JPH0621923B2 - Photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material having improved physical properties, and more particularly to a photographic light-sensitive material having a graft copolymer containing a silicone unit in at least one of photographic constituent layers. The present invention relates to a photographic light-sensitive material which does not adversely affect the coating characteristics during the production of the material and has improved sliding characteristics even after development processing.

(Description of Prior Art) A photographic light-sensitive material is generally a photosensitive photographic emulsion layer and optionally an intermediate layer, a protective layer, a support such as glass, paper, plastic film or paper covered with plastic.
The photographic light-sensitive material constituting layers such as a back layer, an anti-halation layer and an antistatic layer are coated in various combinations. Photosensitive materials include coating, drying, processing, and other manufacturing processes, as well as handling during shooting, developing, printing, projection, and other winding, rewinding, or transporting.
Connection between various devices, machines, cameras and other photosensitive materials, or connection with deposits such as dust and fiber scraps or contact between photographic photosensitive materials such as between the photosensitive material surface and back surface Friction is often negatively affected. For example, scratches and abrasions on the surface of the photosensitive material or back surface, deterioration of drivability of the photosensitive material in the camera and other equipment, and generation of film scraps in the camera and other equipment.

To increase the scratch resistance of the photographic constituent layers of the photographic light-sensitive material,
By reducing the sliding friction of the photographic light-sensitive material, the physical properties of the film magazine, camera gates, camera gates such as projector gates and printing gates can be freely moved without damaging the photographic constituent layers. Various methods for obtaining a photographic light-sensitive material have been proposed so far. For example,
A method for imparting slipperiness 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, described in U.S. Pat. No. 3,080,317. As shown in the photo, a method of applying a mixture of dimethyl silicone and diphenyl silicone to the back surface of a film base to impart slipperiness, and a protective layer containing methylphenyl silicone with a triphenyl end block U.S. Pat. No. 11,431 for imparting a slip property to the film
No. 18 or a U.S. Patent for providing a photographic light-sensitive material having slip and tack resistance by incorporating a di-lower alkyl silicone and a .beta.-alanine surfactant in a photographic emulsion or other hydrophilic colloid layer. The method described in No. 3489567 is known as an example.

However, when it is attempted to improve the physical properties of a photographic light-sensitive material by using these known methods, it does not completely remove the tackiness of the film surface while giving a slight improvement in slipperiness and the like. Since the effect of silicone to impart slipperiness is weak, the amount of silicone required to give good slipperiness to the photographic film becomes large, which adversely affects the coating characteristics during the production of photographic light-sensitive materials and interferes with development processing. In order to provide a photographic film having remarkably liquid repellency and having a practically preferable physical property by using di-lower alkyl or diphenyl silicone, it is inevitable to mix and use a surfactant having a limited structure. There was one of the drawbacks.

In order to improve these drawbacks, a liquid organopolysiloxane having an alkyl group having 5 or more carbon atoms is used, and Japanese Patent Publication No. 53-292, and a U.S. patent using an alkylpolysiloxane having a polyoxyalkylene chain. There is a method described in No. 4047958. However, these methods also show a considerable improvement effect on certain drawbacks, but especially when applied to the backing layer, the added silicone has a bad effect during coating of the photographic emulsion and impairs various coating characteristics. There is. (It is considered that the added silicone migrates to the surface of the support on the side on which the photographic emulsion is coated.) Further, the running property of the film after development processing in the transport roller and the camera may be deteriorated.

As described above, when the conventionally known silicone is used for modifying the physical properties of the surface of the photographic film, various disadvantages due to the above-mentioned migration property are particularly problematic.

As a means for preventing migration of silicone and keeping slipperiness even after development processing, a method using a crosslinkable silicone (using silicone carbinol) as described in US Pat. No. 4,404,276 has recently been disclosed. .

However, in order to improve the slipperiness of the photographic film surface by using this method, it is a method of crosslinking by a reaction in the coating process, so the restriction of the coating solution (a solvent that does not react with silanol must be used. ), It is difficult to control the formation of a crosslinked product, and it is necessary to use a crosslinking agent (which may adversely affect photographic properties).

(Object of the Invention) A first object of the present invention is to reduce the sliding friction of a photographic light-sensitive material without adversely affecting the photographic characteristics (sensitivity, fog, etc.), and to make a camera such as a film magazine, a camera gate, or a projector gate. An object of the present invention is to provide a photographic light-sensitive material having improved physical properties so that the gate can move smoothly.

The second object is to provide a photographic light-sensitive material having improved slipperiness without impairing the coating characteristics during the production of the photographic light-sensitive material.

A third object is to provide a photographic light-sensitive material having a dried film having a good slip property after development.

A fourth object is to provide a photographic light-sensitive material which is free from the limitation of a coating solution containing a slip agent and has a controlled slip performance.

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one photographic emulsion layer on a support, and at least one surface layer of the light-sensitive material has at least an affinity for a photographic polymer. The following general formula [I], which has a vinyl polymer as a trunk polymer and has a low affinity with photographic polymers
A silver halide photographic light-sensitive material characterized by containing a graft copolymer containing a polysiloxane represented by

General formula [I] In the formula, R ₁ represents H or CH ₃ .

It represents an _{R 2, R 3, R 4} , R 5, R 6, R 7 is an alkyl group or an aryl group having 6 to 20 carbon atoms of the carbon atoms of the same or different 1 to 20.

m represents an integer of 0 to 400 and n represents an integer of 0 to 50.

A represents a divalent group.

B represents a substituted alkyl group having a reactive group.

That is, no application of the polysiloxane graft polymer to a photographic light-sensitive material is known at all, and for the first time, we have found that it is remarkably and characteristically effective as a slip agent for a photographic film. That is, the slipperiness can be effectively maintained by using a small amount without causing the above-mentioned problems in coating.

The method for improving the slipperiness of a photographic film by the polysiloxane graft polymer of the present invention is different from the method using an ordinary polysiloxane oligomer, and has a polysiloxane group effective for improving the slipperiness and scratch resistance of the photographic film surface. A component having affinity with the component and a polymer used as a binder of a photographic constituent layer (for example, a hydrophilic polymer such as gelatin, a hydrophobic polymer such as cellulose acetate, polymethylmethacrylate, etc. and hereinafter referred to as a photographic polymer). It is based on the fact that the graft copolymer having the structure consisting of is useful, and it goes without saying that its performance is changed depending on the structures of the polysiloxane and the affinity component.

In the present invention, a component having an affinity with a photographic polymer is used as a trunk polymer portion, and a small amount of a copolymer having a low affinity polysiloxane is present in the surface layer of a photographic light-sensitive material. The layer to be added may not necessarily be the surface layer, but it is necessary that at least the polysiloxane component is present in the surface layer. The photographic film surface coating film obtained by the present invention has excellent slipperiness and scratch resistance, and the presence of the affinity component with the photographic polymer allows the polysiloxane graft copolymer to form a coating film. It is a feature of the present invention that the problem of coating the photographic emulsion associated with the transfer of the polysiloxane can be solved and the slipperiness can be maintained because it does not easily desorb and migrate from the surface.

Next, preferred examples of the graft component polysiloxane of the polysiloxane graft copolymer used in the present invention (indicated by the following general formula [I]) will be given.

General formula [I] In the formula, R ₁ represents H, CH ₃ .

_{R 2, R 3, R 4} , R 5, R 6, the alkyl group of _{R 7} is the number of carbon atoms of the same or different 1 to 20, for example methyl, ethyl, propyl, dodecyl, substituted alkyl for example alkoxyalkyl, arylalkyl, C 6-20 aryl groups such as phenyl, substituted aryl groups such as tolyl,
It represents a cycloalkyl group such as cyclohexyl, but is preferably a methyl group. m represents an integer of 0 to 400, preferably 10 to 100 n represents an integer of 0 to 50, and preferably 1 to 20 m + n = 0 to 450.

When m and n are 0, R ₅ , R ₆ and R ₇ are And R ₈ , R ₉ and R ₁₀ are the above R ₂ , R ₃ and R
_4, the same meaning as _{R 5, R 6, R 7} .

A represents a divalent group.

B is alcohol, amine, carboxyl, mercapto,
It represents a substituted alkyl group having a reactive group such as a halogen or an epoxy group.

For example (R is H, alkyl), On the other hand, comonomers include all monomers derived from copolymerizable monomers containing ethylenically unsaturated groups.

The trunk polymer includes all polymers such as vinyl polymers and condensation polymers, but it is important that they have an affinity with the photographic polymer to be used.

Examples include acrylic acid, methacrylic acid, and alkyl esters thereof (methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate decyl acrylate, β-cyanoethyl acrylate, β-chloroethyl acrylate, 2
-Ethoxyethyl acrylate, sulfopropyl methacrylate, etc., vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl butyrate, etc.), vinyl ethers (for example, methyl vinyl ether, butyl vinyl ether, oleyl vinyl ether, etc.), vinyl ketones (for example, methyl vinyl ketone) , Ethyl vinyl ketone, etc.), styrenes (for example, styrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, methoxystyrene, cyanostyrene, chloromethylstyrene, vinylbenzoic acid). , Styrene sulfonic acid, α-
Methyl styrene, etc.), vinyl heterocyclic compounds (for example, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, ethylene, propylene, butadiene, diisobutylene, isoprene, chloroprene,
Examples thereof include tetrafluoroethylene. The present invention is not limited to the above-mentioned copolymerizable monomers, and may be any copolymer as long as it has the structural unit represented by the above general formula. These comonomers can be used alone or in combination of two or more kinds.

The type, molecular weight, and type and ratio of the graft component polysiloxane represented by the general formula [I] used in the present invention are the photographic constituent layers applied as a slip agent, which is the object of the present invention. A wide range can be selected according to the composition content of That is, the type and ratio of the polymerizable ethylenic monomer and comonomer derived from polysiloxane, or the ratio of the introduced polysiloxane when the reactive polysiloxane is bonded to the trunk polymer by the polymer reaction, the type of polymer, etc. It can be freely changed according to the purpose, and the graft polymer produced accordingly takes various forms such as oil, jelly and solid.

Next, specific examples of the graft polymer having a typical polysiloxane unit used in the present invention will be shown.

Compound example (1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) The method for producing the polysiloxane graft copolymer used in the present invention is known, and various methods such as a grafting method using radiation, light and plasma and a method for binding a reactive polysiloxane to a trunk polymer have been recently developed. The method of using a polysiloxane macromonomer is more preferable because a clear graft polymer can be obtained with less by-products such as homopolymers.

For example, see Polymer J. 14 (11) 913
(1982), Proceedings of the Oil Chemistry Debate, C10, 107.
(58 '), Macromolecules 3 , 458.
(1970), Makromal. Chem. 185
9-18 (1984) JP-A-58-167606 Yamashita et al., Oil Chemistry 29 (4) 219 (1980) JP-A-58-
152022 and the like, the method of copolymerizing the polysiloxane macromonomer and the comonomer can be performed in the same manner as the conventionally known method. For example, it can be easily polymerized by using a radical polymerization initiator. Examples of the method of grafting a reactive polysiloxane to a polymer include JP-B-46-9355 and JP-A-52-135391, which are synthesized with reference to these patents.

A synthesis example of the graft polymer of the present invention is shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 1) i) Synthesis of Macromonomer In a two-necked three-necked flask equipped with a stirrer and a reflux condenser,
200 ml of ethyl acetate and 200 ml of xylene were added and the mixture was heated to 80 ° C under a nitrogen stream. 500 g of methyl methacrylate,
Thioglycolic acid 20 ml, 2,2'-Asobis- (2,
4-Dimethylvaleronitrile) 6 g ethyl acetate 100
The solution dissolved in ml was added over 5 hours with stirring at the same dropping rate. After the completion of dropping, the temperature was raised and the mixture was heated under reflux with stirring for 4 hours. Ethyl acetate was distilled off under reduced pressure, and 4 ml of glycidyl methacrylate and 0.5 ml of dimethyllaurylamine were added to the cooled methyl methacrylate polymer solution.
Was added and the mixture was heated under reflux for 5 hours. The product was repeatedly reprecipitated with n-hexane and dried to obtain 260 g of polymethylmethacrylate macromer. The number average molecular weight measured by gel permeation chromatogram was 4,500.

ii) Synthesis of graft polymer 20 g of macromer synthesized in i) and 20 g of silicone monomer 50 ml of toluene 300 ml equipped with stirrer and reflux condenser
Put it in a 0 ml three-necked flask and add 2,2'-azobis-
0.13 g of (2,4-dimethylvaleronitrile) was added and the temperature was raised to 60 ° C. to carry out polymerization for 5 hours.

After cooling, reprecipitation was repeated and dried with n-hexane,
34 g of the graft polymer of Exemplified Compound 1 was obtained.

Synthesis Example 2 (Exemplified Compound (3)) Synthesis of 4-pentenyl methacrylate 86 g (1 mol) of 4-penten-1-ol and 103 g (1.3 mol) of pyridine were dissolved in 500 ml of chloroform and kept at 0 to 5 ° C. While stirring, 115 g (1.1 mol) of methacryloyl chloride was added dropwise, and the mixture was further stirred for 3 hours. The reaction solution was added to ice water 3 to separate the organic solvent layer for dehydration, and then the solvent was distilled off. The yellow oil was distilled under reduced pressure. b. 4-Pentenyl methacrylate was obtained with p53 ° C./4 mmHg and a yield of 63%.

Synthesis of lithium trimethylsilanolate 81 g (0.9 mol) of trimethylsilanol was reacted with 6.94 g (1 mol) of lithium in dry toluene under argon gas. After the solvent was distilled off under reduced pressure, it was stored under argon gas.

Synthesis of 5- (chlorodimethylsilyl) pentylmethacrylate 94.5 g (1 mol) of chlorodimethylsilane was dissolved in 500 ml of toluene, and 0.03 g of chloroplatinic acid catalyst was dissolved in this.
Add. While stirring, 154 g (1 mol) of 4-pentenyl methacrylate was added, and the mixture was stirred with heating at 60 ° C for 3 hours. After removing the catalyst by filtration, the product was distilled under reduced pressure to obtain the desired product. The yield was 60%.

Synthesis of polysiloxane macromer Lithium trimethylsilanolate under argon gas 2.
50g containing 6g (0.027mol) and 100ml THF
Place a 0 ml round bottom flask in an ice-cooled bath equipped with a magnetic stirrer and add hexamethylcyclotrisiloxane 10
4.3 g of THF solution was added. The mixture was stirred under ice cooling for 8 hours. After warming to room temperature, 12.4 g (0.05 mol) of 5- (chlorodimethylsilyl) pentylmethacrylate was added. The reaction mixture was further stirred at room temperature for 30 minutes. After reprecipitation with a toluene-methanol system, vacuum drying was performed.

Synthesis of Graft Polymer A weight ratio of polysiloxane macromer and methyl methacrylate was set to 1: 1 and AIBN (initiator) was added to monomer 1.
60% in toluene (monomer concentration 20%) with 0 mol% addition
Polymerization was carried out at ° C for 8 hours. Next, the polymer was extracted and washed with hexane, the solvent was distilled off, and the polymer was dried under vacuum.

Yield 60%, siloxane content (wt%) 45%, n4
It was 50,000 and w8,000.

Also, some of these polysiloxane graft copolymers have only recently become commercially available. (For example, Toagosei Kagaku Co., Ltd.) In carrying out the present invention, polysiloxanes used in the present invention in advance in various coating liquids (surface layer or layers below) for forming a surface layer on the side of a photosensitive photographic emulsion. The graft polymer is added after being dissolved in water, an organic solvent or a mixed solvent thereof, or added as an aqueous dispersion prepared in advance in the presence of an appropriate dispersant such as a surfactant, which is then added to the photographic emulsion layer. Alternatively, they can be coated on a support or overcoated or impregnated after each photographic constituent layer is coated on a support.

For application of the present invention, a method of incorporating it in the backing layer of the light-sensitive material is more effective and more preferable.

The amount of the polysiloxane graft polymer used in the present invention is not particularly limited. However, when it is used as a photographic constituent layer by adding it to a coating solution before being coated on a support, it is 0.02 based on the solid weight in the coating composition.
To 300 (weight) percent, particularly preferably 0.1 to
150 (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.

Examples of the coating or penetrating method include US Pat.
5026, a discharge method such as that described in U.S. Pat. No. 2,761,791, and an extrusion method such as that described in U.S. Pat.
It can be applied or permeated from the outside by a method such as a spray method as described in No. 67.

The polysiloxane graft polymer of the present invention is preferably present in an amount of about 0.001 to 1.0 g per square meter of the photographic light-sensitive material, and particularly preferably 0.005 to 0.5 g. However, it goes without saying that the above range varies depending on the type, form or coating method of the photographic photosensitive material used. In applying the compound of the present invention to the back surface, as the binder having a film-forming state used, cellulose triacetate, cellulose diacetate, cellulose acetate malate, cellulose acetate phthalate,
Cellulose esters such as hydroxyalkyl cellulose phthalate: polycondensation polymers of formaldehyde and cresol, salicylic acid or oxyphenylacetic acid, or polycondensation polymers of terephthalic acid or isophthalic acid and polyalkylene glycol: acrylic acid, Homopolymers such as methacrylic acid, styrenecarboxylic acid or styrenesulfonic acid, or copolymerization of these monomers or maleic anhydride with a styrene derivative, alkyl acrylate, alkyl methacrylate, vinyl chloride, vinyl acetate, alkyl vinyl ether or acrylonitrile. Polymerization fatigue such as a combination thereof, ring-opening half-esters or half-amides thereof, partially hydrolyzed polyvinyl acetate: polyvinyl alcohol, etc. Alone obtained from a monomer having a coupling also has a synthetic polymer such as a copolymer.

Also when using a binder, water, an organic solvent, or a mixture thereof can be used as a solvent.

Both the above-mentioned organic solvents and the organic solvents mentioned here include the following solvents. Examples of this type of solvent include alcohols such as methanol, ethanol and butanol: acetone, ketones such as methyl ethyl ketone: methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as chloroform: diethyl ether, dioxane, tetrahydrofuran, etc. There are ethers, aromatic hydrocarbons such as benzene, toluene and xylene.

When the compound of the present invention is mixed with the above binder and applied to the back side, the amount is in the range of about 1 to 300% by weight, more preferably 2 to 150% by weight, based on these binders constituting the backing layer. Is added.

When the polysiloxane graft polymer used in the present invention is applied to the back surface, the amount used is 0.01 to 1 square meter.
It is 1 g, preferably 0.05 to 0.5 g.

The polysiloxane graft polymer used in the present invention has a photographic effect on a photographic light-sensitive material (fogging, desensitization, etc.).
It is possible to improve physical properties such as slipperiness and scratch resistance without giving In particular, the great advantage of the present invention is that
Compared to the polysiloxane graft polymer of the present invention, which has many coating failures when organosilicones, which are known as slip agents for photography, are applied to the photosensitive material backing layer against coating failures during the production of photographic light-sensitive materials. When it is applied, no coating failure occurs, and the sliding property of the film after the development processing is not impaired. This means that even when subjected to severe processing with an automatic photographic processor under conditions of high pH, high temperature, and high speed, the photographic emulsion layer surface will not be damaged, and it will withstand repeated light-sensitive materials for rapid processing or repeated projection. This is a particularly important advantage in the production of positive photosensitive materials for motion pictures, etc., in which the mechanical strength of the obtained film surface is large.

The polysiloxane graft polymer used in the present invention imparts an appropriate slip property to the applied photographic light-sensitive material, and can improve the compatibility particularly under the use conditions of a film for movie photography and a projector. it can.

Since the movie film in which the present invention is carried out has good slipperiness and adhesion resistance in a photographing machine, there is an advantage that it can be driven extremely smoothly and the noise of the film during use can be remarkably reduced. Also, depending on the type of camera, the stress in the contact area of the film during driving is too sharp or too strong, so that the photographic emulsion layer may be partially destroyed to generate scraps in the camera. The negative film for movies embodying the present invention can eliminate such a failure.
It is considered that these advantages are derived from the characteristics of the polysiloxane graft polymer of the present invention as described above.

In the photographic light-sensitive material of the present invention, all those usually used as a support for a photographic light-sensitive material are used. For example, there are cellulose acetate film, cellulose acetate butyrate film, polystyrene film, polyethylene terephthalate film, other laminated materials thereof, paper and the like. Variator or α-olefin polymer, especially polyethylene, polypropylene, etc. 2 to 1 carbon atoms
Examples include paper coated or laminated with a 0-polymer of α-olefin.

Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention. Examples of hydrophilic colloids used as a binder for photographic emulsions and / or other photographic constituent layers include gelatin, colloidal albumin, casein, and carboxymethyl. Cellulose, hydroxyethyl cellulose and other cellulose derivatives, agar, sodium alginate, starch derivatives and other sugar derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamides or derivatives thereof.・
Partial hydrolysates and the like can be mentioned. If desired, compatible mixtures of two or more of these colloids are used.

The most commonly used of these is gelatin.

In the photographic emulsion layer and other layers used in the present invention, a synthetic polymer compound, for example, a latex-like water-dispersed vinyl compound polymer, especially a compound which increases the dimensional stability of a photographic material, is used alone or in combination ( Heteropolymers) or in combination with hydrophilic water-permeable colloids. There are many polymers, for example US Pat. Nos. 2,376,005 and 2,739,137.
No. 2,853,457, No. 3,062,674
No. 3, 3,411,911, 3,488,708
Issue 3, Issue 3,525,620, Issue 3,635,715
Issue 3, Issue 607,290, Issue 3,645,740
No., British Patent Nos. 1,186,699 and 1,307,
No. 373, etc. Among them, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alcoholoxyalkyl acrylate. ,
A copolymer or homopolymer selected from alcooxymethacrylate, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride is generally used.

Hardening of the photographic emulsion and / or other photographic constituent layers can be carried out by a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3. , 5-triazine, other U.S. Pat. Nos. 3,288,775, 2,732,303, British Patent 974,723,
Compounds having a reactive halogen, such as divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1, as shown in No. 1,167,207.
3,5-triazine and others US Pat. No. 3,635,35
No. 718, No. 3,232,763, No. 3,49
Nos. 0,911, 3,642,486, British Patent 994,869, and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide, and other US Pat. N-methylol compounds as shown in US Pat. Nos. 732,316 and 2,586,168, isocyanates as shown in US Pat. No. 3,103,437, US Pat. Three
Aziridine compounds such as those shown in US Pat. No. 2,7,280, and No. 2,983,611.
25,294, 2,725,295 and the like, acid derivatives as shown in US Pat. No. 3,100,70.
Carbodiimide compounds as shown in US Pat. No. 4, etc., epoxy compounds as shown in US Pat. No. 3,091,537, US Pat. No. 3,321,3
13 and 3,543,292, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or inorganic hard films. Examples of the agent include chrome alum and zirconium sulfate. Instead of the above compounds, precursors in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, and primary aliphatic nitroalcohols may be used.

A silver halide photographic emulsion is usually a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide).
It is prepared by mixing with a solution in the presence of an aqueous polymer solution such as gelatin. As this silver halide, in addition to silver chloride and silver bromide, mixed silver halide such as chlorobromide,
Iodobromide, silver chloroiodobromide and the like can be used.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process of the light-sensitive material, during storage or during processing. Those compounds include 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, and mercury-containing compounds. , Mercapto compounds and metal salts have been known for a long time.

The silver halide emulsion can be chemically sensitized by a conventional method. Chemical sensitizers include, for example, gold compounds such as chloroaurate and gold trichloride, salts of precious metals such as platinum, palladium, iridium, rhodium and ruthenium, and sulfur compounds that react with silver salts to form silver sulfide. , Stannous salts, amines, and other reducing substances.

The photographic emulsion can be spectrally sensitized or supersensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in rough combination or in combination with styryl dyes, if necessary. .

The photographic light-sensitive material of the present invention contains a stilbene, triazine, oxazole and coumarin-based compound as a whitening agent in a non-photosensitive photographic constituent layer; and a benzotriazole, thiazolidine, cinnamic acid ester-based compound as an ultraviolet absorber. : Various photographic filter dyes known as light absorbers: If necessary, as anti-adhesion agents, for example, British Patent Nos. 1,320,564 and 1,320,56
5, water-insoluble substances as described in US Pat. No. 3,121,060 and US Pat. No. 3,617,2.
Surfactants such as those described in No. 86 can be included. Further, as a matting agent, a silver halide having an appropriate particle diameter, silica, an inorganic compound such as strontium barium sulfate, and a polymer latex such as polymethyl methacrylate can be contained.

The photographic light-sensitive material of the present invention is used as an antistatic agent in photographic constituent layers such as a photographic emulsion layer, particularly in an antistatic layer provided on the outermost side of a photographic light-sensitive material, for example, US Pat.
No. 5,297, No. 2,972,535, No. 2,97
2,536, 2,972,537, 2,97
2,538, 3,033,679 and 3,073
2,484, 3,262,807, 3,52
No. 5,621, No. 3,615, 531, No. 3,63
0,743, 3,653,906, 3,65
Hydrophilic polymers such as those described in US Pat. Nos. 5,384,3,655,386, and British Patents 1,222,154, 1,235,075 are described in, for example, US Pat. No. 2,973. Nos. 2,263,2,976,148, and hydrophobic polymers such as those described in, for example, U.S. Pat. Nos. 2,584,362 and 2,591,590. Compounds are prepared, for example, in US Pat. Nos. 2,639,234 and 2,649,372.
Nos. 3,201,251 and 3,457,076, sulfonic acid type anion compounds such as those described in, for example, U.S. Pat. Nos. 3,317,344 and 3,5.
Phosphoric acid esters and quaternary ammonium salts as described in US Pat.
82,157, 2,982,651, 3,39
9,995, 3,549,369, 3,56
Cationic compounds such as those described in US Pat. No. 4,043, such as those described in US Pat. No. 3,625,695, etc., such as those described in US Pat. No. 3,736,268, etc. And the complex compounds described in, for example, US Pat. No. 2,647,836 and the like, for example, US Pat. Nos. 2,717,834 and 3,655,387. Can include organic salts as described in.

The compound of the present invention can be applied to all kinds of photographic light-sensitive materials regardless of black and white or color.

The silver halide emulsion contains an ortho emulsion, a panchromatic emulsion, an infrared ray emulsion, an X-ray or other invisible light recording emulsion, a color photographic emulsion such as an emulsion containing a color-forming coupler, an emulsion containing a dye developing agent and a bleachable dye. And various silver halide photographic emulsions such as emulsions.

The color photographic emulsion may contain 2 equivalents or 4 equivalents of a color forming coupler. For example, open-chain type ketomethylene yellow-forming couplers such as benzoylacetanilide type or pivaloylacetanilide type, magenta color forming couplers such as pyrazolone type or indazolone type, and cyan forming couplers such as phenol type or naphthol type are preferably used. For example, Japanese Patent Publication Sho 48
No. 18256, a yellow coupler represented by the general formula [I], a magenta coupler described in Japanese Patent Application No. 44-56670, a cyan coupler described in Japanese Patent Application No. 46-76515, a U.S. Pat. No. 2,428,054, Same 2,449,
966, 2,455,170, 2,600,7
88, 2,983,608, 3,148,06
Colored couplers described in U.S. Pat.
The release-inhibiting coupler described in No. 7,554 can be used.

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A coating solution having the following composition was coated on a triacetyl cellulose film support and dried (90 ° C., 3 minutes) to form a back layer.

Comparative compound-1 Comparative compound-2 An undercoat layer is provided on the opposite side of the five base back layers, and an antihalation layer, a red emulsion layer, a gelatin intermediate layer, a green emulsion layer, a yellow filter layer, a blue emulsion layer, and a protective layer are formed in this order on the undercoat layer. The color negative films for movies 1-1, 1-2, 1-3, 1-4, 1-5 corresponding to the respective films were applied. As the red-sensitive and green-sensitive emulsions, silver iodobromide emulsions containing 6 mol% iodine were used. As the blue-sensitive emulsion, a silver iodobromide emulsion containing 8 mol% iodine was used.

These films were aged for 1 week at 25 ° C. and 60% RH, and then cut into a width of 35 m / m to obtain a roll-shaped film of 400 feet. The coating suitability of the photographic emulsion layer and the driving performance of the film in the atmosphere of 25 ° C. and 60% RH in the production of these films were examined. The test items are (1) Applicability of the coating liquid to the support (2) Static friction coefficient measurement (3) Corresponding to practical skill The resistance force when pulling out the film from between the camera's aperture plate and brush plate ( This is a measurement that corresponds well to the running performance of the camera during shooting.

(1) Applicability of coating liquid to support A coating liquid for the antihalation layer and a coating liquid for the red-sensitive emulsion layer on a support having an undercoat layer on the side opposite to the base back layer, and a gelatin intermediate layer. The layer coating solution was applied at a conveying speed of 80 m / min, and dried at a dry-bulb temperature of 35 ° C and a wet-bulb temperature of 18 ° C to obtain an intermediate product of a color negative film for movies.

The surface of the obtained intermediate product was visually observed with reflected light.

Evaluation No coating unevenness occurs: ○ Very uneven coating occurs: △ Coating unevenness occurs: × Many coating unevennesses: × × (2) Static friction coefficient measurement method T.Anvelt, JFCarroll, JR, .and L, J, Sugden, J.SMPTE,
The maximum coefficient of static friction of the film back surface was determined using the paper clip method described in 80 (9) 734-739 (1971).

(3) Measurement of pull-out resistance force The camera's aperture plate and press plate (ARRIFLEX 35IIA made by ARNOLD & RICHTER) are fixed on the moving table. After sandwiching the sample between the apparition plate and the press plate and fixing one end of the sample to the load cell, move the moving table at 10 m / min, and find the maximum frictional resistance force of the film generated at that time. It was

(4) Development processing The processing was performed according to the following development processing steps.

Treatment process Temperature Color development 41 ° C 3 minutes Stop 38 ° C 30 seconds Water washing 〃 30 seconds Pre-bath 〃 30 seconds Bleaching 〃 3 minutes Water washing 〃 1 minute Fixing 〃 2 minutes Water washing 〃 2 minutes Stabilizing bath 〃 10 seconds Treatment liquid used Has the following composition:

Color developer 2g 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 Water was added and the total amount was 1 Stabilizing bath Formaldehyde (37%) 10 ml Water was added and the total amount 1 The results obtained are shown in Table 2.

As is clear from the results in Table 2, it is understood that the sample to which the polysiloxane graft polymer of the present invention is added has no coating failure as compared with the sample to which the comparative compound is added.

Further, it can be seen that the friction coefficient and the drawing resistance after the development processing are equal to or better than those of the comparative sample.

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Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photographic emulsion layer on a support, wherein at least one surface layer of the light-sensitive material comprises at least a vinyl polymer having an affinity for a photographic polymer as a trunk polymer. And a graft copolymer containing a polysiloxane represented by the following general formula [I], which has a low affinity for a photographic polymer, and a silver halide photographic light-sensitive material. General formula [I] In the formula, R ₁ represents H or CH ₃ . It represents an _{R 2, R 3, R 4} , R 5, R 6, R 7 is an alkyl group or an aryl group having 6 to 20 carbon atoms of the carbon atoms of the same or different 1 to 20. m represents an integer of 0 to 400 and n represents an integer of 0 to 50. A represents a divalent group. B represents a substituted alkyl group having a reactive group.