JPH117103A - Silver halide photographic sensitive material and magnetic record medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having excellent adhesion property to a supporting body and excellent scratching resistance before, during and after development. SOLUTION: This material has at least one photosensitive silver halide emulsion layer on a polyester supporting body. At least one surface of the supporting body is subjected to surface treatment. A layer containing water-soluble or water-dispersible polymers having 2-oxazolite groups expressed by the formula is coated on the adjacent layer to the treated surface. In the formula, R1 , R2 , R3 , R4 are independently halogen, alkyl, aralkyl, phenyl or substd. phenyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material and a magnetic recording medium. Specifically, a silver halide photographic material having excellent adhesion and scratch resistance between a support and an adjacent layer before and during and after development, and a magnetic material having excellent scratch resistance against passage of a magnetic head. The present invention relates to a silver halide photographic material having a recording medium and a magnetic recording layer.

[0002]

2. Description of the Related Art Conventionally, when a photographic film is generally scratched, an unnecessary streak is formed in a printed photographic image and the commercial value is lost. Therefore, it has been practiced to improve the film strength of each layer constituting the film and prevent abrasion.
However, even if the film strength of each layer is high, if the adhesive strength between the support and the adjacent layers and between the layers is insufficient, peeling may occur from the interface and the film may peel off like a scratch.
In particular, it is difficult to achieve adhesion between the hydrophobic polyester support and its adjacent layers.

[0003] Techniques for improving the adhesion between the support and the adjacent layer include a technique in which a pretreatment such as corona discharge treatment and a glow discharge treatment is applied to the surface of the support in advance, and a technique in which a crosslinking agent is added to the support adjacent layer. Alternatively, it is known to use these techniques in combination. Specific examples of the crosslinking agent are described in JP-A-51-1.
No. 03422, Epoxy compounds described in
And triazine compounds described in JP-A-114120.

However, as manufacturing processes, pre-development preparations, development processing, and printing processing have become increasingly faster, scratches are more likely to occur, and in the prior art, the adhesive force between a support and an adjacent layer is increased. Has become insufficient.

Also, in the case of a magnetic recording medium, if the adhesive strength between the support and the adjacent layer is insufficient, abrasion is caused when the magnetic head passes during writing or reading of the magnetic field, resulting in a fatal defect in magnetic recording. Becomes Particularly, in recent years, as described in U.S. Pat. Nos. 3,782,947, 4,279,945 and 4,302,523, a transparent magnetic recording layer is formed on the back surface of a photosensitive material. However, it has been proposed that the magnetic recording medium having such a silver halide photosensitive layer maintain the same adhesive strength even after the development processing, and the adhesive strength was not sufficient in the prior art.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve the adhesiveness and scratch resistance between a support and an adjacent layer before and during development and after development. Another object of the present invention is to provide a silver halide photographic light-sensitive material having excellent magnetic recording medium and a silver halide photographic light-sensitive material having a magnetic recording layer having excellent scratch resistance against passage of a magnetic head.

[0007]

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

(1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a polyester support, at least one surface of the support is subjected to a surface treatment, and the surface treatment is performed. Wherein a layer containing a water-soluble or water-dispersible polymer having a 2-oxazoline group represented by the following general formula (A) is provided on a layer adjacent to the surface on which silver halide has been applied. material.

[0009]

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Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl. (2) The support is made of polyethylene terephthalate or polyethylene The silver halide photographic material as described in the above item (1), comprising naphthalate as a main component.

(3) The silver halide photographic material as described in (1) or (2) above, wherein the surface treatment is a corona discharge treatment, a glow discharge treatment, an ultraviolet irradiation treatment, or a flame treatment.

(4) The silver halide photographic light-sensitive material according to the above (3), wherein 5% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-soluble polymer having a 2-oxazoline group. material.

(5) The silver halide photograph as described in (3) above, wherein 15% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group. Photosensitive material.

(6) The silver halide photograph as described in (5) above, wherein 60% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group. Photosensitive material.

(7) After applying a layer containing a polymer having a 2-oxazoline group, heat-treating at 90 to 150 ° C. for 1 minute or more. 2. The silver halide photographic material according to claim 1.

(8) The number of oxygen atoms (atomic%) of the surface layer of the surface-treated support after the surface treatment.
The silver halide photographic light-sensitive material according to any one of the above (1) to (7), wherein is higher by 1.5 to 10 atomic% than before surface treatment.

(9) In a magnetic recording medium having at least one magnetic recording layer on a polyester support, at least one surface of the support is subjected to a surface treatment, and is adjacent to the surface that has been subjected to the surface treatment. The layer has the following general formula (A)
A magnetic recording medium comprising a layer containing a water-soluble or water-dispersible polymer having a 2-oxazoline group represented by the formula:

[0018]

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(Wherein, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent hydrogen, halogen, alkyl, aralkyl, phenyl, or substituted phenyl). (10) The support is made of polyethylene terephthalate or polyethylene The magnetic recording medium according to (9), wherein naphthalate is a main component.

(11) The magnetic recording medium according to (9) or (10), wherein the surface treatment is a corona discharge treatment, a glow discharge treatment, an ultraviolet irradiation treatment, or a flame treatment.

(12) The magnetic recording medium according to (11), wherein 5% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-soluble polymer having a 2-oxazoline group.

(13) The magnetic recording medium according to (11), wherein 15% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group.

(14) The magnetic recording medium according to (13), wherein 60% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group.

(15) After applying a layer containing a polymer having a 2-oxazoline group, heat-treating at 90 to 150 ° C. for 1 minute or more.
4. The magnetic recording medium according to any one of 4).

(16) Atomic% of oxygen atoms in the surface layer of the surface-treated support after surface treatment.
%) Is 1.5 to 10 atomic compared to before surface treatment.
(9) to (15), wherein
The magnetic recording medium according to the above.

Hereinafter, the present invention will be described in detail.

An example in which an oxazoline compound is contained in a layer adjacent to a support is disclosed in JP-A-4-181244. However, the technology disclosed here is a technology aimed at improving the film strength by the reaction between the carboxyl group and oxazoline in the binder in the adjacent layer, and is different from the present invention because it is premised that no surface treatment is performed. Technology. This technique did not provide sufficient adhesion between the support and the adjacent layer to satisfy the above circumstances.

In the present invention, it has been found that a combination of an oxazoline compound and a surface treatment provides an unexpectedly high adhesive strength and an adhesive strength satisfying the above requirements. Although the detailed mechanism is unknown, the reactivity between the oxygen-containing group and the 2-oxazoline group generated in the surface layer of the support by the surface treatment is extremely high, and the adhesive force is obtained by directly crosslinking with the support. I guess.

The water-soluble polymer having a 2-oxazoline group of the present invention is a water-soluble polymer having a 2-oxazoline group represented by the following general formula (A) as a pendant.

[0030]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl, preferably hydrogen or lower alkyl. In particular, And the like.

JP-A-5-2952 as a water-soluble polymer
No. 75 polymer (B). In particular,
As monomers having a 2-oxazoline group, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Solution polymerization of 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and at least one other monomer as necessary in an aqueous medium by a conventionally known polymerization method. Can be synthesized.

The amount of the monomer having a 2-oxazoline group is not particularly limited.
It is preferable that the content of the monomer having a 2-oxazoline group is at least 5% by weight, more preferably at least 5% by weight and at most 100% by weight.

Other monomers include, for example, methyl acrylate, ethyl acrylate, n- or i-propyl acrylate, n-, i- or t-butyl acrylate,
2-hydroxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol acrylate, α-chloro-methyl acrylate, α-chloro-ethyl acrylate, methyl methacrylate, ethyl methacrylate, n
-Or i-propyl methacrylate, n-, i- or t
-Butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate,
Acrylates such as propylene glycol dimethacrylate and polyethylene glycol methacrylate, methacrylates, or α-chloro-acrylates, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl benzoate, etc. Vinyl esters, ethyl vinyl ketone,
Vinyl ketones such as cyclohexyl vinyl ketone, styrenes such as styrene, methyl styrene, chlorostyrene and divinyl benzene, acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, n- or i-dipropylacrylamide, n-, i
-Or acrylamides such as t-dibutylacrylamide, and chloroolefins such as vinyl chloride and vinylidene chloride.

However, in order to impart water solubility to the polymer, it is necessary that at least 50% of the constituent monomers are hydrophilic monomers. As the hydrophilic monomer, the above-mentioned monomer having a 2-oxazoline group, and as other monomers, 2-hydroxyethyl acrylate, methoxypolyethylene glycol acrylate, 2-aminoethyl acrylate and salts thereof, acrylamide, N-methylolacrylamide, N- (2 -Hydroxyethyl) -acrylamide, acrylonitrile, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, aminoethyl methacrylate and salts thereof, methacrylamide, N-methylol methacrylamide, N- (2-hydroxyethyl) -methacrylamide, methacryl Nitrile, sodium styrenesulfonate and the like.

Specific examples (numerical values are molar ratios) include: W-1: 2-isopropenyl-2-oxazoline (10
0) W-2: 2-vinyl-2-oxazoline / ethyl acrylate (70/30) W-3: 2-isopropenyl-2-oxazoline / 2-
Hydroxyethyl methacrylate / n-butyl methacrylate (60/20/20) W-4: 2-vinyl-5-methyl-2-oxazoline /
Acrylamide (80/20) and the like can be mentioned, but it is not limited to these. In addition, commercially available water-soluble polymers can also be used. For example, Epocross WS-500, WS-300
(Each is Nippon Shokubai Co., Ltd.).

The water-dispersible polymer having a 2-oxazoline group according to the present invention is a water-dispersible polymer having a 2-oxazoline group represented by the above formula (A), and is specifically described in JP-A-2-99537. Described polymer (B).

Specifically, for example, a monomer having a 2-oxazoline group as described above and, if necessary, at least one other monomer as described above are emulsified by a conventionally known emulsion polymerization method or a core / shell structure. It can be synthesized by performing a polymerization method or the like.

The amount of the monomer having a 2-oxazoline group is not particularly limited.
It is preferable that the content of the monomer having a 2-oxazoline group is at least 5% by weight, more preferably at least 5% by weight and at most 100% by weight.

The synthesis method is described, for example, in W. R. Sorenso
n, T. W. The compound can be synthesized by the method described in “Experimental Method for Polymer Synthesis”, pages 144 and 152 (Tokyo Kagaku Dojin), co-authored by Cambell (translated by Toshio Hoshino and Naoya Yoda).
Emulsion polymerization for forming a core / shell structure can be synthesized by a method described in JP-A-8-286301.

As specific examples (numerical values are molar ratios), P-1: 2-isopropenyl-2-oxazoline / styrene / ethyl acrylate (30/40/30), P-2: 2-vinyl-2-oxazoline / Methyl methacrylate / cyclohexyl methacrylate (40/40
/ 20), P-3: 2-isopropenyl-4-methyl-2-oxazoline / n-butyl acrylate / styrene (30/3
5/35), P-4: 2-isopropenyl-2-oxazoline / n-
Butyl acrylate / styrene / divinylbenzene (3
0/30/30/10), and the like, but are not limited thereto. In addition, commercially available water-dispersible polymers can also be used, and Epocross K-1010E, K-1020E,
K-1030E, K-2010E, K-2020E, K
-2030E (Nippon Shokubai Co., Ltd.).

Next, the polyester support used in the present invention will be described. The polyester support used in the present invention is a polyester containing a dicarboxylic acid component and a diol component as main components.

The main dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid,
Examples thereof include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, and phenylindanedicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexane dimethanol,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 9,
Examples thereof include 9-bis (4,4′-di-β-hydroxyethyl) fluorene, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

Among the polyesters containing these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and diol components as a dicarboxylic acid component from the viewpoint of transparency, mechanical strength, dimensional stability and the like. And polyesters containing ethylene glycol and / or 1,4-cyclohexanedimethanol as main constituents. Among them, a polyester containing a polyethylene terephthalate unit and a polyethylene-2,6-naphthalate unit is preferable. Ethylene terephthalate unit or ethylene-2, for polyester
When the 6-naphthalate unit is contained in an amount of 70% by weight or more, a film having excellent transparency, mechanical strength, dimensional stability and the like can be obtained.

As long as the effects of the present invention are not impaired, the polyester constituting the polyester film used in the present invention may be further copolymerized with other copolymer components or may be mixed with other polyester. May be.
Examples of these include the above-mentioned dicarboxylic acid components and diol components, and polyesters.

The polyester used in the present invention preferably contains a dye for the purpose of preventing the light piping phenomenon. Dyes to be compounded for such purposes are not particularly limited in type, but it is necessary to have excellent heat resistance in film production, and anthraquinone-based and perinone-based dyes are used. No. Further, as the color tone, gray dyeing is preferable as seen in general photographic light-sensitive materials.

Although the thickness of the polyester film is not particularly limited, it is 20 to 125 μm, especially 40 to 90 μm.
μm is preferred.

The haze of the polyester film is preferably 3% or less. More preferably, it is 1% or less. If the haze is more than 3%, when the film is used as a support for a photographic light-sensitive material, an image printed on a photographic paper becomes blurred and unclear. The haze is
It is measured according to ASTM-D1003-52.

The glass transition point Tg of the polyester film used in the present invention is preferably 60 ° C. or higher, and more preferably 7 ° C.
The temperature is preferably from 0 ° C to 150 ° C. Tg is determined by measuring with a differential scanning calorimeter. When the Tg is in this range, the photosensitive material is free from deformation of the film in the drying step of the development processor and has a small curl after development.

Next, a method for producing the polyester film used in the present invention will be described, but is not particularly limited. A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method.
For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled, solidified, and unstretched Get a sheet. Next, the obtained unstretched sheet is heated in a range from Tg of the polyester to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and subjected to single-stage or multi-stage longitudinal stretching. Stretching ratio is usually 2.5 times
In the range of 6 times, it is necessary to set the range in which the subsequent transverse stretching is possible.

The polyester film uniaxially stretched in the machine direction obtained as described above is subjected to Tg to Tm (melting point)-
In the temperature range of 20 ° C., the film is stretched laterally and then heat-set.
The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is to measure the physical properties of the obtained biaxially stretched film.
It is adjusted appropriately so as to have preferable characteristics. Generally, it is preferable to balance the physical properties in the width direction and the longitudinal direction, but they may be changed according to the purpose of use. At this time, it is preferable to perform transverse stretching while sequentially increasing the temperature in the range of 1 to 50 ° C. in the stretching region divided into two or more portions because the distribution of physical properties in the width direction can be reduced, which is preferable. Further, after the transverse stretching, the film is brought into a temperature range of Tg-40 ° C. or higher at a temperature not higher than the final transverse stretching temperature.
Holding for 5 minutes or less is preferable because the distribution of physical properties in the width direction can be further reduced.

The heat setting is carried out at a temperature higher than the final transverse stretching temperature and within a temperature range of Tm-20 ° C. or lower, usually from 0.5 to 30 ° C.
Heat set for 0 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature in a range of 1 to 100 ° C. in the two or more divided regions.

The heat-fixed film is usually cooled to Tg or less, cut off the clip holding portions at both ends of the film, and wound up. At this time, within the temperature range of not more than the final heat-setting temperature and not less than Tg, 0.1 to 0.1 in the width direction and / or the longitudinal direction.
It is preferable to perform a 10% relaxation treatment. Further, it is preferable that the cooling is gradually performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second.

Since the most optimal conditions of the heat setting, cooling and relaxation treatment conditions differ depending on the polyester constituting the film, the physical properties of the obtained biaxially stretched film are measured and adjusted appropriately so as to have preferable characteristics. It may be determined by doing so.

For the polyester film, various methods are used to reduce the curl. For example, JP
As described in JP-A-16358, there is a method of performing heat treatment at a temperature lower than the glass transition point Tg of the polyester film by 30 ° C. to 5 ° C. Also, JP-A-1-131550
In Japanese Patent Application Publication No. 2000-216, there is described a method in which, in a sequential biaxial stretching step, a permanent curl is imparted by giving a difference in crystallinity and orientation by giving a temperature gradient between the front and back of the film between longitudinal stretching and transverse stretching. In addition, a method of canceling the curl with the lapse of time during storage when the product is wound up in a direction opposite to the curl when winding the product, or a method of forming a polyester film formed by giving a temperature difference during stretching to a temperature of 50 ° C. or lower below the glass transition point. A heat treatment is also known. The support, which is unlikely to be effectively curled by heat treatment, has a glass transition point of 90 ° C or more and 200 ° C or more.
The following polyesters are preferred. This is because the effect of this heat treatment disappears when exposed to a temperature exceeding the glass transition point, so that the highest temperature to which the general user is exposed during use (the temperature in a car in summer may exceed 80 ° C.).
This is because it preferably has a glass transition point of 90 ° C. or more based on the above. Further, there is no general-purpose polyester film having transparency and a glass transition point exceeding 200 ° C. at present.

Particularly preferred as the polyester is a support containing polyethylene terephthalate or polyethylene naphthalate as a main component. The support is a film made of polyethylene terephthalate or polyethylene naphthalate or a copolymer thereof, or a film made of a composition using these as a raw material. The support is preferably used after heat-setting after biaxial stretching, and may be thermally relaxed if necessary.

In this case, it is necessary to perform the heat treatment at a temperature of 50 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. Among them, a particularly preferable heat treatment method is, for example, T in the case of polyethylene naphthalate.
g is about 120 ° C. Therefore, it is preferable to heat-treat at a temperature of 119 ° C. or less for 0.2 to 72 hours, and more preferably at 115 ° C. or less for about 24 hours. In particular, in order to perform heat treatment in a short time, it is very efficient and preferable to raise the temperature once to Tg or more and gradually cool around Tg. In the case of polyethylene naphthalate, as an example, the heat treatment time can be significantly reduced by once maintaining the temperature between 130 ° C. and 200 ° C., cooling to 125 ° C., and then gradually cooling to 100 ° C. for 40 minutes. When the support subjected to such heat treatment is measured by a differential thermal analyzer, an endothermic peak appears near Tg, and the larger the endothermic peak is, the less likely the winding habit is. Also, 100mcal / g
As described above, it is preferable that the heat treatment be performed so as to be 200 mcal / g or more.

The surface treatment of the support of the present invention will be described. Examples of the surface treatment of the present invention include corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, high frequency treatment, active plasma treatment, and laser treatment. Among them, corona discharge treatment, glow discharge treatment, ultraviolet light Irradiation treatment and flame treatment are preferred.

Among the surface treatments, corona discharge treatment is the most well-known method.
Nos. 43 and 47-51905, and JP-A-47-2806.
No. 7, No. 49-83770, No. 51-41770,
The method can be performed by the method disclosed in JP-A-51-131576 or the like.

The discharge frequency is 50 Hz to 5000 kHz,
Preferably, a frequency of 5 kHz to several 100 kHz is appropriate. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes occur in the object to be processed, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the price of the device, which is not preferable. Regarding the treatment intensity of the object to be treated, 0.001 kV
A · min / m ^{2 to 5} kV · A · min / m ² , preferably
An appropriate value is from 01 kV · A · min / m ^{2 to 1} kV · A · min / m ² . The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

In many cases, glow discharge treatment, which is the most effective surface treatment, can be performed by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578, 36-10336, 45-22004, and 45-22004. 45-22005, 45-2005
No. 24040, No. 46-43480, U.S. Pat.
57,792, 3,057,795, 3,17
9,482, 3,288,638, 3,30
9,299, 3,424,735, 3,46
No. 2,335, No. 3,475,307, No. 3,76
1,299, British Patent 997,093,
No. 129262 can be used.

In general, the glow discharge treatment conditions are as follows:
005 to 20 Torr, preferably 0.02 to 2 Torr
r is appropriate. If the pressure is too low, the effect of the surface treatment is reduced. If the pressure is too high, an excessive current flows, sparks are likely to occur, which is dangerous, and there is a possibility that the object to be treated may be destroyed. The discharge is generated by applying a high voltage between metal plates or metal rods arranged at one or more spaces in a vacuum tank. This voltage depends on the composition of the atmosphere gas,
Although various values can be taken depending on the pressure, a stable steady-state glow discharge generally occurs at a voltage of 500 to 5000 V within the above-mentioned pressure range. A particularly suitable voltage range for improving the adhesion is from 2000 to 4000V. Also,
As the discharge frequency, as seen in the prior art, from DC to several 1000 MHz, preferably 50 Hz to 20 MHz
Is appropriate. Regarding the discharge treatment strength, 0.01 kV · A · min / m ² -5
kV · A · min / m ^2, preferably 0.15kV · A · min / m ² ~1kV · A · min / m ^2, is suitable.

The ultraviolet irradiation treatment is described in, for example, Japanese Patent Publication No. 43-2
No. 603, No. 43-2604, and No. 45-3828.

Regarding the method of irradiating ultraviolet rays, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source unless the surface temperature of the support rises to about 150 ° C. if the performance of the support is not a problem. . When low-temperature treatment is required, a low-pressure mercury lamp having a main wavelength of 254 nm is preferred. It is also possible to use an ozone-less high-pressure mercury lamp and a low-pressure mercury lamp. Regarding the amount of processing light, as the amount of processing light increases, the adhesive strength between the support and the adjacent layer increases, but the problem arises in that the support is colored and the support becomes brittle as the amount of light increases. Therefore, an ordinary polyester film is irradiated with a high-pressure mercury lamp having a main wavelength of 365 nm using an irradiation light amount of 20 to 10,000 (m).
J / cm ² ), more preferably 50-2000.
(MJ / cm ² ). In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 10,000.
(MJ / cm ² ), more preferably 300 to 15
00 (mJ / cm ² ).

The fire processing will be described. The gas used for the fire treatment may be any of natural gas, liquefied propane gas and city gas, but the mixing ratio with air is important. This is because the effect of the surface treatment by the fire treatment is considered to be brought about by the plasma containing active oxygen, and the plasma activation (temperature) which is an important property of the fire is considered.
The point is how much oxygen there is. These two factors are determined by the gas / oxygen ratio. When the reaction is performed without excess or deficiency, the energy density becomes highest and the plasma activity becomes high. Specifically, the preferred mixing ratio of natural gas / air is 1/6 to 1/10 by volume, preferably 1
/ 7 to 1/9. In the case of liquefied propane gas / air, it is 1/14 to 1/22, preferably 1/16 to 1/1.
9. In the case of city gas / air, the ratio is 1/2 to 1/8, preferably 1/3 to 1/7.

The fire treatment rate is 1 to 50 kcal / m.
² , more preferably in the range of 3 to ²⁰ kcal / m ² . The distance between the tip of the internal flame of the burner and the support is 3
7 cm, more preferably 4-6 cm. Burner nozzle shapes are Flynn Burner (US) ribbon type, Wise (US) multi-hole type, Aerogen (UK) ribbon type, Kasuga Electric (Japan) staggered multi-hole type, Koike oxygen ( The Japanese staggered multi-hole type is preferred. The backup roll that supports the support in the fire treatment is a hollow roll, which is preferably cooled with water through cooling water and always treated at a constant temperature of 20 to 50 ° C.

The atomic number% (atomic%) of oxygen atoms in the surface layer of the support before and after the surface treatment was determined by XPS (X-ray photoelectron spectroscopy).
It was measured by a surface analyzer. The method will be described below.

First, the XPS surface analyzer is set under the following conditions.

X-ray anode: Mg X-ray output: 600 W Photoelectron take-up angle: 30 to 60 degrees Resolution: 1.5 to 1.7 eV (resolution is defined by the half width of 3d5 / 2 peak of clean Ag) No so-called adhesive tape is used for fixing the sample. The model of the XPS surface analysis apparatus is not particularly limited, and various apparatuses can be used. In this application, VG ESCALAB-200R was used.

In the measurement, the elements were qualitatively determined by a wide scan, and the detected elements were further subjected to a narrow scan to measure the spectrum of each element. At this time, the data capture interval was 0.2 eV. Next, a Count Scale calibration is performed for each element, and a 5-point smoothing process is performed. Further, the peak area intensity (cps * eV) is obtained for each element,
Corrected by the sensitivity coefficient, the atomic% of each element was determined.

The measurement of X-ray photoelectron spectroscopy
For example, D. Brix, M.S. P. Shia (Yoichi Koshi,
"Surface Analysis-Basics and Applications-" (Agne Shofusha) etc. can be referred to.

The undercoat layer (layer adjacent to the support) of the present invention will be described.

The undercoating material that can be used in the present invention is not particularly limited as long as it is a material having good film-forming properties. Examples thereof include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, Examples include acrylic copolymers, vinylidene copolymers, epoxy copolymers, and gelatin, and these may be used alone or as a mixture.

Further, the water-soluble or water-dispersible polymer having a 2-oxazoline group of the present invention is mixed with the above-mentioned material. The amount of addition is preferably 5% by weight or more in the case of a water-soluble oxazoline group-containing polymer, and preferably 15% by weight or more of a water-dispersible oxazoline group-containing polymer. Further, the content of the water-dispersible oxazoline-containing polymer is more preferably 60% by weight or more, and the water-dispersible oxazoline-containing polymer may be used alone without being used in combination with the above materials.

If necessary, in addition to the above materials, a matting agent, a surfactant, inorganic fine particles, a pH adjuster and the like may be added. Further, a conductive material may be used in combination with the conductive layer. Is also good.

The means for coating the undercoat layer of the present invention is not particularly limited, and a known method can be used.
In general, the timing of applying the undercoat layer is before or after stretching during film formation of the support.

Further, in the present invention, after the layer containing the polymer having a 2-oxazoline group is applied, the temperature is from 90 ° C. to 1 ° C.
The heat treatment is preferably performed at 50 ° C. for 1 minute or more. There is no particular limitation on the timing of the heat treatment. For example, the heat treatment can be performed continuously after the coating and drying of the layer. In addition, the heat treatment can also be performed together with the above-described heat treatment for curling reduction.

In the present invention, it is preferable that at least one antistatic layer is provided on either side of the support.

For the conductive layer used in the present invention, generally, most of antistatic agents and antistatic compositions useful for silver halide photographic materials can be used. For example, styrene-sodium maleate copolymer described in JP-B-47-28937 or JP-B-49-23828, sodium vinylbenzylsulfonate copolymer described in JP-A-53-82876, JP-B-48-23451. Anionic antistatic agents such as sodium styrene sulfonate polymer or copolymer described in JP-A-51-42535,
Ionene polymers described in JP-A-54-159222 and JP-A-55-7763 (for example, a polymer of triethylenediamine and xylidenedichloride), and polyene described in U.S. Pat. No. 2,882,157 Methacrylylethyldiethylmethylammonium methylsulfonate, JP-B-60-51693, JP-A-61-223
No. 736 and Japanese Unexamined Patent Publication No. 62-9346, crosslinked copolymer particles having a quaternary ammonium group in the side chain (for example,
Copolymer [N, N, N-trimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene]), copolymer particles having a cross-linked ionene polymer or having an ionene polymer as a side chain described in JP-A-7-28194 (E.g., a crosslinking reaction product of polyvinyl benzyl chloride and terminal N- (polymer of triethylenediamine and xylidenedichloride));
Those containing alumina sol as a main component described in JP-B-57-12979 and Zn described in JP-A-57-104931.
O, SnO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
_{O 2, MgO, BaO, MoO} 3, ZiO particulate metal oxides such as _2, V ₂ O ₅ or the like of the metal oxide antistatic agent described in JP-B-55-5982, higher fatty described in JP-B-52-32572 Alcohol phosphate antistatic agent, poly (isothianaphthene) described in JP-A-2-252726
System, JP-A-2-255770 or JP-A-2-308
No. 246, such as a conjugated double bond conductive polymer.

In particular, among the above-described antistatic agents, it is preferable to use a copolymer of sodium styrenesulfonate or a metal oxide as a main component.

Next, the magnetic recording layer will be described. As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, and the like can be used. Methods for producing these magnetic powders are 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, and 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. For example, it may be surface-treated with a substance containing an element such as titanium, silicon, or aluminum, or may be an adsorption having a nitrogen-containing heterocyclic ring such as carboxylic acid, sulfonic acid, sulfate ester, phosphonic acid, phosphate ester, and benzotriazole. It may be treated with an organic compound such as an acidic compound. The pH of the magnetic powder is not particularly limited, but is preferably in the range of 5 to 10.

Regarding the size of the magnetic particles, it is known that there is a correlation between the size and the transparency.
Vol. 20, No. 2, "Characteristics of Ultrafine Particle Translucent Magnetic Recording Media and Their Applications". For example, γ-Fe ₂ O ₃
In the acicular powder, the light transmittance is improved by reducing the particle size.

US Pat. No. 2,950,971 describes that a magnetic layer composed of magnetic iron oxide dispersed in a binder transmits infrared rays, and US Pat. No. 4,279,945. The specification describes that, even when the concentration of magnetic particles in the magnetic layer is relatively high, reducing the particle size improves the transmittance of helium-neon laser light having a wavelength of 632.8 nm.

However, when a magnetic recording layer is provided in an image forming area of a silver halide color photographic light-sensitive material, not only a red area but also a green area and a blue area must have high light transmittance.

For this reason, the particle size of the magnetic particles is reduced, and the amount of the magnetic particles applied is also limited.

If the particle diameter of the magnetic particles is reduced to a certain degree or more, required magnetic characteristics cannot be obtained. Therefore, it is preferable to reduce the particle size of the magnetic powder as long as necessary magnetic characteristics can be obtained. Also, the coating amount of the magnetic particles is
If the amount is reduced to a certain degree or more, the required magnetic characteristics cannot be obtained. Therefore, it is preferable to reduce the amount as long as the required magnetic characteristics can be obtained.

Practically, the coating amount of the magnetic substance 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, and mixtures thereof, which are conventionally used for magnetic recording media, can be used.

The thermoplastic resin has a glass transition point Tg of -4.
0 ° C. to 150 ° C., preferably 60 ° C. to 120 ° C., and a weight average molecular weight of 10,000 to 300,000
Are preferred, and more preferably those having a weight average molecular weight of 50,000 to 200,000.

The binder of the magnetic recording layer in the present invention preferably comprises a cellulose ester as a main component. Specifically, cellulose binders such as cellulose diacetate, cellulose acetate butyrate and cellulose acetate propionate; cellulose nitrate System; cellulose sulfate system and their mixed ester system, etc.
Preference is given to cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, especially cellulose diacetate.

The binder may be hardened. Hardening agents that can be used include aldehyde compounds, ketone compounds, compounds having reactive halogens, compounds having reactive olefins, N-hydroxymethylphthalimide, N-methylol compounds, isocyanates, and aziridines. Examples include compounds, acid derivatives, epoxy compounds, halogen carboxaldehydes and inorganic compound hardeners.

The hardener is usually added in an amount of 0.1 to the binder.
0.1 to 30% by weight, preferably 0.05 to 20%
% By weight.

The magnetic material powder is dispersed in a binder using a solvent as 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 that the magnetic particles are dispersed and dispersed as much as possible without damaging the magnetic particles.

When forming an optically transparent magnetic recording layer, the binder is used in an amount of 1 to 20 parts by weight based on 1 part by weight of the magnetic powder.
It is preferred to use parts by weight. More preferably, the amount is 2 to 15 parts by weight based on 1 part by weight of the magnetic powder. The solvent is used in such an amount that the coating can be easily performed.

The thickness of the magnetic recording layer is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, even more preferably from 0.5 to 3 μm.

The coating liquid for forming the magnetic recording layer contains a lubricant, an antistatic agent, etc. in order to provide the magnetic recording layer with functions such as imparting lubricity, preventing static electricity, preventing adhesion, and improving friction and abrasion characteristics. Various additives such as an agent can be added. In addition, in addition to the coating liquid, for example, a plasticizer to give flexibility to the magnetic recording layer, a dispersant to help disperse the magnetic material in the coating liquid, to prevent clogging of the magnetic head Abrasive can be added.

If necessary, a protective layer may be provided on the outermost layer adjacent to the magnetic recording layer to improve the scratch resistance. For imparting scratch resistance, a compound generally known as a slipping agent can be used, and a higher fatty acid ester is preferable. In the case where the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic substance may be provided thereon to eliminate a step due to the magnetic recording layer.
In this case, the transparent polymer layer may have the various functions described above.

The silver halide emulsion of the light-sensitive material of the present invention comprises
For example, Research Disclosure (hereinafter abbreviated as “RD”) No. 17643, 22-23 (1978)
December, "I. Emulsion production (Emulsion pre
para-tion and types) "and N
o. 18716, p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkide)
s, Chemic etPhisique Photo
graphique, Paul Montel, 196
7), Duffin, "Photographic Emulsion Chemistry," published by Focal Press (GF Duffin, Photographic)
Emulsion Chemistry, Focal
Press 1966), Zerikman et al., "Manufacture and Coating of Photographic Emulsion", published by Focal Press (VL Zeli).
kman et al, Making and Coa
ting Photographic Emulsio
n, Focal Press, 1964).

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,665,394 and British Patents 1,4.
The monodisperse emulsion described in JP-A-13,748 is also preferable.

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.
18716 and the same No. 308119 (hereinafter RD17643, RD18716 and RD308119, respectively)
Abbreviated).

When the light-sensitive material of the present invention is a color photographic light-sensitive material, the photographic additives that can be used are also those of the above-mentioned R.
D. Further, various couplers can be used, and specific examples thereof are also RD17643 and RD30.
8119.

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

The color photographic light-sensitive material includes RD30 as described above.
An auxiliary layer such as a filter layer or an intermediate layer described in 8119 II-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 of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The T
heavy of The Photographic
Process Forth Edition) No. 291
Pages-334 and Journal of the American Chemical Society (Journal of the Ame)
rice chemical Society) No. 7
3, page 3,100 (1951),
Known developers can be used. Also,
The color photographic light-sensitive material is RD17643 28-2 described above.
9 pages, RD18716 pages 615 and RD308119
Development can be carried out by the usual method described in XIX.

[0107]

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

Example 1 <Preparation of support> 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol, and A transesterification reaction was performed according to the following.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.03 parts by weight of trimethyl phosphate was added.
Then, gradually raise the temperature and reduce the pressure, 290 ° C, 0.05 mm
Polymerization was performed under Hg conditions to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

This was vacuum-dried at 150 ° C. for 8 hours, melt-extruded in a layer form from a T-die at 300 ° C., brought into close contact with a cooling drum at 50 ° C. while applying static electricity, solidified by cooling, and unstretched sheet was formed. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. at a total transverse stretching ratio of 3. The film was stretched three times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while relaxing in the transverse direction by 5% to obtain a polyethylene naphthalate (PEN) film having a thickness of 85 μm.

This is wound around a stainless steel core, and
The support was prepared by heat treatment at 10 ° C. for 48 hours.

Furthermore, a polyethylene terephthalate (PET) film having a thickness of 90 μm was prepared.

One surface of the support thus obtained is subjected to a surface treatment such as a corona discharge treatment with the strength shown in Table 1. On the undercoat layer, as an undercoat layer containing the 2-oxazoline group-containing polymer of the present invention, the following undercoat material and crosslinking agent were used.
The mixture was mixed in the ratio described, and the compound UL-1 was further added.
A liquid to which 1 wt% of a solid content (described later) was added was applied to a dry film thickness of 0.2 μm and dried.

Further, a corona discharge treatment (12 W / m ² / min) was performed on the undercoating layer, and a conductive layer coating solution A-1 was applied as a recording material constituting layer to a dry film thickness of 0.2 μm, and dried. Subsequently, heat treatment was performed under the conditions shown in Table 1 to obtain a sample No. 101-119 were obtained. The drying was performed at 90 ° C. for 10 seconds.

Next, 0.1 Torr, O ₂ partial pressure 70%,
Discharge frequency 20 kHz, output 2500 W, processing intensity 0.
Glow discharge treatment was performed at 5 kV · A · min / m ² for 5 seconds. 120 was obtained.

A 365 cm of 50 cm wide and 30 cm arc length provided in parallel at a distance of 10 cm from the support.
UV irradiation was performed at 110 ° C. for 2 minutes in air using a cylindrical high-pressure mercury lamp of 1 kW quartz having a main wavelength of 2 nm. 121 was obtained.

Further, a liquefied propane gas / air mixing ratio of 1
/ 17, and flame treatment was performed at a flame treatment amount of 15 kcal / m ² . 122 was obtained.

<Subbing material> B-1: butyl acrylate 60% by weight, styrene 30
B-2: 40% by weight of butyl acrylate, 20% by weight of styrene
B-3: gelatin B-4: aqueous dispersion A (60 mol% of dimethyl terephthalate, 30 mol% of dimethyl isophthalate as a dicarboxylic acid component) 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol and 50 mol% of diethylene glycol as glycol components were copolymerized by a conventional method, and the copolymer A was heated at 95 ° C. for 3 hours in hot water. The mixture was stirred to obtain a 15% by weight aqueous dispersion A.) <Crosslinking agent> H-1: (Comparative compound having the following structure) H-2: Epocros K2020E (Nippon Shokubai Co., Ltd.)
(The compound according to the present invention described above) H-3: Epocross WS300 (Nippon Shokubai Co., Ltd.) (the compound according to the present invention described above) H-4: Epocross WS500 (Nippon Shokubai Co., Ltd.) (the compound according to the present invention described above)

[0119]

Embedded image

<Conductive Layer Coating Solution A-1> Tin oxide-antimony oxide composite fine particles (average particle size: 0.2 μm) 44 g Aqueous dispersion A (described above) 109 g The above compound (UL-1) 0.4 g Finished with water 1000 ml The obtained sample was evaluated by the following evaluation method. Table 1 shows the results.

(Adhesion between Support and Adjacent Layer) Three samples were cut out, and one was left as it was at 23 ° C. and 55% RH.
For 12 hours. The other sheet was treated with the following color developing solution adjusted to 38 ° C. for 3 minutes and 15 seconds, washed with running water for 3 minutes, dried, and allowed to stand at 23 ° C. and 55% RH for 12 hours. Then, for each sample, the diameter of the tip was 150
μm sapphire needle vertically, 20 to 1 with continuous load
20 g was scratched at a speed of 10 mm / sec. The other sheet was similarly treated with the color developing solution for 3 minutes and 15 seconds, and then immediately scratched with a sapphire needle in a wet state as described above. Each sample after scratching was observed with an optical microscope at a magnification of 100, and the load at which peeling started between the support and the undercoat layer was determined as the adhesiveness between the support and the adjacent layer. The larger the value, the better the adhesion. If it is 70 or more, it can withstand practical use, but it is preferably 100 or more.

<Color developing solution> Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4- Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

[0123]

[Table 1]

The results in Table 1 show that 2-
It was found that the layer containing the polymer having an oxazoline group had significantly improved adhesion to the support by the surface treatment. The samples in the present invention had excellent adhesion between the support and the adjacent layer before, during and after the treatment. In particular, a sample containing 5 wt% or more of a water-soluble polymer having a 2-oxazoline group, a sample containing 60 wt% or more of a water-dispersible polymer having a 2-oxazoline group,
The samples heat-treated at 90 ° C. for 1 minute or more and the samples in which the number of atomic atoms (at%) of oxygen atoms in the surface layer increased by 1.5 at% or more after the surface treatment were good.

Example 2 A magnetic recording layer (coating solution M) was formed on the conductive layer of each sample of Example 1.
-1, dry film thickness 0.8 μm), sliding layer (coating solution O-1,
A dry film thickness of 0.2 μm) was provided in this order. 20
1-222 were obtained.

<Coating liquid M-1> Magnetic material (Co-coated γ-Fe ₂ O ₃ , coercive force 900 Oe, surface area 40 m ² / g, short axis 0.03 μm) 4.8 parts by weight Binder Cellulose di Acetate (55% acetylation degree, weight average molecular weight 180,000) 100 parts by weight Tolylene diisocyanate 17.0 parts by weight Abrasive particles A (r ₂ / r ₁ = 1.1, Al ₂ O ₃ , central particle size: 0,1) 8 μm) 1.2 parts by weight Acetone 1130.0 parts by weight Cyclohexanone 280.0 parts by weight was mixed, mixed with a dissolver for 1 hour, and then dispersed with a sand mill for 2 hours to obtain a dispersion.

<Coating Liquid O-1> Carnauba wax 7 g Toluene 700 g Methyl ethyl ketone 300 g The scratch resistance (abbreviated as magnetic head scratch resistance) of the obtained sample against passage through a magnetic head was evaluated by the following method.
Shown in

(Magnetic head scratch resistance) HEIDONN-1
Head load 300 using 4DR (Shinto Kagaku Co., Ltd.)
g, 100 passes over the film at a speed of 100 mm / sec. Thereafter, the state of the flaw was evaluated on the following three scales and shown in Table 2.

A: no scratch B: weak scratch C: strong scratch

[0130]

[Table 2]

[0131] When a scar was observed on the scratched sample with a scanning electron microscope, all the scratches were caused by peeling of the support from the adjacent layer.

From the results shown in Table 2, the samples in the present invention were excellent in the scratch resistance of the magnetic head. In particular, a sample containing 5 wt% or more of a water-soluble polymer having a 2-oxazoline group,
-60 wt% of a water-dispersible polymer having an oxazoline group
% Or more, a sample subjected to heat treatment at 90 ° C. for 1 minute or more, and the atomic number% (at
%) Increased by 1.5 at% or more.

Example 3 An undercoat layer similar to each sample of Example 1 was provided on both surfaces of a support. Further, a conductive layer was formed on one surface as a recording material constituent layer in the same manner as in Example 1, and a corona discharge treatment of 12 W / m ² / min was performed on the undercoat layer on the other surface as a recording material constituent layer. After the application, the following processing liquid A-2 was dried at a dry film thickness of 0.1.
Then, the same heat treatment as in Example 1 is performed. Further, the same magnetic layer and sliding layer as in Example 2 were provided on the side on which the conductive layer was provided, and on the opposite side, Konica Color LV400, a color negative film commercially available from Konica Corporation.
The same photographic emulsion layer was provided. 301-322
I got

Working fluid A-2 Gelatin 10 g The above compound (UL-1) 0.2 g The following compound (UL-2) 0.2 g Silica particles (average particle size 3 μm) 0.1 g The following crosslinking agent H-5 1 g With water Finish 1000ml

[0135]

Embedded image

Each sample was subjected to a development process by the following method, and then the magnetic head scratch resistance of the surface provided with the magnetic layer after the development process was evaluated in the same manner as in Example 2.

<Development Processing> Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C. Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ° C Rinse 3 minutes and 15 seconds 24-41 ° C 4. 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 ° 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 anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2 0.0 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 solution> Ammonium ethylenediaminetetraacetate (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make up to 1 liter, and the pH was adjusted to 6.0 using ammonia water. Adjust to 0.

<Fixing Solution> 175.0 g of ammonium thiosulfate 8.5 g of anhydrous sodium sulfite 2.3 g of 2.3 g of sodium metasulfite 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 KONIDAX (manufactured by Konica Corporation) 7.5 ml Make up to 1 liter by adding water.

Further, the adhesiveness of the undercoat to the support before, during and after the development on the emulsion layer side of each sample was evaluated by the following method. Table 3 shows the evaluation results.

(Adhesion between support of silver halide light-sensitive material and layer adjacent thereto) Three samples were cut out, and one of them was left as it was at 23 ° C. and 55% RH for 12 hours. The other sheet is processed by the above-described method, and then is subjected to 23 ° C. and 55% R
H for 12 hours. Thereafter, a sapphire needle having a tip diameter of 25 μm was vertically applied to the coated surface of each sample, and the sample was scratched at a speed of 10 mm / sec by applying 0 to 100 g with a continuous load. The other sheet was similarly treated with the color developing solution for 3 minutes and 15 seconds, and then immediately scratched with a sapphire needle in a wet state as described above. Each sample after scratching was observed with an optical microscope at a magnification of 100, and the load at which peeling started between the support and the undercoat layer was determined as the adhesiveness between the support and the adjacent layer. The higher the value, the better the adhesion.

[0143]

[Table 3]

From the results shown in Table 3, the sample of the present invention has excellent adhesion between the support and the adjacent layer before, during, and after the treatment, and has a satisfactory magnetic head scratch resistance even after the development treatment. It was excellent. In particular, a sample containing 5 wt% or more of a water-soluble polymer having a 2-oxazoline group,
A water-dispersible polymer having a 2-oxazoline group is used for 60 w
Samples having t% or more, samples heat-treated at 90 ° C. for 1 minute or more, and samples in which the number of atomic atoms (at%) of oxygen atoms in the surface layer increased by 1.5 at% or more after surface treatment were good. .

[0145]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having excellent adhesion to a support before and during and after development and after development. Furthermore, it is possible to provide a magnetic recording medium having excellent scratch resistance against passage of a magnetic head and a silver halide photographic material having a magnetic recording layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G11B 5/704 G11B 5/704 // C08J 7/00 301 C08J 7/00 301 302 302 302 7/04 CFD 7/04 CFDG

Claims (16)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a polyester support, wherein a surface treatment is performed on at least one surface of the support, and the surface treatment is performed. A layer containing a water-soluble or water-dispersible polymer having a 2-oxazoline group represented by the following general formula (A) on a layer adjacent to the surface on which the silver halide is applied: . Embedded image (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent hydrogen, halogen, alkyl, aralkyl, phenyl, or a substituted phenyl group.) 2. A silver halide photographic light-sensitive material according to claim 1, wherein said support comprises polyethylene terephthalate or polyethylene naphthalate as a main component. 3. The silver halide photographic material according to claim 1, wherein the surface treatment is a corona discharge treatment, a glow discharge treatment, an ultraviolet irradiation treatment, or a flame treatment. 4. The silver halide photographic material according to claim 3, wherein 5% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-soluble polymer having a 2-oxazoline group. 5. A water-dispersible polymer having a 2-oxazoline group in an amount of 15% by weight or more of a layer containing a polymer having a 2-oxazoline group.
The silver halide photographic light-sensitive material as described above. 6. A water-dispersible polymer having a 2-oxazoline group in an amount of 60% by weight or more of the layer containing a polymer having a 2-oxazoline group.
The silver halide photographic light-sensitive material as described above. 7. The method according to claim 1, wherein after applying a layer containing a polymer having a 2-oxazoline group, heat treatment is performed at 90 to 150 ° C. for 1 minute or more. Silver halide photographic material. 8. The method according to claim 1, wherein the atomic number (atomic%) of oxygen atoms in the surface layer of the support after the surface treatment is increased by 1.5 to 10 atomic% as compared with before the surface treatment. The silver halide photographic light-sensitive material according to any one of claims 1 to 7, wherein 9. A magnetic recording medium having at least one magnetic recording layer on a polyester support, wherein at least one surface of the support is subjected to a surface treatment, and a layer adjacent to the surface-treated surface is provided. A magnetic recording medium comprising a layer containing a water-soluble or water-dispersible polymer having a 2-oxazoline group represented by the following general formula (A). Embedded image (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent hydrogen, halogen, alkyl, aralkyl, phenyl, or a substituted phenyl group.) 10. The magnetic recording medium according to claim 9, wherein said support comprises polyethylene terephthalate or polyethylene naphthalate as a main component. 11. The magnetic recording medium according to claim 9, wherein the surface treatment is a corona discharge treatment, a glow discharge treatment, an ultraviolet irradiation treatment, or a flame treatment. 12. The method according to claim 11, wherein 5% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-soluble polymer having a 2-oxazoline group.
The magnetic recording medium according to the above. 13. The magnetic recording medium according to claim 11, wherein 15% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group. 14. The magnetic recording medium according to claim 13, wherein 60% by weight or more of the layer containing the polymer having a 2-oxazoline group is a water-dispersible polymer having a 2-oxazoline group. 15. The method according to claim 9, wherein after applying a layer containing a polymer having a 2-oxazoline group, a heat treatment is performed at 90 to 150 ° C. for 1 minute or more. Magnetic recording medium. 16. The method according to claim 16, wherein the atomic number (atomic%) of oxygen atoms in the surface layer of the support after the surface treatment is increased by 1.5 to 10 atomic% as compared with before the surface treatment. The magnetic recording medium according to any one of claims 9 to 15, wherein: