JPH032285B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic light-sensitive material with improved physical properties, and in particular, the presence of a liquid polyorganosiloxane and a polymer consisting of a siloxane unit having an active reactive group makes it possible to improve The present invention relates to a photographic material having improved sliding properties even after development without adversely affecting coating properties. (Prior Art) Photographic materials are generally made of a support such as glass, paper, plastic film, or paper coated with plastic, and a light-sensitive photographic emulsion layer and optionally an intermediate layer, a protective layer, a back layer, and an antihalation layer. , an antistatic layer and other constituent layers of photographic light-sensitive materials are coated in various combinations. Photographic materials are used in various equipment, machines, cameras, etc. during manufacturing processes such as coating, drying, and processing, as well as during handling such as winding, rewinding, and transportation during photographing, developing, printing, and projection. Undesirable effects may be caused by contact friction between photographic materials, such as contact parts with photosensitive materials, or contact friction between attached materials such as dust or fiber debris, or contact friction between photographic materials, such as between the surface of the photosensitive material and the back surface. For example, scratches or abrasions on the photosensitive surface or back surface, deterioration of the driveability of the photosensitive material in cameras and other devices, and film debris in cameras and other devices are common. By increasing the scratch resistance of the photographic constituent layers of photographic light-sensitive materials or by reducing the sliding friction of photographic light-sensitive materials, the photographic constituent layers can be protected from damage to camera gates and printing gates such as film magazines, camera gates, and projector gates. Various methods have been proposed so far for obtaining photographic materials with improved physical properties that allow them to move freely without being affected. For example, a method of imparting smoothness to a photographic film by simultaneously containing dimethyl silicone and a specific surfactant in a photographic emulsion layer or a protective layer as described in U.S. Pat. No. 3,042,522, and U.S. Pat. No. 3,080,317 A method of applying a mixture of dimethyl silicone and diphenyl silicone to the back surface of a photographic film base to impart slipperiness, as described in the above issue, and a method in which methyl phenyl silicone in the form of a triphenyl end block is added to the protective layer. The method described in U.S. Pat. No. 1,143,118, in which lower alkyl silicone and β-
U.S. Patent No. 1, which provides a photographic light-sensitive material having slipperiness and anti-adhesion properties by incorporating an alanine-based surfactant into a photographic emulsion or other hydrocolloid layer.
The method described in No. 3489567 is known as an example. However, when trying to improve the physical properties of photographic materials using these known methods,
Although it provides some improvement in slip properties and other properties, it does not completely remove the stickiness on the film surface, and the silicone used has a weak effect on imparting slip properties, so silicone is necessary to impart good slip properties to photographic film. A large amount of
In order to provide a photographic film with remarkable liquid repellency that interferes with the development process, or to obtain a photographic film with practically preferable physical properties using di-lower alkyl or diphenyl silicone, it is necessary to mix a surfactant with a certain limited structure. It had some drawbacks, such as being forced to use it. Moreover, in order to improve these drawbacks, a liquid organopolysiloxane having an alkyl group having 5 or more carbon atoms is used. There is a method described in Japanese Patent Publication No. 53-292 and US Pat. No. 4,047,958 which uses an alkylpolysiloxane having a polyoxyalkylene chain. However, although these methods can be seen to have a considerable improvement effect on certain drawbacks, the added silicone may have an adverse effect during the coating of the photographic emulsion and impair various coating properties, especially when applied to the back layer. be. (It is believed that the added silicone migrates to the surface of the support on the side where the photographic emulsion is coated). Furthermore, the running properties of the film after the development process on the conveying roller and within the camera were sometimes reduced. As a method to eliminate the drawback that the slipperiness effect is lost after development processing, a US patent has recently been proposed.
A method using crosslinkable silicone (silicone polycarbinol) as described in No. 4404276 is disclosed. However, when trying to improve the physical properties of photographic materials using this method, although it is true that the slipperiness after development is maintained, the improvement effect is not sufficient in terms of coating properties during the production of photographic materials. It wasn't. In other words, simultaneous multi-layer coating, high-speed coating,
The occurrence of so-called coating unevenness, in which a coating solution consisting of a hydrophilic colloid such as a photosensitive emulsion cannot be uniformly coated on a support, which occurs when coating a thin layer, has not been improved. (Object of the Invention) The first object of the present invention is to reduce the sliding friction of a photographic light-sensitive material and improve its physical properties so that it can smoothly move through camera gates such as film magazines, camera gates, and projector gates. Our objective is to provide photographic materials. The second object is to provide a photographic light-sensitive material with improved slip properties without impeding the coating properties during production of the photographic light-sensitive material. The third object is to provide a photographic material in which the dried film after development has good slip properties. (Structure of the Invention) These objects are to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer on at least one side of a support. This was achieved by the presence of a liquid organopolysiloxane consisting of siloxane units having active reactive groups represented by the general formula [] and a polymer. General formula [] A is a divalent group (e.g. alkylene having 2 to 10 carbon atoms, substituted alkylene (e.g. -
CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ O
(CH ₂ CH ₂ O−) _o CH ₂ CH ₂ −), etc.). B is -Y-CH=CH ₂ group (Y is -CO-, -
NHCO− or −SO ₂ −)

[Formula] group, -COCH ₂ G group, (G represents a halogen atom, preferably F or Cl), -
COOCH ₂ G group,

【formula】

【formula】

It represents an active vinyl group, an epoxy group, a group having an active halogen, an active ester group, and a maleimide group, as shown in the following formula. Among the organopolysiloxanes used in the present invention, organopolysiloxanes represented by the following general formula [] consisting of siloxane units represented by the above general formula [] and dimethylsiloxane units are particularly preferably used. General formula [] l: an integer of 5 to 400, preferably 10 to 100 m: an integer of 1 to 50, preferably 1 to 20 l+m=6 to 450 A, B are synonymous with general formula () Liquid organopolysiloxane used in the present invention There are, for example, the following two methods for manufacturing. One is a method of bonding a compound having an active reactive group to a silane or silicone base, and the other is a method of bonding a compound having an active reactive group to a silane or silicone base having a functional group such as a hydroxyl group, an amino group, or a carboxyl group. This is a method of introducing groups. Regarding the method of introducing reactive groups, see, for example, Japanese Patent Application Laid-open No. 48
−74832, No. 51-126124, Special Publication No. 51-41608
No., UK Patent No. 1071298, US Patent No. 2992109
No., etc., Yukagaku Vol. 67, No. 4, p. 592 (1964
Reactive groups were introduced with reference to Organic Syntheses Collective Volume, Vol. 5, p. 944 (1973), etc. In addition, methods for synthesizing compounds having effective substituents for introducing these reactive groups (for example, a method for substituting a hydroxyl group with a halogen group, a method for substituting a halogen group with an amino group) are described in, for example, the Journal of
the Chemical Society p. 684 (1942), p. 99 (1943), p. 3650 (1950), Journal of the Chemical Society
American Chemical Society Vol. 54, p. 1499, Vol. 54, p. 3441 (1932) Vol. 61, p. 3585,
There are many known synthesis methods, such as Organic Reactions, Vol. 8, p. 197 (1954) and Chemistry Letter, p. 577 (1975). Bonding of compounds having active reactive groups to silicone is described, for example, in Japanese Patent Publication No. 35-10771, Japanese Patent Publication No. 10771,
43-2869 and Japanese Patent Publication No. 45-14898, etc., the addition reaction of dimethylpolysiloxane containing ≡SiH groups to olefins (olefins having active reactive groups) using a metal catalyst, or ≡ It is easily synthesized by a condensation reaction of dimethylpolysiloxane containing SiOR (R is H or CH ₃ , C ₂ H ₅ ) group and alcohol (alcohol having an active reactive group) using picoline or the like as a catalyst. Ru. Examples of typical liquid organopolysiloxanes are listed below, but the present invention is not limited thereto. Synthesis Example 1 (Synthesis of Compound 5) Synthesis of allyl glycidyl ether 232 g (4 mol) of allyl alcohol was placed in a three-necked flask, and 0.01 mol of tin tetrachloride was added thereto. Next, 92.5 g (1 mol) of epichlorohydrin is added dropwise while stirring while maintaining the temperature at 30 to 35°C.
After the addition is complete, continue stirring at the same temperature for about 1 hour. The mixture was further heated and boiled and refluxed for about 2 hours to complete the reaction. α-allyl-α′-chlorohydrin ether (yield 85%) is obtained. 1 mol of α-allyl-α'-chlorohydrin ether was placed in a three-necked flask, heated to 85-95°C, and 1.2 mol of a 25% caustic soda aqueous solution was added dropwise over 30 minutes with strong stirring. Continue stirring vigorously at 100℃ for 1 hour. After the reaction, a small amount of water necessary to dissolve the precipitated inorganic salt is added, and when the mixture is left to cool, it separates into two layers. Remove the upper layer and dry with anhydrous potassium carbonate. Purify by vacuum fractional distillation. Allyl glycidyl ether, bp73-75℃/50
mmHg, 152-4°C/750mmHg yield of 80% is obtained. Synthesis of compound 5 233 g of the silicone having the ≡SiH group described above is placed in a reaction vessel, and 0.003 g of chloroplatinic acid catalyst is added thereto. Allyl glycidyl ether with stirring 8.4
g is added and the reaction mixture is heated to 55°C, an exothermic reaction begins. While maintaining the reaction temperature at about 80-90°C, 60 g of allyl glycidyl ether is gradually added dropwise. After the addition is complete, continue stirring at the same temperature for 2 hours. After the reaction, excess allyl glycidyl ether was distilled off under reduced pressure to obtain the desired product. In addition, alkali treatment was performed to destroy ≡SiH that may be contained in trace amounts. Synthesis Example 2 (Synthesis of Compound 2) Sodium bisulfite 65.5g (0.63mol) water
97.8 g (0.6 mol) of β-chloroethanesulfonyl chloride and 64.4 g of sodium hydroxide dissolved in 240 ml of water are simultaneously added dropwise to the 400 ml solution at about 5°C. After 30 minutes, 80 g of a 50% sulfuric acid aqueous solution was added dropwise, and the mixture was stirred for 1 hour and filtered. Add the following silicone to the liquid A solution prepared by dispersing 403.3 g in 1 part water was added dropwise at 10° C. or below, left to stand for 3 days under refrigeration, and then concentrated under reduced pressure to obtain the desired product. Synthesis Example 3 (Synthesis of Compound 1) 44.9 g (0.01 mol) of Compound 2 obtained in Synthesis Example 2 was dissolved in 200 ml of acetonitrile, and while stirring, 6.1 g (0.06 mol) of triethylamine dissolved in 50 ml of acetonitrile was heated at 0°C. After dropping, stir at room temperature for 5 hours. After removing the precipitated triethylamine hydrochloride by filtration, the mixture is concentrated under reduced pressure. After washing with a small amount of water, it was dried to obtain Compound-1. Synthesis Example 4 (Synthesis of Compound 3) The following silicone was dissolved in 300 ml of acetonitrile in a solution of 9.1 g (0.1 mol) of acrylic acid chloride in 200 ml of acetonitrile. Add 32 g (0.01 mol) dropwise at 0°C. After stirring for 1 hour, the solvent and by-produced hydrochloric acid were distilled off under reduced pressure to obtain the desired product. Synthesis example 6 (compound 8) Dissolve 99.2 g (0.01 mol) in 500 ml of acetonitrile and heat to 20°C with stirring to dissolve maleic anhydride.
Add 19.6 g (0.2 mol) in several portions. After stirring for 1 hour, add 70ml of acetic anhydride,
Add 6.6 g of anhydrous sodium acetate and heat on a steam bath for 30 minutes. After distilling off the solvent, it was dispersed in 1 ml of water and visualized with 500 ml of ether. After drying the organic layer over anhydrous sodium sulfate, the ether is distilled off to obtain the desired product. The refractive index of the organopolysiloxane used in the present invention is not particularly limited, but it is usually appropriate that the measured value at 25°C is about 1.405 to 1.650, and preferably the measured value at 25°C is in the range of 1.415 to 1.550. Something is valid. If a refractive index smaller than 1.405 or larger than 1.650 is used, it may affect the transparency of the applied photographic material, especially the dried photographic material after photoprocessing. There is. The viscosity of the organopolysiloxane used in the present invention is not particularly limited, and any of the above-mentioned liquid organopolysiloxanes that can be synthesized by a general method can provide the desired effect.
Suitably, those having a viscosity of about 20 to about 100,000 centistokes as measured at The polymer used in the present invention is not particularly limited, but one type is one that has a functional group that can bond with the reactive silicone of the present invention. For example, it is a polymer having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a phenol group. Next, specific examples will be given, but the present invention is not limited thereto. Poval, polyhydroxymethyl acrylate, polyhydroxyethyl acrylate, polyhydroxypropyl methacrylate, polyhydroxymethylstyrene, poly-N-methylolacrylamide and copolymers thereof. Cellulose derivatives such as cellulose acetate and cellulose nitrate. Gelatin, starch, dextran.
Polyaminoethyl acrylamide, polyvinylamine aminomethylstyrene and their copolymers. Polyacrylic acid, polymethacrylic acid and copolymers thereof. The above comonomers include all vinyl monomers having α,β-unsaturated bonds. Examples of copolymers include poly-(hydroxyethyl methacrylate-acrylic acid methyl ester), poly-(aminoethyl acrylamide-co-acrylic acid methyl ester), poly-(acrylic acid-co-acrylic acid methyl ester), and the like. Other types of polymers used in the present invention may be bonded not directly to the reactive silicones of the present invention, but also via crosslinking groups. Examples include the following reactive polymers. Examples include methyl vinyl ether/maleic anhydride copolymer and glycidyl acrylate. Examples of crosslinking agents include all those having two or more functional groups, such as those listed below. ethylene glycol, pentaerythritol,
Hexamethylene diol, resorcinol, glycerol, aminoethyl alcohol, ethylenediamine, diethylenetriamine, triethylenetetramine, succinic acid, glutaric acid, adipic acid,
These include suberic acid, sebacic acid, and 1,10-decamethylene dicarboxylic acid. In addition, when the above-mentioned crosslinking agent is present, the polymer used in the present invention does not necessarily need to be bonded to the silicone of the present invention, and the polymer used in the present invention does not necessarily have a functional group, such as polymethyl acrylate or triacetylcellose. It is also effective for polymers such as However, when the present invention is applied to the back layer, a hydrophobic polymer is preferable, but for example, a method of blending a small amount of the above-mentioned hydrophilic polymer with a hydrophobic polymer or a copolymer of a hydrophilic polymer/hydrophobic polymer can be used. A method using a copolymer with a small proportion of hydrophilic polymer is also useful. In carrying out the present invention, the organopolysiloxane used in the present invention, the general formula: After [] is dissolved in water, an organic solvent, or a mixed solvent thereof, it is added, or it is added as an aqueous dispersion prepared in advance in the presence of a suitable dispersant such as a surfactant, and this is applied to the photographic emulsion layer. Alternatively, it can be coated on the support, or overcoated or impregnated after each photographic constituent layer is coated on the support. Further, when a crosslinking agent is used in carrying out the present invention, it is added and used together with the organopolysiloxane in the same manner as described above. In application of the present invention, a method of incorporating it into the back layer of a photosensitive material is more preferable since it is more effective. There is no particular restriction on the amount of organopolysiloxane used in the present invention. However, when used as a photographic constituent layer by adding it to a coating solution before being coated on a support, it is preferably 0.02 to 300% (by weight), particularly preferably 0.1%, based on the solid weight in the coating composition. ~150 (by weight) percent is used. If it is less than 0.02%, it is difficult to obtain the desired effect, and if it is more than 300%, it is economically disadvantageous. Application or infiltration methods include dip methods such as those described in US Pat. No. 3,335,026, extrusion methods such as those described in US Pat. No. 2,761,791, and extrusion methods such as those described in US Pat. It can be applied from the outside or penetrated by a method such as a spray method such as that described above. The compound of general formula () is preferably present in an amount of about 0.001 to 0.5 g, particularly preferably 0.005 to 0.1 g, per square meter of the photographic light-sensitive material. However, it goes without saying that the above range varies depending on the type, form, or coating method of the photosensitive material used. When applying the compound of general formula () to the back surface,
Examples of the binder having film-forming ability that can be used include the following, including the above-mentioned polymers. Cellulose triacetate, cellulose diacetate, cellulose acetate malate,
Cellulose esters such as cellulose acetate phthalate, hydroxyalkyl alkyl cellulose phthalate, etc. Polycondensates of formaldehyde and cresol, salicylic acid or oxyphenylacetic acid, or polycondensates of terephthalic acid or isophthalic acid and polyalkylene glycol. Polymers: homopolymers of acrylic acid, methacrylic acid, styrene carboxylic acid or styrene sulfonic acid, or monomers thereof or maleic anhydride and styrene derivatives,
Copolymers with alkyl acrylates, alkyl methacrylates, vinyl chloride, vinyl acetate, alkyl vinyl ethers or acrylonitrile,
Alternatively, there are synthetic polymers such as homopolymers or copolymers obtained from monomers having a polymerizable unsaturated bond such as ring-opened half-esters or half-amides thereof, partially hydrolyzed polyvinyl acetate: polyvinyl alcohol, and the like. Even when a binder is used, water, an organic solvent, or a mixture thereof can be used as the solvent. Both the aforementioned organic solvents and the organic solvents mentioned herein include the following solvents. This kind of solvent is
For example, 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 include ethers such as diethyl ether, dioxane, and tetrahydrofuran, and aromatic hydrocarbons such as benzene, toluene, and xylene. When the compound of the general formula () is mixed with the above-mentioned binder and applied to the back surface, about 1%
Amounts ranging from ~300 weight percent, more preferably 2 to 150 weight percent are added. The amount of the polymer used in the present invention is 0.01 to 1 g per square meter, preferably 0.05 to 0.5 g. When using a crosslinking agent in the present invention, the general formula ()
The amount is 0.2 to 20 times, preferably 1 to 10 times, the reactive group equivalent of the compound. The organopolysiloxane used in the present invention can improve physical properties such as slip properties and scratch resistance without imparting photographic effects (fogging, desensitization, etc.) to photographic materials. In particular, the great advantage of the present invention is that coating failures during the production of photographic light-sensitive materials often occur when organosilicones, known as known photographic slip agents, are applied to the back layer of the light-sensitive material. In comparison, when the organopolysiloxane of the present invention is applied, coating failures do not occur at all, and the film does not lose its slip properties after development. This means that the surface of the photographic emulsion layer will not be damaged even when subjected to severe processing using an automatic photoprocessing machine under conditions of high pH, high temperature, and high speed, or that can withstand repeated projection. This is a particularly important advantage in the production of positive light-sensitive materials for movies, etc., where the resulting film surface has high mechanical strength. The organopolysiloxane used in the present invention can impart appropriate slipperiness to the photographic material to which it is applied, and can particularly improve compatibility under the conditions of use in motion picture film cameras and projectors. . The motion picture film obtained by implementing the present invention has good slip properties and anti-adhesive properties in a camera, so it has the advantage of being extremely smoothly driven and significantly reducing the noise of the film during use. Also, depending on the type of camera, the stress at the part where the film comes into contact with the camera during operation may be too sharp or strong, causing the photographic emulsion layer to be partially destroyed and debris to be generated inside the camera. The motion picture negative film according to the present invention can eliminate such failures. It is believed that these advantages derive from the active reactive groups of the organopolysiloxanes of the present invention. That is, the number of active reactive group units can be freely increased or decreased depending on the properties of the polymer used. It is presumed that the organosiloxane of the present invention and the polymer form a more dense network structure. In the photographic light-sensitive material of the present invention, any support that is normally used as a support for photographic light-sensitive materials can be used. For example, cellulose acetate film, cererose acetate butyrate film,
Examples include polystyrene film, polyethylene terephthalate film, other laminates thereof, and paper. Baryta or α-olefin polymers, especially polyethylene, polypropylene, etc. with 2 or more carbon atoms
Examples include paper coated or laminated with a polymer of 100 α-olefin. Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention, and hydrophilic colloids used as binders for photographic emulsions and/or other photographic constituent layers include gelatin, colloidal albumin, casein, carboxymethyl Cellulose, cellulose derivatives such as hydroxyethylcellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, or derivatives thereof.・Partial hydrolysates, etc. Compatible mixtures of two or more of these colloids are used if desired. Among these, gelatin is the most commonly used. The photographic emulsion layer and other layers used in the present invention contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, in particular compounds that increase the dimensional stability of photographic materials, either singly or in combination. (of different types of polymers) or in combination with hydrophilic water-permeable colloids.
There are many types of polymers, such as U.S. Pat. No. 2,376,005, U.S. Pat.
No. 3062674, No. 3411911, No. 3488708, No. 3488708, No. 3411911, No. 3488708, No.
No. 3525620, No. 3635715, No. 3607290, No. 3607290, No. 3635715, No. 3607290, No.
3645740, British Patent No. 1186699, British Patent No. 1307373, etc. Among these, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl Copolymers and homopolymers selected from acrylates, alkoxymethacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride are commonly used. Hardening of the photographic emulsion and/or other photographic constituent layers can be carried out according to conventional methods. Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl urea), 2-hydroxy-4,
6-dichloro-1,3,5-triazine, other compounds having reactive halogens as shown in U.S. Patent No. 3288775, U.S. Patent No. 2732303, British Patent No. 974723, U.K. Patent No. 1167207, etc., divinyl sulfone , 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and other U.S. Patent Nos. 3635718, 3232763, and U.S. Pat.
Compounds with reactive olefins such as those shown in U.S. Pat. N-methylol compounds as shown in US Pat. No. 3,103,437, etc., aziridine compounds as shown in US Pat. Acid derivatives such as those shown in Patent Nos. 2725294 and 2725295, U.S. Patent No.
Carbodiimide compounds as shown in US Patent No. 3100704, epoxy compounds as shown in US Patent No. 3091537, US Patent No.
3321313 and 3543292; halogenocarboxaldehydes such as mucoacrylic acid; dioxane derivatives such as dihydroxydioxane and dichlorodioxane; Vanilla, zirconium sulfate, etc. Moreover, instead of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, etc. may be used. Silver halide photographic emulsions are usually prepared by mixing a water-soluble silver salt (eg, silver nitrate) solution and a water-soluble halide salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiobromide, etc. can be used. Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds are 4-hydroxy-6-methyl,
A large number of compounds such as 1,3,3a,7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, etc. It has been known since ancient times. Silver halide emulsions can also be chemically sensitized by conventional methods. Chemical sensitizers include, for example, gold compounds such as chlorauric acid salts and gold trichloride, platinum,
Examples include salts of noble metals such as palladium, iridium, rhodium, and ruthenium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, amines, and other reducing substances. The photographic emulsion can be spectral sensitized or superchromically sensitized, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like. The photographic light-sensitive material of the present invention contains brighteners such as stilbene, triazine, oxazole and coumarin compounds in the non-light-sensitive photographic constituent layer; ultraviolet absorbers such as benzotriazole,
Thiazolidine, cinnamic acid ester compounds: Various photographic filter dyes known as light absorbers: If necessary, as anti-adhesion agents, for example, British Patent No. 1320564, British Patent No. 1320565, U.S. Patent No.
Water-insoluble materials such as those described in US Pat. No. 3,121,060 and surface-active materials such as those described in US Pat. Further, as a matting agent, inorganic compounds such as silver halide, silica, barium strontium sulfate, etc., and polymer latexes such as polymethyl methacrylate, etc., having a suitable particle size can be included. The photographic light-sensitive material of the present invention is applied as an antistatic agent to the photographic constituent layers including the photographic emulsion layer, especially to the antistatic layer provided on the outermost side of the photographic material, for example, as disclosed in U.S. Pat. ,same
No. 2972536, No. 2972537, No. 2972538, No. 2972536, No. 2972537, No. 2972538, No.
No. 3033679, No. 3072484, No. 3262807, No. 3033679, No. 3072484, No. 3262807, No.
No. 3525621, No. 3615531, No. 3630743, No. 3630743, No. 3615531, No. 3630743, No.
Hydrophilic polymers such as those described in UK Patent Nos. 3653906, 3655384, 3655386 and UK Patent Nos.
Hydrophobic polymers such as those described in US Pat. No. 2,973,263 and US Pat.
No. 2,591,590, for example, US Pat. No. 2,639,234, US Pat.
Sulfonic acid type anion compounds as described in No. 2649372, No. 3201251, No. 3457076,
For example, phosphoric acid esters and quaternary ammonium salts as described in US Pat. No. 3,317,344 and US Pat. No. 3,514,291 are combined with
No. 2982651, No. 3399995, No. 3549369, No.
Cationic compounds such as those described in US Pat. No. 3,564,043; nonionic compounds such as those described in US Pat. No. 3,625,695; amphoteric compounds such as those described in US Pat. No. 3,736,268; Complex compounds such as those described in US Pat. No. 2,647,836 and the like can be included, as well as organic salts such as those described in US Pat. No. 2,717,834 and US Pat. No. 3,655,387. The compounds of the present invention can be applied to all kinds of photographic materials, regardless of whether they are black and white or color. Silver halide emulsions include ortho emulsions, panchromatic emulsions, infrared emulsions, emulsions for X-ray and other invisible light recording, color photographic emulsions, such as emulsions containing color-forming couplers, emulsions containing dye developers, and dyes that can be bleached. It includes various silver halide photographic emulsions such as emulsions that Color photographic emulsions may contain 2 or 4 equivalents of color-forming couplers. For example, open chain ketomethylene yellow forming couplers such as benzoylacetanilide or pivaloylacetanilide, magenta forming couplers such as pyrazolone or indazolone, and cyan forming couplers such as phenol or naphthol are preferably used. For example, the special public interest public in 1977-
A yellow coupler represented by the general formula [] described in No. 18256, a magenta coupler described in Japanese Patent Application No. 1973-56670, a cyan coupler described in Japanese Patent Application No. 46-76515,
U.S. Patent No. 2428054, U.S. Patent No. 2449966, U.S. Patent No. 2455170
Colored couplers described in US Pat. No. 2,600,788, US No. 2,983,608, US Pat.
The detachment suppressing coupler described in the above issue can be used. The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 A coating solution consisting of the following composition was coated and dried on a triacetyl cellulose photographic film support (90°C,
3 minutes) to form a back layer.

[Table] An undercoat layer is provided on the opposite side of the five types of base back layers, and on top of that is an antihalation layer, a red-sensitive emulsion layer, a gelatin intermediate layer, a green-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer, and a protective layer. Motion picture color negative film 1-1, 1 in which layers are applied in order and correspond to each other
-2, 1-3, 1-4, and 1-5 were obtained. Silver iodobromide emulsions each containing 6 mol % of iodine were used as the red and green emulsions. A silver iodobromide emulsion containing 8 mol % of iodine was used as a blue-sensitive emulsion. These films were aged for one week at 25° C. and 60% RH, and then cut to a width of 35 m/m to obtain a 400 foot film roll. We investigated the coating suitability of the photographic emulsion layer and the driving performance of the film in an atmosphere of 25°C and 60% RH when producing these films. The test items are (1) suitability for coating the coating liquid on the support, (2)
(3) Measuring the resistance force when pulling out the film from between the aperture plate and pressure plate of the camera (which corresponds well to the running performance of the camera during shooting). (1) Suitability for coating the coating solution onto the support On the support with the undercoat layer on the opposite side of the base back layer, the coating solution for the antihalation layer and the coating solution for the red-sensitive emulsion layer are added, as well as the gelatin intermediate layer. The coating liquid for the layer was applied at a conveying speed of 80 m/min, and the dry bulb temperature was
An intermediate product of color negative film for motion pictures was obtained by drying at 35°C and a wet bulb temperature of 18°C. The surface of the obtained intermediate product was observed with the naked eye using reflected light. Evaluation No coating unevenness: 〇 Very weak coating unevenness: △ Coating unevenness: × Frequent coating unevenness: ×× (2) Static friction coefficient measurement method T.Anvelt.JFCarroll.JR., and LJSugden J.
The maximum static friction coefficient of the film back surface was determined using the paper clip method described in SMPTE-80(9) 734-739 (1971). (3) Pull-out resistance measurement Place the camera aperture plate and pressure plate (ARNOLD & RICHTER) on the moving table.
(ARRIFLEX35A) is fixed. After sandwiching the sample between the aperture plate and the pressure plate and fixing one end of the sample to the load cell, move the moving table at 10 m/min, and calculate the maximum frictional resistance force of the film generated at that time. Ta. (4) Development processing Processing was performed according to the following development processing steps. Processing process temperature Time Color development 41℃ 3 minutes Stop 38℃ 30 seconds water wash 38℃ 30 seconds before bath 〃 30 seconds bleach 〃 3 minutes Water wash 〃 1 minute Fixing 〃 2 minutes Water wash 〃 2 minutes Stable Bath 〃 10 seconds The treatment solution used has the following composition. Color developer Sodium hydroxide 2g Sodium sulfite 2g Potassium bromide 1.4g Sodium chloride 1g Borax 1g Hydroxylamine sulfate 4g Ethylene diamine tetraacetate disodium 2g 4-Amino 3-methyl-N-ethyl-N-(β
-Hydroxyethyl)aniline monosulfate 4 g Add water, total amount 1 Stabilizing bath Formaldehyde (37%) 10 ml Add water, total amount 1 The results obtained are shown in Table 2.

[Table] As is clear from the results in Table 2, the samples to which the organopolysiloxane of the present invention was added had no coating failures at all, compared to the samples to which the comparative compound was added. Furthermore, it can be seen that the friction coefficient and pull-out resistance after development are equal to or better than those of the comparative sample.

Claims (1)

[Scope of Claims] 1. In a photographic light-sensitive material having at least one photographic emulsion layer on a support, at least one of the surface layers of the light-sensitive material has a liquid state having a siloxane unit represented by the following general formula []. A silver halide photographic material characterized by the presence of an organopolysiloxane and a polymer. General formula [] In the formula, A represents a divalent group. B represents an active vinyl group, epoxy group, active halogen group, active ester group, or maleimide group.