JPH1010674A - Manufacture of support with backing layer for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material having a superior surface state on the backing layer including a magnetic recording layer. SOLUTION: This silver halide photographic sensitive material has the backing layer on one side of the support and this support with the backing layer is manufactured by incorporating a higher fatty acid ester in the layer farthest from the support and conveying the photosensitive material after coating the support with the backing layer to the end of its drying process without any coating of the backing layer with any part of an automatic developing machine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention improves the surface condition of the backing layer of a silver halide photographic light-sensitive material, and produces a support having a backing layer for a silver halide photographic light-sensitive material having a smooth backing layer with excellent slipperiness. About the method.

[0002]

2. Description of the Related Art Various compounds have been proposed and used as a slipping agent for the uppermost layer of a silver halide light-sensitive material. These compounds are described, for example, in Research Disclosure (RD) 30710.
5 (Nov. 1989), Chapter XII. These slip agents are roughly classified into relatively high molecular weight, amorphous (wax-like) natural or synthetic compounds containing silicone compounds and polymers.
Among them, as the latter compound, higher fatty acids and salts thereof, or derivatives thereof (esters, amides)
Are known and used for photosensitive materials to give good sliding properties.

On the other hand, in the production of a photographic light-sensitive material, a method of drying after applying a coating solution is described in, for example, RD30710
5. Reference can be made to the documents in Chapter XV. As a method of applying energy for drying (mainly thermal energy), convective heat transfer from hot air, conduction and radiation are used.

However, due to the manufacturing cost and equipment cost of the photographic light-sensitive material, the drying step in the manufacturing tends to apply high heat energy to narrow the drying zone and finish the drying in a short time. In particular, the tendency is large for a backing layer having no photosensitive layer. Therefore, in the case of using the above-mentioned relatively high-molecular-weight amorphous slip agent, if high thermal energy is applied and dried, even if it is solidified in the form of a wax at around normal temperature, it will be in a molten state if it receives high thermal energy. It has been found that the state of dispersion of the slip agent in the layer is changed, which is a cause of deterioration of surface quality such as slipperiness and smoothness and production trouble.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a support having a backing layer for use in the production of a silver halide photographic light-sensitive material. When dry, the dry state is good,
An object of the present invention is to provide a method for producing a support having a backing layer for a silver halide photographic light-sensitive material having a good backing layer surface condition.

[0006]

The above objects of the present invention have been attained by the following means. (1) In a method for producing a support having a backing layer for a silver halide photographic material having a backing layer on one side of the support, a higher fatty acid ester compound is added to a layer of the backing layer furthest from the support. Producing a support having a backing layer for a silver halide photographic light-sensitive material, wherein the backing layer of the support is transported in a dry zone from the application of the backing layer to the end of drying after the application of the backing layer. Method.

(2) The method for producing a support having a backing layer for a silver halide photographic material as described in (1), wherein the higher fatty acid ester compound is represented by the general formula (I). Formula (I) (R ₁ ) _p- (COO) _q- (R ₂ ) _{r wherein} R ₁ is an alkyl group, an alkenyl group, and an alkynyl group each having 6 to 60 carbon atoms and R ₂ having _{1 to} 60 carbon atoms. , An aralkyl group or an aryl group. p, q and r each represent an integer of 1 to 6.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the higher fatty acid ester compound which is a slip agent used in the present invention will be described. The higher fatty acid ester compound used in the present invention is represented by the following general formula (I). Formula (I) (R ₁ ) _p- (COO) _q- (R ₂ ) _{r wherein} R ₁ is a substituted or unsubstituted straight chain having 6 to 60 carbon atoms and R ₂ is a substituted or unsubstituted 1 to 60 carbon atoms; A branched or cyclic alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted aryl group. p, q, and r are 1 to 6, respectively.
Represents an integer. In the present invention, the total number of carbon atoms of R ₁ and R ₂ is preferably 20 or more. Further, 30 or more is more preferable. When p and r are 2 to 6, the total of the number of carbon atoms of (R ₁ ) _p and (R ₂ ) _r is preferably 30 or more, more preferably 40 or more.

Examples of the substituent include a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acylamino group, a sulfonylamino group, and a ureido. Groups, carbamoyl, sulfamoyl, acyl, sulfonyl, sulfinyl, aryl and alkyl groups. These groups may further have a substituent. Preferred substituents are a halogen atom, a hydroxy group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a sulfonylamino group, an acyl group and an alkyl group. As the halogen atom, a fluorine atom and a chlorine atom are preferable. Alkoxy group, an alkylthio group, an alkyl group of the alkoxycarbonyl groups are the same alkyl group R ₂ described above. The amino group of the acylamino group and the sulfonylamino group may be an N-substituted amino group, and the substituent is preferably the above-mentioned alkyl group. An acylamino group, a group bonded to a carbonyl group of an acyl group and a sulfonyl group of a sulfonylamino group are an alkyl group,
Although it is an aryl group, the above-mentioned alkyl group is preferable.

Preferred examples of R ₁ and R ₂ include butyl, octyl, t-octyl, dodecyl, tetradecyl, hexadecyl, 2-hexyldecyl, octadecyl, CnH _{2n + 1} (n represents 20 to 60), eicosyl , Docosanyl, mericinyl, octenyl, myristoyl, oleyl, ersyl, phenyl, naphthyl, benzyl, nonylphenyl, dipentylphenyl, cyclohexyl, and groups having the above substituents. Further, R ₁ and R ₂ are ethylene,
It may contain a divalent group such as propylene or phenylene, or a group containing glycerin, trimethylolpropane, pentaerythritol, sorbitol or the like as a linking group.

The higher fatty acid ester compound of the present invention may be a natural product or a synthetic product. Natural products,
Alternatively, even if it is a synthetic product, synthetic compounds obtained from natural higher fatty acids or alcohols as raw materials include those having different numbers of carbon atoms, straight-chain and branched ones, and a mixture thereof. You can do nothing at all. As the compound, those which are to be the main components are shown.
Specific examples of preferred higher fatty acid ester compounds are shown below.

[0012]

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[0013]

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These compounds are described in, for example, JP-A-58-1983.
No. 90633 is partially described. In addition to the above compounds, examples of natural products include montanic acid esters and carnauba WA
X, oleostock, etc. can also be added. Most of these compounds are amorphous at ordinary temperature.

In the present invention, in addition to the higher fatty acid ester compound, other known slipping agents can be used in combination. Known slip agents include, for example, higher aliphatic amides similar to the compound represented by the general formula (I) described in US Pat. No. 4,275,146, and US Pat. No. 3,933,51.
No. 6, higher fatty acids or metal salts thereof, other higher alcohols and derivatives thereof, and polyoxyethylene alkylphenyl ether compounds. In addition, natural fats and oils, waxes and oils, such as beeswax, can also be used in combination.

Further, as a known slipping agent which can be used in combination,
Examples include commercially available or synthetically available silicone compounds. Polyorganosiloxanes are preferred among the silicone compounds. The synthesis method of these compounds and the compounds are described in German Patent 1,933.
No. 8,959, U.S. Pat. No. 2,694,637, U.S. Pat. No. 3,042,522, JP-B-51-33600.
No., JP-B-52-22040, JP-A-59-3154
No. 3, JP-A-62-203152, JP-A-62-26
9139, JP-A-60-54015, JP-A-2-3
01750, JP-A-2-11536, JP-B-3-3
2285, JP-A-6-102615 and the like.

Various commercially available silicone compounds are available from Dow Corning, USA, BYK Chemie, Germany, Shin-Etsu Chemical Co., Ltd., Toshiba Silicone Co., Ltd., Toray Silicone Co., Ltd., Nippon Unicar Co., Ltd. and Chisso Co., Ltd. Is easily available as a commercially available chemical product. Further, these commercially available silicones can be easily derivatized by ordinary chemical reactions using them as raw materials.

In the present invention, the layer farthest from the support of the backing layer (uppermost layer) contains at least one higher fatty acid ester compound of the above-mentioned slipping agent. in the range of 1 to 100 mg / m ^2. Preferably 2 to 50 mg / m ^2, in particular in the range of 5 to 30 mg / m ² is preferred. Even when the higher fatty acid ester compound is used in combination with another slip agent, the total coating amount is within the above range. When used in combination, the higher fatty acid ester compound is desirably 30% by weight or more of the total slip agent. In particular, 50% by weight or more is preferable.

In the present invention, a binder is used to carry the above-mentioned slipping agent on the uppermost layer. As the binder, known compounds, for example, various gelatins (alkali treatment, acid treatment, enzyme treatment, modification (phthalation, succination,
Such as trimellitization), denaturation, gelatin with special molecular weight distribution, etc.), substituted or unsubstituted celluloses, hydrophilic binders such as natural gum arabic and dextran, and soluble in common organic solvents and development processing solutions. Hydrophobic binders that are completely or almost insoluble in water and have film-forming properties, for example, homo- or copolymers such as polystyrene, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, cellulose diacetate, cellulose triacetate And cellulose derivatives such as cellulose nitrate and cellulose propionate; and acetal such as polyvinyl acetal, polyvinyl benzal and polyvinyl formal. These may be used in combination of two or more.

In the present invention, gelatin or a substituted or unsubstituted cellulose derivative, particularly a substituted alkyl cellulose, is preferably used as the hydrophilic binder, and a cellulose derivative is preferably used as the hydrophobic binder. In particular, use of hydroxyalkyl (alkyl group having 1 to 5 carbon atoms) celluloses and cellulose diacetate is preferable, and use of hydroxyalkyl (2 to 4 carbon atoms) cellulose is most preferable.

When using a hydrophilic binder, it is desirable to use a curing agent to make it water-insoluble or hardly soluble. In the case of various gelatins, known hardeners can be used. These are, for example, the RD30710
5. The compounds described in the literature of Chapter X can be used. For hydroxyalkyl celluloses, it is preferable to use a polyfunctional isocyanate compound having two or more isocyanate groups. By using such a curing agent, the molecular weight is increased, the hydrophilicity is reduced, and the film becomes insoluble or hardly soluble in water such as a developing solution, and film forming properties can be imparted.

Solvents for the lubricant of the higher fatty acid ester compound of the present invention include ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.) and lower fatty acid esters having 1 to 5 carbon atoms (ethyl acetate, butyl acetate, ethyl pyropionate, etc.). ), Haloalkanes (methylene dichloride, ethylene dichloride, tricrene, trichloromethane, trichloroethane, carbon tetrachloride, etc.), phenols (phenol, resorcinol, etc.), glycol derivatives (cellosolve, ethylene glycol diethyl ether, propylene glycol monomethyl ether, etc.) , Alcohols (isopropyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, etc.), benzene derivatives (benzene, toluene, Emissions, etc.), etc. ethers (dioxane), other DMF, may suitably selected conventional organic solvents such as DMSO. These can be used alone or in combination of two or more.

The slip agent of the higher fatty acid ester compound of the present invention is used by dissolving or melting the slip agent using the above organic solvent and dispersing in the binder. Those which form a homogeneous phase with the binder may be used as they are.
Those which form a heterogeneous phase with the binder are used in the form of a fine particle dispersion together with the binder. For the preparation of the fine particle dispersion, a conventionally known dispersion technique, for example, the RD
307105, and a dispersing means such as a document described in Chapter XIV. The particle size of the fine particle dispersion is in the range of 1 × 10 ^{−3 to} 10 μm. Preferably, it is in the range of 1 × 10 ^{-2 to} 1 μm. At the time of dispersion, it is preferable to use a dispersant. Known surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be appropriately used according to the purpose.
In order to further enhance the slipperiness, it is preferable to use the above-mentioned fluorine-containing ionic / nonionic surfactant. The uppermost layer may contain other auxiliary agents such as a matting agent, an abrasive, and an antifoaming agent, if necessary, in addition to the slipping agent and the above compounds.

The amount of the binder used is such that the weight ratio of total slip agent / total binder is in the range of 1 to 10 ⁴ .
Preferably from 1 to 10 ^3. In the present invention, the layer containing the slip agent of the higher fatty acid ester compound is applied to the layer (top layer) farthest from the support of the backing layer. The coating can be applied by any known coating method, for example, any of the methods described in RD307105 and the literature listed in Chapter XV.
When the structure of the backing layer is composed of a plurality of layers, the coating may be a multi-layer simultaneous coating method, or may be performed sequentially for each layer. In the production of a photographic light-sensitive material, a photographic component layer including a silver halide emulsion layer is usually provided on the undercoat layer on the opposite side of the support after the application of the backing layer.

In any of the coating methods, when the application of the uppermost layer containing the slip agent of the backing layer is completed, the support undergoes a drying step. Characterizing drying in the production of a photographic material, including the application of a backing layer, is as follows: Drying is mainly performed by convective heat transfer by hot air.・ It is drying of long web (long flexible body, support)
Roller-supported or air-supported transport is used. -The liquid that evaporates is water and organic solvents. -Depending on the binder of the coating solution, the performance of the product after drying (film properties, film surface, etc. in the backing layer) is affected by the drying process. In the initial stage of drying, the re-dissolution and flow of the binder and the compound used occur, so that the temperature and the velocity of the hot air cannot be increased without limit. And the like. Further, when the drying step is viewed from the transfer of heat and water and / or an organic solvent, the coating → set zone (the transfer of water and / or the organic solvent between the coated film and the support, the cooling of the coated film and the water and / or organic solvent). (Gelation by a solvent) → so-called drying zone → liquid content adjustment zone (water and / or organic solvent) → winding (→ storage).

Further, in the above-mentioned drying process, drying can be classified into the following three stages. Preheating period: The period during which the coated support is preheated (cooled or heated) to a certain temperature. It corresponds to the early stage of the set zone. -Constant-rate drying period: A period in which the drying speed is constant and the temperature of the coated support is almost constant. The above-mentioned so-called drying zone is the main. -Decreasing drying period: A period during which the drying speed is slow and the temperature of the coated support rises.

As a typical drying apparatus used in the drying step characterized above, a festoon (Fe) is used in which a web is hooked on a stick and conveyed and dried in a loop shape.
stoon) expression has been known for a long time. At present, the air loop type is a linear or U-shaped air loop type for conveying and drying air that is jetted from a duct of the same shape to a roller-supported web to increase space efficiency. Further, the web is wound in a helical shape around a cylindrical duct described in JP-B-43-20438, and the tension applied to the web is applied to the web in a radially inward direction. A web is floated at a position where the static pressure generated by the wind is balanced, and the web is floated in a non-contact manner and conveyed and dried. A string winding type, which is also a static pressure support type, but another type such as TEC's mild float, high float The ducts are installed alternately up and down as typified by, and the web is conveyed in a non-contact manner in a sine curve shape and dried. For example, J of JSME vol.69. N
o. 570 (1966) is a mainstream air-floating type drying apparatus. In addition, a device combining these two methods, for example, a string-winding type drying device is used for the main part of the drying process, and during a reduced-rate drying period, the device is conveyed using an air loop type roller and wound up. Is also used. The drying device after the completion of the backing layer coating of the present invention can use any of the above-described air loop type and air floating type. Preferably, it is an air floating type drying device. In addition, the drying speed in the drying device, air temperature, humidity,
It depends on the shape and arrangement of the blowout of the air jet and the air volume. In particular, if the temperature of the drying step, which is also the rate-decreasing drying period, is higher than the melting point or melting point of the slip agent used, the dispersion state of the slip agent may change (for example, coarsening) and may be destroyed (for example, sweating phenomenon). Therefore, care must be taken when setting the temperature.

According to the present invention, when a slip agent of a higher fatty acid ester compound is used for the uppermost layer of the backing layer, the web is conveyed by a roller in a drying device or the web comes into contact with a pass roller before winding. Then
The amorphous, softened slip agent that is softened by the high temperature in the drying device and changes its surface state upon contact. In order to prevent this, the present invention uses an air-floating method as a drying method and intends to maintain the effect of the slip agent of the present invention having excellent slipperiness.

The support which can be used in the present invention is, for example, R
D. No. 17643, page 28, and No. 18716, 64
From the right column on page 7 to the left column on page 648, and the above-mentioned No. 307
105, page 879. Preferred are polyester-based supports.

Next, the polyester support preferably used will be described. The details are described in the public technical bulletin, official technical report No. 94-6023 (Invention Association; 1994. 3.15). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components,
2,6-, 1,5-, 1,4 as aromatic dicarboxylic acids
-And 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the 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-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The polyester of the present invention has a Tg of 50 ° C. or more, and further has a Tg of 90 ° C.
The above is preferred.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl. 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 from 0.1 hour to 1500 hours, more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. The surface is roughened (for example,
Conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₃ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the backing layer (antistatic agent, slip agent, etc.), or after the 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, Mitsubishi Chemical's Diaresin,
The purpose can be achieved by kneading a dye or pigment commercially available for polyesters such as Kayaset manufactured by Nippon Kayaku.

The support is preferably subjected to a surface treatment in order to adhere the support to the backing layer and the light-sensitive material constituting layer. 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, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S)
-Triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ ,
TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Next, as one of the layers constituting the backing layer,
The included magnetic recording layer will be described. With a magnetic recording layer
Is an aqueous dispersion of magnetic particles in a binder or
An organic solvent-based coating solution is applied on a support. Book
The magnetic particles used in the present invention are γFe_TwoO_ThreeSuch as ferromagnetic
Iron oxide, Co-coated γFe _TwoO_Three, Co-coated magnetite, Co-containing
Magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, strong magnetic
Alloy, hexagonal Ba ferrite, Sr ferrite, Pb
Ferrite, Ca ferrite, etc. can be used. Co deposited γFe
_TwoO_ThreeCo-coated ferromagnetic iron oxide such as As shape
May be needle-shaped, rice-shaped, spherical, cubic, plate-shaped, etc.
No. The specific surface area is S_BETAt 20m^Two/ G or more is preferable,
30m^Two/ G or more is particularly preferred. Saturation magnetization of ferromagnet
(Σs) is preferably 3.0 × 10^Four~ 3.0 × 10
^FiveA / m, particularly preferably 4.0 × 10^Four~ 2.
5 × 10^FiveA / m. Ferromagnetic particles
And / or surface treatment with alumina or organic material
Is also good. Further, magnetic particles are disclosed in JP-A-6-160332.
A silane coupling agent on the surface as described in
It may be treated with a titanium coupling agent. Japanese Patent Laid-Open No. 4
-259911, 5-81652
Magnetic particles coated with organic materials can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 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 tolylene diisocyanate, 4,4 ', diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3 mol of tolylene diisocyanate)
And 1 mol of trimethylolpan) and polyisocyanates formed by condensation of these isocyanates.
7.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. 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, 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 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ³ g / m ² .
To ² g / m ² , more preferably 0.02 to 0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 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 for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 or the like is preferable.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. 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. US Pat. No. 5,336,589 and US Pat.
250,404, 5,229,259, 5,21
5,874, EP 466,130.

In the present invention, an antistatic agent is preferably used for the backing layer. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. Most preferred as the antistatic _{agent, ZnO, TiO 2, SnO 2} , Al 2 O 3, In 2 O 3, Si
Particle size of at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. 0.001 to 1.0
μm crystalline metal oxides or fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides .
The addition amount to the photographic material, 5 to 500 mg / m ² is preferably 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 1/300 to 100/1.
/ 100 to 100/5. The antistatic agent may be used as one layer constituting the backing layer or as an antistatic layer, or may be used as another layer constituting the backing layer.

The backing layer of the present invention preferably contains a matting agent. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and both may be used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
(Methacrylic acid = 9/1 or 5/5 (molar ratio)), and the particle size of polystyrene particles is in the range of 0.8 to 10 μm. The particle size distribution is preferably narrower, and it is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. Also, in order to enhance the matt property, the content is set at 0.
It is also preferable to add fine particles of 8 μm or less at the same time, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methallylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene particles (0.25 μm).
m) and colloidal silica (0.03 μm).

In the present invention, each of the constituent layers of the backing layer described above may be composed of a plurality of layers. In addition to the constituent layers described above, a layer for providing another function, for example, an antihalation layer or an intermediate layer may be provided. The support having a backing layer according to the present invention may be a transmission type photographic material such as a color photographic material such as a B / W photographic material, a color negative film for general or movie use, a color reversal film for slide or TV, and a color positive film. It is applied to. Preferably, the present invention is applied to a B / W light-sensitive material for photography and a color light-sensitive material. Further, the present invention can also be applied to a film unit with a lens described in Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication No. 3-39784.

[0040]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist 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 10
After drying 0 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 30 parts were dried.
After being melted at 0 ° C., it was extruded from a T-die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds. Thus, a PEN film having a thickness of 90 μm was obtained. The PEN film has a blue dye, a magenta dye and a yellow dye (Publication Technical Report: I-1, described in Official Technical Publication No. 94-6023,
I-4, I-6, I-24, I-26, I-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 with which a winding habit was not easily formed. The length in the width direction of the support is 14 cm.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces, and then gelatin was added to each surface at 0.1 g / m ² and sodium α- Suruhoji-2-ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04g / 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, using a bar coater ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C). 3) Coating of Back Layer An antistatic layer and a magnetic recording layer having the following composition were successively provided as a backing layer on one surface of the support after the undercoating.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
g / m ^2, it was coated with poly (polymerization degree 10) oxyethylene -p- nonylphenol 0.005 g / m ^2, and resorcin.

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / G, major axis 0.
14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g, Fe
^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 54 mg / m ² of diacetyl cellulose 1.2 g / m ² (iron oxide dispersion is open Carried out in a kneader and sand mill), C ₂ H ₅ C as hardener
(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 form a 1.2 μm-thick magnetic recording layer. Obtained. Silica particles (0.3μm) as matting agent
And aluminum oxide (0.15 μm) as an abrasive coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight)
mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 11
5 ° C). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 × 1
0 ⁴ A / m, the squareness ratio was 65%.

3-3) Preparation of Coating Solution for Uppermost Layer In order to provide a layer farthest from the support (uppermost layer) on the antistatic layer and the magnetic recording layer provided as the backing layer, the following: It was prepared on the basis of a coating solution. 15.0 g of Compound Example (6) and C ₅₀ H ₁₀₁ O- (CH
_{2 CH 2 O) - 16 H} 15.0g xylene / propylene glycol monomethyl ether (1/1 weight ratio, solvent (1) and to) was added 1.0 kg, the crude dispersion was prepared by a homomixer. 0.3 kg of the solvent (1), 6.5 kg of isopropyl alcohol (IPA) and 0.25 kg of methyl alcohol were added to the crude dispersion, and 5% by weight as a binder was further added.
80 g of an IPA solution, 60 g of a 5% by weight methyl alcohol solution as a surfactant, and 4% by weight of a silicone compound (polyester-modified dimethylpolysiloxane; BYK-310, a trade name of BYK-Chemie Japan)
75 g of IPA solution was added, and the mixture was cooled to a low temperature (about-
10 ° C.) and the average particle size is 0.01 μm by ultrasonic dispersion.
m of fine particle dispersion. This fine particle dispersion was coated with 30 g of silica particles having an average particle diameter of 0.3 μm as a matting agent and 3-polyoxyethylene (degree of polymerization 15) -propyloxytrimethoxysilane (15% by weight) as an abrasive. 30 g of aluminum oxide having a diameter of 0.15 μm was added to form a uniform dispersion (by ultrasonic dispersion), which was used as a coating liquid.

3-4) Coating of uppermost layer Using the above-mentioned coating solution, a coating rate of 50 was obtained by coating with a bar coater method so that the composition of the coating solution had the following coating amount.
m / min. Binder (hydroxypropylcellulose) 2.0 mg / m ² slip agent (Compound Example (6)) 7.5 mg / m ² slip agent (C ₅₀ H ₁₀₁ O- (CH ₂ CH ₂ O) ₁₆ -H) 7.5 mg / M ² slip agent (silicone compound, BYK-310) 1.5 mg / m ² surfactant (C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ )-(CH ₂ CH ₂ O) _n- (CH ₂ ) _4- SO ₃ Na, 1.5 mg / m ² (n ≒ 4)) Matting agent (silica particles) 15.0 mg / m ² Abrasive (aluminum oxide particles) 15.0 mg / m ²

Drying is performed by a string-winding air-floating type apparatus. The preheating period (initial setting zone) is set to a web length of 50 m, and the constant rate drying period and the reduced rate drying period are set to web lengths of 200 m and 100 m, respectively. After setting, a fixed amount of hot air at 130 ° C. was blown, and the web was dried by non-contact conveyance. The support with a backing layer manufactured as described above is referred to as Sample 101. Then, sample 1
02 and thereafter, sample 111 was prepared by replacing the exemplary compound (6) of the slip agent with another slip agent of the present invention as shown in Table 1 by an equal weight.
Up to Further, Samples 112 and after were prepared by replacing the slip agent of the present invention with a comparative slip agent shown in Chemical formula 3 by an equal weight. In these samples, the web was conveyed without any contact in the drying apparatus from the application of the uppermost layer to the winding step through the drying zone.

[0047]

[Table 1]

[0048]

Embedded image

Sample 10 of the backing layer-coated support thus prepared
1 to 116 are 3 ° C at 25 ° C and 55% relative temperature after winding.
After storage for one day, a portion was cut out from these samples and examined for slipperiness. The evaluation of the slipperiness was performed by measuring the dynamic friction coefficient. The measurement condition is that the tip is 5mm in diameter
The resistance was measured by applying a load of 100 g and sliding the ball over the backing layer at a speed of 60 cm / min. The smaller the value, the better the slipperiness. The results are shown in Table 1 above.

From the table, it is clear that the higher fatty acid ester compound of the present invention, which is represented by the general formula (I), provides excellent lubricating properties as compared with the comparative samples. The applicability was good by observing the surface of the backing layer by visual observation, but no abnormalities were observed in any of the samples.

Example 2 On the antistatic layer and the magnetic recording layer of Example 1 provided,
The drying of these samples corresponding to the samples 101 to 116 provided with the uppermost layer by applying various kinds of slip agent-containing coating liquids was carried out with the following changes. These samples were prepared at 201-216.
And A portion corresponding to the preheating period and the constant-rate drying period was a string-winding air floating system, and a portion corresponding to a web length of 100 m during the reduced-rate drying period was passed through a device using a pass roller. The pass roller is provided with rollers at the top and bottom, and the web passes between the upper roller and the lower roller. The ratio of the number of the upper roller to the number of the lower roller is 1/5, and the number of the upper roller is 100.
It is. At this time, the back layer may come into contact with the upper roller. The drying temperature is 130 ° C., the same as in Example 1.

Dye 201 which has passed through the above-mentioned drying apparatus
-216 were evaluated as follows. The evaluation was performed after the sample was stored under the same conditions as in Example 1 after coating. The judgment was made by visual observation by 10 judges. The criteria were as follows. 1: All members judged that the surface was smooth without any scratches. 2: Slight flaws and the like are slightly observed.
Man). 3: Same as above (3 to 5 persons). 4: Same as above (6 to 8 people). 5: Same as above (9 or more). Table 2 shows the results.

[0053]

[Table 2]

From the table, it can be seen that the samples 201 to 211 containing the slip agent of the present invention in the uppermost layer show the scratches on the backing layer even when the samples pass through the drying zone after application and may contact the pass roller. Example 1
In the non-contact conveyance, no flaws or the like were observed at all, whereas in this embodiment, it was observed. From this, it is clear that non-contact conveyance is preferable in the drying zone.

[0055]

According to the present invention, the layer farthest from the support of the backing layer contains a higher fatty acid ester compound as a slipping agent,
The web is conveyed without contact through a drying zone until the end of drying after coating the layer, and has a good coated surface state,
In addition, it is possible to provide a support having a backing layer for a silver halide photographic light-sensitive material which is excellent in slipperiness.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C07C 323/52 7419-4H C07C 323/52 G03C 11/16 G03C 11/16 (72) Inventor Nakanishi Masatoshi 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Masayoshi Toyoda 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A method for producing a support having a backing layer for a silver halide photographic light-sensitive material having a backing layer on one side of the support, wherein a layer of the backing layer furthest from the support is a higher fatty acid ester compound. Containing, and
A method for producing a support with a backing layer for a silver halide photographic light-sensitive material, wherein the backing layer of the support is transported in a drying zone from the application of the backing layer to the end of drying without contact. 2. The method for producing a support having a backing layer for a silver halide photographic light-sensitive material according to claim 1, wherein the higher fatty acid ester compound is represented by the general formula (I). Formula (I) (R ₁ ) _p- (COO) _q- (R ₂ ) _{r wherein} R ₁ is an alkyl group, an alkenyl group, and an alkynyl group each having 6 to 60 carbon atoms and R ₂ having _{1 to} 60 carbon atoms. , An aralkyl group or an aryl group. p, q and r each represent an integer of 1 to 6.