JP2838420B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide having improved lubricity, scratch resistance and adhesion resistance and improved generation of contamination in a developing solution during development processing. It relates to a photographic material.

[Prior art and its problems] Conventionally, in handling a silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material), for example, the manufacturing process such as coating, drying, processing, etc .; During handling such as take-up, rewind, transport, etc. or during storage, the photosensitive material may be in contact with the photosensitive material, i.e., between the outermost layer on the silver halide emulsion layer side and the outermost surface layer on the back surface, or in contact with the photosensitive material. Adhesion or contact friction with other objects often resulted in serious failures.

Such failures include, for example, generation of scratches on the outermost layer or the back surface on the emulsion layer side, deterioration of the drivability of the photosensitive material in equipment such as a camera, and peeling of the photographic constituent layer due to adhesion. No.

In recent years, the use of photosensitive materials has become more severe than before, especially due to the expansion of use and processing methods for photosensitive materials (for example, rapid shooting and rapid processing) and diversification of the environment when used in high-temperature and high-humidity atmospheres. Due to the increased exposure to conditions, adhesion and contact failure relating to the surface layer of the photosensitive material are likely to occur.

As a means for solving these problems, for example, as a method of improving the outermost layer on the side of the silver halide emulsion layer, an inorganic substance such as silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, polymethyl methacrylate, cellulose A method has been proposed in which fine particles of an organic substance such as acetate propionate are included to increase the roughness of the surface of the photosensitive material and to form a so-called matte material to reduce the adhesiveness and contact friction. In particular, a color photographic material contains a large amount of an additive such as a coupler in a photographic constituent layer, so that it is necessary to use a large amount of a matting agent because of particularly high adhesiveness.

However, since the matting agent is insoluble in the developing solution and remains in the photosensitive material after the developing process, when a large amount of the matting agent is used, the transparency of the formed image is deteriorated or the image quality is deteriorated. There were drawbacks.

In order to avoid such a problem, a matting agent which is insoluble in a neutral or acidic solution and soluble in an alkaline solution has been proposed, for example, Japanese Patent Publication No. 57-9054, Japanese Patent Application Laid-Open No.
Specific examples are disclosed in JP-A-66937 or JP-A-60-126644.

On the other hand, as means for improving the outermost surface layer of the back surface, it is known that the outermost surface layer of the back surface contains a fine particle matting agent such as silica or polymethyl methacrylate, or that a fluorine-based surfactant is used. .

However, none of the above methods can provide sufficient adhesion resistance and slipperiness. Especially in the manufacturing process and in the processes of photographing, developing, baking, etc., the back surface is often handled so as to come into contact with other objects in order to protect the emulsion layer side. Scratches occurred on the back surface, causing serious problems such as affecting image quality.

It is well known that a slip agent is applied to the outermost surface layer of the back surface in order to solve these problems. As such a slipping agent, esters of higher fatty acids having a relatively small number of carbon atoms, and organopolysiloxanes as disclosed in JP-A-50-117414 are conventionally known.

However, in the conventional methods as described above, since the effect of imparting the adhesion resistance and the slipperiness of the slip agent used is not sufficient, it is necessary to use a large amount of the slip agent to obtain a good effect. The coating agent of the photographic emulsion may be impaired by the transfer of the slipping agent to the undercoat layer on the side of the silver halide emulsion layer. Further, during the development processing, these slip agents are eluted into the processing solution, and when the alkali-soluble matting agent as described above is used on the emulsion layer side, these alkali-soluble matting agents are also eluted into the processing solution as well. In addition, the matting agent and the slipping agent combine in the processing solution to generate turbidity and sludge. As a result, during or after the development processing, deposits may be formed on the transport rollers of the developing machine, causing serious film failures such as uneven density of the film.

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having improved slipperiness, scratch resistance and adhesion resistance.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which does not cause development processing solution or roller contamination of a developing machine during development processing.

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, the above objects of the present invention have been made at least on one side of a support with at least one photosensitive silver halide emulsion layer and In a silver halide photographic material having a non-photosensitive protective layer as an outermost layer and at least one back layer on the side opposite to the support, the non-photosensitive protective layer is preferably an alkali-soluble matting agent. And wherein the outermost surface layer of the at least one backing layer contains a compound represented by the following general formula [I]. I found that.

In the general formula [I] R ₁ COR ₂ [wherein, R ₁ represents an alkyl or alkenyl group having 12 or more carbon atoms, when R ₁ is an alkyl or alkenyl group having a carbon number of 12 to 24, R ₂ Is an -OR ₃ group, R ₃ represents an alkyl group or an alkenyl group having 25 or more carbon atoms, and when R ₁ is an alkyl group or an alkenyl group having 25 or more carbon atoms, R ₂ represents an -OH group represents a -NH ₂ group or -OR ₃ group, R ₃ represents an alkyl or alkenyl group having 12 or more carbon atoms. Hereinafter, the present invention will be described in more detail.

Specific examples of the compound represented by the general formula [I] (hereinafter, referred to as the compound of the present invention) contained in the outermost surface layer of the back layer of the present invention are shown below, but the present invention is not limited thereto. is not.

(1) C ₂₅ H ₅₁ COOH (2) C ₂₇ H ₅₅ COOH (3) C ₃₀ H ₆₁ COOH (4) C ₂₅ H ₅₁ CONH ₂ (5) C ₂₈ H ₅₇ CONH ₂ (6) C ₂₇ H ₅₅ COOC ₁₄ H ₂₉ (7) C ₂₇ H ₅₅ COOC ₁₆ H ₃₃ (8) C ₂₅ H ₅₁ COOC ₃₀ H ₆₁ (9) C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ (10) C ₁₇ H ₃₅ COOC ₂₅ H ₅₁ Are alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride and carbon tetrachloride; ethers such as diethyl ether and dioxane; aromatics such as benzene and toluene. Used by dissolving in a solvent such as hydrocarbons.

The compound of the present invention may of course be used alone, but may be used in combination with a binder. As binders that can be used in combination, for example, polystyrene,
Polymethyl methacrylate, polyvinylidene chloride, polymers or copolymers such as polyacrylonitrile and polyvinyl acetate, cellulose diacetate, cellulose triacetate, cellulose nitrate, ethyl cellulose, cellulose derivatives such as cellulose propionate, further polyvinyl formal, Acetals such as polyvinyl acetal and polyvinyl benzal are exemplified, but are not limited to the above as long as they have a film-forming ability and are soluble in a solvent.

The amount of a compound of the present invention the photosensitive material 1 m ² per
It is preferably from 500 to 500 mg, particularly preferably from 5 to 100 mg.

A layer containing an antistatic agent can be usually provided on the side of the support from the outermost surface layer of the back layer of the present invention. Such a layer is used as an antistatic agent as an ionene-type polymer as disclosed in JP-B-57-56059 and JP-A-61-2237.
A crosslinked polymer having a vinylbenzyl quaternary ammonium salt at the polymer position as disclosed in JP-A-36-136, an alumina sol having an electrolyte as disclosed in JP-B-57-12979, and JP-A-56-143431. It may contain crystalline metal oxide fine particles as disclosed in the gazette.

In particular, when an ionene-type polymer is used as an antistatic agent,
The resistance to the aqueous developing solution composition is poor, and scum may occur in the photosensitive material.However, when the layer containing the compound of the present invention is used as the outermost surface layer of the back layer, This has the effect of suppressing leaching of the ionene-type polymer into the developing solution, and can improve the above-mentioned disadvantages.

In particular, when the antistatic agent is an alumina sol having an electrolyte or crystalline metal oxide fine particles, the coatability of the outermost surface layer on the back surface is good, and the adhesion between the outermost surface layer and the layer containing the antistatic agent is good. Good scratch resistance, excellent slipperiness,
A photosensitive material having improved drying unevenness can be obtained.

The outermost surface layer of the back surface containing the compound of the present invention or the layer containing an antistatic agent may further contain a matting agent, a surfactant, a dye, and the like, if necessary.

As the matting agent, silicon dioxide fine particles having an average particle size of 0.01 to 10 μm are preferable. The above various additives, and various additives of the photosensitive silver halide emulsion layer on the opposite side of the back surface, the production method,
There is no particular limitation on the above, and for example, the description in Research Disclosure Magazine, Vol. 176, pp. 22-31 (Dec. 1978) can be referred to.

Further, another layer such as a binder layer may be provided between the outermost surface layer of the back layer and the layer containing the antistatic agent.

As a method for applying the layer containing the compound of the present invention, known methods, for example, curtain coating, reverse roll coating,
Fountain air doctor application, slide hopper application, extrusion application, dip application and the like can be used.

In the present invention, the non-light-sensitive protective layer means a layer which is outside the emulsion layer on the side of the support on which the silver halide emulsion layer is provided and does not contain the light-sensitive silver halide emulsion. The non-photosensitive protective layer of the present invention may be composed of two or more layers.

In the present invention, the alkali-soluble matting agent contained in the outermost layer of the non-photosensitive protective layer refers to a matting agent that is insoluble in a neutral or acidic solution and soluble in an alkaline solution.

Such matting agents include, for example, U.S. Pat.
No. 992,102 discloses methyl methacrylate (hereinafter M
A copolymer having a molar ratio of MA) / methacrylic acid (hereinafter abbreviated as MAA) of 1/1, and having an MMA / MAA ratio of about 6/4 to 9/1 disclosed in Japanese Patent Publication No. 57-9054. (Molar ratio), a copolymer of ethyl methacrylate (hereinafter abbreviated as EMA) / MAA (containing 20-50% by weight of MAA) disclosed in JP-A-58-66937, and more particularly Matting agents comprising a copolymer of EMA, MMA and MAA disclosed in JP-A-60-126644.

Among such alkali-soluble matting agents, in the present invention, a copolymer having MMA / MAA of about 6/4 to 9/1 (molar ratio),
Alternatively, a terpolymer of EMA, MMA and MAA is preferably used.

In the present invention, EMA as described above, MMA and unsaturated vinyl monomers other than MAA, for example, acrylonitrile,
Known monomers that can be copolymerized with the above three monomers, such as vinyl acetate, styrene, ethyl vinyl ether and butyl vinyl ether, are used in a small amount (preferably 5%) as long as they do not adversely affect the object of the present invention. % By weight).

In the present invention, the alkali-soluble matting agent is finely dispersed and contained in the non-photosensitive protective layer which is the outermost layer of the light-sensitive material. These matting agents are low-boiling organic solvents such as ethyl acetate, butanol-containing ethyl acetate (butanol 50% by weight).
), A solution of the copolymer dissolved in a solvent such as butanol-containing methanol (butanol less than 50% by weight) is dispersed in an aqueous gelatin solution under rapid stirring. The size of the matting agent of the present invention can be freely changed in a wide range, but in the present invention, it is preferably in the range of 0.2 to 10 µm, particularly preferably 0.5 to 5 µm. The aqueous gelatin solution containing the matting agent obtained as described above can be coated as a non-photosensitive protective layer on the outermost layer of a photographic material by any method known in the field of photography.

The alkali-soluble matting agent of the present invention is preferably contained in the outermost layer in an amount of 50 mg to 500 mg, particularly 100 mg to 400 mg per square meter.

In the present invention, examples of the hydrophilic colloid binder constituting the outermost non-photosensitive protective layer include gelatin, gelatin derivatives (eg, acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, and the like. Is preferred. Further, in the present invention, if necessary, a hardener, a smoothing agent,
Various additives such as a surfactant, an antistatic agent, a thickener, and a polymer latex can be contained. Examples of the hardener include aldehyde compounds, 2-hydroxy-4,6
Compounds having an active halogen, such as -dichloro-1,3,5-triazine, vinyl sulfone compounds, N-methylol compounds, and halogen carboxaldehyde compounds such as mucochloric acid can be used. As the leveling agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones and the like can be used. Examples of the surfactant include natural surfactants such as saponin, nonionic surfactants such as alkylene oxides, cationic surfactants such as higher alkylamines and quaternary ammonium salts, and acidic groups such as carboxylic acid and sulfonic acid. Any of anionic surfactants including As the antistatic agent, the above-mentioned surfactants, alkali metal salts such as styrene-maleic acid-based copolymers and acrylonitrile-acrylic acid-based copolymers, and further US Pat.
The antistatic agents described in JP-A-6,312 and JP-A-3,428,451 can be contained.

In the present invention, various known matting agents, for example, a matting agent composed of silicon dioxide, polymethacrylate and the like can be used in combination in the non-photosensitive protective layer. However, since such a known matting agent remains in the processed photographic material, it is preferably used in a smaller amount than the copolymer of the present invention, for example, up to 50 mg per square meter.

The silver halide emulsion used in the light-sensitive material of the present invention may be a common single-jet method, a double-jet method,
It can be prepared by any method such as an acidic method, an ammonia method and a neutral method, and the shape, size and size distribution of silver halide grains are not particularly limited. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like can be used.

Examples of hydrophilic colloid binders used in silver halide emulsions include gelatin, modified gelatin, gelatin derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, poly-N-pyrrolidone, polyacrylic acid copolymer, polyacrylamide, and the like. These may be used alone or in combination of two or more. Further, the photographic constituent layer according to the present invention may contain a latex water-dispersible vinyl compound. As such a latex, a homo- or copolymer such as alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, and vinylidene chloride is used.

The silver halide emulsion used in the present invention can be chemically sensitized by a conventional method. For example, U.S. Pat.No. 2,399,083
Nos. 2,597,856 and the like, and salts of noble metals such as platinum, palladium, rhodium and iridium, U.S. Pat.Nos. 2,410,689 and 3,501,3.
Chemical sensitization can be carried out with a sulfur compound, a stannous salt, an amine or the like described in the specification of No. 13, etc.

The silver halide emulsion used in the present invention may contain a stabilizer or an antifoggant. For example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3
Many compounds such as -methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts can be used.

In the silver halide emulsion used in the present invention, various spectral sensitizing dyes such as a merocyanine dye, a carbocyanine dye and a cyanine dye can be used depending on the purpose.

In the present invention, 4-equivalent methylene yellow couplers, 2-equivalent diketomethylene yellow couplers, 4-equivalent or 2-equivalent pyrazolone-based magenta couplers, indazolone-based magenta couplers, α-naphthol-based cyan couplers and phenols are used as color couplers. For example, a cyan cyan coupler can be used. Also called DI
R couplers can also be used.

Further, the photographic constituent layer of the present invention may contain a dye, an ultraviolet absorber, a hardener as described above, a surfactant, and a polymer latex.

Supports that can be used in the light-sensitive material of the present invention include, for example, films such as polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, polyesters such as polyethylene terephthalate or baryta paper, synthetic paper or paper. Supports comprising sheets coated on both sides with these polymer films and the like and the like are included.

The photographic component layer of the light-sensitive material of the present invention includes dip coating,
Various methods such as air knife coating, curtain coating, and extrusion coating can be used to apply one by one or multiple layers simultaneously.

Various additives used in the present invention, vehicles, supports,
For details on application methods, see Product Licensing Index, Vol. 92, 107-11
The description on page 0 (December 1971) can be referred to.

The light source for exposure of the photosensitive material of the present invention is not particularly limited, and can be used from low illuminance to high illuminance, and the exposure time can range from several tens of seconds to 10 ^-6 seconds. .

The light-sensitive material applicable to the present invention is a black-and-white photographic light-sensitive material,
Color photographic light-sensitive materials, or for general use, for printing X-rays, for radiation, etc. Specifically, black and white negative films, papers, reversal photographic light-sensitive materials and color negative films, papers, reversals and The present invention can be applied to any silver halide photographic light-sensitive material such as a so-called external color photographic light-sensitive material containing a color former in a processing solution.

When the photosensitive material of the present invention is a color photosensitive material,
After exposure, it is developed to form a dye image. Here, the development processing basically includes at least one color development step, and in some cases, a pre-hardening step, a neutralization step,
A first development (black-and-white development) step is included. The above steps and subsequent steps (eg, bleaching, fixing, bleach-fixing, intensification,
The selected combination (stability, washing, etc.) is treated at 30 ° C. or higher, particularly preferably at 35 ° C. or higher.

The color developing solution used in the color developing step is a compound in which an oxidation product thereof reacts with a color forming agent (color coupler) to form a color forming product, that is, p-phenylenediamines (for example, N, N- Diethyl-p-phenylenediamine, N, N-diethyl-3-methyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N
-Methanesulfonamidoethylaniline, 4-amino-
3-methyl-N-ethyl-N-β-hydroxyethylaniline, N-ethyl-N-β-hydroxyethyl-p-
Phenylenediamine) or an alkaline aqueous solution (pH 8 or more, preferably pH 9 to 12) containing a salt thereof (eg, hydrochloride, sulfate, sulfite). As such developing agents, U.S. Pat.Nos. 2,193,015 and 2,592,364,
The compounds described in JP-A-48-64933 and the like can be used. Other color developing solutions include salts such as sodium sulfate, pH adjusters and buffers such as sodium hydroxide, sodium carbonate and sodium phosphate (eg, acids such as acetic acid and boric acid or salts thereof), development accelerators (For example, various pyridinium compounds, cationic compounds, potassium nitrate, sodium nitrate described in U.S. Pat. Nos. 2,648,604 and 3,671,247, U.S. Pat.
533,990, 2,577,127, 2,950,970 and the like, represented by polyethylene glycol condensates and derivatives thereof described in British Patent Nos. 1,020,032 and 1,020,033. Nonionic compounds such as polythioethers, U.S. Pat.No. 3,068,097
Polymer compounds having a sulfite ester as represented by the compounds described in the specification, organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine and the like). The color developer is
Further, antifoggants (for example, alkali bromide, alkali iodide, nitrobenzimidazoles, benzotriazole-based compounds, mercaptotetrazole-based compounds, etc.), stains described in US Pat. No. 3,161,514, British Patent No. 1,144,481, etc. Or sludge inhibitor, U.S. Pat.
No. 536,487, etc., may also contain an overlay effect promoter and a preservative (for example, sulfite, acid sulfite, hydroxylamine hydrochloride, formaldehyde-alkanolamine sulfite adduct, etc.).

As a processing step prior to the development step, there is usually a pre-hardening bath, and aldehydes having an action of reacting and hardening gelatin which is a constituent factor in a photographic emulsion, for example, U.S. Pat. No. 3,232,761 Described in US Pat. Nos. 3,565,632, 3,667,760, and at least one aromatic aldehyde described in the specification. An aqueous solution is used. This solution may contain inorganic salts such as sodium sulfate, pH adjusters and buffers such as borax, boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, etc., and developing agents such as alkali halides (eg, potassium bromide). Contains antifoggants.

Generally, a neutralization bath is provided for the purpose of preventing aldehydes used in the pre-hardening step from being brought into the developing step. Aldehyde removers such as hydroxylamine and L-ascorbic acid are added to the neutralization bath, and inorganic salts, pH adjusters and buffers are also added.

The first developing solution for the color reversal film is also a step prior to color development, and an aqueous alkali solution containing at least one developing agent such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p-aminophenol is used. In addition, inorganic salts such as sodium sulfate, pH adjusters and buffers such as borax, boric acid, sodium hydroxide and sodium carbonate, alkali halides (eg, potassium bromide), and other development antifoggants Is included.

The various additives exemplified in the above-mentioned respective processing steps and the amounts thereof are well known in color photographic processing.

After color development, color photographic materials are usually bleached and fixed. Bleaching and fixing can be combined to form a bleach-fixing bath. Many compounds are used as bleaching agents, among which ferricyanates, dichromates, water-soluble iron (III) salts, water-soluble cobalt (III) salts, water-soluble copper (II)
Salt, water-soluble quinones, nitrosophenol, iron (II
Complex salts of organic acids with polyvalent cations such as I), cobalt (III) and copper (II), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, malon Metals such as acids, tartaric acid, malic acid, diglycolic acid, and dithioglycolic acid, and copper complex salts of 2,6-dipicolinic acid; and peracids such as alkyl peracids, persulfates, permanganates, and hydrogen peroxide. , Hypochlorite, chlorine, bromine, mash powder, etc., alone or in an appropriate combination are generally used. In addition, bleaching accelerators described in U.S. Pat. No. 3,042,520, Copper No. 3,241,966, JP-B Nos. 45-8506 and 45-836 can be added.

For the fixing, any of conventionally known fixing solutions can be used. That is, as the fixing agent, ammonium, sodium and potassium salts of thiosulfate are used in an amount of about 50 to 200 g / l, and in addition, a sulfite, a stabilizer such as isometric bisulfite, and a hardening agent such as potassium alum. Agents, pH buffers such as acetates and borates, and the like.

Bleaching agents, fixing agents and bleach-fixing baths are described in U.S. Pat. No. 3,582,322.

As the intensifying liquid, a method using a Co (III) salt, a method using hydrogen peroxide, or an intensifying liquid based on a method using chlorous acid can be used.

For the image stabilizing bath, the methods described in U.S. Pat. Nos. 2,515,121 and 3,140,177 can be used.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 The following composition for the first layer on the back surface was applied on a cellulose triacetate film so as to be 20 ml / m ² ,
Dried for minutes.

Composition for first layer On the first layer, a coating solution composition for the back surface second layer shown in Table 1 below was applied so as to have a concentration of 25 ml / m ² , and dried at 100 ° C. for 3 minutes.

Next, a silver halide emulsion layer and a protective layer were coated on the surface of the cellulose triacetate opposite to the back layer as follows.

It contains 300 g of gelatin per mole of silver halide and as a yellow coupler α-pivaloyl-α- (1-benzyl-2,4-dioxyimidazolin-3-yl) -2
-Chloro-5 [γ- (2,4-tert-aminophenoxy)
Butylamide] acetanilide 2.5 × 10 ^-2 mol and 1,2-bis (vinylsulfonyl) ethane as a hardener 0.02 g per 1 g of gelatin blue-sensitive silver iodobromide for color (silver iodide content 7 mol) %) The emulsion was adjusted. MMA / MAA = 6/4 for the protective layer (2-1) together with this emulsion.
(Molar ratio) of the alkali-soluble matting agent (100 mg / m ² ) of the present invention having a particle size of 2 to 4 μm having a composition of
Sodium ethylhexyl sulfosuccinate (coating aid)
(0.01 g / m ² ) and a gelatin solution (0.5 g / m ² ) containing the above-mentioned hardener (0.02 g / 1 g gelatin) on a cellulose triacetate support having an undercoat layer by a slide hopper method from the support side. A silver halide emulsion layer and a protective layer were coated in this order. Also, a gelatin solution having the same composition as that for the protective layer 2-1 was used as the protective layer 2-2 except that the alkali-soluble matting agent was not used, and the gelatin solution was applied in the same manner as in the case of 2-1.

 The dry thickness of each protective layer was 1.5 μm.

Sample Nos. 1 to prepared in the combinations shown in Table 2 as described above
Each of No. 9 was divided into 5 cm ² for 2 minutes and stored for 1 day in an atmosphere of 23 ° C. and 80% RH so that they did not come into contact with each other. Make contact with the surface layer, apply a load of 800 g, and
The sample was stored in an atmosphere of 80 ° C. and 80% RH, and then the area of the bonded portion when the sample was peeled was measured to evaluate the adhesion resistance.

 The evaluation criteria are as follows.

Rank Area ratio (%) of bonded portion A 0-20 B 21-40 C 41-60 D 61 or more The results are shown in Table 2.

From the results in Table 2, it can be seen that even in the case where the compound of the present invention was contained in the outermost surface layer of the back layer, samples Nos. 8 and 9 in which the non-photosensitive protective layer did not contain an alkali-soluble matting agent exhibited extremely poor adhesion resistance. In addition, even if the non-photosensitive protective layer contains the alkali-soluble matting agent of the present invention, in the case of Samples Nos. 6 and 7, in which the compound contained in the outermost surface layer of the back layer is a compound other than the compound of the present invention, The adhesion is slightly improved but insufficient.

On the other hand, in the case of Sample Nos. 1 to 5 of the present invention in which the non-photosensitive protective layer contains the alkali-soluble matting agent of the present invention and the outermost surface layer of the back layer contains the compound of the present invention, the adhesion resistance is It turns out that it is remarkably excellent.

Example 2 The dynamic friction coefficient and scratch resistance of each of the back surfaces of Sample Nos. 1 to 7 prepared in Example 1 were measured by the following method, and after the above sample was subjected to a development treatment with the following processing solution, ,
The dynamic friction coefficient and scratch resistance were measured in the same manner.

The coefficient of kinetic friction was measured by the JIS method using a steel ball. The load was continuously changed in the range of 200 g, and the evaluation was made by obtaining the load of the needle that caused damage to the film surface of the sample.

Processing time (38 ° C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Is as follows.

Table 3 shows the above results.

As can be seen from Table 3, Samples Nos. 1 to 5 of the present invention had smaller dynamic friction coefficients and excellent scratch resistance than Comparative Samples Nos. 6 and 7, and were contained in the outermost surface layer of the back layer. The compound of the present invention does not elute into the developing solution and has excellent slip properties and scratch resistance even after the developing process.

Example 3 On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

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

Gelatin 2.2 g / m ² Second layer: Intermediate layer A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² Third layer: low-sensitivity red-sensitive silver halide emulsion layer Monodisperse emulsion composed of AgBrI containing an average grain system of 0.30 μm and AgI of 6.0 mol% (emulsion I): Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: 1.0 × 10 ⁻⁵ mol per mol of silver Cyan captor (C-1): 0.06 per mol of silver Mol Colored cyan coupler (CC-1): 0.003 mol per mol of silver DIR compound (D-1): 0.0015 mol per mol of silver DIR compound (D-2): 0.002 mol per mol of silver Gelatin 1.4 g / m ² Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer Monodisperse emulsion composed of AgBrI containing 0.5 mol% of average particle size and 7.0 mol% of AgI (emulsion II): Silver coating amount 1.3 g / m ⁽²⁾ Sensitizing dye I: 3 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: 1.0 × 10 ⁻⁵ mol per mol of silver Cyan captor (C-1): 0.02 per mol of silver Mole Colored cyan coupler (CC-1): 0.0015 mol per mol of silver DIR compound (D-2): 0.001 mol per mol of silver Gelatin 1.0 g / m ² Fifth layer: Intermediate layer Same as the second layer Gelatin layer.

Gelatin 1.0 g / m ² 6th layer: low-sensitivity green-sensitive silver halide emulsion layer Emulsion I: silver coating amount 1.5 g / m ² sensitizing dye III: 2.5 × 10 ^-5 mole sensitizing dye per mole of silver IV: 1.2 × 10 ^-5 mol per mol of silver Magenta coupler (M-1): 0.050 mol per mol of silver Colored magenta coupler (CM-1): 0.009 mol per mol of silver DIR compound ( D-1) 0.0010 mol per mol of silver DIR compound (D-3) 0.0030 mol per mol of silver Gelatin 2.0 g / m ² 7th layer: Highly sensitive green-sensitive silver halide emulsion layer Emulsion II ... coating silver amount 1.4 g / m ² sensitizing dye III ... 1.0 × 10 ^-5 mol magenta coupler relative to 1.5 × 10 ^-5 mol sensitizing dye IV ...... silver mole per silver mole (M-1 ) ... 0.020 mol per mol of silver Colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-3) ... 0.0010 mol per mol of silver Gelatin 1.8 g / m ² Eighth Layer: Gelatin layer containing an emulsified dispersion of the yellow filter layer Yellow colloidal silver and 2,5-di -t- octylhydroquinone.

Gelatin 1.5 g / m ² Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer Monodisperse emulsion composed of AgBrI containing 0.48 μm in average particle size and 6 mol% of AgI (emulsion III): increased silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ⁻⁵ mol per mol of silver Yellow coupler (Y-1): 0.29 mol per mol of silver Gelatin 1.9 g / m ² 10th layer: high-sensitivity blue-sensitive emulsion layer Average grain size Monodisperse emulsion composed of AgBrI containing 0.8 μm in diameter and containing 15 mol% of AgI (emulsion IV): silver coating amount 0.5 g / m ² sensitizing dye V: 1.0 × 10 ⁻⁵ mol per mol of silver Yellow coupler (Y- 1) 0.08 mol per mol of silver DIR compound (D-2) 0.0015 mol per mol of silver Gelatin 1.6 g / m ² 11th layer: 1st protective layer Silver iodobromide (AgI 1 mol% average Particle size 0.07μm) ... Amount of silver applied
Gelatin layer containing 0.5 g / m ² UV absorbers UV-1 and UV-2 Gelatin 1.2 g / m ² 12th layer: 2nd protective layer (0.8 μm) EMA: MMA: MAA = 20 with particle size of 2-4 μm 30:50 (molar composition ratio) matting agent (100 mg / m ² ), gelatin layer containing polymethyl methacrylate particles (average particle size 3.5 μm) and formalin scavenger (HS-1), gelatin 1.2 g /
m ^2.

In addition, in each layer, in addition to the above components,
% By weight of a polyethylene acrylate latex (average particle size 0.07 μm), a gelatin hardener (H-1) and a surfactant were added.

Samples Nos. 10 to 16 were prepared by sequentially forming layers having the following compositions on the back surface from the support side.

First layer on back surface The following composition for an antistatic layer was applied at a rate of 20 ml / m ² and dried at 80 ° C. for 5 minutes.

Second layer on back surface The composition for the second layer shown in Table 1 was applied to a concentration of 25 ml / m ² and dried at 100 ° C. for 3 minutes.

 The compounds contained in each layer are as follows.

Sensitizing dye I: anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: anhydro-9-ethyl-3,3 '-Di- (3
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III: anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl Propyl) oxacarbocyanine hydroxide Sensitizing dye IV: anhydro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V: anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiocyanine Each of the obtained samples was subjected to the development processing performed in Example 2, and the presence or absence of dust on the sample surface after the development processing was visually evaluated. Further, "development unevenness" caused by dust adhering in the developer was evaluated on the following three scales.

A: No development unevenness is observed.

B: Development unevenness is slightly observed.

C: Development unevenness is remarkably observed.

Next, the insolubles floating in the fixing solution when 500 sheets of 25 × 30 cm samples were developed using the newly prepared processing solution were evaluated as the fixing solution contamination on the following three scales.

A: No suspended matter is recognized.

B: Slight floating substances are observed.

C: Suspended matters are remarkably observed.

 Table 4 shows the results.

From Table 4, it can be seen that Comparative Sample No. 15 was used in Sample Nos. 10 to 14 of the present invention.
It can be seen that there is no adhesion of dust on the sample surface, there is no development unevenness due to dust, and no fixer contamination is observed at all, as compared with Nos. 16 and 17.

[Effects of the Invention] As described in detail above, a silver halide photographic light-sensitive material which has improved slipperiness, scratch resistance and adhesion resistance according to the present invention and which does not cause contamination of a developing solution due to development processing is provided. Can be provided.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-55-126238 (JP, A) JP-A-55-79435 (JP, A) JP-A-62-186255 (JP, A) JP-A-1- 161337 (JP, A) JP-A-1-154141 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/76

Claims (1)

(57) [Claims] 1. A support having at least one light-sensitive silver halide emulsion layer on one side and a non-light-sensitive protective layer as an outermost layer, and at least one back layer on the opposite side of the support. In a silver halide photographic light-sensitive material having
The non-photosensitive protective layer contains an alkali-soluble matting agent, and the outermost surface layer of the at least one back layer contains a compound represented by the following general formula [I]. Photosensitive material. In the general formula [I] R ₁ COR ₂ [wherein, R ₁ represents an alkyl or alkenyl group having 12 or more carbon atoms, when R ₁ is an alkyl or alkenyl group having a carbon number of 12 to 24, R ₂ Is an -OR ₃ group, R ₃ represents an alkyl group or an alkenyl group having 25 or more carbon atoms, and when R ₁ is an alkyl group or an alkenyl group having 25 or more carbon atoms, R ₂ represents an -OH group represents a -NH ₂ group or -OR ₃ group, R ₃ represents an alkyl or alkenyl group having 12 or more carbon atoms. ]