates, vinyl chloride, vinyl acetate, alkyl vinyl ethers or acrylonitrile, or ring-opening half-esters or half-amides thereof, There are synthetic polymers such as hydrolyzed polyvinyl acetate; homopolymers and copolymers obtained from monomers having a polymerizable unsaturated bond such as polyvinyl alcohols.

Even when a binder is used, water, an organic solvent or a mixture thereof can be used as a solvent. Examples of the above-mentioned organic solvents and the organic solvents described herein include alcohols such as methanol, ethanol and butanol; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride and chloroform; Examples thereof include ethers such as diethyl ether, dioxane, and tetrahydrofuran, and aromatic hydrocarbons such as benzene, toluene, and xylene.

When the ester compound used in the present invention is mixed with the binder and applied to the back surface, about 1 to 300% by weight, more preferably 2 to 150% by weight, based on the binder constituting the back layer is used. Add a range of amounts.

In forming the surface layer according to the present invention, it is preferable to use a matting agent together with the above ester compound. As a matting agent, silica, inorganic compounds such as strontium barium sulfate, polymethyl methacrylate, organic polymers such as polystyrene and the like, the average particle size 0.01 to 10μ
m are preferred.

Next, the silver halide photographic environment material of the present invention having a surface layer containing the above-mentioned ester compound containing a branched aliphatic hydrocarbon group will be described.

The silver halide photographic material of the present invention has a silver halide emulsion layer on a support as a basic constitution. As described above, the silver halide photographic light-sensitive material of the present invention includes an embodiment in which auxiliary layers having various functions are further provided in the above-described basic structure.

 The main components will be described below in order.

The silver halide emulsion layer is a layer comprising silver halide and a binder or protective colloid.

Silver halides that can be used in photographic materials include silver bromide,
Silver iodobromide, silver iodochlorobromide, silver chloroiodide and silver chloride are preferred.

The silver halide grains used in the present invention have a regular crystal form such as cubic or octahedral, or irregular such as spherical or plate-like.
Or a complex form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may have a uniform phase. Grains in which a latent image is mainly formed on the surface (for example, a negative emulsion) may be formed, and grains in which a latent image is mainly formed inside the grains (for example, an internal latent image type emulsion, a directly overlaid emulsion which has been previously covered). It may be. Preferably, the particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
An average grain emulsion having a particle size of not more than 0.3 μm, preferably not more than 0.3 μm, preferably not less than 0.6 μm, and having an average aspect ratio of not less than 5 occupies 50% or more of the total photographed area, Monodisperse emulsions having a coefficient of variation (a value S / d obtained by dividing a standard deviation S by a diameter d in a distribution represented by a diameter when the projected area is approximated by a circle) of 20% or less are preferable. The average grain emulsion and monodispersed emulsion were
Species or more may be mixed.

The photographic emulsion used in the present invention is Chemie Physique Photographeque by P. Glafkides.
(Paul Montell, 1967), GFDuffuin, Photographic Emulsion, Chemistry (Photographic Emulsion Chemistr)
y) (Focal Press, 1966), VLZelikman et al., Making and
Coating Photographic Emulsion (Ma
king and Coating Photographic Emulsion) (Focal Press, 1964) and the like.

In forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
No. 374) and thione compounds (for example, JP-A-53-144319).
Nos. 53-82408 and 55-77737) and amine compounds (for example, JP-A-54-100717).

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyan dyes as basic heterocyclic nuclei 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 the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which a hydrocarbon ring is fused, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus Etc. can be applied. These nuclei may have a substituent on a carbon atom.

Merocyanine dyes or complex merocyanine dyes include:
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiozolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound which is a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721);
It may contain an aromatic organic acid formaldehyde condensate (eg as described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. U.S. Patent 3,615,61
The combinations described in Nos. 3, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

Various compounds can be contained in the silver halide photographic emulsion for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles , Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1 , 3,3a, 7) Tetraazaindenes, pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonamide Can be added.

Gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer (or the auxiliary layer, or sometimes a hydrophilic colloid layer) of the photographic light-sensitive material of the present invention. Other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate;
Various sugar derivatives such as starch derivatives; mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

In addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Phot. Ja
pan) No. 16, page 30 (1966), oxygen-treated gelatin may be used, or a hydrolyzate of gelatin may be used.

The layer containing the hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.) are specific examples. Active halogen compounds (2,4-dichloro-6-hydroxy-1,
3,5-triazine and its sodium salt, etc. and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfonyl Vinyl-based polymers having a group in the side chain) are preferred because they have a fast curing speed and provide stable photographic properties. N-carbamoyl ridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have fast and excellent curing rates.

Emulsion layers, hydrophilic colloid layers, etc. of light-sensitive materials are used for various purposes such as coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, acceleration of development, high contrast, sensitization). The above surfactant may be contained.

The light-sensitive material may contain an aqueous dye in a hydrophilic colloid layer as a filter dye or for prevention of irradiation or halation or other various purposes. Such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes,
Anthraquinone dyes and azo dyes are preferably used. In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The light-sensitive material of the present invention can be used as a multilayer multicolor photographic material having at least two different spectral sensitivities on a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. In addition, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity.
The three-layer structure may further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. The sensitivity can be improved by providing a reflective layer of fine silver halide or the like under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer.

It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations may be used depending on the case. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

There is no particular limitation on the support on which the silver halide photographic emulsion layer is provided. A flexible support such as a plastic film, paper, cloth or the like or a rigid support such as glass, pottery or metal which is generally known as a support for photographic light-sensitive materials can be used. Useful as flexible supports are
Films composed of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layers or α-olefin polymers (eg, polyethylene, polypropylene, ethylene / butene) (A copolymer) or the like. The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

The silver halide photographic light-sensitive material of the present invention is prepared by preparing a coating solution (photosensitive solution) in which a silver halide emulsion and a binder or the like are dissolved or dispersed, coating the coating solution on the above support, and drying. Can be manufactured. Also,
An optional hydrophilic colloid layer can be provided in a similar manner to have a desired function.

For coating the photographic emulsion layer and other new aqueous colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. U.S. Pat.No. 2,681,294 as required
Nos. 2,761,791, 3,526,528 and 3,50
Multiple layers may be simultaneously coated by the coating method described in JP-A-8,947 or the like.

The photographic light-sensitive material of the present invention can be used as various color and black-and-white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. (Research Disclosure, No.17123
(July 1978), or by using a black color coupler described in US Pat. No. 4,126,461 and British Patent No. 2,102,136 for X-rays, etc. The light-sensitive material of the present invention can also be used as the black-and-white light-sensitive material. The present invention is also applied to plate making films such as squirrel films or scanner films, direct / indirect medical or industrial X-ray films, negative black-and-white films for photography, black-and-white photographic paper, COM or ordinary microfilms, and print-out type photosensitive materials. Of photosensitive materials can be used.

Next, a method for using the photographic light-sensitive material of the present invention will be described.

The photographic light-sensitive material of the present invention is used after being subjected to exposure, development and fixing. Hereinafter, description will be made in order.

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD), or a micro-shutter array using lanthanum-doped lead zirconate titanate (PLZT) is linear or surface-mounted. Exposure means combining a light source in the form of a circle can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The developing solution used for the black-and-white photographic processing may contain a developing agent. Developing agents include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), 1-phenyl-3-pyrazolin , Ascorbic acid, and 1,2,3,4 described in U.S. Pat.No. 4,067,872
-Heterocyclic compounds in which a tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. In particular, it is preferable to use pyrazolidones and / or aminophenols together with dihydroxybenzenes. In general, other known preservatives, alkali agents, pH buffers, antifoggants, and, if necessary, dissolution aids, color tones, development accelerators, surfactants, defoamers, and hardened water softeners are used in the developer. Agents, hardeners, viscosity-imparting agents, and the like. The processing temperature is usually set between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and as typical examples, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β
-Methoxyethylaniline and their sulfates, hydrochlorides or lead p-toluenesulfonate. These diamines are generally more stable in a salt than in a free state, and are preferably used.

A color developing solution is a pH buffer such as an alkali metal carbonate, boric acid or phosphate, a development inhibitor such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common to include If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity enhancers, aminopolycarboxylic acids,
Various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, and antioxidants described in West German Patent Application (OLS) No. 2,622,950 can be added to a color developer. Good.

In the development processing of the reversal color photosensitive material, color development is usually performed after black-and-white development. Known black-and-white developers such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. Examples of the bleaching agent include iron (III), cobalt (III), chromium (I
Compounds of polyvalent metals such as V) and copper (II), peracids, quinos, nitroso compounds and the like are used. Ferricyanides as representative bleaches; dichromates; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid Such as aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates;
Nitrosophenol or the like can be used. Of these, iron (III) ethylenediaminetetraacetate, iron (III) diethylenetriaminepentaacetate and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleaching accelerators are described in the following specification or publication.

U.S. Patent 3,893,858, West German Patent 1,290,812,
2,059,988, JP-A-53-32736, JP-A-53-57831, and JP-A-5-57831
No. 3-37418, No. 53-65732, No. 53-72623, No. 53-95
No. 630, No. 53-95631, No. 53-104232, No. 53-124424
Compounds having a mercapto group or a disulfide group described in JP-A Nos. 53-141623, 53-28426, and Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives as described in JP-B-45-8506, JP-A-52-20832, and 53-3
No. 2735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, and iodides described in JP-A-58-16235: polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-B-45-8836;
-59644, 53-94927, 54-35727, 55-265
The compounds described in Nos. 06 and 58-163940 and iodine and bromide ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,2
Compounds described in JP-A-90-812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compound thioureas, a large amount of iodide and the like, and thiosulfate sulfate is generally used.
As the bleach-fixing solution and the preservative, a sulfite, a bisulfite, or a carbon bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. Various known compounds may be added to the washing step and the stabilizing step for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid; Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardeners can be added as necessary. Or West, Photographic Science and Engineering magazine (LEWest, Poht.Sc
i.Eng.), Vol. 6, pp. 344-359 (1965). In particular, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are generally countercurrently washed to save water. Further, instead of washing with water, Japanese Patent Laid-Open No. 57-85
A multi-stage countercurrent stabilization process as described in JP-A-43-43 may be performed. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid and polycarboxylic acid) and formalin can be mentioned as typical examples. In addition, if necessary, a chelating agent (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), a disinfectant (penzoisothiazolinone,
Irithiazolone, 4-thiazoline benzimidazole,
Various additives such as halogenated phenols, sulfanilamides, benzotriazoles), surfactants, optical brighteners and hardeners may be used, and two or more of the same or different target compounds may be used in combination. Is also good.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In the color light-sensitive material for photographing, the step (washing-stabilization) after fixing, which is usually performed, can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). At this time, when the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The water washing and stabilization processing time of the present invention depends on the type of the photosensitive material,
Although it varies depending on the processing conditions, it is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, U.S. Pat. No. 3,342,599, Research Disclosure No. 14850 and No. 1
No. 5,159, Schiff's base type compound, No. 13924, aldol compound, U.S. Pat.No. 3,719,492, metal salt complex, and urethane compounds described in JP-A-53-135628. No. 56-6235, 56-1613
No. 3, No. 56-59232, No. 56-67842, No. 56-83734,
56-83735, 56-83736, 56-89735, 56
-81837, 56-54430, 56-106241, 54-10
The precursors of various salt types described in JP-A-7236, JP-A-57-97531 and JP-A-57-83565 can be mentioned.

Various 1-phenyl-3-pyrazolidones may be incorporated in the silver halide color light-sensitive material as needed for the purpose of accelerating color development. A typical compound is
JP-A-56-64339, JP-A-57-1444547, JP-A-57-111147
No. 58-50532, No. 58-50533, No. 58-50534,
Nos. 58-50535, 58-50536 and 58-115438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate processing and reduce processing time, or lower temperatures can improve image quality and stability of processing solutions. . In addition, the patent of West Germany is made to save silver in photosensitive materials.
The treatment using cobalt intensification or hydrogen peroxide intensification described in US Pat. No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the various treatment baths as needed.

In the case of continuous processing, a certain finish can be obtained by using a replenisher of each processing liquid to prevent fluctuation of the liquid structure. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like.

When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

 Hereinafter, Examples and Comparative Examples of the present invention will be described.

[Example 1] The following coating composition was applied on a cellulose acetate film (support) so as to be 50 ml / m ² , and dried at 80 ° C for 5 minutes to form a surface layer. did.

Coating composition The following compound (I-3) according to the present invention 0.3 g methylene chloride 30 ml acetone 270 ml diacetyl cellulose 1 g The branched aliphatic carboxylic acid residue represented by C ₁₈ H ₃₅ (iso) of the above compound contains, as a main component, the branched aliphatic carboxylic acid residue represented by (C-3) on page 20 of the present specification. It is a thing.

Example 2 A compound (I-9) according to the present invention described below was used instead of the compound (I-3) according to the present invention used in preparing the coating composition of Example 1. A sample (B) was prepared in the same manner as in Example 1.

The branched aliphatic carboxylic acid residue represented by C ₂₄ H ₄₇ (iso) in the above compound contains a branched aliphatic carboxylic acid residue represented by (C-6) on page 21 of the present specification as a main component. It is a thing.

Comparative Example 1 A comparison was made in the same manner as in Example 1 except that the following butanediol behenate diester was used instead of the compound (I-3) used in preparing the coating composition of Example 1. A sample (X) was prepared. (Butanediol behenic acid diester) Comparative Example 2 Comparative Example 1 was repeated except that the butanediol behenate diester was not used when preparing the coating composition of Comparative Example 1.
A sample for comparison (Y) was prepared in the same manner as described above.

[Evaluation as Surface Layer of Photosensitive Material] Samples (A) and (B), (X) and (Y) obtained in Examples 1 and 2 and Comparative Examples 1 and 2 described above.
The surface layer was evaluated for dynamic friction coefficient and scratch resistance by the following methods.

Measurement of Dynamic Friction Coefficient The dynamic friction coefficient was measured and evaluated under the conditions of a load of 10 g and a speed of 20 cm / min using a steel ball having a diameter of 5 mm manufactured by Toyo Baldwin.

Measurement of scratch resistance The scratch resistance was measured using a Heide-18 type measuring device (manufactured by Shinto Kagaku Co., Ltd.) with a diamond needle of 0.025 mmR with a continuous load of 0 to 100 g and visible light attached. The starting load (g) was measured and evaluated.

The above measurements were performed immediately after the formation of the surface layer and three months after the formation, and evaluated.

 Table 1 shows the above results.

As is clear from the results in Table 1, the samples (A) and (B) having the surface layer containing the compound according to the present invention have a smaller and higher dynamic friction coefficient than the sample (Y) for comparison. It had scratch resistance. Further, the surface layers of Samples (A) and (B) did not show any change in appearance, and no change over time was observed. The coating composition of Comparative Example 1 had poor liquid stability, became cloudy, and could not be applied.

For each of the samples (A) and (B) obtained above, an indirect radiograph containing 9% by weight of gelatin and 9% by weight of silver halide was placed on the support opposite to the side on which the surface layer was provided. A photographic emulsion was applied and each sample (A) and (B)
Photosensitive materials (A) and (B) according to the present invention corresponding to
It was created. And for each photographic material,
The photosensitive surface and the back surface (surface layer) were overlapped so as to be in contact with each other, and stored at room temperature for 3 months. The sensitivity and fog of the photosensitive material were examined, but no change was found. Further, there was no stain on the back surface due to bleeding of the ester compound according to the present invention.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-90633 (JP, A) JP-A-1-304449 (JP, A) JP-A-51-141623 (JP, A) JP-A 64-64 61741 (JP, A) JP-A-53-1521 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support, wherein the support has a surface back layer opposite to the silver halide emulsion layer. And the following general formula [I]: [I] (In the above formula, R ¹¹ and R ¹² are each independently, one of them is a branched aliphatic hydrocarbon group having 12 or more carbon atoms, and the total carbon number of R ¹¹ and R ¹² is Represents an aliphatic hydrocarbon group having 12 to 70 carbon atoms having 32 to 140 carbon atoms;
Represents a divalent linking group. A silver halide photographic light-sensitive material comprising an aliphatic group-containing diester compound represented by the formula: