JP3496180B2 - Silver halide photographic material and magnetic recording medium - Google Patents

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 a magnetic recording medium, and particularly to a silver halide photographic light-sensitive material having a back layer excellent in scratch resistance and adhesion resistance, and scratch resistance and resistance. The present invention relates to a magnetic recording medium having excellent adhesiveness.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) is generally prepared by forming a light-sensitive silver halide emulsion layer and, if necessary, a light-sensitive silver halide emulsion layer on a support such as glass, paper, plastic film or plastic-coated paper. Accordingly, various non-photosensitive layers such as an intermediate layer, a protective layer, a back layer, an antihalation layer and an antistatic layer are coated in combination. Such a light-sensitive material is coated, dried,
In addition to manufacturing processes such as processing, shooting, development processing, winding, rewinding during printing, handling such as conveyance, between various devices, machines, cameras, etc. and photosensitive materials, or between photosensitive materials There is a problem that contact and friction occur between the surface of the photographic emulsion layer side and the back layer surface, and scratches occur on the back layer. In addition, particles of small dust such as dust intrude into the camera or the like and rub the back layer, which often causes a more serious failure.

As a means for solving these problems, for example, a method of providing a back layer with a layer containing a slip agent is well known. As an example of using such a slip agent, for example, an example of using organopolysiloxane in JP-A-50-117414 is disclosed in JP-A-1-161337.
Japanese Patent Application Laid-Open No. 4-1750 discloses a method of using a higher fatty acid or its ester.

However, in recent years, due to expansion of usage and processing methods for light-sensitive materials (for example, quick photography and quick processing), diversification of environments during use such as high temperature and high humidity atmosphere and dusty environment. In addition, the photosensitive material is often exposed to more severe handling conditions than ever before, and there is a problem that contact friction or contact failure involving the surface layer of the photosensitive material is likely to occur.

In order to solve these problems, it is conceivable to increase the content of the slip agent, but in this case, excessive slippage causes misalignment due to conveyance defects in the manufacturing process, camera, laboratory equipment, etc. However, there is a problem that problems such as meandering of the film are likely to occur, and that adhesion between the surface of the photographic emulsion layer and the back layer is likely to occur.

Further, in recent years, a magnetic recording layer is provided on a back layer of a silver halide photographic light-sensitive material in order to input various information such as information at the time of photographing with a camera and information obtained at the time of printing into the photographic light-sensitive material. A new system called Advanced Photo System (APS) has been released. In APS, the back layer is rubbed by a magnetic head for inputting / outputting magnetic information, and the film after development is stored in a cartridge, so that demands for scratch resistance and adhesion resistance become more severe than in the past. ing.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a first object of the present invention is to cause a defective conveyance in a manufacturing process, a camera, a laboratory equipment or the like. Another object is to provide a silver halide photographic light-sensitive material having a back layer excellent in scratch resistance and adhesion resistance.

A second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in abrasion resistance and a magnetic recording medium.

A third object of the present invention is to provide a silver halide photographic light-sensitive material and a magnetic recording medium having a magnetic recording layer excellent in scratch resistance and adhesion resistance.

[0010]

The above object of the present invention has been achieved by the following constitution.

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

(2) The silver halide photographic light-sensitive material as described in 1 above, wherein the outermost layer of the back layer and its adjacent layer are formed by simultaneous coating.

(3) The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the outermost surface of the back layer has a coefficient of dynamic friction with respect to the polystyrene plate of 0.15 to 0.40.

(4) At least one on one side of the support
In a magnetic recording medium having one magnetic recording layer, the outermost layer on the side having the magnetic recording layer has an elastic modulus of 350 kgf / m.
m ² or more, and the elastic modulus of the adjacent layer is 300 kg
A magnetic recording medium having a f / mm ² or less.

(5) The magnetic recording medium as described in 4 above, wherein the outermost layer and its adjacent layer are formed by simultaneous coating.

(6) The magnetic recording medium as described in 4 or 5 above, wherein the coefficient of dynamic friction with respect to the polystyrene plate on the outermost surface on the magnetic recording layer side is 0.15 to 0.40.

The present invention will be described in more detail below. The outermost layer in the present invention is a layer (back layer) on the side opposite to the side having the silver halide emulsion layer with respect to the support,
It refers to the outermost layer having a film-forming ability as viewed from the support. In addition, the adjacent layer in the present invention refers to a layer of the back layer that is adjacent to the inside of the outermost layer with respect to the support and has a film forming ability. In order to provide the outermost layer and its adjacent layer with the 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 may be used. it can.

Examples of the above-mentioned thermoplastic resins 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 mentioned.

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

Examples of thermosetting resins and other reactive resins include phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

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 acid type copolymers, maleic anhydride copolymers and the like. Examples of the cellulose ether include carboxymethyl cellulose and hydroxyethyl cellulose. As the latex polymer, a vinyl chloride-based copolymer, a vinylidene chloride-based copolymer, an acrylic ester-based copolymer, a polyester-based copolymer, a vinyl acetate-based copolymer,
A latex such as a butadiene-based copolymer can be used.

The binder may be hardened. Examples of hardeners 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. Examples thereof include derivatives, epoxy compounds, and halogen carboxaldehydes. Inorganic hardeners can also be used, and carboxyl group active type hardeners can also be used.

The hardener is usually 0.01 with respect to the binder.
-30% by weight, preferably 0.05-20% by weight.

The film thickness of the outermost layer in the present invention is 0.01 μm.
m-2 μm is preferable, and 0.02 μm-1.5 μm is more preferable.

The thickness of the adjacent layer in the present invention is 0.01 μm.
m to 10 μm is preferable, 0.05 μm to 2 μm is more preferable, and 0.10 μm to 1.5 μm is further preferable.

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

The elastic modulus in the present invention is determined according to JIS K by peeling the outermost layer and its adjacent layer from the back layer.
It can be determined by the method for measuring the tensile elastic modulus described in 7113 Plastic tensile test method (hereinafter abbreviated as JIS method). However, the shape of the test piece such as the film thickness may be appropriately changed as necessary.

When it is difficult to measure the elastic modulus by the above-mentioned method because it is difficult to peel off the layer, the components constituting the layer and the conditions such as the composition ratio are set. The elastic modulus may be measured using the films prepared by making the same as the test piece.

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

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

[0033] _{e a = (E 2 -e b} × c b) / c a ( Equation _{2) c a + c b =} 1 ( Equation 3) where e _a and c _a are components having no film-forming ability, respectively 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 by changing the volume fraction at three or more points and 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 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.

The elastic modulus of the adjacent 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 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, but includes, for example, dioctylphthalic acid (DOP), dibutylphthalic acid (DBP), triphenyl phosphate (TPP),
Tricresyl phosphate (TCP) and the like are preferably used. These can be used alone or in combination.

The inorganic particles are not particularly limited, but for example, metal oxides are preferably used. Aluminum oxide (Al ₂ O ₃ ) and 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 the like, or a composite oxide thereof.

A lubricant may be added to impart lubricity. The lubricant may be applied to the outside of the outermost layer as an overcoat layer without a binder, or the outermost layer and / or its adjacent layer may contain the lubricant.

The method of applying the lubricant without the binder is not particularly limited. For example, the method of applying the lubricant by dissolving it in a solvent, or the method of emulsifying the lubricant and applying its dispersion liquid. and so on.

The method of incorporating the lubricant into the outermost layer and / or its adjacent layer is not particularly limited. For example, a method of dissolving the binder and the lubricant in a solvent that dissolves both and then applying the solution together with the binder, and JP-A-H07-76187. There is a method in which a wax as described in JP-A-270983 is dispersed in a solvent to be contained in a binder and then applied.

The lubricant is not particularly limited, and examples thereof include silicone oil such as polysiloxane, fine powder such as polyethylene and polytetrafluoroethylene, higher fatty acid, higher fatty acid ester, higher fatty acid derivative, and fluorocarbon. These may be used alone or in combination.

The coating amount of the lubricant is not particularly limited, but it is preferably coated 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, and more preferably 0. It is to be applied so that it falls within the range of 20 to 0.35.

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

Examples of the antistatic agent include conductive polymers and inorganic metal oxides. The conductive polymer is not particularly limited and may be anionic, cationic, amphoteric or nonionic, and among them, anionic and cationic are preferable. More preferred are sulfonic acid-based and carboxylic acid-based polymers when anionic, and tertiary amine-based and quaternary ammonium-based polymers or latexes when cationic.

Examples of these electrically conductive polymers include 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 57-57. -5
6059, 58-56856, U.S. Pat. No. 4,1.
Examples thereof include cationic polymers or latexes described in No. 18,231.

As the inorganic metal oxide, Japanese Patent Laid-Open No. 56-1 is used.
Crystalline oxide particles as disclosed in JP-A-43431, amorphous stannic oxide sol as disclosed in JP-B-35-6616, and amorphous as described in JP-A-55-5982. Vanadium pentoxide, Japanese Patent Publication No. 57-129
An alumina sol having an electrolyte as disclosed in No. 79 is mentioned.

In addition, a matting agent may be added to the outermost layer and / or its adjacent layer in order to have a function of preventing adhesion.

The matting agent is not particularly limited, and may be an inorganic substance, an organic substance, or a mixture of two or more kinds. Examples of the inorganic matting agent include silicon dioxide, aluminum oxide,
Examples thereof include barium sulfate, manganese colloid, titanium dioxide, and strontium barium sulfate.

Examples of the monomer used in the organic matting agent include acrylic acid esters, acrylic acid-based compounds,
Examples thereof include polymers or copolymers of styrenes and vinyl esters. Also, divinylbenzene, N, N '
-Adding a cross-linking 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, and examples thereof include metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder. Powder etc. can be used. The method for producing these magnetic powders is known, and the magnetic powders used in the present invention can also 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 shape such as a needle shape, a rice grain shape, a spherical shape, a cubic shape, or a plate shape, but a needle shape or a plate shape is 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 5-10.

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

As the binder used in the magnetic recording layer, known thermoplastic resins, radiation curable resins, thermosetting resins, other reactive resins, hydrophilic resins and the like which have been conventionally used for magnetic recording media are used. Mixtures of 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, rubber resins. Resins, silicone resins, fluorine resins and the like can be mentioned.

The radiation-curable resin is a resin which is cured by radiation such as electron beam and ultraviolet rays, and examples thereof include maleic anhydride type, urethane acryl type, ether acryl type and epoxy acryl type.

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

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 acid type copolymers, maleic anhydride copolymers and the like. Examples of the cellulose ether include carboxymethyl cellulose and hydroxyethyl cellulose. As the latex polymer, a vinyl chloride-based copolymer, a vinylidene chloride-based copolymer, an acrylic ester-based copolymer, a polyester-based copolymer, a vinyl acetate-based copolymer,
A latex such as a butadiene-based copolymer can be used.

Preferably, the binder of the magnetic layer contains cellulose ester as a main component. In particular, it is cellulose diacetate.

The binder may be hardened. Examples of hardeners 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. Examples thereof include derivatives, epoxy compounds, and halogen carboxaldehydes. Inorganic hardeners can also be used, and carboxyl group active type hardeners can also be used.

The hardening agent is usually 0.01 with respect to the binder.
-30% by weight, preferably 0.05-20% by weight.

The magnetic powder is dispersed in the binder using a solvent if necessary to form a coating liquid. A ball mill, homomixer, sand mill, or the like can be used to disperse the magnetic powder. In this case, it is preferable to disperse the magnetic particles one by one 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 to the magnetic recording layer such as imparting lubricity, antistatic property, antiadhesive property, and improving friction and wear characteristics. Various additives can be added. Besides, for example, a plasticizer, a dispersant, an abrasive and the like can be added to the coating liquid.

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 the magnetic recording layer, or the magnetic recording layer may be provided inside the adjacent layer.

As the coating method of the outermost layer and its adjacent layer of the present invention, various known methods such as curtain coating,
Reverse roll coating, Fountain air doctor coating,
Slide hopper coating, extrusion coating, dip coating, blade coating, air knife coating, squeeze coating, impregnation coating, transfer roll coating, gravure coating, kiss coating, cast coating, spray coating and the like can be used.

The outermost layer and the adjacent layer may be sequentially coated, but simultaneous coating is more preferable. Simultaneous coating in the present invention includes simultaneous coating at different positions and simultaneous multilayer coating. The coating method used in the present invention will be described with reference to the drawings.

FIG. 1 is a schematic diagram of sequential coating, in which the support 3
Is first applied by the coater 1 of the coating liquid for the adjacent layer, dried in the drying zone 2 and then coated by the coater 1'of the outermost layer coating liquid, and dried in the drying zone 2 '.
The on-dry coating type is shown.

FIG. 2 is a schematic view of simultaneous coating at different positions. This is a method in which the adjacent layer is first applied with the coater 1 for the adjacent layer coating solution and then applied as quickly as possible in the wet state with the coater 1'for the outermost layer coating solution, which is the so-called wet-on-wet coating method. Indicates.

FIG. 3 is a schematic view of simultaneous extrusion coating of multiple layers (hereinafter referred to as simultaneous multilayer coating). The coater for the adjacent layer coating liquid and the coater for the outermost layer coating liquid are installed in the simultaneous multilayer coating coater 4, and the adjacent layer coating liquid and the outermost layer coating liquid are sequentially discharged from the coater 4 as a laminar flow on the support 3. And is sent to the drying zone 2 and dried.

For simultaneous coating, JP-A-2-251265
And the coating method described in JP-A-2-286862.

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

The support may be surface-treated. Examples of the surface treatment preferably used include 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. To be

The silver halide emulsion used in the silver halide emulsion layer is, for example, Research Disclosure (R
D) No. 17643, 22-23 (December 1978)
Mon) ”I. Emulsion preparation
"and and types)" and the same (RD) N
o. 18716, pp. 648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel.
s, Chemic et Phisique Photo
graphique, Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (GF Duffin, Photographic.
Emulsion Chemistry, Focal
Press 1966), "Photographic emulsion production and coating" by Zelikmann et al., Published by Focal Press (VL Zeli).
kman et al, Making and Coa
toning Photographic Emulsio
n, Focal Press, 1964) and the like.

Emulsions include US Pat. Nos. 3,574,628, 3,665,394 and British Patent 1,4.
The monodisperse emulsions described in 13,748 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 RD No. 17643, the same No. 1
8716 and the same No. 308119 (respectively R
D17643, RD18716, RD308119).

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

Further, these additives are RD308119.
It can be added to the photographic light-sensitive layer by the dispersion method described in page XIV, page 1007.

For the color photographic light-sensitive material, the above-mentioned RD30 is used.
Auxiliary layers such as a filter layer and an intermediate layer described in 8119 VII-K can be provided.

When the color photographic light-sensitive material is constituted, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item RD308119 VII-K can be adopted.

To develop a silver halide photographic light-sensitive material, for example, T.I. H. James Theory of Theory
The Photographic Process 4th Edition (The Th
eory of The Photographic P
process Forth Edition) pp. 291 to 334 and Journal of the American
Chemical Society (Journal of the
American Chemical Societ
y) Developers known per se, which are described in Vol. 73, page 3,100 (1951), can be used. Further, the color photographic light-sensitive material is the above-mentioned RD17643.
28-29, RD18716, 615 and RD3
Development can be performed by a usual method described in 08119 XIX.

[0082]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 Onto a cellulose triacetate film, the following first layer coating liquid 1-1 was coated so as to have a concentration of 20 ml / m ² , and then 80
Dry at 5 ° C for 5 minutes.

<Coating Liquid 1-1 for First Layer> Cellulose diacetate 5 g DOP See Table 1 SiO ₂ particles (particle size 0.02 μm) See Table 1 Acetone 500 ml Ethyl acetate 500 ml Next, on the first layer, the following 20 layers of 2-layer coating liquid 2-1
The solution was applied so that the amount became ml / m ² and dried at 80 ° C. for 5 minutes.

<Second Layer Coating Liquid 2-1> Cellulose diacetate 5 g SiO ₂ particles (particle diameter 0.02 μm) See Table 1 Acetone 500 ml Ethyl acetate 500 ml However, DOP and SiO _{2 of} the first and second layers The addition amount of each particle was changed, and the addition amount is described in Table 1.

Next, the following overcoat layer (OC layer) coating liquid O-1 was applied on the second layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes.

<Overcoat Coating Liquid O-1> Carnauba Wax See Table 1 Toluene 700 ml Methyl ethyl ketone 300 ml However, the addition amount of carnauba wax of the overcoat layer was changed so as to have the coating amount shown in Table 1. ing.

Further, on the surface of the support opposite to the back layer, an undercoat layer and a photographic emulsion layer which are the same as those of the commercially available Konica Color Negative Film Konica Color LV400 are provided, and Sample 101 having the content shown in Table 1 is provided. ~ 129 were made.

However, the elastic modulus in Table 1 shows the value calculated by the method described in the detailed description.

The scratch resistance, adhesion resistance (raw) and dynamic friction coefficient of each of the produced samples 101 to 129 were measured by the following methods. The evaluation results are shown in Table 1.

<Scratch resistance> A sapphire needle having a tip of 25 μm (diameter) was pressure-bonded to the surface of the back layer of the sample, and was moved parallel to the surface of the film at a speed of 1 cm per second for 0 to 50 g.
The load (g) of the needle that causes damage to the back layer of the sample was examined by continuously changing the load within the range. The larger the value, the better the scratch resistance. If it is 15 g or more, there is no problem in practical use, but it is more preferably 20 g or more, further preferably 30 g or more.

<Adhesion resistance (raw)> Four samples before development were prepared for each sample, stacked in the same direction and sandwiched with thick paper of the same size, and fixed with a rubber band, then at a temperature of 55 ° C. and relative humidity. The sample was allowed to stand in an atmosphere of 90% RH for 3 days, and the ratio (%) of the ferro-shaped area due to contact in the total area of the three pieces sandwiched between the four samples was measured. The evaluation was ranked by the area of the ferro-like shape. If it is better than C rank, there is no problem in practical use, but B rank or higher is more preferable.

A less than 5% A ′ 5% or more and less than 10% B 10% or more and less than 20% C 20% or more and less than 30% D 30% or more and less than 50% E 50% or more <Dynamic friction coefficient> Temperature of sample before development After conditioning the humidity for 6 hours or more in an atmosphere of 23 ° C. and relative humidity of 55% RH,
The dynamic friction coefficient of the back layer surface was measured by IDON-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.

[0094]

[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 adhesion resistance can be obtained.

Example 2 Using the apparatus shown in FIG. 1, a coating solution 1-2 for the first layer below and a coating solution 2-2 for the second layer below were each made to be 20 ml / m ² on the cellulose triacetate film. Were sequentially applied to Drying was performed at 80 ° C. for 5 minutes. Next, the following overcoat layer coating liquid O-2 was applied onto the second layer so as to have a concentration of 10 ml / m ² , and then 100
Sample 201 was prepared by drying at 0 ° C. for 3 minutes.

Using the apparatus shown in FIG. 2, the coating liquid 1-2 for the first layer and the coating liquid 2-2 for the second layer described below were separately placed on the cellulose triacetate film so that the coating liquid was 20 ml / m ^2. Co-applied. Drying was performed at 80 ° C. for 5 minutes. Next, the following overcoat layer coating liquid O-2 was applied onto the second layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes to prepare a sample 202.

Simultaneous multi-layering was carried out on the cellulose triacetate film using the apparatus shown in FIG. 3 so that the coating solution 1-2 for the first layer below and the coating solution 2-2 for the second layer below were each 20 ml / m ^2. Applied. Drying was performed at 80 ° C. for 5 minutes. Then, the following overcoat layer coating solution O-2 was applied onto the second layer so that the coating solution O-2 was 10 ml / m ² .
Sample 203 was prepared by drying at 100 ° C. for 3 minutes.

<First layer coating liquid 1-2> Cellulose diacetate 5 g Acetone 500 ml Ethyl acetate 500 ml <Second layer coating liquid 2-2> Cellulose diacetate 5 g SiO ₂ particles (particle diameter 0.02 μm) 26 g Acetone 500 ml Ethyl acetate 500 ml <Overcoat coating liquid O-2> Carnauba wax 0.52 g Toluene 700 ml Methyl ethyl ketone 300 ml The elastic modulus of the first layer is 300 kg / mm ² and the elastic modulus of the second layer is 350 kg / mm ² . there were.

Further, on the surface of the support opposite to the back layer, an undercoat layer and a photographic emulsion layer, which are the same as those of the commercially available Konica Color Negative Film Konica Color LV400, are provided. ~ 203 were produced.

The scratch resistance and the adhesion resistance (raw) of each of the produced samples 201 to 203 were measured in the same manner as in Example 1. Further, the abrasion resistance was measured by the following methods. The evaluation results are shown in Table 2.

<Abrasion resistance> The sample before development was heated to a temperature of 23.
After conditioning the humidity for 6 hours or more under an atmosphere of ℃ and relative humidity of 55% RH, a HEIDON-14D was used to apply a load of 300 g to a stainless ball having a diameter of 2 mm and a moving speed of 1 cm / s.
The abrasion resistance of the back layer surface was measured by reciprocating at ec.
The evaluation was ranked by the number of reciprocations until the film started to peel. If it is B level or higher, there is no practical problem, but A'level or higher is preferable, and A level or higher is more preferable.

[0103] A 50 times or more A'49 to 40 times B 39 to 25 times C 24 to 10 times D 9 times or less

[0104]

[Table 2]

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

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

12 W / m ² / m on the back surface of this support
in corona discharge treatment, and the undercoating coating liquid B-1 is applied to 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, on the opposite surface of this support, 12 W / m ² / min
Corona discharge was applied to the undercoating coating solution B-1 to give a dry film thickness of 0.
It is coated so as to have a thickness of 4 μm, and the undercoating coating solution B-
2 was applied so that the dry film thickness was 0.02 μm.

After coating each layer, each layer was dried at 90 ° C. for 10 seconds, after coating four layers, heat-treated at 110 ° C. for 2 minutes and then cooled at 50 ° C. for 30 seconds.

<Undercoating liquid 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 Finish with water 1000 ml <Tin oxide dispersion A> Ishihara Sangyo Co., Ltd. antimony-doped tin oxide SN A tin oxide dispersion liquid A was prepared by adjusting a pH of a mixed liquid of 400 g of -100P powder and 600 g of water to 7.0 and then dispersing the mixture with a stirrer and a sand mill. <Conductive 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 Finish with water 1000 ml <Undercoating coating liquid 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 diameter: 3 μm) 0.1 g Finish with water 1000 ml

[0110]

[Chemical 1]

Further, as shown in FIG.
The magnetic layer coating solution M-1 described below was applied to a dry film thickness of 1.0 μm using the apparatus described in 1 above, and dried at 80 ° C. for 5 minutes.

On the magnetic layer, using the device shown in FIG. 1,
The following protective layer coating liquid H-1 was applied to a dry film thickness of 0.2 μm and dried at 80 ° C. for 5 minutes.

Next, the following coating solution O-3 for overcoat layer (OC layer) was applied on the protective layer so as to have the coating amounts shown in Table 3, and dried at 100 ° C. for 3 minutes.

Further, the same photographic emulsion layer as Konica Color LV400, a color negative film commercially available from Konica Corporation, was provided on the surface of the support opposite to the back layer, and samples 301 to 307 and 312 having the contents shown in Table 3 were provided. ~ 319
Was produced.

In addition, on the conductive layer on the back surface side, as shown in FIG.
The coating solution M-1 for magnetic layer below and the coating solution H-1 for protective layer below were respectively dried using the apparatus described in 1.
And 0.2 μm were simultaneously coated at different positions. Drying was performed at 80 ° C. for 5 minutes. Then, the composition O-2 for the overcoat layer was applied on the second layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes. Furthermore, a color negative film Konica Color LV40 manufactured by Konica Corporation, which is commercially available, is provided on the surface of the support opposite to the back layer.
The same photographic emulsion layer as No. 0 was provided, and Samples 308 and 309 having the contents shown in Table 3 were prepared.

Further, on the conductive layer on the back surface side, as shown in FIG.
The coating solution M-1 for magnetic layer below and the coating solution H-1 for protective layer below were respectively dried using the apparatus described in 1.
And 0.2 μm at the same time. Drying was performed at 80 ° C. for 5 minutes. Then, the composition O-2 for the overcoat layer was applied on the second layer so as to have 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 surface of the support opposite to the back layer, and Sample 3 having the contents shown in Table 3 was provided.
10, 311 were produced.

<Coating Liquid M-1 for Magnetic Layer> Cellulose diacetate 82 g Co Coated γ-Fe ₂ O ₃ (long axis 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 oersted) 6.6 g DOP See Table 3 Acetone 990 g Cyclohexanone 110 g The above compositions were mixed, mixed with a dissolver for 1 hour, and then dispersed with a sand mill for 2 hours. Furthermore, tolylene diisocyanate trimethylol propane (TDI / TM
P) (15 g) was added, and the mixture was mixed with a dissolver for 1 hour to obtain a magnetic layer coating solution M-1.

<Protective Layer Coating Liquid H-1> Cellulose diacetate 5 g α-alumina particles (particle size 0.2 μm) See Table 3 Acetone 990 g Cyclohexanone 110 g However, the DOP of the magnetic layer coating liquid M-1 and the protective layer The addition amount of each α-alumina particle of the coating liquid H-1 for use was changed, and the addition amount is shown in Table 3.

[0119] <Overcoat coating liquid O-3>   Carnauba wax See Table 3   700 ml of toluene   Methyl ethyl ketone 300 ml.

The scratch resistance and the dynamic friction coefficient were measured for each of the prepared samples 301 to 319. Further, the adhesion resistance (after development) and the film adhesion were measured by the following methods. The evaluation results are shown in Table 3.

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

The development processing of each sample was performed as follows.

[0123] <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 Washing with water ... 3 minutes 15 seconds 24-41 ° C     4 Stationary ・ ・ ・ ・ 6 minutes 30 seconds 38.0 ± 3.0 ℃     5 Washing with water ... 3 minutes 15 seconds 24-41 ° C     6 Stability ・ ・ ・ ・ 3 minutes 15 seconds 38.0 ± 3.0 ℃     7 Drying ... 50 ° C or less The composition of the treatment liquid used in each step is shown below.

[0124] <Color developer>   4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline   ・ Sulfate 4.75g   Anhydrous sodium sulfite 4.25g   Hydroxylamine 1/2 sulfate 2.0g   Anhydrous potassium carbonate 37.5g   Sodium bromide 1.3g   Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g   1.0 g potassium hydroxide   Add water to make 1 liter (pH = 10.1) <Bleaching solution>   Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g   Ethylenediaminetetraacetic acid diammonium salt 10.0 g   Ammonium bromide 150.0 g   Glacial acetic acid 10.0g   Water is added to make 1 liter, and the pH is adjusted to 6.0 with aqueous ammonia.

[0125] <Fixer>   Ammonium thiosulfate 175.0 g   Anhydrous sodium sulfite 8.5g   Sodium metasulfite 2.3g   Add water to make 1 liter, and adjust to pH 6.0 with acetic acid.

[0126] <Stabilizer>   Formalin (37% aqueous solution) 1.5 ml   Conidax (Konica Corporation) 7.5 ml   Add water to make 1 liter.

<Adhesion resistance (after development)> Four samples after development were prepared for each sample, stacked in the same direction, sandwiched with thick paper of the same size, and fixed with a rubber band, and then heated to 55 ° C.
Leave for 3 days in an atmosphere of ℃ and 90% RH for 4
The ratio (%) of the ferro-like area due to contact to the total area of the three small pieces sandwiched between the samples was measured. The evaluation was ranked by the area of the ferro-like shape. If it is better than C rank, there is no problem in practical use, but B rank or higher is more preferable.

A less than 5% A ′ 5% or more and less than 10% B 10% or more and less than 20% C 20% or more and less than 30% D 30% or more and less than 50% E 50% or more <With film> 23 before development After adjusting the humidity to 55 ° C. at 55 ° C., a razor blade is used to make scratches reaching the support at a 45 ° angle in a grid pattern on the surface of the back layer, and then adhesive tape (cellophane adhesive tape) is pressure-bonded onto the scratches. About 4 of this tape
It peels off rapidly at an angle of 5 °. 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 the evaluation is made according to the following 6 levels. If it is better than C rank, there is no problem in practical use, but B rank or higher is more preferable.

A 0 A'less than 5% B 5% or more and less than 10% C 10% or more and less than 20% D 20% or more and less than 50% E 50% or more <Magnetic output error after development> Each sample is a film 25 for APS. Cut into 100 pieces in the form of a single sheet, and A
It was packed in a PS cartridge and a magnetic signal was input with a commercially available APS camera. After this was subjected to the above-mentioned development processing, 100 magnetic recording devices of a photographic printer were continuously passed through to measure reduction in reproduction output. The evaluation was ranked as follows according to the maximum output reduction width during 100 runs. If it is Δ or more, there is no problem in practical use.

[0130] ○: No decrease △: Decrease within -4db X: -4db or more decrease

[0131]

[Table 3]

From Table 3, it was found that by using the present invention, a silver halide photographic light-sensitive material having a magnetic recording layer excellent in scratch resistance and adhesion resistance can be obtained.

Further, it was found that simultaneous coating of the outermost layer of the back layer of the present invention and its adjacent layer further improved the film deposition.

Example 4 On the cellulose triacetate film, using the apparatus shown in FIG. 1, 20 ml / m of the following first layer coating liquid 1-4 was prepared.
^It was applied so as to be ^2, and dried at 80 ° C. for 5 minutes.

Next, the following conductive layer coating liquid A-4 was coated on the first layer using the apparatus shown in FIG. 1 so as to have a concentration of 20 ml / m ² , and dried at 80 ° C. for 5 minutes. .

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

Further, the same photographic emulsion layer as the commercially available Konica Color Negative Film Konica Color LV400 was provided on the surface of the support opposite to the back layer, and samples 401 to 410 having the contents shown in Table 4 were prepared. did.

On the cellulose triacetate film, using the apparatus shown in FIG. 2, the following first layer coating solution 1-
4 and the following conductive layer coating liquid A-4 20 ml each
/ M ² was simultaneously applied at different positions. Dry at 80 ℃
For 5 minutes. Then, the composition O-2 for the overcoat layer was applied on the conductive layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes. Further, the same photographic emulsion layer as the commercially available Konica Color Negative Film Konica Color LV400 was provided on the surface of the support opposite to the back layer.
1, 412 were produced.

On the cellulose triacetate film, the following coating solution for the first layer 1-using the apparatus shown in FIG.
4 and the following conductive layer coating liquid A-4 20 ml each
Simultaneous multi-layer coating was performed so as to be / m ² . Drying was performed at 80 ° C. for 5 minutes. Then, the composition O-2 for the overcoat layer was applied on the conductive layer so as to have a concentration of 10 ml / m ² , and dried at 100 ° C. for 3 minutes. Further, the same photographic emulsion layer as the commercially available Konica Color Negative Film Konica Color LV400 was provided on the surface of the support opposite to the back layer, and a sample 413 having the contents shown in Table 4 was prepared.
414 was produced.

<First Layer Coating Liquid 1-4> Cellulose diacetate 5 g DOP See Table 4 SiO ₂ particles (particle size 0.02 μm) See Table 4 Acetone 500 ml Ethyl acetate 500 ml <Conductive layer coating liquid A-4 > 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 liquid is dispersed with a stirrer and a sand mill to prepare a coating liquid A-4 for a conductive layer. did. However, DOP and SiO ₂ particles of the coating liquid 1-4 for the first layer, and antimony-doped tin oxide SN of Ishihara Sangyo Co., Ltd. of the coating liquid A-4 for the conductive layer
The amount of each -100P powder (hereinafter SnO2) was changed, and the amount added is shown in Table 4.

The scratch resistance and the adhesion resistance (raw) of each of the prepared samples 401 to 414 were measured. The conductivity was measured by the following method. The evaluation results are shown in Table 4.

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

<Conductivity> The sample was left for 12 hours in an environment of 23 ° C. and 55% RH. After that, in the same environment,
The surface resistivity was measured using a teraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. Conductivity is 1 × 10
There is no problem in practice if it is ¹² Ω / □ or less, but it is 1 × 10 ¹¹ Ω
/ □ or less, more preferably 1 × 1
It is less than 0 ¹⁰ Ω / □.

[0144]

[Table 4]

From Table 4, it was found that by using the present invention, a silver halide photographic light-sensitive material excellent in scratch resistance and adhesion resistance can be obtained.

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

[0147]

According to the present invention, there is provided a silver halide photographic light-sensitive material having a back layer which is excellent in scratch resistance and adhesion resistance without causing conveyance defects in manufacturing processes, cameras, laboratory equipment and the like. I was able to. It also has excellent wear resistance,
A silver halide photographic light-sensitive material and a magnetic recording medium having a magnetic recording layer excellent in scratch resistance and adhesion resistance were obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of sequential coating.

FIG. 2 is a schematic view of simultaneous coating at different positions.

FIG. 3 is a schematic diagram of simultaneous multilayer coating.

[Explanation of symbols]

1 Coater for adjacent layer coating liquid 1'Coater for outermost layer coating liquid 2 drying zone 2'dry zone 3 support 4 Simultaneous multilayer coating coater

─────────────────────────────────────────────────── ─── Continued Front Page (56) References JP-A-7-20610 (JP, A) JP-A-7-181638 (JP, A) JP-A-8-161731 (JP, A) JP-A-8- 235561 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/76 502 G03C 1/74 G03C 1/00 G11B 5/62-5/82

Claims (6)

(57) [Claims] 1. A silver halide photographic light-sensitive 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 outermost layer of the back layer has an elastic modulus of 350 kgf / mm ² or more, and the adjacent layer has an elastic modulus of 300 kgf / m 2.
A silver halide photographic light-sensitive material characterized by having a size of m ² or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the outermost layer of the back layer and its adjacent layer are formed by simultaneous coating. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the outermost surface of the back layer has a dynamic friction coefficient with respect to the polystyrene plate of 0.15 to 0.40. 4. In a magnetic recording medium having at least one magnetic recording layer on one side of a support, the outermost layer on the side having the magnetic recording layer has an elastic modulus of 350 kgf / mm ² or more, and Elastic modulus of adjacent layer is 300kgf / m
A magnetic recording medium characterized by being m ² or less. 5. The magnetic recording medium according to claim 4, wherein the outermost layer and its adjacent layer are formed by simultaneous coating. 6. The magnetic recording medium according to claim 4, wherein the coefficient of dynamic friction with respect to the polystyrene plate on the outermost surface on the magnetic recording layer side is 0.15 to 0.40.