JP2579210B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having improved physical properties (hereinafter, referred to as a photographic light-sensitive material), and more particularly, to slippage during high-speed running in a camera. The present invention relates to a photographic material having improved properties and scratch resistance at the same time.

"Prior art" A photographic light-sensitive material usually has a surface layer using a hydrophilic colloid as a binder such as gelatin.
During handling such as drying, processing, winding, rewinding or transporting in photography, development processing, printing, projection, etc., contact friction with various substances or the surface of photosensitive material and back surface In many cases, the undesired influence is caused by the contact friction between the photographic light-sensitive materials. For example, generation of scratches or scratches on the surface or back surface of the photosensitive material, poor running property of the photosensitive material in a photographing machine, a printer, or a camera, generation of film dust, and the like. In particular, poor running performance is a serious problem in continuous shooting of long films such as negative films for movies, if the running resistance of the film is large, camera noise, film dust, double images, etc. occur. Becomes In order to solve this problem, various studies have hitherto been made. Part 1
One method is to reduce the sliding friction of the photographic light-sensitive material so that the photographic light-sensitive material can run smoothly in a photographing machine or camera without being damaged.

For example, there is a method described in U.S. Pat. No. 3,054,522, in which dimethylsilicone and a specific surfactant are simultaneously contained in a photographic emulsion layer or a protective layer to impart slickness to a photographic film. A mixture of dimethyl silicone and diphenyl silicone and a fatty acid ester of a polyhydric alcohol such as described in British Patent No. 1466304 are applied to the back surface of a photographic material as described in U.S. Pat. There is a method of imparting lubricity by coating, and a method described in British Patent No. 1143118 for imparting lubricity to a photographic material by incorporating methylphenyl silicone having a triphenyl terminal block in a protective layer. Further, as one of means for improving adhesion prevention, scratch resistance, and slipperiness, inorganic substances such as silicon dioxide, magnesium oxide, and titanium dioxide are formed on a surface layer made of a hydrophilic colloid using gelatin as a binder of a photographic material. By adding an acrylic acid or methacrylic acid alkyl ester such as polymethyl methacrylate, or a fine particle powder of an organic substance such as cellulose acetate propionate (hereinafter referred to as a matting agent) to increase the surface roughness, Methods for matting and improving adhesion prevention, scratch resistance and slipperiness are widely used.

However, in the case of using these known methods to improve the running property of a photographic film in a camera, each of them has some effect but is not sufficient, and often has other adverse effects. Once.

For example, when silicones are applied to the base backing layer, the sliding friction of the backing layer can be greatly reduced, but when actually passed through a camera, the running performance has not been much improved, and running inside the camera There were many occurrences of noise, film dust, and double images of the photographing surface image.

The present applicant has filed an application by finding that the use of a carbon black having a primary particle size of 40 μm or more improves the slipperiness during high-speed running (Japanese Patent Application No. 63-78463). Certainly, the sliding friction of the photographic light-sensitive material was reduced from low speed to high speed, and the running noise in the camera and the occurrence of double images of the photographed image were also improved. However, it has been found that carbon black having a large primary particle size has a problem that gloss is reduced and scratches are easily caused thereafter.

"Problem to be Solved by the Present Invention" A first object of the present invention is to provide a photographic light-sensitive material in which the surface of a backing layer containing carbon black (hereinafter referred to as a resin back layer) is hardly damaged.

A second object of the present invention is to provide a photographic light-sensitive material having a high gloss on the surface of the resin backing layer.

A third object is to provide a photographic light-sensitive material having improved running properties in a camera.

"Means for Solving the Problems" The object of the present invention has been achieved by using a carbon black having a primary particle size of 40 mμ or more, in which a graphitic structure is particularly developed.

That is, in a silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, the outermost layer of the backing layer has an average primary particle size of Is a carbon black of 40mμ or more, and the plasmon loss energy of carbon measured by ESCA is 26.5eV or more, or a tangent line contributing to a plane spacing of 3.58 ° or less by X-ray diffraction. This has been attained by a silver halide photographic light-sensitive material characterized in that it contains a carbon black.

As described in JIS K6221, a carbon black refers to "an aggregate of crystallites obtained by burning or thermally decomposing a compound containing a hydrocarbon or carbon in an insufficient air supply". Depending on the production method, contact black (contact the flame with iron or stone, etc.), furnace black (mass-produced by continuously pyrolyzing gaseous or liquid raw materials in a reaction furnace), thermal black (gas Raw materials are placed in a cracking furnace and are obtained by intermittent pyrolysis with an external heat source).

Although the particle size differs depending on the production method, classification is also made according to the primary particle size. For example, "Carbon Black Handbook",
According to the book publishers, published in 1984, they are classified by primary particle size as shown in the table below.

Carbon Black Association "Carbon Black Handbook"
According to (1972) etc., when carbon black is heat treated, the average spacing decreases, and the heat treatment at 2700 ~ 3000 ℃
It is known to reach a nearly constant value. The material heat-treated to such a temperature is called a graphitized carbon black (graphite carbon black), and has a shell-like structure in which the carbon layer surface is parallel to the surface, and voids are observed inside. As the graphite structure develops, the kinetic energy of the inner shell electrons of the carbon atoms that fly out by X-ray irradiation increases by π electron clouds attributed to the carbon hexagonal ring.
Weakened by electron clouds (so-called plasmon loss),
ESCA (Electron Spectrometer for Chemical Analysis
Abbreviation), the interval (loss energy) between the carbon / S peak and the plasmon peak expands.

Therefore, the degree of graphitization of the surface can be quantified by this plasmon loss energy.

Heckman, FA: Rubber Chem. And Tech. 37, 1245 (1
964), the average interplanar spacing 002, etc. can be determined by X-ray diffraction (2Q scan) to quantify the degree of graphitization.

 The measurement method will be described below.

(1) Method of measuring plasmon loss energy A pellet (5 mmφ) obtained by pressure-molding various carbon blacks with a double-sided tape is placed in a 5 mmφ sample holder using ESCA750 (manufactured by Shimadzu Corporation). 0.5 × sample chamber
Reduce the pressure to 10 ^-6 Torr or less and irradiate it with an Xray voltage of 8 kv to septum electrons C _1S
The binding energy (eV) of is measured. C _1S shows a peak around 285ev, but a small plasmon peak appears on the high energy side (ie, low kinetic energy side) of 20 to 30 eV. The integration and smoothing were performed using ESCAPAC760 (an analysis machine), and the energy difference between the two peaks was read to obtain the plasmon loss energy.

The 9th Symposium on lon sources and lon−Assist
The method described in ed Technology (1985), 247 can be referred to.

The plasmon loss energy of the carbon black used in the present invention is 26.5 eV or more.

(2) Measurement method of average plane distance ₀₀₂ Carbon black powder 0.4 g is pressure-molded and placed in a sample holder of an X-ray diffractometer (manufactured by Rigaku Corporation). The diffraction intensity is measured with a wide-angle goniometer (reflection method). The measurement conditions are as follows.

Time constant: 2 seconds Scan Speed: 2 degrees / minute Divergency Slit: 1 degree Scattering Slit: 1 degree Receiving Slit: 0.6 mn Target: Cu-Kα ray (1.5418Å) Diffraction angle of (002) plane of graphite structure Equivalent 26.
The peak position (2θ) near 0 ° was obtained, and the surface interval ₀₀₂ was calculated as follows. ₀₀₂ = ^nλ / 2siθ where λ = 1.5418 °, n = 1 The d002 of the carbon black used in the present invention is 3.58 ° or less.

The graphitized carbon black used in the present invention is not limited by the production method, but generally the above-mentioned furnace black is obtained by heat-treating a thermal black.
In the present invention, an average primary particle size of 40 mπ or more is used, but a graphitized carbon black having an average particle size of 60 to 100 μm is preferred. The layer containing the graphitized carbon black of the present invention only needs to be the outermost layer of the backing, and may serve as the resin backing layer or may be overcoated on the resin backing layer made of another carbon black. or,
Anti-halation, anti-curl and anti-static layers can also be used.

 Next, the binder of the backing layer will be described.

Generally, the backing layer containing carbon black is
It is designed so that the film is removed when entering a washing step via a pre-bath in a developing process. The pre-bath usually has a pH of 9.
25 ± 0.10 alkaline aqueous solution. The alkaline aqueous solution may contain a water-soluble organic solvent.

The binder used in the present invention is a binder that is soluble or swellable in an aqueous alkaline solution.

Specific examples include hydroxypropylmethylcellulose hexahydrophthalate, cellulose acetate hexahydrophthalate, hydroxypropylmethylcellulose acetylphthalate, and polyacrylate.

The thickness of the layer containing the graphitized carbon black of 40 μm or more is preferably 0.01 to 10 μm, particularly preferably 0.04 to 0.5 μm.

The weight ratio of graphitized carbon black / alkaline soluble binder is preferably 0.1 to 1.0, more preferably 0.3 to 1.0.
It is preferably 0.6.

 Next, the support will be described.

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, a laminate thereof, and paper. Baryta or α-olefin polymer, especially polyethylene, polypropylene, etc.
Paper coated or laminated with a polymer of α-olefin.

 Next, the silver halide emulsion will be described.

Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention. Examples of the hydrophilic colloid used as a binder for a photographic emulsion and / or another photographic component layer include gelatin, colloidal albumin, casein, carboxymethyl cellulose. , Cellulose derivatives such as hydroxyethylcellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid copolymer, polyacrylamide or derivatives / parts thereof. Hydrolyzate and the like. Optionally, two or more compatible mixtures 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-dispersible vinyl compound polymer, particularly a compound that increases the dimensional stability of a photographic material, alone or in combination ( Or a combination thereof with a hydrophilic water-permeable colloid. There are many polymers, for example, U.S. Patent Nos. 2,376,005, 2,739,137, and 2,853,457
No. 3,062,674, No. 3,411,911, No. 3,488,708,
3,525,620, 3,635,715, 3,607,290, 3,6
No. 45,740, British Patent Nos. 1,186,699 and 1,307,373. Among those descriptions, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate, Copolymers and homopolymers selected from alkoxymethacrylate, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride are generally used.

Hardening of the photographic emulsion and / or other photographic constituent layers can be carried out according to 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-chloroethyl urea),
Hydroxy-4,6-dichloro-1,3,5-triazine, and U.S. Pat. Nos. 3,288,775 and 2,732,303. British Patent No. 974,723, compounds having a reactive halogen such as those shown in 1,167,207, divinyl sulfone,
5-acetyl-1,3-diacryloylhexahydro-1,
3,5-triazine, and other U.S. Patent Nos. 3,635,718, 3,232,763, 3,490,911, 3,642,486,
Compounds having a reactive olefin such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent Nos. 2,732,316 and 2,582
N-methylol compounds as shown in US Pat. No. 6,168, etc., isocyanates as shown in U.S. Pat.No. 3,103,437, U.S. Pat.Nos. 3,017,280 and 2,983,6
Aziridine compounds as shown in No. 11, etc., U.S. Pat.No. 2,725,294, acid derivatives as shown in U.S. Pat.No. 2,725,295, carbodiimides as shown in U.S. Pat. Based compounds, U.S. Patent No.
Epoxy compounds as shown in 3,091,537 and the like, U.S. Patent No. 3,321,313, isoxazole-based compounds as shown in 3,543,292, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, Examples thereof include dioxane derivatives such as dichlorodioxane, N-carbamoylpyridinium salts, haloamidinium salts, and inorganic hardeners such as chromium ban and zirconium sulfate. In place of the above compounds, precursors in the form of a precursor, for example, an alkali metal bisulfite aldehyde adduct, a methylol derivative of hydantoin, or a nitro alcohol of a primary fatty acid may be used.

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

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and generation of fog during the production process, storage or processing of the photographic material. Those compounds are 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5
-Many compounds such as mercaptotetrazole, many heterocyclic compounds, 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 noble 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 subjected to spectral sensitization and supersensitization by using, as necessary, cyanine, merocyanine, carbocyanine and other Shinian dyes, alone or in combination, or in combination with a styryl dye or the like.

The photographic light-sensitive material of the present invention comprises, as a whitening agent, for example, stilbene, triazine, oxazole and coumarin-based compounds in a non-photosensitive photographic component layer:
For example, benzotriazole, thiazolidine, and cinnamic acid ester-based compounds may be used: Various known photographic filter dyes as light absorbers may be contained.

In addition to the compounds used in the present invention, if necessary, as other slipping agents or antiadhesives, for example, US Pat.
32305, 4042399, 3121060 and British Patent No. 1
Amides or esters of fatty acids and polyesters, such as those described in U.S. Pat.
No. 4,320,565, U.S. Pat.No.3,121,060, and water-insoluble materials as described in U.S. Pat.
Surfactants such as those described in No. 6 may be included.

The photographic light-sensitive material of the present invention may be used as an antistatic agent in photographic constituent layers such as a photographic emulsion layer, in particular, in an antistatic layer provided on the outermost side of the photographic light-sensitive material.
No. 297, No. 2,972,535, No. 2,972,536, No. 2,972,537
Nos. 2,972,538, 3,033,679, 3,072,484,
3,262,807, 3,525,621, 3,615,531, 3,6
No. 30,743, No. 3,653,906, No. 3,655,384, No. 3,655,38
6, and British Patent Nos. 1,222,154, 1,235,075, and hydrophilic polymers such as those described in U.S. Pat.Nos. 2,973,263, 2,976,148, U.S. Patent 2,584,362
No. 2,591,590, and bigumamide compounds as described in, for example, U.S. Pat.Nos. 2,639,234, 2,649,3
No. 72, 3,201,251, and 3,457,076, a sulfonic acid type anion compound, for example, phosphate esters and quaternary ammonium salts as described in U.S. Pat. For example, U.S. Pat.Nos. 2,882,157, 2,982,651, 3,399,995
Nos. 3,549,369 and 3,564,043, for example, cation compounds as described in U.S. Pat.
A nonionic compound as described in No. 5, for example, an amphoteric compound as described in U.S. Pat.No. 3,736,268, and a complex compound as described in U.S. Pat. For example, organic salts such as those described in U.S. Patent Nos. 2,717,834 and 3,655,387 can be included.

The present invention can be applied to all kinds of photographic materials regardless of black and white or color.

Silver halide emulsions include ortho emulsions, panchromatic emulsions, infrared emulsions, X-ray and other invisible light recording emulsions, color photographic emulsions such as emulsions containing color-forming couplers, emulsions containing dye developers, and dyes that can be bleached. And various silver halide photographic emulsions.

Color photographic emulsions may contain 2 or 4 equivalents of a color forming coupler. For example, an open-chain ketomethylene yellow-forming coupler such as a benzoylacetanilide type or a pivaloylacetoanilide type, a magenta color-forming coupler such as a pyrazolone type or an indazolone type, and a cyan-forming coupler such as a phenol or naphthol type are preferably used. For example, Tokiko 48
-18256, a yellow coupler represented by formula (I), JP-B-48-38416, a magenta coupler, JP-A-48-42732, a cyan coupler, U.S. Pat.
8,054, 2,449,966, 2,455,170, 2,600,788
And colored couplers described in U.S. Pat. Nos. 2,983,608 and 3,148,062, and decoupled couplers described in U.S. Pat. No. 3,227,554 can be used.

[Effects of the Invention] The photographic light-sensitive material of the present invention uses a material having a developed graphite structure as compared with a case using a conventional carbon black (however, an average primary particle size of 40mμ or more). , Scars are less likely to form. In addition, since dispersion is facilitated, coarse protrusions on the surface are reduced, and the glossiness of the coated surface is increased.

Further, the friction between the graphite layers is likely to be shifted laterally and the layer structure is developed parallel to the surface, so that the friction coefficient is further reduced.

The backing outermost layer of the present invention is particularly effective for a photographic light-sensitive material of the type which is continuously run at a high speed, such as a motion picture film.

"Example" Hereinafter, the present invention will be further described with reference to examples.

Example 1 First, a coating solution shown in Table 1 was coated at 35 CC / cm ² on a 132 μm triacetyl cellulose film prepared by the production method described in JP-A-62-115035, and applied at 90 ° C. for 3 minutes. After drying, a first backing layer was formed.

Next, 70 parts by weight of carbon black was dispersed in 100 parts by weight of hydroxypropyl methylcellulose hexahydrophthalate, and a coating solution dissolved in methanol was added at 10 CC / m ^2.
It was applied so that the solid content became 120 mg / m ² . 90 after application
C. for 3 minutes to form a second backing layer. At this time, using the carbon black shown in Table 2,
6 backing layers were formed.

An undercoat layer was provided on the side opposite to the backing layer obtained, and multilayer color light-sensitive materials (Nos. 1 to 6) each having the following composition were prepared thereon.

First layer: anti-halation layer Black colloidal silver: 0.18 g / m ² UV absorber C-1: 0.16 g / m ² UV absorber C-2: gelatin containing 0.77 g / m ² layer second layer; intermediate layer compound H-1 ····· 0.18g / m ² silver iodobromide emulsion (silver iodide 1 mol%, mean grain size 0.07) · · silver coverage (hereinafter the same) 0.15 Gelatin layer containing g / m ² Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion 0.72 g / m ² (silver iodide 6 mol%, average grain size 0.5 μ) Sensitizing dye I: 7.0 × 10 ^-5 mol sensitizing dye II per mol of silver 2.0 × 10 ^-5 mol sensitizing dye III: 1 mol of silver per mol of silver 2.8 × 10 ^-4 mol of sensitizing dye IV... 2.0 × 10 ^-5 mol per mol of silver Coupler C-3 ... 0.35 g / m ² Coupler C-4 ... gelatin layer a fourth layer including a 0.01 g / m ² coupler ^{C-5 ···· 0.01g / m 2} ; 2 red-sensitive emulsion layer Silver iodobromide emulsion ······ 1.2g / m ² (silver iodide 10 mol%, average particle size 1.2 microns) with respect to the sensitizing dye I · · · · 1 mol of silver 5.2 × 10 ^-5 mol Sensitizing dye II: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye III: 2.1 × 10 ^-4 mol per mol of silver Sensitizing dye IV · · · 1.5 × 10 per 1 mol of silver ^-5 mol coupler C-3 ···· 0.20g / m ² coupler C-4 ···· 0.01g / m ² coupler C-5 ···· 0.01 Gelatin layer containing g / m ² Fifth layer; Third red-sensitive emulsion layer Silver iodobromide emulsion 2.0 g / m ² (10 mol% of silver iodide, average grain size 1.8 μ) Dye I: 5.5 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.6 × 10 ^-5 mol per mol of silver Sensitizing dye III: 1 mol per silver 2.2 × 10 ^-5 moles of sensitizing dye IV 1.6 × 10 ^-5 moles per mole of silver Coupler C-3 ··· Gelatin layer containing 0.10 g / m ² sixth layer; intermediate layer Compound H-1 ··· Gelatin layer containing 0.02 g / m ² seventh layer; first green-sensitive emulsion layer Silver iodobromide emulsion 0.55 g / m ² (silver iodide 5 mol%, average grain size 0.4 μ) Sensitizing dye V 3.8 × 10 ^-4 mol per 1 mol of silver Sensitizing dye VI・ ・ 3.0 × 10 ^-5 mol per mol of silver Coupler C-6 ・ ・ ・ ・ 0.29g / m ² Coupler C-7 ・ ・ ・ ・ 0.04g / m ² Coupler C-8 ・ ・ ・ ・ 0.04g / m ² coupler C-4 · · · · gelatin layer eighth layer containing 0.01 g / m ^2; the second green-sensitive emulsion layer silver iodobromide emulsion · · · · · 1.0 g / m ² (silver iodide 10 Mol%, average particle size 1.2 μ) Sensitizing dye V: 2.7 × 10 ^-4 mol per mol of silver Sensitizing dye VI: 2.1 × 10 ^-5 mol per mol of silver Coupler C-9 ···· 0.04g / m ² coupler C-7 ··· 0.001g / m ² coupler C-8 ··· 0.00 Gelatin layer containing 1 g / m ² Ninth layer; Third green-sensitive emulsion layer Silver iodobromide emulsion 1.5 g / m ² (10 mol% of silver iodide, average grain size 1.8 μ) Dye V: 3.0 × 10 ^-4 mol per mol of silver Sensitizing dye VI: 2.4 × 10 ^-5 mol per mol of silver Coupler C-9: 0.03 g / m ² coupler C-8 ··· 0.001g / m gelatin layer tenth layer comprising ^2; yellow filter layer yellow colloidal · · · 0.054 g / m ² compound H-1 ····· 0.20g / m ² compound II -(2) ··· Gelatin layer containing 0.001 g / m ² 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion ··· 0.32 g / m ² (5 mol% of silver iodide, Average grain size 0.3μ) Coupler C-10: 0.68 g / m ² Coupler C-4: Gelatin layer containing 0.03 g / m ² 12th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion ···· 0.29 g / m ² (silver iodide 10 mol%, average grain size 0.8μ) Coupler C −10: gelatin layer containing 0.22 g / m ² 13th layer; third blue-sensitive emulsion layer Silver iodobromide emulsion: 0.79 g / m ² (silver iodide 14 mol%, average grain size) 1.8μ) Sensitizing dye VII ・ ・ ・ 2.3 × 10 ^-4 mol per mol of silver Coupler C-10 ・ ・ ・ Gelatin layer containing 0.19 g / m ² 14th layer; 1st protective layer UV absorber C -1 ・ ・ ・ 0.20 g / m ² UV absorber C-2 ・ ・ ・ Gelatin layer containing 0.90 g / m ² 15th layer; 2nd protective layer Polymethyl methacrylate particles (1.5 μm in diameter) ・ ・ ・ ・ 0.05 Gelatin layer containing g / m ^{2 In} addition to the above composition, a gelatin hardener C-11 and a surfactant were added to each layer. The sample manufactured as described above was used as Sample 101.

 The compounds used to make the samples are shown below.

The obtained six types of samples Nos. 1 to 6 were aged for one week and then cut into a width of 35 mm to obtain a roll film of 400 feet.

The test items were (1) static friction coefficient, (2) dynamic friction coefficient,
(3) scratch resistance and (4) glossiness.

 The respective evaluation methods and results (Table 3) are shown below.

(1) Measurement method of static friction coefficient A paper clip is used for the foot at the center of a 60-g yarobe, and it is balanced and rested so that only the clip contacts the backing layer of the film. 0.03 per sample film base with film
directed inclined at an angular velocity of deg / sec, the maximum static friction coefficient from the sample table of angle θ when the balancing toy begins to slip μ _{S =} tan
θ was determined. However, the sample is 23 ± 3 ℃, 65 ± 5% R
H, humidified for more than 10 minutes.

(2) Dynamic friction coefficient measurement method A 400-foot roll film is attached to a delivery rod, and the sample is wound through a nip roll for controlling a driving speed. A sample table was attached before the nip roll, and the dynamic friction coefficient was measured in the same manner as in (2).
The driving speed of the nip roll was 60 m / min, and the load was 200 g.

(3) Method for measuring scratch resistance A sample surface of a surface property measuring device (HEIDON-14) manufactured by Shinto Kagaku Co., Ltd. was fixed with the backing layer of the film facing upward, and a / mnR sapphire needle was attached to the attachment.
Scratching was performed at a speed of 30 cm / min with various loads, and the load at which scars began to be seen under a fluorescent lamp was determined. 10 g or more is practically required.

(4) Method for measuring glossiness The glossiness was determined at an angle of 60 ° according to JIS Z 8741 using a variable angle glossmeter VG-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.

The values of the static friction coefficient and the kinetic friction coefficient of films Nos. 1 to 6 depend on the average primary particle diameter, and the carbon black (No. 2, 3, 4, 6) having a particle diameter of 40 mμ or more has low dynamic friction coefficient . On the other hand, with respect to the scratch resistance, it can be seen that Nos. 4 to 6 having a high graphite fraction are very superior to Nos. 1 to 3 of the comparative examples. In other words, the carbon blacks of Nos. 1 to 3 have a low plasmon loss energy and a large large average plane spacing, and thus have poor scratch resistance, but have a large plasmon loss or a small plane spacing.
o.4, 5, and 6 have very good scratch resistance. However, No. 5 has a high dynamic friction coefficient due to small particle size. In comparison with Nos. 1 and 3, No. 5 and No. 6 having the same particle size had a higher graphitization and higher gloss.

Example 2 On the same support as in Example 1, the first backing layer of Example 1 was formed.

At this time, samples Nos. 1 to 4 were prepared by changing the carbon black of the coating solution to the four types of carbon blacks shown in Table 4.

An undercoat layer was provided on the side opposite to the backing layer, and a multilayer color light-sensitive material (Nos. 1 to 4) composed of the following layers was formed thereon.

First layer: Blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 0.2 mol%) Silver coating amount: 1.0 g / m ² Sensitizing dye (1): 3 per mol of silver × 10 ^-1 mol Coupler EX-1 2 × 10 ^-4 mol per mol of silver Coupler EX-2 2 × 10 ^-1 mol per 1 mol of silver Second layer: middle Layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Gelatin 0.5 g / m ² Third layer: Red-sensitive emulsion layer Silver chlorobromide emulsion (silver bromide 30 mol%) ............... 6 × 10 ^-5 mol silver coverage of 0.5 g / m ² sensitizing dye (II) with respect ............ silver mole coupler EX-3 ............ 2 per mole of silver × 10 ^-1 mol Coupler EX-4 4 × 10 ^-1 mol per mol of silver 4th layer: intermediate layer Same as 2nd layer 5th layer: green-sensitive emulsion layer Silver chlorobromide emulsion …………… Average silver coating amount 500mg Sensitizing dye (III) ……… 0.5 per mole of silver 10 ^-3 mole coupler EX-5 ............ 1 mol of silver relative to 2 × 10 ^-1 mol Layer 6: Green-sensitive emulsion layer Silver chlorobromide emulsion ........................ coated silver amount 200 mg / m ² sensitizing dye (III): 1.0 × 10 ^-3 mol per mol of silver Coupler EX-5: 2 × 10 ^-1 mol per mol of silver Seventh layer: protection Layer Gelatin: Sensitizing dyes and couplers used at 0.7 g / m ² are as follows.

The prepared photosensitive material was cut in the same manner as in Example (1), and the coefficient of static friction, the coefficient of dynamic friction, and the scratch resistance were measured. 4th result
It is shown in the table.

It can be seen that the scratch resistance of No. 4 of the present invention is superior to Nos. 1 and 2 of Comparative Examples. No. 3 has excellent scratch resistance, but has a high coefficient of friction and poor slippage due to its small particle size.

No. 4 of the present invention is excellent in both slip property and scratch resistance.

Claims (1)

(57) [Claims] In a silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, the outermost layer of the backing layer has a primary grain size. A carbon black having an average particle size of 40 mμ or more, and the plasmon loss energy of carbon measured by ESCA is 26.5 eV or more, which is attributed to a plane spacing of 3.58 ° or less by X-ray diffraction. A silver halide photographic material comprising a carbon black which gives a diffraction line.