JPH09179240A - Silver halide photographic sensitive material and its packed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a satisfactory state of a coated face, to suppress the sticking of dust, etc., to a sensitive material and to prevent input and output errors in a magnetic recording layer and the contamination of a magnetic head by incorporating a fluorine-contg. compd. into layers on both sides of a substrate and incorporating a hydroxyalkylcellulose compd. into a layer on the rear side of the substrate. SOLUTION: This sensitive material has at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer on one side of the substrate and a magnetic recording layer on the other side as the rear side, contains a specified hydroxyalkylcellulose compd. in at least one of the layers on the rear side and contains a fluorine-contg. compd., preferably different fulorine-contg. compds. in at least one of the layers on the photosensitive layer side of the substrate and at least one of the layers on the rear side, respectively. At least one of the fluorine-contg. compds. is preferably a fluorine-contg. compd. having an anionic group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material and a package thereof. More specifically, it relates to a silver halide photographic light-sensitive material that provides a good coating surface condition, improves wettability during development processing, and reduces the adhesion of dust and the like to the light-sensitive material, and a package that houses the light-sensitive material. is there.

[0002]

2. Description of the Related Art In recent years, many disclosures have been made regarding a photosensitive material having a magnetic recording layer on the back surface of a silver halide photographic photosensitive material (hereinafter sometimes simply referred to as photosensitive material or film). By applying a magnetic recording layer to the light-sensitive material, it is possible to incorporate various kinds of information into the light-sensitive material, which has been difficult in the past, by applying the technique, and it is considered necessary to introduce the information. Further, in providing a magnetic recording layer on the back surface of a light-sensitive material, the process of manufacturing the light-sensitive material is usually a photographic light-sensitive material. It is common to apply a back layer of a layer (including an undercoat layer, an antistatic layer, a slip layer, etc.) that holds various functions including a non-photosensitive magnetic recording layer on the opposite side of the support. . Further, even in the manufacturing facility for the light-sensitive material, it is possible to continuously manufacture the photosensitive layer on the opposite side of the back surface with the support interposed therebetween immediately after the coating of each back layer on the back surface. After coating the back surface, it is wound to guarantee the performance and / or stabilize the performance of each back layer, including the support, and then sorted according to the sensitive material to be manufactured. And may be supplied.

However, when coating each back layer including the magnetic recording layer on the back surface, particularly when the support is a polyester polymer support, the support and the undercoat layer, and the undercoat layer and each back layer For example, diacetyl cellulose is used as a binder in order to make the adhesiveness strong. Relatively large water droplets remain after washing, and after drying, the silicates and calcium salts contained in the washing bath,
Other components contained in the treatment liquid dry up and appear as water droplets, which are reflected during printing and impair the print quality, and this problem needs to be solved.

Further, depending on the kind and the amount of the surfactant used for the purpose of preventing static charge on the back surface when the winding step is carried out after coating each back layer on the back surface of the support, When diacetyl cellulose is used as the binder, when wound up, the back surface and the layer provided with the photosensitive layer on the opposite side (usually the undercoat layer) sandwiching the support to be applied later are in contact with each other, and the surface activity is increased. The agent diffuses and transfers,
If the amount is large, coating unevenness occurs during subsequent coating of the photosensitive layer and the surface state of the photosensitive layer deteriorates. There is a problem that dust spots sometimes occur and the surface state of the photosensitive layer is impaired.

Furthermore, in coating the photosensitive layer, the upper layer (the layer farther from the support), especially the uppermost layer, is antistatic,
Surfactants are used for the purpose of imparting slipperiness, but similar to the above, depending on the type and amount used, static marks may occur, impairing image quality, degrading print quality, and removing dust and sensitive materials. There are problems such as adhesion of processing chips, which lowers the quality of the film, causes magnetic input / output errors to the magnetic recording layer, stains on the magnetic head of the device that reads magnetic information from the sensitive material, and causes read errors. The current situation is that these problems must be resolved immediately.

On the other hand, the hydroxyalkyl cellulose compound used as a binder in the coating layer on the back surface according to the present invention is described in, for example, US Pat. No. 4,021,24.
No. 1, British Patent No. 1,435,145, Japanese Patent Laid-Open No. 2-0.
It is described in, for example, Japanese Patent Publication No. 0948. Regarding the use of a fluorine-containing compound in a light-sensitive material, for example, US Pat.
589,906, 3,754,924, 3,850,640, Japanese Patent Publication No. 57-6577, and the like, fluorine-containing surfactants, or US Pat. No. 716, British Patent No. 4,087,3
There are many known documents such as fluoropolymers described in JP-A No. 94-Japanese Patent Publication No. 52-129520. But,
A fluorine-containing compound is used for the layer constituting the back surface of the light-sensitive material having a magnetic recording layer and a layer constituting the photosensitive layer on the opposite side with the support interposed, and a hydroxyalkyl cellulose compound is used for the layer constituting the back surface. No predictable description is found for the sensitive material of the invention for a particular application.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention provides a light-sensitive material with a good coating surface condition, improves wettability at the time of development processing so that water drainage is good, and no traces of water drops are left. In particular, by reducing the adhesion of dust and debris on the back surface, magnetic input / output errors on the magnetic recording layer, dirt on the magnetic head of the device that reads magnetic information from the photosensitive material, and halogenation to prevent reading errors It is an object of the present invention to provide a silver photographic light-sensitive material and a package containing the silver halide photographic light-sensitive material.

[0008]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that in order to improve the above-mentioned coating characteristics and wettability, reduce errors in magnetic information, and maintain magnetic devices, one side of a support is photosensitive. A silver halide photographic light-sensitive material having a layer and a back side having a magnetic recording layer on the opposite side, containing a fluorine-containing compound on both sides, and using a specific hydroxyalkyl cellulose compound on the back side. The inventors have found what can be achieved and have completed the present invention. That is, the present invention comprises (1) at least one photosensitive silver halide emulsion layer and one non-photosensitive layer on one surface of a support,
In a silver halide photographic light-sensitive material having a magnetic recording layer containing magnetic particles on the back surface on the opposite side of the support,
Containing a fluorine-containing compound in the photosensitive layer and the back surface,
A silver halide photographic light-sensitive material characterized by containing a hydroxyalkyl cellulose compound on the back surface.

(2) At least one kind of the fluorine-containing compound is a compound having an anionic group
The silver halide photographic light-sensitive material as described in (1).

(3) The fluorine-containing compound used for the photosensitive layer and the back surface are not the same compound.
The silver halide photographic light-sensitive material described in (1) or (2).

(4) Inside the cartridge body 101,
A spool 103 around which a photographic light-sensitive material 102 having an emulsion layer on a support is wound is rotatably accommodated, and the tip of the photographic light-sensitive material can be freely sent out of the cartridge by the rotation of the spool. In order to feed the photographic light-sensitive material, it has a photographic light-sensitive material feed-out passage having a light-shielding mechanism, and inside the spool shaft 112 of the spool, inside the both ends of the spool shaft 112, a pair of flanges 113 with lips, respectively.
In the photographic light-sensitive material package 100 in which 114 is attached for holding the photographic light-sensitive material,
A photographic light-sensitive material package, which is the silver halide photographic light-sensitive material described in (1) to (3).

In the above embodiment (1), one side of a support is provided with a photosensitive layer having at least one photosensitive silver halide emulsion layer and a non-photosensitive layer, and the two layers are opposite to each other with the support interposed therebetween. Side back surface has a magnetic recording layer, and at least one layer constituting the back surface contains a specific hydroxyalkyl cellulose compound, and the photosensitive layers on both surfaces sandwiching a support A light-sensitive material containing a fluorine-containing compound in at least one of each of the layers constituting the back surface and the back surface. The light-sensitive material having such a structure improves the coated surface state of the back surface and the photosensitive layer. For example,
It is possible to eliminate wavy coating unevenness, etc., and at the time of development processing, dry the calcium salts, silicates, and other compounds contained in the washing water by improving drainage by washing with water in the final treatment bath. It is possible to eliminate traces of water droplets generated by solidification, reduce the adhesion of dust and processed material of the sensitive material, especially to the back surface, magnetic information input / output error and magnetic information input / output device magnetic head. It is possible to reduce stains and troubles on the part, and it is possible to achieve the object of the present invention brilliantly.

At least one kind of the fluorine-containing compound used in at least one layer on each of the photosensitive layer and the back surface is a fluorine-containing compound having an anionic group, and a light-sensitive material containing the compound is used. Is a preferred embodiment (2), and when using the fluorine-containing compound or the fluorine-containing compound having the anionic group, it is preferable that these fluorine-containing compounds used on both sides are not a photosensitive material containing the same compound. (3) The above-mentioned object of the present invention can be achieved more brilliantly by using such a preferred embodiment of the light-sensitive material.

Aspect (4) is any one of the above (1) to (3)
In the case of using a specific cartridge that accommodates two sensitive materials, it is possible to prevent the attachment of dust and the unique waste generated from the cartridge when such a cartridge is used. According to the present invention, it is possible to prevent an input / output error of magnetic information, a stain or a failure of the magnetic head portion of the magnetic information input / output device, which is one of the objects of the present invention, and to achieve the action and effect brilliantly. It is a thing.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the fluorine-containing compound used in the present invention will be described in detail. The fluorine-containing compound of the present invention is a compound containing at least three low molecular weight or high molecular weight fluorine atoms. These compounds may also contain a nonionic, anionic, cationic or betaine functional group as a hydrophilic group. Among these functional groups, anion type, cation type and betaine type are preferable, and anion type is particularly preferable.

Fluorine-containing compounds used in the present invention include, for example, British Patent Nos. 1,293,189 and 1,259,
398, U.S. Patent Nos. 3,589,906, 3,6
66,478, 3,754,924, 3,77
Nos. 5,236 and 3,850,640,
No. 48520, No. 56-114944, No. 50-16
No. 1236, No. 51-151127, No. 50-590
No. 25, No. 50-113221, No. 50-99525
No., JP-B-48-43130, JP-B-57-6577,
JP-A-58-200235 and JP-A-58-196544.
JP-A-53-84712 and JP-A-57-64228.
No., I & EC Product Research and Development 1 (3) (19
62.9) Fluorine-containing surfactants described in Oil Chemistry 12 (12) (1963), p.653 to 622, or JP-A-54-1.
No. 58222, No. 52-129520, and Japanese Patent Publication No. 49-
No. 23828, British Patent Nos. 1,352,975, 1,497,256, and U.S. Pat. No. 4,087,394.
Issue No. 4,016,125, No. 3,240,604
Nos. 3,679,411, 3,340,216
No. 3,632,534, JP-A-48-30940.
No. 52-129520, US Pat. No. 3,753.
Fluorine-containing polymers described in 3,716, etc. are preferably used.

The fluorine-containing compound particularly preferably used is a fluorine-containing surfactant and is represented by the following general formula. General formula (I) Rf-AX In the formula, Rf represents a partially fluorinated or fully fluorinated substituted or unsubstituted alkyl group, alkenyl group, or aryl group containing at least three fluorine atoms. A represents a divalent linking group, and X represents a water-soluble group. A is
Preferably, it represents an alkylene group, an arylene group or a composite group thereof, which is a divalent substituted or unsubstituted linking group interrupted by a hetero atom such as oxygen, an ester group, an amide group, a sulfonyl group or sulfur. Is also good.

X is a hydrophilic group, for example, the general formula- (BO)
_n- R ₄ polyoxyalkylene group (where B is -CH ₂ CH
_2- , -CH ₂ CH ₂ CH ₂ -or -CH ₂ CH (OH) CH _2- , n represents an average degree of polymerization of a polyoxyalkylene group, and 1 to 50
Is the number of The R ₄ are a substituted or unsubstituted alkyl group, nonionic group represented by an aryl group), a hydrophilic betaine group, for example, _{^{- + N (R 5) (}} R 6) -AlK-COO - and - ⁺ N ( R
_{5) (R 6) -AlK-} SO 3 - (AlK wherein lower alkylene group having 1 to 5 carbon atoms, such as methylene, ethylene, propylene,
Represents butylene, R ₅ and R ₆ are substituted with 1 to 8 carbon atoms,
Unsubstituted alkyl group, aryl group such as methyl group, ethyl group, benzyl group) and hydrophilic cation group,

[0019] For example _{^{- + N (R 5) (}} R 6) (R 7) · Y - ( wherein,
R ₅ , R ₆ and R ₇ have the same meanings as R ₅ above, Y ⁻ represents an anion, and is a hydroxy group, a halogen group, a sulfuric acid group, a carbonic acid group, a perchloric acid group, an organic carboxylic acid group, an organic sulfonic acid. Group, an organic sulfate group and the like), and preferably a hydrophilic anion group such as -SO ₃ M, -OSO ₃ M, -COOM, -O.
Examples include -PO (OM) ₂ and -O-PO (OM) (OA-Rf). Here, M represents an inorganic or organic cation, and is preferably a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkylamine or the like. A and Rf are as defined above. Among these fluorine-containing surface active compounds, compounds having an anionic hydrophilic group are particularly preferable.

Specific examples of typical fluorine-containing compounds of the present invention are shown below.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

[Chemical 6]

The layer to which the fluorine-containing compound of the present invention is added is
There is no particular limitation. Layers that make up the back surface,
For example, it can be used in any of the constituent layers such as an undercoat layer, an antistatic layer, a magnetic recording layer, and a sliding layer, and is a layer that constitutes a photosensitive layer on the opposite side of the back surface with a support. It can be used in any of a silver halide photosensitive layer and a non-photosensitive layer (for example, an undercoat layer, an antihalation layer, an intermediate layer, a yellow filter layer, a protective layer, etc.). Preferably, both surfaces sandwiching the support are used for a layer (upper layer) farther from the support. It is more preferable to use both layers in the layer farthest from the support (uppermost layer). The amount of the fluorine-containing compound used in the present invention is generally in the range of 0.5 to 500 mg / m ² on the photosensitive layer side of the light-sensitive material. It is preferably 1 to 200 mg, more preferably 2 to 100 mg. The back surface of the photosensitive material 1m ² per 0.
It is in the range of 05 to 30 mg. Preferably 0.1-10 mg
And more preferably in the range of 0.3 to 5 mg. If the amount used is less than the above amount, for example, adhesion of dust or debris is large, and if the amount used is more than the above amount, for example, static marks are likely to occur, and the objects of the present invention cannot be effectively achieved together. .

Further, when the fluorine-containing compound is used, it is desirable that the fluorine-containing compound is stably present in the hydroxyalkyl cellulose according to the present invention used in the back layer when it is used in the back surface, and it is stably present in gelatin in the photosensitive layer. Desirable to be present. Therefore, in the present invention, the fluorine-containing compound used on the side of the photosensitive layer on the opposite side with the back surface and the support interposed therebetween has characteristics of the respective binders (for example, hydrophilicity,
It is preferable to use different fluorine-containing compounds because of their lipophilicity. Further, since the fluorine-containing compound, which is selectively used according to the characteristics of each binder, is stably present in each binder, diffusion transfer occurs even if the photosensitive layer and the back surface come into contact with each other when wound after the production of the photosensitive material. It is difficult to do so, which is preferable.

In using the fluorine-containing compound of the present invention in a light-sensitive material, the solvent used when dissolving and adding the fluorine-containing compound is water, alcohols (methanol,
Ethanol, isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, etc., methyl, ethyl, propyl, butyl esters, etc.) , Hydrocarbon type (hexane, cyclohexane, etc.) halogenated hydrocarbon type (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbon type (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amide System (dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ether system (diethyl ether, dioxane, tetrahydrofuran, etc.), diacetone alcohol, propylene glycol monomethyl ether Which ether alcohols, glycerin, diethylene glycol, dimethyl sulfoxide and the like are preferable.

More preferably, water, methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, diacetone alcohol,
Propylene glycol monomethyl ether. More preferred are water and alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, 1-propanol and 2-propanol, and further, any mixture thereof.

The fluorine-containing compound of the present invention is not particularly limited as an additive used in the coating liquid, and examples thereof include binders, plasticizers, other surfactants other than the present invention, and other coating aids. Can be used.

Next, the hydroxyalkyl cellulose compound used in the present invention will be described. The hydroxyalkyl cellulose used in the present invention has a hydroxyl group-containing carbon atom of 2
To a cellulose derivative modified with an alkyl group having 8 to 8, preferably a cellulose derivative etherified with an alkyl group having a hydroxyl group and having 2 to 6 carbon atoms, and particularly preferably a hydroxyethyl cellulose or a hydroxypropyl cellulose derivative. The remaining hydroxyl groups of these cellulose derivatives may be modified, for example, an alkyl group (having 1 to 8 carbon atoms: methyl group, ethyl group, butyl group, etc.), aryl group (phenyl group, etc.),
Examples thereof include those modified with an acyl group (having 2 to 8 carbon atoms: acetyl group, propionyl group, etc.) and polyoxyalkylene group (for example, polyoxyethylene, polyoxypropylene group, etc.). The molecular weight of the hydroxyalkyl cellulose used in the present invention is not particularly limited, but it is preferably 3,000 to 3,000,000, particularly preferably 10,000 to 1,500,000.

The hydroxyalkyl cellulose of the present invention can be obtained, for example, from US Pat.
266,894, 3,615,422, 3,8
No. 32,173, British Patent No. 1,435,145, German Patent No. 2,116,780, Japanese Patent Publication No. 45-1843
5, JP-A-63-153538, JP-A-1-221
No. 281, JP-A-1-255858, JP-A-2-94
Those described in No. 8 etc. are preferably used.

The hydroxyalkyl cellulose used in the present invention can be generally easily synthesized by the reaction of cellulose and alkylene oxide. For example, US Pat. No. 3,392,022, Japanese Patent Publication No. 49-17367, etc. There is a detailed description. As a compound, hydroxyethyl cellulose is commercially available from Hercules, Inc. or Daicel Chemical Industry Co., Ltd., hydroxypropyl cellulose from Nippon Soda Co., Ltd., Shin-Etsu Chemical Co., Ltd., etc., and ethyl hydroxyethyl cellulose from Hercules America. It is easily available as a product. In addition, these commercially available hydroxyalkyl celluloses can be easily derivatized by ordinary chemical reactions using the starting materials. For the derivatization reaction, see, for example, Takayuki Otsu and Masayoshi Kinoshita, "Experimental Methods for Polymer Synthesis" (Kagaku Dojin, 1972), 380.
Pp. 382 to 382, edited by The Society of Polymer Science, “Functional Polymer Series 2 Synthesis and Reaction of Polymers” (Kyoritsu Shuppan, 1991) 5
The methods described on pages 07 to 512 are preferably used.

Specific examples of the hydroxyalkyl cellulose used in the present invention are shown below, but the present invention is not limited thereto. The numbers in parentheses represent the average number of the corresponding functional groups (units) introduced per one pyranose ring forming a cellulose structure. HAC-1,2-hydroxyethyl cellulose (hydroxyethyl group 1.0) HAC-2,2-hydroxyethyl cellulose (hydroxyethyl group 2.0) HAC-3,2-hydroxyethyl cellulose (hydroxyethyl group 3.0) HAC- 4,2-Hydroxypropyl cellulose (Hydroxypropyl group 1.5) HAC-5,2-Hydroxypropyl cellulose (Hydroxypropyl group 2.0) HAC-6,2-Hydroxypropyl cellulose (Hydroxypropyl group 3.3) HAC -7,2-Hydroxyethyl ethyl cellulose (hydroxyethyl group 1.25, ethyl group 1.0) HAC-8,2-hydroxypropylmethyl cellulose (hydroxypropyl group 1.0 methyl group 1.2) HAC-9,2- Hydroxy butylse Lulose (hydroxybutyl group 0.15) HAC-10,2- (2-hydroxyethoxyethyl) cellulose (2-hydroxyethoxyethyl group 1.7) HAC-11,2-hydroxyethyl-4-hydroxybutylmethylcellulose (2 -Hydroxyethyl group 1.2
8,4-hydroxybutyl group 0.06, methyl group 0.9
9) HAC-12,2-hydroxyethyl cellulose acetate (2-hydroxyethyl group 2.55, acetyl group 0.
84) HAC-13,2-hydroxypropyl-2-hydroxyethyl cellulose (2-hydroxyethyl group 1.1, 2
-Hydroxypropyl group 1.55)

The hydroxyalkyl cellulose compound of the present invention is used for the back surface of a light-sensitive material. For example, any of the back surface layers such as an undercoat layer, an antistatic layer, a magnetic recording layer and a sliding layer can be used. It can be used and is not particularly limited. It is preferably used in the layer farther from the support (upper layer) in order to improve drainage of the back surface after development processing by improving the hydrophilicity of hydroxyalkyl cellulose. It is more preferable to use at least the layer farthest from the support (uppermost layer). In addition, it should be used together with a binder used in each of the above layers constituting the back surface, for example, various resins, polymers, natural product polymers including gelatin, and mixtures thereof described in JP-A-4-219569 described below. You can

The amount of the hydroxyalkyl cellulose compound used in the present invention is generally 1 mg or more and 1000 per 1 m ² of the light-sensitive material.
It is less than or equal to mg, and can be arbitrarily used within a range in which it can be mixed and used with the above various binders. Preferably 1 to 30
It is in the range of 0 mg, more preferably in the range of 3 to 100 mg. If the amount used is less than the above amount, the water draining effect is small, and it is difficult to achieve the object of the present invention. The compatibility of the product deteriorates, resulting in a defective coated surface. The solvent of the hydroxyalkyl cellulose compound is the same as the solvent used for the binder to be mixed and used. Therefore, it is used as a uniform mixture with other binders.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposited γFe ₂ O ₃
Co-coated ferromagnetic iron oxide such as The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like.
Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. Ferromagnetic particles,
Surface treatment with silica and / or alumina or an organic material may be performed. Further, magnetic particles are disclosed in JP-A-6-1610.
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 32. Also JP
The magnetic particles described in 4-259911 and 5-81652 whose surface is coated with an inorganic or organic substance can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product weight. Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable as in the method described in JP-A-6-35092, and the combined use is also preferable. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

For the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the structure of the photographic light-sensitive material package of the present invention (hereinafter, also referred to as "photographic film cartridge") 100 of the present invention will be described with reference to the drawings. 1 is an exploded perspective view of the photographic film cartridge, FIG. 2 is a view of the photographic film cartridge viewed from the radial direction, and FIG. 3 is a view of the photographic film cartridge viewed from the radial direction at a position different from FIG. The photographic film cartridge 100 includes a cartridge body 101 in which a spool 103 around which a photographic photosensitive material (photo film) 102 is wound is rotatably housed.
A cartridge label 104 is adhered to the outer periphery of 1.
The cartridge body (patrone body) 101 is composed of upper and lower cases 105 and 106 which are two molded parts.

An upper case 105 having a gate 150,
Photo film 1 on the front side joint with the lower case 106
A film delivery port 107 (passage) for delivering 02 is formed. A lid member 108 for preventing light from entering there is behind the film delivery port 107.
And a separation claw 109 which is arranged at the back of the separation film and separates the tip of the photographic film 102. The lid member 108 has key grooves 110,
111 is formed, and the keyway 11 is formed when loaded in the camera.
The opening / closing drive shaft on the camera side that engages with 0 and 111 is rotated between a closed position that closes the film feed opening 107 and an open position that allows entry and exit of the photographic film. FIG. 5 shows a state in which the lock pawl 144 and the lid member 108 are engaged with each other and the lid member is locked at the closed position.

The spool 103 includes a pair of lip flanges 113, 1 on the inner sides of the spool shaft 112, respectively.
14 is attached, and a data disk is provided on the outside of one flange 113. The other flange 1
A use display member 123 is attached to the outer side of 14. A data label is attached to the data disk 115. A pair of flange engaging portions 1 with which the spool shaft 112, the data disk 115, and the respective flanges 113 and 114 are engaged.
17, 118, slit 11 for locking the rear end of the photographic film
9 and the use display member supporting portion 120 are formed integrally with each other, and when the spool 10 is mounted on the camera,
The drive shaft on the camera side is engaged with the key grooves 121 and 122 on the key holes provided at both ends of the drive shaft 3, and is rotated by the rotation of the drive shaft.

The use display member 123 includes a bearing portion 12
The four ratchet pawls 125, the gear 126, and the use display plate 127 are integrally formed, and these rotate integrally with the spool shaft 112.

The inside of the photographic film cartridge 100 is
A spool lock 128 is housed so as to mesh with the gear 126. This spool lock 128 is a lid member 1.
When 08 is in the closed position, the gear 126 is engaged to lock the rotation of the spool shaft 112, prevent careless feeding of the photographic film 102, and cover member 108.
When is in the open position, it disengages from the gear 126.

The pair of flanges 113 and 114 are made of a plastic material and have a thin cup-shaped cross section. The cup-shaped bottom has a flange engaging portion 117,
Round holes 129 and 130 are rotatably engaged with 118, respectively. Also, the cup-shaped opening edge 13
1, 132 are arranged to face each other when attached to the spool shaft 112, and wrap around the outermost ends of the photographic film 102 wound between them (see FIG. 6). The opening edge portions 131 and 132 allow the rotation of the spool 103 to be transmitted to the outermost periphery of the photographic film 102 and prevent the film roll 142 from being loosened.

The flange 114 is formed with four holes 133 at a predetermined pitch so as to surround the round hole 130. These holes 133 are provided with a display member 123 for use when the spool shaft 112 rotates in the photo film feeding direction.
Ratchet claw 125 of is engaged. Ratchet claw 125
Transmits the rotation of the spool shaft 112 to the flange 114 when engaged with the hole 133, and when the spool shaft 112 rotates in the photo film winding direction, the ratchet claw 125 of the use indicating member 123 causes the hole 133 to rotate. Therefore, the rotation of the spool shaft 112 is not transmitted to the flange 114.

By the way, when the photographic film 102 is fed, the spool 103 is rotated in the film feeding direction. When the spool 103 is rotated in the film feeding direction, the tip of the photographic film 102 is separated by the separation claw 10.
9 and is separated from the part wound inside the leading edge of the photographic film. When the spool 103 is subsequently rotated, since the pair of thin flanges 113 and 114 has elasticity, the pair of flanges 113 and 114 are pushed outward by the separated film tips. The leading edge of the photographic film (143 in FIG. 3) released from the wrapping is delivered to the outside of the photographic film cartridge 100 through the film delivery port. Further, when the spool shaft 112 rotates in the photo film winding direction (the direction opposite to the photo film feeding direction), the flanges 113 and 114 do not rotate integrally with the spool shaft 112. Therefore, the photographic film 102
Since the flanges 113 and 114 do not rotate when the film is wound, a slip occurs between the opening edge portions 131 and 132 and the photographic film 102, and the photographic film 102.
Slides under the opening edges 131, 132 of the flanges to wrap the photographic film.

The data disk 115 has a large-diameter fan-shaped portion 1
34 and a notch portion 135. The barcode label 116 has a shape similar to that of the data disc 115 and is attached to the data disc.

A bar code is printed on the bar code label 116 and represents various information such as the type of the photo film 102 to be stored. This information is obtained when the spool 103 is rotated in the film feeding direction.
As shown in FIG. 5, it is read by a reading sensor provided on the camera side through an opening 136 formed on one side surface of the upper case 105 to calculate an exposure value and count the number of exposures of stored photo films. Used.

In this photographic film cartridge 100,
Since even the leading edge of the photographic film 102 is stored, it is indistinguishable from the external appearance whether the unexposed photographic film or the exposed photographic film is stored. Therefore, in order to prevent the photographic film cartridge 100 containing the exposed photographic film from being reloaded into the camera and taking pictures, a post-loading prevention opening 137 is formed on one side surface of the lower case 106. There is. This one side surface is a side that is inserted toward the cartridge chamber of the camera, and a lever that enters the opening 137 is provided in the cartridge chamber.

The photographic film cartridge 100 stores the unexposed photographic film so that the large-diameter fan-shaped portion 134 is exposed in the opening 137 when the exposed photographic film is stored. If so, the stop position of the spool 103 is controlled by the drive shaft on the camera side so that the large-diameter fan-shaped portion 134 is not exposed in the opening 137. Therefore, by detecting the amount of movement of the lever, the camera side can discriminate between the exposed and unexposed photographic film.

Further, in order to allow the user to grasp from the appearance, the photo film patrone 100 is
As shown in FIG. 4, on the other side surface (the side surface opposite to the side surface on which the openings 136 and 137 are provided), an opening 138 for displaying the usage state when the unexposed photo film is stored, a part thereof is photographed. When the photographic film is stored, the usage status display opening 139, when the exposed photo film that has been photographed on all is stored, the usage status display opening 140, and when the developed photographic film is stored Of the four use status display openings 138 to 141 are formed by exposing the use display plate 127 located in the back by controlling the stop position of the spool 103. The usage status of the film is displayed.

Further, the present cartridge 100 is provided with a sensitivity detecting notch 145 used for detecting the sensitivity of the stored photographic film 102. This is a notch for detecting sensitivity with an inexpensive camera that does not have a bar code reader that reads the bar code written on the bar code label. When the sensitivity detecting notch 145 is provided as shown in FIG. 5, the stored photographic film 102 is IS.
The O sensitivity is 400 or more, and the ISO sensitivity is 400 or less when there is no notch.

Further, the present cartridge 100 is provided with a developed display tab showing whether or not the stored photographic film 102 has been developed. As shown in FIG.
The tab 147 is provided in an opening 146 provided on one side surface of the cartridge 100, and when the tab 147 is broken off, it means that the stored photographic film 102 has been developed.

Next, a typical example of the manufacturing method of the cartridge 100 of the present invention will be specifically described. Upper case / lower case 1
05, 106, the spool 103, and the lid member 108,
High-impact polystyrene resin (Denkastyrol HI-R-Q manufactured by Denki Kagaku Kogyo) is added with 1.0% by weight of carbon black (Mitsubishi Carbon Black # 950 manufactured by Mitsubishi Chemical) for imparting light-shielding properties, and lubricity. Silicone oil for use (Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone KF96H-viscosity 30,000 cs) is molded by injection molding using a resin kneaded with 1.5% by weight. The use indication member 123 is made by injection molding using a resin obtained by kneading the above-mentioned high impact polystyrene resin with 0.01% by weight of the above carbon black and 3.5% by weight of titanium oxide (CR60-2 manufactured by Ishihara Sangyo). Mold.

The flanges 113 and 114 are formed by a vacuum / pressure method using a film having a thickness of 150 μm made from a polymer alloy of polystyrene resin and polyphenylene ether resin (Zylon X9101 manufactured by Asahi Kasei).

The Patrone label 104 has a thickness of 50.
A coating for imparting printability is provided on one side of a polystyrene film containing a white pigment having a thickness of μm, an adhesive is attached to the back side thereof, and a release paper is attached to the release label to prepare an adhesive label stock. As shown in FIG. 7, on the surface of the original fabric,
Patrone ID number printing space written in numbers 15
1. A manufacturer name, a product name, a film type / sensitivity / the number of exposures, a cautionary note, and a print space 152 for a product type for printing a memo field to be filled by the user, and a bar code print space 153. First, a printing space such as a product type is printed, then half-cut processing is performed, and thereafter, a barcode and a Patrone ID number are printed to create. The bar code contains the manufacturer's name, production lot, production date, type of photo film stored, sensitivity, number of exposures,
Also, the Patrone ID number and the like are encoded and printed. The cartridge ID number is a unique number attached to each cartridge.

The bar code label 116 has a thickness of 50 μm.
A transparent vapor deposition polystyrene film with a thickness of about 400 Å is provided on one side of the transparent vapor deposition film, and an adhesive label is attached on top of it to create an adhesive label with release paper, and a bar on the opposite side of the aluminum vapor deposition layer. After printing the code, half cut the outer peripheral part, and then punch out the center to create.

The present invention is one in which the photographic light-sensitive material is housed in a package having the structure and manufacturing method exemplified above. The photographic light-sensitive material housed in such a package is less likely to have dust and dust generated from the package, which is one of the objects of the present invention, and can prevent magnetic input / output errors in the magnetic recording layer. It can be reduced.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. When the light-sensitive layer is a color light-sensitive material, it is a unit light-sensitive layer having color sensitivity to any of blue light, green light and red light. In a multilayer silver halide color photographic light-sensitive material, it is generally a unit light-sensitive material. The photosensitive layers are arranged in order from the support side, in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer.
However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB 92
As described in 3,045, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the photosensitivity becomes lower toward the support. In addition, JP-A-57-112751,
As described in JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL)
/ High-sensitivity blue-sensitive layer (BH) / High-sensitivity green-sensitive layer (GH) /
Low-sensitive green photosensitive layer (GL) / high-sensitive red photosensitive layer (RH) / low-sensitive red photosensitive layer (RL), or BH / BL / GL / GH / RH
It can be installed in the order of / RL or BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. US Pat. Nos. 4,663,271 and 4,7
05,744, 4,707,436, JP-A-62-160448, 63-8985
It is preferable to dispose the donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in No. 0, adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ", and No. 18716 (November 1979), p. 648,
Id. No. 307105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.
Glafkides, Chemie et Phisique Photographique, Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion
Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VLZ).
elikman, et al., Making and Coating Photographic E
mulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 17643.
18716 and No. 307105, and the relevant locations are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. U.S. Pat.No.4,082,553.
It is preferable to apply the silver halide grains and the colloidal silver covered with the inside of the grains described in 9-214852 to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm
, Particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

In the multilayer color light-sensitive material, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . Fine grain silver halide is
The content of silver bromide is 0 to 100 mol%, and silver chloride and / or silver iodide may be contained if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain diameter (average diameter of circles equivalent to the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
Is more preferred. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. The silver coating amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, and 4.5 g / m ^2.
Most preferred is m ² or less.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the color light-sensitive material, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by the formula (I) in paragraph 0008 of JP-A-4-274425; A coupler according to claim 1 of page 4 of EP 498,371 A1 (particularly D-35 on page 18); a coupler of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) on lines 36 to 58 of column 4, 476, 219 (especially II-17, 19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (bottom right of page II), L
-68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257 (A-4
] -63 (p.134), (A-4) -73, -75 (p.139); EP486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Cyan coupler; CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,110 (page 35) of JP-A-4-43345, 34,3
5 (page 37), (I-1), (I-17) (pages 42 to 43); A coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler; P-1, P-5 of JP-A-2-44345 (page 11)
.

Examples of couplers in which the coloring dye has a suitable diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention includes various color light-sensitive materials such as B / W sensitive materials, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Can be applied to. Also, it is suitable for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643's
28, page 647, right column to page 648, left column of the same No. 18716, and page 879 of the same No. 307105. A support using a polyester polymer is preferable. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, and 23 μm or less.
m or less is more preferable, 18 μm or less is further preferable, 16
Especially preferred is μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is
When the saturated film thickness is 90% of the maximum swollen film thickness reached when processing with color developer at 30 ° C for 3 minutes and 15 seconds, the film thickness is half that
Is defined as the time to reach. The film thickness means the film thickness measured under a humidity condition of 25 ° C and a relative humidity of 55% (2 days).
_1/2 is for Photographic Science and Engineering (Photog
r.Sci.Eng.), 19th volume, 2, 124 to 129, using a swellometer of the type described. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150-40
0% is preferable. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, the total dry film thickness of the back layer on the side opposite to the side having the emulsion layer is from 2 μm to
It is preferably 20 μm. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the RD. No. 17
Development can be carried out by a usual method described on pages 28 to 29 of 643, 651 left column to right column of No. 18716, and pages 880 to 881 of No. 307105. Next, 1 of the present invention
The processing liquid for the color negative film used in the embodiment will be described. The compounds described in JP-A-4-121739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used in the color developing solution used in the present invention. As a color developing agent for particularly rapid processing, 2-methyl-4-
[N-ethyl-N- (2-hydroxyethyl) amino]
Aniline, 2-methyl-4- [N-ethyl-N- (3-
Hydroxypropyl) amino] aniline, 2-methyl-
4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred. It is preferable to use these color developing agents in the range of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol, and further 0.02 to 1
It is preferably used in the range of 0.05 mol. The replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times the concentration.

Hydroxylamine can be widely used as a preservative for the color developing solution, but when higher preservability is required, substitution of an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine. The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, and further preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution). The color developer contains
Sulfite is used as an anti-talling agent for oxides of color developing agents. The sulfite is preferably used in an amount of 0.01 to 0.05 mol, and particularly preferably 0.02 to 0.04 mol, per liter. In the replenisher, these 1.1 ~
It is preferable to use it at a concentration of 3 times. Further, the pH of the color developing solution is preferably in the range of 9.8 to 11.0, but particularly 10.0
˜10.5 is preferable, and in the replenisher, it is preferable to set a high value in the range of 0.1 to 1.0 from these values. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishing amount of the color developing solution is preferably 80 to 1300 ml per 1 m ² of the light-sensitive material, but it is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically 80 to 6
It is preferably 00 ml, more preferably 80 to 400 ml. The bromide ion concentration in the color developing solution is usually 0.01 to 1 liter / liter.
Although it is 0.06 mol, it is preferably set to 0.015 to 0.03 mol per liter for the purpose of suppressing the fog while maintaining the sensitivity, improving the discrimination, and improving the graininess. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions. C = A-W / V C: Bromide ion concentration in the color developing replenisher (mol / liter) A: Target bromide ion concentration in the color developing solution (mol / liter) W: 1m ² of light-sensitive material is colored Amount of bromide ion eluted from the light-sensitive material to the color-developing solution when developed (mol) V: Replenishment amount of color-development replenisher for a light-sensitive material of 1 m ² (liter). When the bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 can be used as a method for increasing the sensitivity.
It is also preferable to use a development accelerator such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having a bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312 is preferred. In addition, in order to improve the biodegradability of the bleaching agent, JP-A-4-218845, 4-268552, EP588,
289, 591,934, and the compound ferric complex salts described in JP-A-6-208213 are preferably used as a bleaching agent. The concentration of these bleaching agents is 0.05 per liter of bleaching solution.
The amount is preferably from 0.3 to 0.3 mol, and particularly from the viewpoint of reducing the amount discharged to the environment, it is preferably designed from 0.1 to 0.15 mol. Further, when the bleaching solution is a bleaching solution, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, particularly 0.3 to 0.8 mol. The replenisher for the bleaching solution basically contains the concentrations of the respective components calculated by the following formula. This allows
The concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank liquid) C _P : Consumed during treatment Concentration of components V ₁ : Replenishing amount of replenisher having bleaching ability for 1 m ² of light-sensitive material (mL) V ₂ : Bring-in amount of 1 m ² of light-sensitive material from the previous bath (mL) It is preferable to contain an agent, and it is particularly preferable to contain a dicarboxylic acid having a low odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US 3,893,858. The bleaching solution is preferably replenished with 50 to 1000 ml of the bleach replenishing solution per 1 m ² of the light-sensitive material, particularly 80 to 500 ml, more preferably 100 to 300 ml. Further, it is preferable to perform aeration on the bleaching solution.

Regarding the processing liquid having fixing ability, Japanese Patent Application Laid-Open No.
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. It is preferable. In addition to the p-toluenesulfinic acid salt, the sulfinic acid described in JP-A 1-224762 can also be used.
It is preferable from the viewpoint of improving the homeostasis. It is preferable to use ammonium as a cation in a solution having a bleaching ability and a solution having a fixing ability from the viewpoint of improving desilvering ability, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. . In the bleaching, bleach-fixing and fixing steps, jet stirring described in JP-A-1-309059 is particularly preferable. The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700 ml, and particularly preferably 200, per 1 m ² of the light-sensitive material.
~ 600 ml. In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-piped to form a multistage countercurrent system. Generally, the two-tank cascade configuration is efficient because of the balance with the size of the developing machine.
The ratio of the processing time in the front tank and the rear tank is
The range of 0.5: 1 to 1: 0.5 is preferable, and the range of 0.8: 1 to 1: 0.8 is particularly preferable. In the bleach-fixing solution or the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservative property. It is preferred to use chelating agents.

Regarding the washing and stabilizing steps, the above-mentioned JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, 16th page
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used. The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 ml / m ² of the light-sensitive material, and particularly 100 to 5 ml.
00 ml, and more preferably 150 to 300 ml, are preferable ranges from the viewpoint of ensuring the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a supplement amount, thiabendazole, 1,2-benzisothiazolin-3one,
Known antifungal agents such as 5-chloro-2-methylisothiazolin-3-one and antibiotics such as gentamicin,
It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics. Also, the liquid in the washing or stabilizing liquid tank is disclosed in JP-A-3-46652, JP-A-3-53246 and JP-A-3-53246.
It is also preferable to perform the reverse osmosis membrane treatment described in 55542, 3-121448, and 3-126030 to reduce the replenishment amount. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in the Technical Report of the Institute of Invention, Technical Report 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the replenishing water for washing.

Examples of the processing agent for the color light-sensitive material used in the present invention include page 15, right column, line 15 to page 4, left column of the above-mentioned published technical report.
Those described in line 32 are preferable. Further, as a developing machine used for this, a film processor described on page 3, right column, lines 22 to 28 is preferable. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are described on page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the treating agent used in the present invention is as follows:
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

Next, the processing solution for the color reversal film used in one embodiment of the present invention will be described. Regarding the processing for the color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of Aztec Co., Ltd. It is described in detail in the line, and any of its contents can be preferably applied. In color reversal film processing, image stabilizers are included in either the conditioning bath or the final bath. Such image stabilizers include, in addition to formalin, formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable,
As the methylolazoles, N-methyloltriazole is particularly preferred. The contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water, etc. described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. Preferred color reversal film processing agents containing the above contents include E-6 processing agent of Eastman Kodak Co., Ltd. and CR-CR of Fuji Photo Film Co., Ltd.
56 treating agents.

Next, the polyester support used in the present invention will be described. For details including photosensitive materials other than the above, processing, cartridges and examples, open technical report, official technique number 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,6 is particularly preferable.
-Naphthalate. The average molecular weight ranges from about 5,000 to 200,000. Tg of the polyester of the present invention is 50 ° C.
And more preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The photosensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles of 0.8 μm or less in order to enhance the matting property. Particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, the cartridge used in the present invention may be one that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
Different patrones may be used.

There are no particular restrictions on various additives and development processing methods used when the present invention is applied to a black-and-white light-sensitive material.
Nos. 9 and 2-58041 can be preferably used.

1. Silver halide emulsion and its production method
From page 6, lower right column, bottom line 6 to page 10, upper right column, line 12 of JP-A-2-68539. 2. Chemical sensitization method: Page 10, upper right column, line 13 to lower left column 16
Line, selenium sensitization method described in JP-A-5-11389. 3. Anti-fogging agent / stabilizer: JP-A-2-68539, No. 10
Line 17 in the lower left column of the page to line 7 in the upper left column of the page 11, and line 2 in the lower left column of the page 3 to the lower left column of the page 4. 4. Spectral increasing dye: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19. 5. Surfactants / antistatic agents: JP-A-2-68539
Page 11, upper left column, line 14 to page 12, upper left column, line 9
No. 58041, page 2, lower right column, line 14 to page 5, line 12 6. Matting agent / Plasticizer / Slipper: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower right column, line 13 to page 10, lower left column 3 Line. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener: Page 12, lower left column, line 17 to page 13, upper right column 6
Line. 9. Development method: Same as page 15, upper left column, line 14 to same, lower left column 13
Line.

[0092]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV irradiation treatment and glow discharge treatment on both surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.
At this time, the coating amount of diacetyl cellulose (DAC) used for the magnetic recording layer and the sliding layer and the coating amount of the hydroxyalkyl cellulose of the present invention were changed as shown in Table 1.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. 3-2) Coating of magnetic recording layer (A) 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, major axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with 2% by weight of iron oxide with silicon oxide aluminum oxide) 0.06 g / m ² of diacetyl cellulose (DAC, see Table 1), hydroxyalkyl cellulose compound of the present invention (see Table 1) (iron oxide was dispersed in an open kneader and a sand mill), and C ₂ H ₅ as a curing agent C (CH ₂ OCONH-C ₆ H
₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agent
Was added so as to be 10 mg / m ² , respectively. Drying is 115
It was carried out at 6 ° C for 6 minutes (115 ° C for all the rollers and conveying devices in the drying zone). The color density increase of D ^B of the magnetic recording layer by X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3 × 10.
^The squareness ratio was ⁴ A / m and 65%.

3-3) Preparation of sliding layer (B) Diacetyl cellulose (DAC, see Table 1), hydroxyalkylcellulose compound of the present invention (see Table 1), C ₆ H ₁₃ C
H (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (C
H ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting it in xylene / propylene glycol monomethyl ether (1/1) at 105 ° C, pouring it into propylene glycol monomethyl ether (10 times volume) at room temperature, and then dispersing it in acetone. Thing (average particle size
0.01 μm) before adding. 15 mg / m ² of silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide coated with 15% by weight (0.15 μm)) as a polishing agent
Was added so that Drying was carried out at 115 ° C. for 6 minutes (115 ° C. for all rollers and conveying devices in the drying zone).
The sliding layer has a dynamic friction coefficient of 0.07 to 0.06 (stainless steel ball of 5 mmφ, load 100 g, speed 6 cm / min), static friction coefficient of 0.08 to 0.
07 (clip method), and the dynamic friction coefficient between the emulsion surface and the sliding layer described later was 0.14 to 0.12.

[0096]

[Table 1]

4) Coating of Photosensitive Layer First, the following emulsion was prepared. Preparation of Emulsion A 25 g of potassium bromide, 15 g of potassium iodide, 1.9 g of potassium thiocyanate and 24 g per liter of water.
While maintaining the temperature of the container containing the gelatin of 60 ° C. at 60 ° C. and vigorously stirring, a double jet of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide was added by an ordinary ammonia method to obtain an iodine content of 10 mol% and an average particle diameter of 1. A thick plate-like silver iodobromide emulsion having a thickness of 0 .mu.m and having a relatively irregular shape was prepared. After this, the temperature is reduced to 3
After the temperature was lowered to 5 ° C. and the soluble salts were removed by the coagulation sedimentation method, the temperature was raised to 40 ° C., 82 g of gelatin was added, and the pH and pAg of sodium hydroxide and sodium bromide were adjusted to 6.40 and 8.40, respectively.
Adjusted to 80. After the temperature was raised to 61 ° C., 0.95 g of 2-phenoxyethanol was added, and 213 mg of sensitizing dye-A shown below was further added. After 10 minutes 1.2 mg of sodium thiosulfate pentahydrate, 2 potassium thiocyanate
8 mg and 0.4 mg of chloroauric acid were added, and after 65 minutes, the mixture was rapidly cooled to solidify.

[0098]

Embedded image

Preparation of Emulsion B 25 g of potassium bromide, 9 g of potassium iodide, 7.6 g of potassium thiocyanate, and 24 g per liter of water.
While keeping the temperature of the container containing gelatin of 40 ° C. at 40 ° C. and vigorously stirring, double jet addition of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide was carried out by an ordinary ammonia method to obtain an iodine content of 6 mol% and an average particle diameter of 0. A 6 μm thick plate-like silver iodobromide emulsion having a relatively irregular shape was prepared. After that, the temperature was lowered to 35 ° C., the soluble salts were removed by a precipitation method, the temperature was raised to 40 ° C., 110 g of gelatin was added, and the pH was adjusted to 6.60 and pAg 8.90 with caustic soda and sodium bromide. After raising the temperature to 56 ° C., 0.8 mg of chloroauric acid, 9 mg of potassium thiocyanate and 4 mg of sodium thiosulfate were added. After 55 minutes, 180 mg of Dye-A was added,
Ten minutes later, it was rapidly cooled and solidified.

Preparation of Coated Samples The same below-mentioned layers were formed on a layer provided with an undercoat layer on the opposite side of the back surface of Samples 101 to 120 provided with the back surface shown in Table 1 with a support in between. Was applied to obtain coating samples 101 to 120.

First Layer (Antihalation Layer) Gelatin 1.0 g / m ² Compound-II 140 mg / m ² Compound-III 15 mg / m ² Dye-I 26 mg / m ² Dye-II 16 mg / m ²

[0102]

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Second layer (intermediate layer) Gelatin 0.4 g / m ² Polypotassium-p-vinylbenzene sulfonate 5 mg / m ²

Third Layer (Emulsion Layer) Emulsion B Coating Silver Amount 1.36 g / m ² Gelatin 2.0 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 15 mg / m ² C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₂₅ H 7 mg / m ² Compound-IV 1.5 mg / m ² Polypotassium-p-vinylbenzenesulfonate 50 mg / m ² Hardener 38 mg / m ²

[0105]

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Fourth Layer (Emulsion Layer) Emulsion A Coating Silver Amount 4.2 g / m ² Gelatin 5.5 g / m ² Dextran (Average Molecular Weight 150,000) 1.8 g / m ² 4-Hydroxy-6-methyl-1 , 3, 3a, 7- tetrazaindene _{^{41mg / m 2 C 18 H 35}} O (CH 2 CH 2 O) 25 H 23mg / m 2 trimethylolpropane 390 mg / m ² Poripotashiumu -p- vinyl sulfonate 88 mg / m ² Polyacrylic acid 54mg / m ²

Fifth layer (surface protective layer) Gelatin 1.2 g / m ² compound-V 13 mg / m ² compound-VI 50 mg / m ² compound-VII (Comparative compound (1)) 2.5 mg / m ² polypotassium -P-Vinylbenzene sulfonate 6 mg / m ² Polymethylmethacrylate fine particles (average particle size 3 μm) 24 mg / m ² Compound-VIII 50 mg / m ²

[0108]

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The light-sensitive material produced as described above is used for 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. A set in which these two sets were provided at intervals of 32 mm was prepared and housed in the plastic film cartridge described in FIGS. 1 to 7. An FM signal having a head gap of 5 μm and a turn count of 2,000 and capable of inputting and outputting from the coated surface side of the magnetic recording layer was used for this sample, and an FM signal was sent at a feed rate of 1,000 / s during the perforation of the photosensitive material. Recorded. F
After recording the M signal, the emulsion surface was uniformly exposed to light and subjected to the development processing described below to obtain an optical density of 2.0.

The developing conditions are as follows. Treatment liquid Temperature Time Image HPD 26.5 ° C 55 seconds Settling Super FUJIFIX DP2 26.5 ° C 76 seconds Water Rinse running water 20 ° C 95 seconds Dry (natural drying) (HPD and Super FUJIFIX DP2 are Fuji Photo Film ( Stock name)

Here, the following main materials were used for the cartridge. Upper and lower cases 105, 106 ... Polystyrene in which black carbon for light shielding is kneaded Spool shaft 112 ... Same as above Lid member 108 ... Same as above Flange 113, 114 ... Polycarbonate

The following evaluations were performed on these samples 101 to 120. (1) Water drop traces At the time when washing, which is the final bath of the development process, is completed, the sample is suspended and automatically dried (room temperature 25 ° C, relative humidity 55%), and the water drop trace is visually observed on the dried sample. It was judged. Ten samples were carried out for each of the same samples. (2) Coated surface state After washing with water, which is the final bath of the development treatment, was completed, the samples were squeezed well and dried at 50 ° C., and the optical density of these samples was measured. If the difference between the maximum density value and the minimum density value is 0.05 or more, it is regarded as a failure, and from less than 0.05 to 0.0
The range of 4 or more was considered to be a little bad, the range of 0.03 to 0.02 was good, and the range of 0.01 or less was good.

(3) Evaluation of waste generation: Zoom Cardia (manufactured by Fuji Photo Film Co., Ltd.) was modified so that the above cartridge could be loaded and a film guide was provided. The sample wound in the cartridge in this camera was ejected 100 times per cartridge, and feeding and winding were repeated 20 times each, and the amount of debris remaining on the camera pressure plate and the film guide on the opposite side was measured with an optical microscope. It was observed and evaluated in 5 steps.

(4) Magnetic reading error: Magnetic information is recorded in the international patent application publication (WO) 90-04205 before the above processing.
100 times by the method disclosed in the above publication, the output error was evaluated after the development processing was performed. Table 2 shows the results
Shown in

[0115]

[Table 2]

From the results shown in Table 2, the hydroxyalkyl cellulose compound of the present invention was used for the back surface of the light-sensitive material, and the fluorine-containing compound of the present invention was used for the back surface and the layer of the photosensitive layer farther from the support. Samples used 103-108
And 111 to 120, the traces of water droplets generated after the development process are reduced, the coated surface state is good, and the generation of dust is significantly reduced.
Moreover, it is clear that the magnetic reading error is remarkably improved, and the object of the present invention is excellently achieved. Further, the fluorine-containing compound of the present invention exhibits good effects when used on both sides (back surface and photosensitive layer) sandwiching a support, and more than when the same fluorine-containing compound is used on both sides. It can be known from the comparison between the sample 106 and the samples 109 and 110 and between the sample 106 and the samples 111 and 112 that it is preferable to use different kinds of fluorine-containing compounds properly. Furthermore, the sample 1 may have a tendency to deteriorate the coated surface when the amount of the fluorine-containing compound used increases.
It can be known when 13 to 115 and the sample 116 are compared.

Example 2 The support used in this example was prepared by the following method. 1) Support The support described in 1) of Example 1 was used. 2) Coating of antistatic layer For a polyethylene naphthalate support having a thickness of 90 μm, the treatment atmosphere pressure is 0.2 Torr, the H ₂ O partial pressure in the atmosphere gas is 75%, the discharge frequency is 30 kHz, and the output is 2500 w on each side. A glow discharge treatment was performed at a treatment intensity of 0.5 kV · A · min / m ² . On one surface of this support, a coating solution having the following composition was applied at a coating amount of 6 cc / m ² by using the bar coating method disclosed in JP-B-58-4589. Conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₅ composite oxide particle concentration 50 parts by weight 10% water dispersion liquid, secondary aggregate with primary particle size 0.005 μm and average particle size 0.05 μm) Gelatin 0.5 parts by weight Water 50 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (polymerization degree 20) oxyethylene sorbitan monolaurate 0.1 parts by weight Furthermore, after applying an antistatic layer, stainless steel with a diameter of 20 cm Wrap around the core, 110 ℃ (Tg of PEN support: 1
(19 ° C.) for 48 hours for heat history. 3) Coating of undercoat layer A coating solution having the following composition was used as an undercoat layer on the surface opposite to the surface on which the antistatic layer was coated, using a bar coating method to obtain 9 cc / m ²
Was applied at the application amount. Gelatin 1.01 part by weight Salicylic acid 0.30 part by weight Polyamide-epichlorohydrin polycondensate 0.07 part by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by weight Water 3.53 part by weight Methanol 84.57 part by weight Parts n-propanol 10.08 parts by weight 4) Coating of back layer On one surface of the above-mentioned support after the undercoating coated with the antistatic layer, as a back layer, an antistatic layer having the following composition, a magnetic recording layer, and a sliding layer. Was painted.

4-1) Coating of Magnetic Recording Layer (A) The following coating liquid for magnetic recording layer was prepared. The coating amount at that time is as shown in Table 3. (A) 3-poly (polymerization degree 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, major axis 0.14 μm, Uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with 2% by weight of iron oxide with silicon oxide oxide) (Iron oxide dispersion is open) 60 mg / m ²・ Diacetyl cellulose (DAC) (see Table 3) ・ Hydroxyalkyl cellulose of the present invention (see Table 3) ・ Millionate MR-400 (manufactured by Nippon Polyurethane Industry Co., Ltd.) 70 mg / M ² · Al ₂ O ₃ (average particle size 1.0 μm) (abrasive) 15 mg / m ²

The solvent of the coating liquid for the magnetic recording layer is 2
-A mixed solvent of butannone / cyclohexane 1/1 (wt ratio) was used. 4-2) Coating of slipping layer (B) 2-propanol / cyclohexanone 85/1 so that the coating amount of the solid content of the compound shown below is as follows.
Prepare a coating solution using a mixed solvent with a composition of 5 (wt ratio),
It was applied using a bar coater. Coating amount is 10.4cc /
It was m ^2. (B) diacetyl cellulose (DAC) (see Table 3) (see Table 3) hydroxyalkyl cellulose of the present invention _{· C 6 H 13 CH (OH} ) C 10 H 20 COOC 40 H 81 ( Compound) (lubricant) 7.5 mg / m ² · C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound) (slipper) 7.5 mg / m ² · BYK-310 (polyester-modified polydimethylsiloxane BYK Chem Japan KK) Product (sliding agent) 1.5 mg / m ² Fluorine-containing compound (see Table 3) Note that the compound and the compound are dispersions (average particle diameter 0.02) in a mixed solvent of 2-propanol / cyclohexanone.
μ) before adding.

The coating was carried out using a bar coater. The coating amount was 29.3 cc / m ² . The drying condition is 110
It was dried at 5 ° C for 5 minutes. X-light (blue filter)
The increase in D ^B color density of the magnetic recording layer was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 emu / g, and the coercive force was 7.3.
The square ratio was × 10 ⁴ A / m and 65%.

[0121]

[Table 3]

5) Coating of Photosensitive Layer Next, the samples 201 to 201 having the back surface shown in Table 3 were prepared.
218) on the opposite side of the backing layer opposite the backing layer, each layer having the following composition was multilayer coated to prepare a color negative film. These are designated as Samples 201 to 218. The multi-layer coating was carried out by simultaneously coating all 15 layers (one coating).

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (first antihalation layer) Black colloidal silver 0.08 gelatin 0.70 Second layer (second antihalation layer) Black colloidal silver 0.09 gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.20 Silver iodobromide Emulsion B Silver 0.23 Silver iodobromide Emulsion C Silver 0.10 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.2 × 10 ^-4 ExC-1 0.125 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 ExC-9 0.050 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion C Silver 0.15 Silver iodobromide emulsion D Silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.10 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.01 ExC-9 0.04 Cpd-4 0.030 Cpd-2 0.05 HBS-1 0.10 gelatin 0.75

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 3.6 × 10 ^-4 ExC-1 0.12 ExC-3 0.11 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 Cpd-4 0.020 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion F Silver 0.22 Silver iodobromide emulsion G Silver 0.35 ExS-7 6.2 × 10 ^-4 ExS-8 1.4 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExM-3 0.410 ExM-4 0.086 ExY-1 0.070 ExY-5 0.0070 HBS-1 0.30 HBS-3 0.015 Cpd-4 0.010 Gelatin 0.95

Ninth layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion G Silver 0.48 Silver iodobromide emulsion H Silver 0.48 ExS-4 4.8 × 10 ^-5 ExS-7 9.3 × 10 ^-4 ExS-8 2.1 × 10 ^-4 ExC-8 0.0020 ExC-10 0.003 ExM-3 0.115 ExM-4 0.035 ExY-1 0.008 ExY-4 0.010 ExY-5 0.0050 Cpd-4 0.011 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 gelatin 0.80

10th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 5.3 × 10 ^-4 ExS-8 1.2 × 10 ^-4 ExC-1 0.021 ExM-1 0.006 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 ExM-7 0.004 Cpd-3 0.017 Cpd-4 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

12th layer (low-sensitivity blue sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.10 Silver iodobromide emulsion L Silver 0.25 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExC-10 0.020 ExY-1 0.030 ExY-2 0.75 ExY-3 0.40 ExY-4 0.040 Cpd-2 0.10 Cpd-4 0.01 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.10

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M Silver 0.58 ExS-9 3.5 × 10 ^-4 ExY-2 0.070 ExY-3 0.070 ExY-4 0.0050 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 Cpd-4 0.02 HBS-1 0.075 Gelatin 0.55

Fourteenth layer (first protective layer) Silver iodobromide emulsion N silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.06 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 Fluorine-containing compound of the present invention See Table 3 ES-1 0.20 Gelatin 0.70

Further, W-1 to W-3, B-4 to B- are added to each layer in order to improve storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. 6, F-
1 to F-18, and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

[0139]

[Table 4]

In Table 4, (1) Emulsions J to M were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions CE, GI, and M were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. And selenium sensitization. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) When a high-pressure electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed. (5) Emulsions A to E, G, H and J to M are Rh, Ir, F
e in an optimal amount. Further, the tabularity is defined as Dc, which is the average circle equivalent diameter in the projected area of the tabular grains, and t which is the average thickness of the tabular grains.
It is defined by Dc / t ² .

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) of the aqueous solution was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The material was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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The light-sensitive material produced as described above was used in Example 1.
Same as above, cut into a width of 24 mm and 160 cm, and further provide two 2 mm square perforations at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. A set in which these two sets were provided at intervals of 32 mm was prepared and housed in the plastic film cartridge illustrated in FIGS. 1 to 7. For this sample, a head gap of 5 μm from the coated surface side of the magnetic recording layer and a head capable of inputting / outputting with a turn count of 2,000 was used to measure 1,0 between the perforations of the photosensitive material.
FM signals were recorded at a feed rate of 00 / s. After recording the FM signal, the emulsion surface was uniformly exposed for 1,000 cms, and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge.

First, the sample 201 was cut into a width of 35 mm and photographed with a camera, the following treatment was carried out for 15 days at a rate of 1 m ² per day (running treatment), and then the treatment was carried out. Each process is an automatic processor F made by Fuji Photo Film Co., Ltd.
The following was performed using P-360B. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Kokai Giho 94-4992. The treatment process and the treatment liquid composition are shown below.

(Treatment process) Process Treatment time Treatment temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 17 liters Bleach 50 seconds 38.0 ° C 5 ml 5 liters Fixed (1) 50 seconds 38.0 ° C -5 Liter settling (2) 50 seconds 38.0 ℃ 8 ml 5 liter water wash 30 s 38.0 ℃ 17 ml 3.5 liter stability (1) 20 s 38.0 ℃ −3 liter stability (2) 20 s 38.0 ℃ 15 ml 3 liter dry Drying 1 min 30 sec 60 ° C * Replenishment amount per 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1) Stabilizer is countercurrent system from (2) to (1), and overflow liquid of washing water is all Introduced in fixing (2). The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.5 ml, 2.0 ml and 2.0 ml, respectively, per 35 mm width of photosensitive material of 1.1 m. Was. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water 1.0 liter 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.0

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
Water is passed through a mixed-bed column packed with B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / L or less. Sodium isocyanurate 20mg
/ L and 150 mg / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 Water added 1.0 liter pH 8.5

The following evaluations were carried out using the samples stored in the original cartridges after the color development was completed. (1) Generation of Scrap As the above-mentioned cartridge, a cartridge made of the material described in Example 1 was used, and the cartridge was evaluated according to (2) Scrap generation evaluation of Example 1. (2) Magnetic read error This was carried out according to (3) of Example 1. The output error was evaluated after the color development process was performed. (3) Static mark Apply a constant load to the rubber roller with a wart (diameter 5 cm ² ) on the photosensitive layer side of the sample before color development processing, and move this roller back and forth at a speed of 0.5 m / sec. (1 time), followed by color development treatment, and evaluation was made by examining the change in optical density (yellow density) due to the occurrence of static. It was found that the samples in which bluish-white light was observed due to static generation in the dark room corresponded to many in which changes in optical density were certainly observed. The evaluation is made by judging whether there are some in the length of 160 cm that appear with an optical density difference of 0.05 or more. One that does not appear at all is set to 1, and one or two is 2 or 3 or more. It was evaluated as 3. (4) Water drop traces According to (1) of Example 1, a constant uniform exposure was given to the sample,
The above color development processing was performed and the same evaluation was performed. However, in the color development, after washing the final bath with water,
The sample was taken out to the outside without being dried by an automatic developing machine, and the same drying as in Example 1 was carried out and examined. Table 5 shows the results.

[0170]

[Table 5]

From the table, a sample in which the hydroxyalkyl cellulose compound of the present invention was used for the back surface of the light-sensitive material, and the fluorine-containing compound of the present invention was used for the back surface and the layer of the photosensitive layer on the side farther from the support. Nos. 203 to 207 and Samples 211 to 218 have the object of the present invention that the generation of dust is significantly reduced, the magnetic reading error is completely eliminated, the generation of static marks is improved, and the traces of water drops are reduced. It is clear that this can be achieved brilliantly even in color light-sensitive materials. It is to be noted that the use of the fluorine-containing compound is effective for achieving the above-mentioned object of the present invention by using it on both the back surface and the photosensitive layer.
It is clear from the comparison of 08 and 209. Further, regarding the use of the hydroxyalkyl cellulose compound on the back surface, it was found that the use of the compound in the outermost layer (the layer farthest from the support) effectively acts on the trace of water droplets. You can learn from It is considered that this effect improves drainage because the hydroxyalkyl cellulose compound is slightly more hydrophilic than diacetyl cellulose.

[0172]

The photosensitive layer is provided on one surface of the support,
A film containing a specific hydroxyalkyl cellulose compound on the back surface of a light-sensitive material having a magnetic recording layer on the opposite back surface of the support, and a fluorine-containing compound on both the back surface and the photosensitive layer. The material gives a good coated surface condition, reduces traces of water drops generated during drying after development processing,
In addition, it is possible to provide a silver halide photographic light-sensitive material in which dust and debris are less attached to the light-sensitive material to reduce input / output errors of magnetic information. Further, even if the sensitive material is stored in a specific cartridge and used, dust can be less attached, and a package of the sensitive material can be provided in which magnetic information input / output errors are reduced.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a photographic light-sensitive material package (photographic film cartridge) according to one embodiment of the present invention.

FIG. 2 is a diagram of the photographic light-sensitive material package as viewed from a radial direction.

FIG. 3 is a view of the photographic light-sensitive material package viewed from a radial direction at a position different from that in FIG.

FIG. 4 is a view of the photographic light-sensitive material package as viewed from one side in the axial direction thereof.

FIG. 5 is a view of the photographic light-sensitive material package as seen from the other axial direction.

FIG. 6 is a sectional view of the photographic light-sensitive material package cut along the axial direction.

FIG. 7 is a diagram showing an adhesive label stock sheet with release paper.

[Explanation of symbols]

 100 Photo Film Patrone 101 Patrone Main Body 102 Photo Film 103 Spool 104 Patrone Label 105 Upper Case 106 Lower Case 107 Film Feed Out Port 108 Lid Member 109 Separation Claw 110 Key Groove 111 Key Groove 112 Spool Shaft 113 Flange 114 Flange 115 Data Disc 116 Bar Code Label 117 Flange engaging portion 118 Flange engaging portion 119 Slit 120 Use display member support portion 121 Key groove 122 Key groove 123 Use display member 124 Bearing portion 125 Ratchet pawl 126 Gear 127 Display plate 128 Spool lock 129 Round hole 130 Round hole 131 Opening edge 132 Opening edge 133 Hole 134 Large-diameter fan-shaped portion 135 Notch 136 Opening 137 Opening 138 Displaying opening 139 Table Display opening 140 Display opening 141 Display opening 142 Film roll 143 Film tip 144 Rock paw 145 Sensitivity detection notch 146 Opening 147 Developed display tab 150 Gate 151 ID number printing space 152 Variety printing space 153 Bar code printing space

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G11B 5/633 G11B 5/633 (72) Inventor Naohiro Matsunaga 210 Nakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Within the corporation

Claims (3)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer and a non-photosensitive layer on one surface thereof, and magnetic particles on the back surface on the opposite side of the support. A silver halide photographic light-sensitive material having a magnetic recording layer containing, characterized in that it contains a fluorine-containing compound on the photosensitive layer or non-photosensitive layer and the back surface, and contains a hydroxyalkyl cellulose compound on the back surface. A silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the fluorine-containing compound is a compound having an anionic group. 3. A cartridge main body 101 is internally rotatably accommodated in a spool 103 around which a photographic light-sensitive material 102 having an emulsion layer provided on a support is wound, and the tip of the photographic light-sensitive material is freely rotated by the rotation of the spool. The cartridge main body has a photographic light-sensitive material feed-out passage having a light-shielding mechanism for feeding out the photographic light-sensitive material, and a pair of flanges 113 with lips are respectively provided inside both ends of the spool shaft 112 of the spool. , 11
4. A photographic light-sensitive material package 100 in which 4 is attached for holding a photographic light-sensitive material, wherein the photographic light-sensitive material is the silver halide photographic light-sensitive material according to claim 1 or 2. body.