JPH11237712A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material having backing layers superior in conveyability and winding slip and scratching resistance in manufacturing processes and cameras and laboratory apparatuses and having a magnetic recording layer superior in abrasion resistance and winding slip. SOLUTION: This heat-developable photographic material has at leat one silver halide emulsion layer on one side of a support and on its other side at least 2 of the backing layers and the outermost backing layer has an elastic modulus of η300 kgf mm<-2> and its adjacent layer has that of >=350 kgf mm<-2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a back layer having excellent scratch resistance and curl shift.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, abbreviated as "light-sensitive material") is generally provided on a support such as glass, paper, a plastic film or paper coated with plastic, and a photosensitive silver halide emulsion layer and a photosensitive material. Depending on this, non-photosensitive layers such as an intermediate layer, a protective layer, a back layer, an antihalation layer, and an antistatic layer are coated in various combinations. Such photosensitive materials are coated, dried,
Including manufacturing processes such as processing, taking, developing processing, winding, rewinding, baking at the time of baking, various devices, machines, cameras and other materials at the time of handling such as photosensitive material or between photosensitive materials There is a problem that contact and friction occur between the surfaces, that is, between the surface on the photographic emulsion layer side and the back layer surface, and scratches occur on the back layer. In addition, small dust particles such as dust enter the camera and rub the back layer, often causing more serious failures.

As a means for solving these problems, for example, a method of providing a layer containing a slip agent in a back layer is well known. As an example using such a slipping agent, for example, an example using an organopolysiloxane in JP-A-50-117414 is disclosed in JP-A-1-161337,
JP-A-4-1750 discloses a method using a higher fatty acid or an ester thereof.

However, in recent years, the use and processing methods for photosensitive materials have been expanded (for example, rapid photographing and rapid processing), and the environment for use has been diversified in high-temperature, high-humidity atmospheres, dusty environments, and the like. In addition, there is a problem that the photosensitive material is often exposed to more severe handling conditions than before, and that contact friction and contact failure involving the surface layer of the photosensitive material are likely to occur.

[0005] In order to solve these problems, it is conceivable to increase the content of the slipping agent. In this case, however, the slippage due to excessive slippage due to poor conveyance in the manufacturing process, in the camera, in laboratory equipment, or the like is considered. However, there is a disadvantage that problems such as film meandering and winding misalignment are likely to occur.

In recent years, a magnetic recording layer is provided on a back layer of a silver halide photographic material in order to input various information, such as information obtained at the time of photographing with a camera and information obtained at the time of printing, into the photographic material. A new system called Advanced Photo System (APS) has been released. In the APS, since the back layer is rubbed by a magnetic head for inputting and outputting magnetic information, requirements for scratch resistance and the like are more severe than in the past.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a first object of the present invention is to provide a manufacturing process, a camera, transportability in laboratory equipment, and a winding shift. An object of the present invention is to provide a silver halide photographic light-sensitive material having a back layer having excellent scratch resistance and scratch resistance.

A second object of the present invention is to provide a silver halide photographic material having excellent abrasion resistance.

A third object of the present invention is to provide a silver halide photographic material having a magnetic recording layer excellent in scratch resistance and winding deviation.

[0010]

The above objects of the present invention have been attained by the following constitutions.

(1) At least one side on one side of the support
In a silver halide photographic material having a silver halide emulsion layer and at least two back layers on the other side, the outermost layer of the back layer has an elastic modulus of 300 kgf / m 2.
m ² or less, and the elastic modulus of the adjacent layer is 350 kg
f / mm ² or more, a silver halide photographic material.

(2) At least one side on one side of the support
In a silver halide photographic material having a silver halide emulsion layer and at least two back layers on the other side, the outermost layer of the back layer has an elastic modulus of 300 kgf / m 2.
m ² or less, and the light-sensitive silver halide photographic material coefficient of dynamic friction polystyrene sheet of the outermost layer of the back layer is characterized by a 0.15 to 0.40.

(3) The silver halide photographic material as described in (1) or (2) above, wherein the outermost layer of the back layer and the layer adjacent thereto are simultaneously coated.

(4) The silver halide photographic material as described in (1), (2) or (3) above, which has at least one magnetic recording layer.

Hereinafter, the present invention will be described in more detail. The outermost layer in the present invention refers to a layer (back layer) on the side opposite to the side having the silver halide emulsion layer with respect to the support (back layer).
Refers to the outermost layer capable of forming a film as viewed from the support.

Further, the adjacent layer in the present invention means a layer having a film forming ability adjacent to the inside of the outermost layer with respect to the support in the back layer. In order to make the outermost layer and its adjacent layer have a film forming ability, a binder may be contained.

The binder used in the present invention is not particularly limited, but known thermoplastic resins, radiation-curable resins, thermosetting resins, other reactive resins, hydrophilic binders and mixtures thereof can be used. it can.

Examples of the above-mentioned thermoplastic resin include vinyl polymers or copolymers, acrylic polymers or copolymers, cellulose derivatives, acetals, polyurethane resins, polyester resins, polyether resins, polyamide resins, rubber resins. Resins, silicone resins, fluorine resins, and the like can be given.

The radiation-curable resin is a resin which is cured by radiation such as an electron beam or an ultraviolet ray, and includes a maleic anhydride type, a urethane acrylic type, an ether acrylic type, an epoxy acrylic type and the like.

Examples of the thermosetting resin and other reactive resins include a phenol resin, an epoxy resin, a polyurethane-based curable resin, a urea resin, an alkyd resin, and a silicone-based curable resin.

As the hydrophilic binder, for example, water-soluble polymers, cellulose ethers, latex polymers, water-soluble polyesters, and mixtures thereof can be used.

Examples of the water-soluble polymer include gelatin, gelatin derivatives, polyvinyl alcohol, acrylic copolymers, and maleic anhydride copolymers. Examples of the cellulose ether include carboxymethyl cellulose and hydroxyethyl cellulose. Latex polymers include vinyl chloride-based copolymers, vinylidene chloride-based copolymers, acrylate-based copolymers, polyester-based copolymers, vinyl acetate-based copolymers,
Latexes such as butadiene copolymers are exemplified.

The binder may be hardened. Examples of the hardening agent that can be used include aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin, N-methylol compounds, isocyanates, aziridine compounds, and acids. Derivatives, epoxy compounds and halogen carboxaldehydes can be mentioned. In addition, an inorganic hardener can be used, and a carboxyl group-active hardener can also be used.

The hardener is usually used in an amount of 0.01 to the binder.
To 30% by weight, preferably 0.05 to 20% by weight.

In the present invention, the thickness of the outermost layer is 0.01 μm.
m to 2 μm is preferable, and 0.02 to 1.5 μm is more preferable.

In the present invention, the thickness of the adjacent layer is 0.01 μm.
m to 10 µm, preferably 0.05 µm to 2 µm, more preferably 0.10 µm to 1.5 µm.

Further, a layer having no film-forming ability may be provided as an overcoat layer outside the outermost layer. For example, there is an example in which a lubricant is applied without a binder.

The modulus of elasticity in the present invention is determined by JIS K
It can be determined by a method for measuring the tensile elastic modulus described in the tensile test method for 7113 plastics (hereinafter abbreviated as JIS method). However, the shape of the test piece such as the film thickness may be appropriately changed as needed.

When it is difficult to measure the elastic modulus by the above-described method because the layer is difficult to peel off, the conditions such as the components constituting the layer and the composition ratio are used. The elastic modulus may be measured using a film prepared in the same manner as a test piece.

When the layer is composed of a plurality of components, the elastic modulus of the present invention can be obtained by the following formula.

E ₁ = Σ (e × c) (Equation 1) where E ₁ is the elastic modulus (kgf / kgf) of the layer in the present invention.
mm ²⁾ represents, e is expressed modulus measured by JIS method alone components constituting the layer (kgf / mm ^2), c represents the volume fraction of the components. When the layer contains a component having no film-forming ability such as inorganic particles or oil, the elasticity of the component having no film-forming ability is as follows:
By measuring the elastic modulus (E ₂ ) of the composite film of the component and the binder, it can be obtained by the following formula.

E _a = (E ₂ −e _b × c _b ) / c _a (Equation 2) c _a + c _b = 1 (Equation 3) Here, e _a and c _a are components having no film-forming ability. It represents the elastic modulus and its volume fraction, e _b and c _b represents the elastic modulus and the volume fraction of the binder. Although c _b can be arbitrarily selected, it is preferable to measure e _{a while} changing the volume fraction at three or more points, and to use the average value as the elastic modulus of the component having no film-forming ability.

The elastic modulus of the outermost layer in the present invention is 300 k
gf / mm ² or less but, more preferably 280 kgf / mm ² or less, more preferably 260kgf / mm ² or less.

In the present invention, the elastic modulus of the adjacent layer is 350 k.
although gf / mm ² or more, more preferably 400 kgf / mm ² or more, 450 kgf / mm ² or more is more preferable.

In order to adjust the elastic modulus of the outermost layer and its adjacent layer, a plasticizer or inorganic particles can be added to the outermost layer and / or its adjacent layer.

The plasticizer is not particularly limited. For example, dioctyl phthalate (DOP), dibutyl phthalate (DBP), triphenyl phosphate (TP)
P), tricresyl phosphate (TCP) and the like are preferably used. These can be used alone or as a mixture.

The inorganic particles are not particularly limited, but, for example, metal oxides are preferably used. Aluminum oxide (Al ₂ O ₃ ), silicon dioxide (Si
O ₂ ), tin oxide (SnO ₂ ), vanadium pentoxide (V
₂ O ₅ ), iron oxide (Fe ₂ O ₃ ), chromium oxide (Cr
₂ O ₃ ), titanium dioxide (Ti ₂ O ₃ ), indium oxide (In ₂ O ₃ ), or a composite oxide thereof.

In the present invention, a lubricant may be added for imparting lubricity. The lubricant may be applied outside the outermost layer as an overcoat layer without a binder, or the outermost layer and / or a layer adjacent thereto may contain a lubricant.

The method of applying the lubricant without a binder is not particularly limited. For example, a method of dissolving the lubricant with a solvent or a method of emulsifying the lubricant and applying a dispersion thereof. and so on.

The method for incorporating the lubricant into the outermost layer and / or the layer adjacent thereto is not particularly limited. For example, a method in which both the binder and the lubricant are dissolved in a solvent capable of dissolving and then coating with the binder is disclosed, There is a method in which wax is dispersed in a solvent, contained in a binder, and applied as described in -270983.

Examples of the lubricant include, but are not particularly limited to, silicone oil such as polysiloxane, fine powder such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, higher fatty acid derivatives, and fluorocarbons. These can be used alone or as a mixture.

The amount of the lubricant applied is not particularly limited. For example, the lubricant is applied so that the dynamic friction coefficient of the back layer with respect to the polystyrene plate falls within the range of 0.15 to 0.40. Preferably, it is applied so as to fall within the range of 0.20 to 0.35.

An antistatic agent can be added to the outermost layer and / or its adjacent layer in order to prevent generation of static marks and adhesion of dust due to static electricity.

Examples of the antistatic agent include a conductive polymer and an inorganic metal oxide.

The conductive polymer is not particularly limited, and may be any of anionic, cationic, amphoteric and nonionic. Among them, preferred are anionic and cationic. More preferred are sulfonic acids and carboxylic acids for anionic and tertiary amines for cationic,
It is a quaternary ammonium-based polymer or latex.

These conductive polymers include, for example, anionic polymers or latexes described in JP-B-52-25251, JP-A-51-29923 and JP-B-60-48024, and JP-B-57-18176 and JP-B-57-18176. -5
Nos. 6059 and 58-56856; U.S. Pat.
18,231 and the like. Examples of the inorganic metal oxide include crystalline oxide particles as disclosed in JP-A-56-143431, amorphous stannic oxide sol as disclosed in JP-B-35-6616, and Kaisho 55
Amorphous vanadium pentoxide described in -5982,
An alumina sol having an electrolyte as disclosed in Japanese Patent Publication No. 57-12979 may be used.

Further, a matting agent may be added to the outermost layer and / or its adjacent layer in order to provide a function such as adhesion prevention.

The matting agent is not particularly limited, and may be inorganic or organic, or may be a mixture of two or more. As the inorganic matting agent, for example, silicon dioxide, aluminum oxide,
Barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate and the like can be mentioned.

Examples of the compound used in the organic matting agent include acrylic esters, acrylic acids,
Polymers or copolymers such as styrenes and vinyl esters are exemplified. Also, divinylbenzene, N, N '
-Adding a crosslinking agent such as methylenebisacrylamide
A copolymer having a three-dimensional network structure may be used.

Next, the magnetic recording layer will be described. The magnetic fine powder used in the magnetic recording layer of the present invention is not particularly limited. For example, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic Powders and the like can be used. Methods for producing these magnetic powders are known, and the magnetic powders used in the present invention can be produced according to known methods.

The shape and size of the magnetic powder are not particularly limited, and can be widely used. The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape, and the like, but the needle shape and the plate shape are preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited. The magnetic powder may be surface-treated. The pH of the magnetic powder is not particularly limited, but is preferably in the range of 5 to 10.

Practically, the coating amount of the magnetic powder is 0.0
01 to 3 g / m ² , and more preferably 0.01 to 1
g / m ² .

As the binder used for the magnetic recording layer,
Conventionally known thermoplastic resins, radiation-curable resins, thermosetting resins, other reactive resins, hydrophilic resins, and mixtures thereof, which are conventionally used for magnetic recording media, can be used.

Examples of the thermoplastic resin include vinyl polymers or copolymers, acrylic polymers or copolymers, cellulose esters, acetals, polyurethane resins, polyester resins, polyether resins, polyamide resins and rubber resins. Resins, silicone resins, fluorine resins, and the like can be given.

The radiation-curable resin is a resin which is cured by radiation such as an electron beam or an ultraviolet ray, and includes a maleic anhydride type, a urethane acrylic type, an ether acrylic type and an epoxy acrylic type.

Examples of the thermosetting resin and other reactive resins include a phenol resin, an epoxy resin, a polyurethane-based curable resin, a urea resin, an alkyd resin, and a silicone-based curable resin.

As the hydrophilic binder, for example, a water-soluble polymer, a cellulose ether, a latex polymer, a water-soluble polyester, and a mixture thereof can be used.

Examples of the water-soluble polymer include gelatin, gelatin derivatives, polyvinyl alcohol, acrylic acid-based copolymers, and maleic anhydride copolymers. Examples of the cellulose ether include carboxymethyl cellulose and hydroxyethyl cellulose. Latex polymers include vinyl chloride-based copolymers, vinylidene chloride-based copolymers, acrylate-based copolymers, polyester-based copolymers, vinyl acetate-based copolymers,
Latexes such as butadiene copolymers are exemplified.

Preferably, the binder of the magnetic layer contains cellulose ester as a main component, and cellulose diacetate is particularly preferred.

The binder may be hardened. Examples of the hardening agent that can be used include aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin, N-methylol compounds, isocyanates, aziridine compounds, and acids. Derivatives, epoxy compounds and halogen carboxaldehydes can be mentioned. In addition, an inorganic hardener can be used, and further, a carboxyl group-active hardener can be used.

The hardener is usually used in an amount of 0.01 to the binder.
To 30% by weight, preferably 0.05 to 20% by weight.

The magnetic powder is dispersed in a binder using a solvent, if necessary, to form a coating solution. For dispersing the magnetic powder, a ball mill, a homomixer, a sand mill, or the like can be used. In this case, it is preferable to disperse and disperse the magnetic particles individually as much as possible without damaging the magnetic particles.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to impart functions such as lubrication, antistatic and antiadhesion, and improvement of friction and wear characteristics to the magnetic recording layer. For example, various additives can be added. In addition, for example, a plasticizer, a dispersant, an abrasive, and the like can be added to the coating solution.

The position of the magnetic recording layer is not particularly limited, and the outermost layer and / or the adjacent layer of the present invention may be a magnetic recording layer, or the magnetic recording layer may be provided inside the adjacent layer.

The outermost layer of the present invention and the layer adjacent thereto may be coated by various known methods, for example, curtain coating,
Reverse roll coating, fountain air doctor coating,
Slide hopper application, extrusion application, dip application, blade application, air knife application, squeeze application, impregnation application, transfer roll application, gravure application, kiss application, cast application, spray application and the like can be used.

The outermost layer and the adjacent layer may be applied successively, but it is more preferable to apply them simultaneously. The successive coating in the present invention is a so-called wet-on-dry coating method in which the outermost layer coating solution is applied after coating and drying the adjacent layer coating solution. This is a so-called wet-on-wet coating method in which the outer layer coating solution is applied in a superposed state in a wet state.

The simultaneous coating includes a method in which one layer is first applied and then the next layer is coated thereon as soon as possible in a wet state (hereinafter referred to as simultaneous coating at another position), and a multilayer simultaneous extrusion coating (hereinafter referred to as “multi-layer coating”). Simultaneous multi-layer coating).

For simultaneous coating, see JP-A-2-251265.
And the coating method described in JP-A-2-268860.

As the support applicable to the present invention, for example, a film such as a polyolefin such as polyethylene, a cellulose derivative such as polystyrene and cellulose triacetate, and a polyester such as polyethylene terephthalate and polyethylene naphthalate are used.

The support may be subjected to a surface treatment. Examples of the surface treatment preferably used include, for example, chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment, ozone oxidation treatment and the like. Can be

The silver halide emulsion used in the silver halide emulsion layer is, for example, Research Disclosure (R)
D) No. 17643, pp. 22-23 (Dec. 1978
Mon) "I. Emulsion prepar
and types (RD) N
o. 18716, 648, Physics and Chemistry of Photography by Grafkid, published by Paul Montell (P. Glafkide)
s, Chemie etPhisique Photo
graphique, Paul Montel, 196
7), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photographic)
Emulsion Chemistry, Focal
Press 1966), "Photographic Emulsion Production and Coating", by Zerikman et al., Published by Focal Press (VL Zeli).
kman et al, Making and Coa
ting Photographic Emulsio
n, Focal Press, 1964).

The silver halide emulsion is disclosed in US Pat.
Monodispersed emulsions described in JP-A-628, JP-A-3,665,394 and British Patent 1,413,748 are also preferred.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RDNo. No. 17643, ibid. 1
No. 8716 and No. 8; 308119 (hereinafter R
D17643, RD18716, and RD308119).

When the photographic material is a color photographic material, photographic additives which can be used are also described in the above RD. Further, various couplers can be used, and specific examples thereof are also RD17643 and RD3081.
19.

Also, these additives are RD308119
It can be added to the photographic photosensitive layer by the dispersion method described in section XIV.

In the color photographic light-sensitive material, the above-mentioned RD30
An auxiliary layer such as a filter layer or an intermediate layer described in section 8119 VII-K can be provided.

When a color photographic light-sensitive material is formed, various layer structures such as a forward layer, a reverse layer, and a unit structure described in the aforementioned RD308119 VII-K can be employed.

To develop the silver halide photographic light-sensitive material, for example, H. By James, Theory of
The Photographic Process 4th Edition (The Th
early of the photographic
Process Forth Edition) No. 291
Pages-334 and the Journal of the American Chemical Society (Journal of the
e American Chemical Society
ty) Developers known per se described in Vol. 73, 3, page 100 (1951) can be used. The color photographic light-sensitive material is RD17643 as described above.
28-29, RD18716 615 and RD3
Development processing can be performed by a usual method described in 08119 XIX.

[0079]

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 The following coating solution 1-1 for the first layer was applied on a cellulose triacetate film so as to have a concentration of 20 ml / m ^2.
Dry at 5 ° C. for 5 minutes.

<First Layer Coating Solution 1-1> Cellulose Diacetate 5 g SiO ₂ Particles (Particle Size 0.02 μm) See Table 1 Acetone 500 ml Ethyl acetate 500 ml Next, the following second layer coating is performed on the first layer. Liquid 2-1 to 20
It was applied to a concentration of ml / m ² and dried at 80 ° C. for 5 minutes.

<Coating solution 2-1 for second layer> Cellulose diacetate 5 g DOP See Table 1 SiO ₂ particles (particle diameter 0.02 μm) See Table 1 Acetone 500 ml Ethyl acetate 500 ml However, the first layer and the second layer The amounts of DOP and SiO ₂ particles were varied respectively, and the amounts are shown in Table 1.

Then, the following coating solution O-1 for overcoat layer (OC layer) was applied on the second layer so as to be 10 ml / m ² , and dried at 100 ° C. for 3 minutes.

<Coating solution O-1 for overcoat> Carnauba wax See Table 1 Toluene 700 ml Methyl ethyl ketone 300 ml However, the amount of carnauba wax in the overcoat layer was changed so that the coating amount shown in Table 1 was obtained. ing.

Further, an undercoat layer and a photographic emulsion layer identical to the commercially available color negative film Konica Color LV400 manufactured by Konica Co., Ltd. were provided on the side of the support opposite to the back layer. . 101 to 129 were produced.

The elastic modulus in Table 1 is a value calculated by the method described in the detailed description.

The sample No. With respect to each of 101 to 129, the scratch resistance, winding deviation property and dynamic friction coefficient were measured by the following methods. Table 1 shows the evaluation results.

Scratch resistance A sapphire needle having a tip of 25 μm (diameter) was pressed against the surface of the back layer of the sample, and a load was continuously applied within a range of 0 to 50 g while being translated on the film surface at a speed of 1 cm per second. The load (g) of the needle that caused damage to the back layer of the sample was examined. The larger the value, the better the scratch resistance. If it is 15 g or more, there is no practical problem, but it is more preferably 20 g or more, and further preferably 30 g or more.

Winding property Each sample was cut to 18 cm × 500 m, and 1.0 (kg /
It is wound around a paper core having a diameter of 10 cm and a length of 28 cm with a tension of 18 cm width). Then, the paper core is set up, and the length of the winding deviation is measured. The evaluation was ranked according to the length of the winding deviation as follows. There is no practical problem if the rank is C or higher, but the B level or higher is preferable, more preferably the A 'level or higher, and further preferably the A level.

A: No winding deviation A ': 0.5 cm or less B: 0.5 to 1 cm C: 1 to 2 cm D: 2 to 3 cm E: 3 cm or more Dynamic friction coefficient A sample before development was heated to a temperature of 23 ° C. and a relative humidity of 55. After humidity control for 6 hours or more in an atmosphere of% RH, the dynamic friction coefficient of the back layer surface was measured by HEIDON-14D using a square polystyrene plate having a side of 1 cm under a load of 100 g. The smaller the value, the easier it is to slip.

[0091]

[Table 1]

As shown in Table 1, it was found that by using the present invention, a silver halide photographic light-sensitive material excellent in both scratch resistance and curl deviation was obtained.

Example 2 A coating solution 1-2 for the first layer and a coating solution 2-2 for the second layer described below were respectively applied on a cellulose triacetate film by 2
The coating was finally performed so as to be 0 ml / m ² . Drying was performed at 80 ° C. for 5 minutes each. Next, a coating solution O-2 for overcoat layer described below was applied on the second layer to a concentration of 10 ml / m ² , dried at 100 ° C. for 3 minutes, and dried.
o. 201 was produced.

The following coating liquid 1-2 for the first layer and coating liquid 2-2 for the second layer described below are formed on a cellulose triacetate film.
Were simultaneously applied at different positions so as to be 20 ml / m ² (the second layer was the outermost layer and the first layer was the adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Next, a coating solution O-2 for overcoat layer described below was applied on the second layer to a concentration of 10 ml / m ² , dried at 100 ° C. for 3 minutes, and dried.
o. 202 was produced.

The following coating liquid 1-2 for the first layer and coating liquid 2-2 for the second layer described below are formed on a cellulose triacetate film.
Was applied simultaneously so as to be 20 ml / m ² (the second layer was the outermost layer and the first layer was the adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Then, the following overcoat layer coating solution O-2 was applied on the second layer to a concentration of 10 ml / m ² , dried at 100 ° C. for 3 minutes, and dried.
203 were produced.

<Coating solution 1-2 for first layer> Cellulose diacetate 5 g SiO ₂ particles (particle size 0.02 μm) 0.26 g Acetone 500 ml Ethyl acetate 500 ml <Coating solution 2-2 for second layer> Cellulose diacetate 5 g acetone 500 ml ethyl acetate 500 ml <coating solution for overcoat O-2> carnauba wax 0.74 g toluene 700 ml methyl ethyl ketone 300 ml The elastic modulus of the first layer is 350 kg / mm ² and the elastic modulus of the second layer is 300 kg / mm ² there were.

Further, an undercoat layer and a photographic emulsion layer identical to those of a commercially available Konica Color LV400 Konica Color Film were provided on the surface of the support opposite to the back layer, and Sample No. 2 having the contents shown in Table 2 was obtained. . 201 to 203 were produced.

For the prepared sample No. The scratch resistance and winding deviation of each of the samples 201 to 203 were measured in the same manner as in Example 1. The abrasion resistance was measured by the following methods. Table 2 shows the evaluation results.

Abrasion Resistance After the sample before development was conditioned for 6 hours or more in an atmosphere of a temperature of 23 ° C. and a relative humidity of 55% RH, a 300 g load was applied to a stainless steel ball having a diameter of 2 mm by HEIDON-14D. The abrasion resistance of the back layer surface was measured by reciprocating at a moving speed of 1 cm / sec. The evaluation was made based on the number of round trips until the film began to peel off. Although there is no practical problem as long as the level is B or higher, it is preferably A 'level or higher, and more preferably A level or higher.

A: 50 times or more A ': 49 to 40 times B: 39 to 25 times C: 24 to 10 times D: less than 10 times

[0101]

[Table 2]

As shown in Table 2, it was found that the abrasion resistance was further improved by simultaneously coating the outermost layer of the back layer of the present invention and the layer adjacent thereto.

Example 3 A commercially available polyethylene naphthalate film having a thickness of 85 μm (hereinafter referred to as PEN) was wound around a stainless steel core and heat-treated at 110 ° C. for 48 hours to prepare a support.

On the back surface of this support, 12 W / m ² / m
in under a corona discharge treatment, a subbing coating solution B-1 was applied so as to have a dry film thickness of 0.4 μm, and 12 W /
A corona discharge treatment of m ² / min was performed, and the conductive layer coating liquid A-1 was applied so as to have a dry film thickness of 0.4 μm. Then, 12 W / m ² / min.
Is applied, and the undercoating coating solution B-1 is dried to a thickness of 0.
4 μm, and the following coating solution B-
2 was applied so that the dry film thickness became 0.02 μm.

Each layer was dried at 90 ° C. for 10 seconds after the application, and after applying the four layers, heat treatment was performed at 110 ° C. for 2 minutes, followed by cooling at 50 ° C. for 30 seconds.

<Undercoat Coating Solution B-1> A copolymer latex liquid of 30% by weight of n-butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate ( (Solid content 30%) 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 1.0 g Finished with water 1000 ml <Tin oxide dispersion A> Antimony-doped tin oxide SN manufactured by Ishihara Sangyo Co., Ltd. A mixture of 400 g of -100P powder and 600 g of water was adjusted to pH 7.0, and then dispersed with a stirrer and a sand mill to prepare a tin oxide dispersion A. <Electroconductive layer coating liquid A-1> 5-sulfoisophthalic acid 5 mol%, isophthalic acid 15 mol%, terephthalic acid 30 mol%, ethylene glycol 25 mol%, diethylene glycol 25 mol% (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Tin oxide dispersion A 560 g Finished with water 1000 ml <Undercoat coating solution B-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound ( UL-3) 0.1 g silica particles (average particle size: 3 μm) 0.1 g finish with water 1000 ml

[0107]

Embedded image

Further, the following coating solution M-1 for a magnetic layer was applied onto the conductive layer on the back surface side so as to have a dry film thickness of 1.0 μm, and dried at 80 ° C. for 5 minutes.

On the magnetic layer, the following coating solution H-1 for protective layer was used.
Is applied to a dry film thickness of 0.2 μm.
Dried for minutes.

Next, the coating solution O-2 for the overcoat layer (OC layer) was applied on the protective layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes.

Further, a photographic emulsion layer identical to the commercially available Konica Color LV400 Konica Color LV400 film was provided on the surface of the support opposite to the back layer, and Sample No. 3 having the contents shown in Table 3 was prepared. 301 to 307 were produced.

Further, the following coating solution M-1 for magnetic layer and the following coating solution H-1 for protective layer were coated on the conductive layer on the back surface side so as to have a dry film thickness of 1.0 μm and 0.2 μm, respectively. (The protective layer is the outermost layer and the magnetic layer is the adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Then, the following composition for an overcoat layer was applied on the protective layer by 10
The solution was applied so as to be ml / m ² and dried at 100 ° C. for 3 minutes. Further, a photographic emulsion layer identical to the commercially available Konica Color LV400 Konica Color LV400 was provided on the surface of the support opposite to the back layer. 308 and 309 were produced.

On the conductive layer on the back surface side, the following coating solution M-1 for magnetic layer and the following coating solution H-1 for protective layer were dried to a dry film thickness of 1.0 μm and 0.2 μm, respectively. (The protective layer is the outermost layer and the magnetic layer is the adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Then
On the protective layer, the overcoat layer composition O-2 was added as 1
It was applied so as to be 0 ml / m ² and dried at 100 ° C. for 3 minutes. Further, the same photographic emulsion layer as Konica Color LV400, a commercially available color negative film manufactured by Konica Corporation, was provided on the surface of the support opposite to the back layer, and Sample No. 3 having the contents shown in Table 3 was used. 310 and 311 were produced.

<Coating Solution M-1 for Magnetic Layer> Cellulose diacetate 82 g Co-coated γ-Fe ₂ O ₃ (major axis 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oersted) 6.6 g α-alumina particles (particle size: 0.4 μm) See Table 3. Acetone 990 g Cyclohexanone 110 g The above composition was mixed, mixed with a dissolver for 1 hour, and then dispersed with a sand mill for 2 hours. Furthermore, tolylene diisocyanate / trimethylolpropane (TDI / TM
P) was added thereto and mixed with a dissolver for 1 hour to obtain a coating liquid M-1 for a magnetic layer.

<Protective Layer Coating Solution H-1> Cellulose Diacetate 5 g DOP See Table 3 α-alumina particles (particle size 0.2 μm) See Table 3 Acetone 990 g Cyclohexanone 110 g However, the coating solution M-1 for the magnetic layer and Coating solution for protective layer H-
The amounts of DOP and α-alumina particles added to No. 1 were changed respectively, and the amounts of addition are described in Table 3.

The sample No. Scratch resistance and winding deviation were measured for each of 301 to 311 in the same manner as in Example 1. The magnetic output error was measured by the following method after coating and after development. Table 3 shows the evaluation results.

However, the elastic modulus in Table 3 is a value calculated by the method described in the detailed description.

The development of each sample was performed as follows.

<Development Processing> 1 Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C. 2 Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ° C. 3 Rinse water ··· 3 minutes 15 seconds 24 to 41 ° C 4 Settled ··· 6 minutes 30 seconds 38.0 ± 3.0 ° C 5 Rinse ··· 3 minutes 15 seconds 24 to 41 ° C 6 Stable ···・ 3 minutes 15 seconds 38.0 ± 3.0 ° C. 7 Drying ・ ・ ・ 50 ° C. or less The composition of the processing solution used in each step is shown below.

<Color developing solution> 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2. 0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) <Bleaching Liquid> Ethylene (III) ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using aqueous ammonia. Adjust to

<Fixing Solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

With a film A sample before development was conditioned at 23 ° C. and 55% RH, and a scratch reaching the support at a 45 ° angle with a razor blade was formed on the surface of the back layer in a grid pattern. After pressing the tape (cellophane adhesive tape), the tape is rapidly peeled at an angle of about 45 °. At this time, the area of the back layer that is peeled off together with the tape is compared with the area where the tape is attached, and evaluated according to the following six grades. If it is better than C rank, there is no practical problem, but it is more preferable that it is B rank or more.

A: 0% A ': less than 5% B: 5% to less than 10% C: 10% to less than 20% D: 20% to less than 50% E: 50% or more Magnetic output after development Error Each sample was cut into 100 pieces of 25 APS films, packed into APS cartridges, and magnetic signals were input with a commercially available APS camera. After carrying out the above-mentioned development processing, 100 pieces were continuously passed through a magnetic reproducing apparatus of a photographic printer, and a decrease in reproduction output was measured. The evaluation was made as follows according to the maximum output reduction width during 100 runs. If it is not less than Δ, there is no practical problem.

：: no decrease Δ: decrease within −4 db ×: decrease of −4 db or more

[0126]

[Table 3]

Table 3 shows that by using the present invention, a silver halide photographic light-sensitive material having a magnetic recording layer excellent in scratch resistance, winding deviation and magnetic output error after development can be obtained.

It was also found that by simultaneously coating the outermost layer of the back layer of the present invention and the layer adjacent thereto, the film formation was further improved.

Example 4 The following conductive layer coating solution A-4 was applied on a cellulose triacetate film in an amount of 20 ml /
m ² and dried at 80 ° C. for 5 minutes.

Next, the following coating liquid H-2 for a protective layer was applied on the conductive layer so as to have a concentration of 20 ml / m ² and dried at 80 ° C. for 5 minutes.

Next, the coating solution O-2 for the overcoat layer (OC layer) was applied on the protective layer to a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes.

Further, the same photographic emulsion layer as Konica Color LV400, a commercially available color negative film manufactured by Konica Corporation, was provided on the side of the support opposite to the back layer. 401 to 410 were produced.

Further, the following coating solution A-4 for a conductive layer and the following coating solution H-2 for a protective layer were simultaneously applied to a cellulose triacetate film at different positions at 20 ml / m ² (protective layer H- 2 is the outermost layer and the conductive layer is an adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Next, the composition for an overcoat layer O-2 is formed on the protective layer.
Was applied so as to be 10 ml / m ² and dried at 100 ° C. for 3 minutes. Further, a photographic emulsion layer identical to the commercially available color negative film Konica Color LV400 manufactured by Konica Corporation was provided on the side of the support opposite to the back layer. 411 and 412 were produced.

Further, the following coating solution A-4 for a conductive layer and the following coating solution H-2 for a protective layer were simultaneously and multi-layer coated onto a cellulose triacetate film so as to have a coating volume of 20 ml / m ² (protective layer H-2). Is the outermost layer and the conductive layer becomes an adjacent layer). Drying was performed at 80 ° C. for 5 minutes. Then
On the protective layer, the overcoat layer composition O-2 was added as 1
It was applied so as to be 0 ml / m ² and dried at 100 ° C. for 3 minutes. Further, a photographic emulsion layer identical to the commercially available color negative film Konica Color LV400 manufactured by Konica Corporation was provided on the side of the support opposite to the back layer. 413 and 414 were produced.

<Coating Solution A-4 for Conductive Layer> Powder of antimony-doped tin oxide SN-100P manufactured by Ishihara Sangyo Co., Ltd. See Table 4. Diacetylcellulose 8.1 g Acetone 700 ml Cyclohexanone 200 ml The above mixed solution was dispersed with a stirrer and a sand mill. Thus, a coating solution A-4 for a conductive layer was prepared. <Protective layer coating liquid H-2> cellulose diacetate 5 g DOP See Table 4 SiO ₂ particles (particle diameter 0.02 [mu] m) See Table 4 acetone 500ml ethyl acetate 500ml However, the conductive layer coating liquid A-4 Ishihara Sangyo Powder of antimony-doped tin oxide SN-100P (SnO)
₂ ) The addition amounts of DOP and SiO ₂ particles of the coating solution H-2 for protective layer and the addition amount thereof are changed, and the addition amounts are described in Table 4.

The sample No. For each of 401 to 414, the scratch resistance and the winding deviation were measured in the same manner as in Example 1. The conductivity was measured by the following method. Table 4 shows the evaluation results.

Here, the elastic modulus in Table 4 is a value calculated by the method described in the detailed description.

The sample was left for 12 hours in an environment of 23 ° C. and 20% RH. Thereafter, under the same environment, the surface resistivity was measured using Tera Ohm Meter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd. There is no practical problem if the conductivity is 1 × 10 ¹² Ω / □ or less, but it is preferably 1 × 10 ¹¹ Ω / □ or less, and more preferably 1 × 10 ¹⁰ Ω / □ or less.

[0139]

[Table 4]

Table 4 shows that the use of the present invention makes it possible to obtain a silver halide photographic light-sensitive material having excellent scratch resistance and curl deviation.

It was also found that simultaneous application of the outermost layer of the back layer of the present invention and its adjacent layer further improved film formation.

[0142]

According to the present invention, a silver halide photographic light-sensitive material having a back layer having excellent transportability in a manufacturing process, in a camera, in laboratory equipment, and the like, and excellent abrasion resistance. An excellent silver halide photographic material was obtained. Furthermore,
A silver halide photographic light-sensitive material having a magnetic recording layer excellent in scratch resistance and winding deviation was provided.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and at least two back layers on the other side.
The elastic modulus of the outermost layer of the back layer is 300 kgf / mm ² or less, and the elastic modulus of the adjacent layer is 350 kgf / m 2.
The silver halide photographic material which is characterized in that m ² or more. 2. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and at least two back layers on the other side,
The silver halide photographic elastic modulus of the outermost layer of the back layer is at 300 kgf / mm ² or less, and the coefficient of dynamic friction against polystyrene sheet of the outermost layer of the back layer is characterized by a 0.15 to 0.40 Photosensitive material. 3. The silver halide photographic material according to claim 1, wherein the outermost layer of the back layer and the layer adjacent thereto are simultaneously coated. 4. The silver halide photographic material according to claim 1, wherein the material has at least one magnetic recording layer.