JPH07119962B2 - Silver halide photographic light-sensitive material - Google Patents

Description

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 particularly to slippage during high-speed running in a camera. The present invention relates to a photographic light-sensitive material having improved characteristics and at the same time improved winding deviation (loose winding) of a long roll film.

"Prior art" Photographic light-sensitive materials usually have a surface layer with a hydrophilic colloid as a binder, such as gelatin, so the manufacturing process such as coating, drying, and processing, as well as photography, development, and baking When handling such as winding, rewinding or conveying in projection, etc., it is not preferable due to contact friction with various substances or contact friction between photographic light-sensitive materials such as between the surface of the photosensitive material and the back surface. Often affected. For example, scratches or abrasions on the surface or back surface of the photosensitive material, poor running property of the photosensitive material in a photographing device, a printer, a camera, or generation of film scraps. In particular, with regard to poor runnability, when a long film is continuously shot like a negative film for movies, if the running resistance of the film is large, camera noise, film scraps, double images, etc. may occur, which is a serious problem. Becomes In order to solve this problem, various studies have been made so far. As one of them, there is a method of reducing sliding friction of the photographic light-sensitive material so that the photographic light-sensitive material in the camera or the camera can be smoothly moved without being damaged.

For example, as disclosed in U.S. Pat. No. 3,042,522, there is a method in which a photographic emulsion layer or a protective layer contains dimethyl silicone and a specific surfactant at the same time to impart a slip property to a photographic film. A mixture of dimethyl silicone and diphenyl silicone on the back side of a photographic light-sensitive material as described in U.S. Pat.
A method of applying a fatty acid ester of a polyhydric alcohol as described in No. 1466304 to impart slipperiness, and a protective layer containing a methylphenylsilicone with a triphenyl end block to make the photographic material slippery. There is a method described in British Patent No. 1143118, which is granted. In addition, as one of means for improving adhesion prevention, scratch resistance, and slipperiness, a surface layer made of a hydrophilic colloid using gelatin as a binder of a photographic light-sensitive material is used as an inorganic substance such as silicon dioxide, magnesium oxide, or titanium dioxide. , An alkyl ester of acrylic acid or methacrylic acid such as polymethylmethacrylate, fine particle powder of an organic substance such as cellulose acetate propionate (hereinafter referred to as a matting agent) to increase the surface roughness, A method of forming a mat to improve adhesion prevention, scratch resistance, and slipperiness is widely used.

However, when it is attempted to improve the running property of a photographic film in a camera by using these known methods, some effects can be seen, but they are not enough.
In addition, there were many cases where other adverse effects occurred together.

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 passing through the camera, the running performance has not improved so much, There were many noises, film scraps, and double images in the shot image.

On the other hand, when a matting agent (fine particle powder) is applied to the surface layer (protective layer or backing layer) of a photographic light-sensitive material by a known method, a considerable improvement in adhesion prevention and scratch resistance was certainly observed. However, almost no improvement effect was obtained in terms of running performance.

"Problems 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 running property of the photographic light-sensitive material in a camera is improved.

That is, it is intended to provide a photographic light-sensitive material capable of smoothly driving a film magazine, a photo-taking machine gate, an aperture part, and the like, without causing noise and generating a double image of a photographed image.

The second purpose is the winding deviation (loose winding) that occurs when a long roll film such as a negative film for movies is loaded into the camera because the surface of the photosensitive material and the back surface are slippery.
The object is to provide a photographic light-sensitive material that does not generate

"Means for Solving Problems" The object of the present invention has been achieved by the following silver halide photographic light-sensitive material.

A support having at least one silver halide emulsion layer on one side of the support and a backing layer containing carbon black having an average primary particle size of 10 to 39 mμ on the other side, and the backing layer side A silver halide photographic light-sensitive material characterized in that a backing layer made of a carbon black having an average primary particle size of 40 mμ or more and a binder soluble or swellable in an alkaline aqueous solution is provided in the outermost layer.

The carbon black in the present invention refers to "an aggregate of crystallites which can be obtained by burning or thermally decomposing a hydrocarbon or a compound containing carbon in a state where the supply of air is insufficient" as in JIS K6221. Depending on the manufacturing method, contact black (a flame is brought into contact with iron, stone, etc.), fannes black (a mass production is carried out by continuously pyrolyzing a gas or liquid raw material in a reaction furnace), thermal black (gas Put the raw material into the decomposition furnace, and obtain it by intermittent thermal decomposition with an external heat source) etc.

Although the particle size differs depending on the manufacturing method, it is also classified according to the primary particle size. For example, according to "Carbon Black Handbook", a book publisher, (published in 1984), they are classified according to the primary particle size as shown in the table below.

The carbon black used in the present invention is not limited by the manufacturing method, but generally the furnace black method is used. In the present invention, those having an average primary particle diameter of 40 mμ or more are used as an essential requirement, but preferably the average particle diameter is 60 to 10
It is a carbon black of 0 mμ.

Next, the binder will be described.

In general, the backing layer is designed so that it is removed when it enters a water washing step through a prebath in the development process. The pre-bath is usually an aqueous alkaline solution with a pH of 9.25 ± 0.10.

Therefore, the binder used in the present invention is a binder that is soluble or swellable in an alkaline aqueous solution. The alkaline aqueous solution preferably has a pH of 8 or more. The alkaline aqueous solution may contain a water-soluble organic solvent.

Specific examples include hydroxypropylmethylcellulose hexahydrophthalate, cellulose acetate hexahydrophthalate, hydroxypropylmethylcellulose acetylphthalate and polyacrylic acid ester.

"Action" The following actions are exhibited by using such means of the present invention.

For example, silicones well known as slip agents as described in the section of the prior art and many of various surfactants have a size of 20 cm when applied to the backing layer of a photographic light-sensitive material.
It has an excellent performance of significantly reducing the friction coefficient at a sliding speed of about / min, but its running performance in the camera was not sufficient. This phenomenon is due to the fact that the friction coefficient is speed-dependent, and even if a sufficiently small friction coefficient is given in the low speed region, the friction coefficient becomes very large in the high speed region of about 60 m / min, which is usually running in the camera. Wakatsuta. That is, Amonton-Coulomb friction law FPBo
wder and D. Tabor, “The Fricion and Lubrication of
This is because Solids "Oxford (1954) does not apply.

On the other hand, when the carbon black having a primary particle size of 40 mμ or more used in the present invention is dispersed and applied in a binder, the friction coefficient is determined by the weight ratio of the carbon black to the binder and the primary particle size of the carbon black, and the value is There is no speed dependence. Therefore, a desired friction coefficient can be given from low speed to high speed.

Further, the surface provided by the present invention has a small coefficient of friction with the aperture or the like that contacts in the camera, but has a large coefficient of static friction with the surface of the photosensitive material, which is also advantageous for loose winding.

As described above, the physical properties of the backing layer can be improved by using the carbon black having an average primary particle size of 40 mμ or more.

However, if the particle size of carbon black becomes large, it is necessary to increase the content of carbon black in order to obtain the required concentration.

At this time, a method of simply increasing the carbon black and a layer containing a carbon black having an average primary particle diameter of 40 mμ or more as an outermost layer, below which an average primary particle diameter of 10 to 39 mμ There is a method of setting the content of carbon black. The latter method can easily increase the concentration depending on the carbon black content of the lower layer.

The thickness of the layer containing carbon black of 40 mμ or more is 0.0
1 to 10 μ is preferable, and 0.04 to 0.5 μ is particularly preferable. The weight ratio of carbon black / alkali soluble binder is
It is preferably 0.2 or more, more preferably 0.5 or more, and particularly preferably 0.6 to 1.0.

The thickness of the layer containing the carbon black of 10 to 39 mμ is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
The weight ratio of carbon black / alkali soluble binder is preferably 0.2 or more, more preferably 0.5 or more, and particularly preferably 0.6 to 1.0.

The photographic light-sensitive material of the present invention will be described in more detail.

In the photographic light-sensitive material of the present invention, any of those usually used as a support for a photographic light-sensitive material can be 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. Baryta or α-olefin polymer, especially polyethylene, polypropylene, etc. 2 to 10 carbon atoms
Paper coated with or laminated with a 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, carboxymethyl cellulose. , Cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide 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, U.S. Pat.Nos. 2,376,005, 2,739,137, and 2,853,457.
No., No. 3,062,674, No. 3,411,911, No. 3,488,708,
3,525,620, 3,635,715, 3,607,290, 3,6
45,740, British Patents 1,186,699, 1,307,373 and the like. Among them, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate, A copolymer or homopolymer selected from alkoxymethacrylate, 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 and others U.S. Pat. Nos. 3,288,775 and 2,732,303. Compounds having a reactive halogen as shown in British Patents 974,723 and 1,167,207, divinyl sulfone, 5
-Acetyl-1,3-diacryloylhexahydro-1,3,5
-Triazine and others U.S. Pat.Nos. 3,635,718,
3,232,763, 3,490,911, 3,642,486, and compounds having reactive olefins such as shown in British Patent 994,869, N-hydroxymethylphthalimide, and other US Patents 2,732,316, 2,586,1
N-methylol compounds such as those shown in No. 68,
Isocyanates as shown in U.S. Pat.No. 3,103,437, aziridine compounds as shown in U.S. Pat.No. 3,017,280, U.S. Pat.No. 2,983,611, U.S. Pat.Nos. 2,725,294, 2,725,295 etc. Acid derivatives as shown in U.S. Pat. No. 3,100,704 and carbodiimide compounds as shown in U.S. Pat.
Epoxy compounds such as those shown in No. 1,537,
U.S. Pat. Nos. 3,321,313 and 3,543,292, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, N-carbamoylpyridinium salts, haloamidinium. Salts and / or inorganic hardeners such as chromium 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, primary fatty acid nitroalcohols, etc. 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. The compounds are 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene,
An extremely large number of compounds such as 3-methyl-benzothiazole, 1-phenyl-5-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. Examples of the chemical sensitizer include gold compounds such as chloroaurate and gold trichloride, salts of precious metals such as platinum, palladium, iridium, rhodium and ruthenium,
Examples thereof include sulfur compounds that react with silver salts to form silver sulfide, stannous salts, amines, and other reducing substances.

If necessary, the photographic emulsion can be spectrally sensitized or supersensitized by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye.

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 a light absorber may be contained.

In addition to the compounds used in the present invention, other sliding agents or anti-adhesive agents may be used, if necessary, for example, US Pat.
305, 4042399, 3121060 and British Patent No. 144
Amides or esters and polyesters of fatty acids, such as those described in 66304, are also disclosed in British Patent 1,320,564.
No. 1,320,565; U.S. Pat. No. 3,121,060; and water-insoluble substances as described in U.S. Pat.
Surfactants as described in US Pat.

The photographic light-sensitive material of the present invention can be 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, U.S. Pat.
No. 7, No. 2,972,535, No. 2,972, 536, No. 2,972,537
No. 2, No. 2,972,538, No. 3,033,679, No. 3,072,484,
3,262,807, 3,525,621, 3,615,531, 3,6
30,743, 3,653,906, 3,655,384, 3,655,38
No. 6, and hydrophilic polymers as described in British Patents 1,222,154 and 1,235,075, for example, hydrophobic polymers as described in U.S. Pat.Nos. 2,973,263 and 2,976,148, for example U.S. Pat. No. 2,584,362,
The biguanide compounds as described in U.S. Pat. No. 2,591,590 are described in, for example, U.S. Pat.Nos. 2,639,234 and 2,649,372.
No. 3,201,251, No. 3,457,076, a sulfonic acid type anionic compound as described in, for example, U.S. Pat.
Phosphoric acid esters and quaternary ammonium salts as described in 3,317,344 and 3,514,291, for example, U.S. Patent Nos. 2,882,157, 2,982,651, and 3,399,995,
No. 3,549,369, Cationic compounds as described in 3,564,043, for example, nonionic compounds such as those described in U.S. Pat.No. 3,625,659, such as those described in U.S. Pat.No. 3,736,268 and the like. Amphoteric compounds, for example complex compounds such as those described in U.S. Pat.No. 2,647,836, for example U.S. Pat.
Organic salts such as those described in Nos. 717,834 and 3,655,387 can be included.

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 48-1
A yellow coupler represented by the general formula [I] described in No. 8256,
Magenta coupler described in JP-B-48-38416, JP-A-48-4
2732 cyan coupler, U.S. Pat.No. 2,428,054
No., No. 2,449,966, No. 2,455,170, No. 2,600,788,
Colored couplers described in U.S. Pat. Nos. 2,983,608, 3,148,062 and the like, and release suppression type couplers described in U.S. Pat. No. 3,227,554 can be used.

〔Example〕

The present invention will be further described below with reference to examples. In addition,
The "parts" added in the examples represents parts by weight.

Example 1 First, 35 CC / m ^{2 of the following} solution A was applied onto 132 μ of triacetylcellulose film produced by the production method described in JP-A-62-115035, and dried at 90 ° C. for 3 minutes, Liquid No. 1 to No. 9 shown below are further applied thereon at 10 CC / m ² and dried at 90 ° C. for 3 minutes to form a solid content as shown in Table 1 to form a backing layer. Let

An undercoat layer is provided on the opposite side of the base back surface, and a film color negative emulsion comprising an anti-halation layer, a red-sensitive emulsion layer, a gelatin intermediate layer, a green-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer and a protective layer on the undercoat layer. Were sequentially 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.

The nine kinds of samples Nos. 1 to 9 thus obtained were aged for 1 hour, and then cut into 35 mm width and 16 mm width, respectively, to obtain 400- and 1000-foot roll-shaped films.

The test items are (1) static friction coefficient, (2) dynamic friction coefficient (30
cm / min), (3) High-speed dynamic friction coefficient (6000 cm / min),
(4) Camera noise, (5) torque, and (6) measurement of the pull-out force of the core of the 1000 foot roll film. Each evaluation method is shown below.

(1) Static friction coefficient measurement method A paper clip is applied to the center foot of a 60 g gabber and the balance is kept so that only the clip comes into contact with the backing layer of the film.
0.03deg / for each table of sample film with film
The maximum static friction coefficient μ _s = tan θ was calculated from the angle θ of the sample stand when the yajibei started to slide at an angular velocity of sec. However, the sample was conditioned at 23 ± 3 ° C., 65 ± 5% RH for 10 minutes or longer.

(2) Dynamic friction coefficient measurement method HEIDON-14 type surface measuring instrument (manufactured by Shinto Kagaku Co., Ltd.) was fixed on the sample stage with the backing layer of the film facing up, and the aperture plate of the 16 mm projector was attached to the attachment. The dynamic friction coefficient obtained from the output of the load cell was measured at a speed of 30 cm / min while applying a load of 200 g.

(3) High-speed dynamic friction coefficient measuring method A 400-foot roll film is attached to a feeding rod, and a sample is wound up through a nip roll that controls a driving speed. A sample table was attached in front of this nip roll and the dynamic friction coefficient was measured in the same manner as in (2). The driving speed of the nickel roll was 60 m / min and the load was 200 g.

(4) Measurement of camera noise The cut roll-shaped film was run by an Arton camera (16 mm film camera, manufactured by Ali) to measure the noise. The noise was measured by converting the noise in the camera into a voltage using a Giorso Audio Spectrum Analyzer while running the film in the camera, and converting the voltage into decibels for comparison. Since the voltage is converted in proportion to the pitch of the sound, the lower voltage (smaller dB value) means less noise.

(5) Measurement of torque At the same time as (4), the torque of the drive motor was measured.

(6) Method for measuring the pull-out force of the winding core (core) The outer peripheral portion of a 1000-foot roll-shaped film was fixed, a load was applied to the winding core, and the load at which winding deviation occurred was measured.

The static friction coefficients of the film Nos. 1 to 9 are not so different, but the high speed dynamic friction coefficient of the film Nos. 5 to 9 of the present invention is lower than that of the films No. 1 to 4. Also, the film noise and the torque of the film Nos. 5 to 9 were small and excellent. Furthermore, it can be seen that the pulling force is high and winding slippage is unlikely to occur.

Reference Example A light-sensitive material was prepared in the same manner as in Example 1 except that only the solution A was applied (no solution B was applied) as the backing layer of the light-sensitive material for color negative for movies of Example 1. At this time, the No. 1 to No. 6 samples were prepared by changing the carbon black of the liquid A to the 6 kinds of carbon black shown in Table 2. These six types of samples were cut in the same manner as in Example 1, and the high speed dynamic friction coefficient and the camera noise were measured as in Example 1. The results are shown in Table 2.

As can be seen from Table 2, Nos. 2 to 6 of the present invention were all excellent in high-speed dynamic friction coefficient and camera noise.

Example 3 A color negative photographic light-sensitive material for movies was prepared in the same manner as in Example 2 except that the triacetyl cellulose film prepared by the solution casting method was used as the support. When the high-speed dynamic friction coefficient and the camera noise were measured in the same manner as in Example 2, substantially the same results as in Example 2 were obtained.

Claims (2)

[Claims] 1. A backing layer having at least one silver halide emulsion layer on one side of a support and carbon black having an average primary grain size of 10 to 39 mμ on the other side. Further, a silver halide photographic light-sensitive material characterized by further comprising a backing layer made of carbon black having an average primary particle size of 40 mμ or more and a binder soluble or swellable in an alkaline aqueous solution in the outermost layer on the side of the backing layer. . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is a film for motion pictures.