JPH09204005A - Production of photographic polyester film base - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently and stably produce a base which is intricate and has a difficulty in quality stability by subjecting the web-shaped polyester base to a vacuum surface treatment, a precoating treatment and a heat treatment under specific conditions. SOLUTION: The one surface of the web-shaped polyester base to be continuously transported is subjected to a vacuum glow discharge treatment as the vacuum surface treatment and the precoating treatment. This base is taken up in a roll form and is continuously subjected in this state to the heat treatment set at the conditions of >=50 deg.C to <= glass transition temp. and the treating time of >=0.1 to <=1500 hours. The silver halide emulsion layer forming surface of the polyester base is coated with a undercoating layer and, thereafter, the surface not formed with the silver halide emulsion layers is coated continuously with a light transparent magnetic recording layer and an overcoating layer in this order. The quantity of dissolved air is preferably specified to <=70% of the saturated air quantity and an aq. coating liquid maintained at a liquid temp. of 20 to 40 deg.C is used in this coating stage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photographic polyester film support having a transparent magnetic recording layer and used for a photographic film capable of recording various information.

[0002]

2. Description of the Related Art Conventionally, it has been known that a polyester-based support has excellent mechanical properties and is suitable for thinning, but when incorporated in a film cartridge or the like used for a photographic film. , There was a problem that the curl did not recover. In view of this problem, as disclosed in US Pat. No. 4,141,735, it has been proposed to heat-treat a polyester-based support in a roll form at a temperature below a glass transition temperature (hereinafter referred to as Tg).

For the purpose of imparting and improving the adhesiveness between the polyester-based support and the photographic photosensitive layer, etc., the surface of the polyester-based support is exposed to a vacuum as described in JP-B-60-166145. It is known to perform glow discharge treatment or ultraviolet irradiation treatment. Further, it has been proposed to form a transparent magnetic recording layer in order to obtain a high quality photographic film capable of recording various information.

[0004]

However, although these methods can reduce or eliminate the curl, the uneven thermal deformation of the support during the heat treatment causes the problem.
There is a problem that so-called squeaking referred to in Japanese Patent No. 23937 occurs, the flatness is deteriorated, and it cannot be used as a photographic support.

Further, when the polyester support is subjected to the above-mentioned surface treatment and then heat-treated, there is a problem that so-called blocking occurs in which the laminated supports adhere to each other. Further, in order to further improve the image quality of photographs in recent years, it is indispensable to clean the manufacturing process, and especially to suppress the adhesion of dust due to electrification of the support surface.

Further, a so-called coating is provided to enable recording of various kinds of information and as an adhesion-imparting layer between the silver halide emulsion layer and the polyester support which is formed to form the final photographic film. It is necessary to form a coating layer having a function according to the purpose by treatment.

As described above, many processes such as vacuum surface treatment, heat treatment, coating treatment, etc. are required in manufacturing a photographic film having a predetermined function. These treatments, heat treatments, coating treatments, etc. are carried out independently for each process, so-called batch treatment is not enough to satisfy manufacturing suitability in terms of equipment installation costs, transportation equipment costs for semi-finished product rolls, etc. Absent.

Further, in such surface treatment and coating process,
It is essential to keep the surface condition of the treatment and coated surface stable, and when each treatment is carried out independently, the polyester support is transported, rolled in a roll, wrapped, transported, and stored in each process. In addition, cleaning of the process, feeding of the polyester support in the form of a web in the form of a web will be carried out, and there are many factors that cause instability in the coating surface, and as a result, inspection is required for each process. Therefore, there are many points to be improved from the viewpoint of quality maintenance.

Therefore, the present invention has been made in view of the above circumstances, and achieves efficiency, labor saving, and quality stabilization at a satisfactory level.

[0010]

[Means for Solving the Problems] At least one surface of a web-shaped polyester support which is continuously conveyed,
Vacuum surface treatment, pre-coating treatment, and heat treatment under the condition that the support is wound into a roll and set to a temperature of 50 ° C. or more and a glass transition temperature (Tg) or less and a treatment time of 0.1 hour or more and 1500 hours or less. After continuous application, an undercoat layer is coated on the silver halide emulsion layer forming surface of the polyester support, and thereafter, a light transmitting magnetic recording layer and a silver halide emulsion layer forming surface of the polyester support are formed. The above problems can be solved at a satisfactory level by using a method for producing a photographic polyester film support, which is characterized in that the overcoat layer is continuously coated in this order.

That is, a continuous heat treatment method for a photographic polyester film support in which a web-shaped polyester support is continuously conveyed and wound in a roll at a glass transition temperature (Tg) or lower, before heat treatment, The web-shaped polyester support being conveyed was continuously conveyed between the atmosphere and the vacuum, and the glow discharge treatment in vacuum was performed on at least one surface of the polyester support, while controlling and controlling the discharge state. During the process of introducing gas, and further between glow discharge treatment and heat treatment, a water-based coating liquid consisting of conductive inorganic particles or organic particles, a surfactant, a hardener, a binder, etc. is dissolved in the anti-emulsion layer surface. Preliminary coating is carried out by applying and drying while maintaining and controlling the amount and liquid temperature at a constant level, and additionally heat treatment is performed at a glass transition temperature (Tg In the following, after the treatment is continuously performed for 0.1 hour to 1500 hours, an undercoat layer is formed on one side of the polyester support on which the silver halide emulsion layer is to be formed, gelatin, an organic solvent and a binder. A coating liquid prepared in a predetermined amount together with an agent and other necessary components is coated with a bar type coating device at a coating amount in the range of 10 to 40 cc / m ² and a temperature of the liquid of 15 to Two
After coating at a temperature of 5 ° C, and immediately thereafter, a light-transmissive magnetic recording layer is continuously mixed with a magnetic substance, an organic solvent, and other necessary components in a predetermined amount in advance to obtain a dispersion liquid. As the coating liquid, a light transmissive magnetic recording layer coating is applied by using a slide hopper type coating device or a bar type coating device, the coating amount is 10 to 40 cc / m ² , and the temperature of the liquid is in the range of 15 to 25 ° C. Then, the overcoat layer is immediately and continuously applied together with an organic solvent, a lubricant, and other necessary components in a predetermined amount in each of which a dispersion liquid which has been uniformly mixed in advance is used as a coating liquid to form a bar type. Using an applicator, the coating amount is 10 to 40 cc / m ² and the temperature of the liquid is 15 to 25 ° C., and an undercoat layer and / or a magneto-optical recording layer and / or an overcoat layer are also applied. When applying In advance 20 to the Riesuteru system support
This can be achieved by maintaining the temperature at 30 ° C.

In the vacuum glow discharge treatment, as shown in Japanese Patent Application Laid-Open No. 7-3056, a method of transporting a support between water-cooled cylindrical electrodes and treating it is used. The material and surface finish of the electrode body are appropriately selected depending on the discharge atmosphere, strength, etc., but SUS, Al, etc. are used,
It is desirable to finish the buff # 250 to 400.

The distance between the electrodes facing each other is 100 to 400 m.
Desirably, m is 200 to 300 mm, which is a range in which treatment effects, heat damage to the support, and the like are taken into consideration. The processing pressure is 6.6 Pa to 2.7 kPa, more preferably 1
It is 3.3 Pa to 270 Pa. Processing voltage is 500-5
It is preferably 500 to 3000 V, more preferably 000 V.

The processing frequency is from direct current to several thousand MHz,
It is preferably 1 kHz to 1 MHz. It is desirable that the discharge voltage, current, frequency, etc. be monitor-controlled. Further, as is well known in the high frequency region, it is desirable to match the power source impedance with the impedance of the discharge part from the viewpoint of effectively consuming the generated power and from the viewpoint of preventing excessive temperature rise of the power source. However, it is essential to control the specifications such that the ratio of power consumption / generated power is 0.9 or more, preferably 0.95 or more.

It is also effective to install the power supply in an atmosphere where the air conditioning is properly controlled. In the glow discharge in vacuum, as shown in JP-B-60-16614, it is desirable to preheat the polyester support immediately before the glow discharge treatment in vacuum. From the viewpoint, sequential heating using at least two or more heating rolls, an infrared heater, and the like are appropriately selected.

As the roll heating means, a known method such as an induction heating method or a jacket method using a heat medium such as steam is appropriately selected. The preheating temperature is 80 to 180 ° C, preferably 100 to T
g is good. Further, when preheating is performed, it is desirable to maintain and control the temperature in the width direction of the polyester-based support at ± 1 ° C or less, more preferably ± 0.5 ° C or less.

In glow discharge in vacuum, Japanese Patent Publication No. 3-
As shown in Japanese Patent No. 39106, it is essential to immediately cool the polyester support immediately after the glow discharge treatment, but in this embodiment, at least two water-cooling jacket type cooling rolls are used for successive cooling. That is appropriately selected. The cooling temperature is 20 to 50 ° C, preferably 30 to 40 ° C.

It is desirable to install the heating roll, the cooling roll, etc. in the vacuum processing apparatus and immediately before / after the glow discharge processing section so that the effects thereof are not impaired. Further, it is desirable to control the heating and cooling means by measuring the surface temperature of the polyester-based support by a known means such as a radiation thermometer and a contact thermocouple. In the vacuum glow discharge treatment, it is essential to provide continuous suitability by providing a step of continuously introducing the polyester support in an air space to a reduced pressure space and a step of performing the treatment.

The process for continuously introducing the polyester-based support in the air space to the reduced pressure space is described in JP-B-63-1686.
Japanese Laid-Open Patent Publication No. 1-5
No. 2473, a system in which a narrow gap is provided between frames facing a roll to convey a support, and the medium is gradually conveyed to a decompressed atmosphere, and further, a non-contact type as shown in JP-A-1-272767. A method of forming a plurality of decompression chambers while transporting the support by opposing roll groups is appropriately selected depending on the support type, installation conditions, and the like.

By using this process, it is possible to incorporate vacuum processing as part of a continuous, continuous process.
Further, in order to control the gas composition in the processing pressure atmosphere, it is essential to introduce an arbitrary amount of a simple substance or a mixed gas from the outside while keeping the processing pressure constant and to change the processing pressure atmosphere. Is.

The gas species in this case are air, oxygen,
Nitrogen, carbon dioxide, water, ammonia, argon or mixtures thereof are used. As a gas introduction method, it is desirable to use a mass flow rate control device and an automatic valve interlocked with this device. In order to maintain and control the processing pressure at the time of introducing the above gas, it is essential to install a device such as a pressure detection device and an automatic valve that compares and corrects the set pressure and the actual pressure between the exhaust device and the processing chamber. Is.

An appropriate amount of gas is introduced from the atmospheric space by a mass flow rate introducing device. The monitor control of the introduction amount can be performed by a mass spectrometer, a color difference meter, or the like. The amount of introduced gas depends on the relationship between the kind of gas, the processing pressure condition, the processing strength, the type of polyester support, and the desired adhesion, but it is preferably 10 to 300 Pa · m ³ / sec in terms of mass flow rate. 20 to 200 Pa · m ³ / sec is preferable in view of the desired effect, the efficiency of the exhaust means, and the like.

Between the surface treatment and the heat treatment, the anti-emulsion surface
In addition, conductive inorganic or organic particles, surfactant, hardener
Applying and drying a conductive layer consisting of film agent, binder, etc.
It is essential to form by. Conductive inorganic fine
The particles are described in JP-A-6-123937.
As shown, ZnO, TiO_Two, SnO_Two, Al_Two
O_Three, In_TwoO_Two, SiO _Two, MgO, BaO, MoO
_Three, V_TwoO_FiveAt least one crystal selected from
Of fine metal oxides or complex oxides of these
You.

Of these, SnO ₂ is particularly preferable.
Is a conductive material containing 5 to 20% of antimony oxide as a main component and / or other components (silicon oxide, boric acid, phosphorus, etc.). An ionic conductive polymer or latex is used as the conductive organic fine particles.

Known surfactants and hardeners may be appropriately used, and a hydrophilic polymer such as a water-soluble polymer, a cellulose ester or a latex polymer may be used as the binder. Such a conductive layer has a resistance of 10e
xp3 to 10exp12Ω, preferably 10exp4 to 1
It is desirable that the coating be performed so that it becomes 0 exp11 Ω.

The coating is carried out by a known means such as dip coating, wire bar coating, curtain coating, etc., and the coating amount is 0.1 to 20 cc / m ^2, preferably 0.5.
It is -10 cc / m ² . Further, in order to prevent dissolved air in the liquid from depositing during coating and causing a failure in the coating layer, the vapor pressure of the liquid is preferably 6.7 kPa, more preferably the vapor pressure is
It is essential that the amount of dissolved air in the liquid is 70% or less, preferably 50% or less of the saturated air amount under a reduced pressure atmosphere of 2.7 kPa.

The liquid is 20 to 40 ° C., preferably 25 to 40 ° C.
It is desirable to keep the temperature at 35 ° C.

In a preferred embodiment, a liquid supply system including a coating process is a circulation system, a liquid immediately before the coating process is stored in a tank capable of decompressing, and a liquid having a predetermined dissolved air amount is delivered. Can be appropriately selected. For drying after coating, a known drying method such as an arch dryer type or an air floating type may be appropriately used.

This conductive layer can prevent dust from adhering to the support due to electrification. Further, when the polyester-based support is subjected to the above-mentioned surface treatment and then heat-treated, the stacked supports adhere to each other. , So-called blocking can be suppressed. Further, the squeaky value of the present conductive layer can be reduced by the method disclosed in JP-A-6-
When measured under the conditions described in Japanese Patent No. 123937, it is in the range of 100 to 250 g, and good flatness can be maintained.

The squeaky value is measured as follows. 1) The support sample is 180 mm (support width direction) x
50 mm (in the longitudinal direction of the support) is cut out, and this is pasted on a smooth plate with the surface opposite to the layer intended for silver halide coating (hereinafter referred to as BC surface) being attached (Sample A). This is attached to the moving stage of the tensile tester so that it becomes horizontal.

2) A support sample was cut out to a size of 80 mm (support width direction) × 18 mm (support length direction), and a flat plate having the same size and a weight of 500 g was coated with the silver halide emulsion coating surface. Stick it on top (Sample B). Furthermore, a thread is attached to the center of this 18 mm side. 3) After mounting the sample B on the sample A, the yarn of the sample B is fixed to the load cell via the pulley of the moving stage of the tensile tester. 4) Lower the moving stage at a speed of 200 mm / min.

The maximum load detected by the load cell at this time is called a squeak value.

Between the coating treatment and the heat treatment, preheating the polyester-based support at a temperature of around Tg or higher and 200 ° C. or lower may reduce internal stress, uneven thickness, etc. generated during film formation of the polyester-based support. It is preferable to eliminate it. By this preheating treatment, the flatness of the support can be improved, and at the same time, it is possible to contribute to the elimination of winding, depression, sagging, etc. during the heat treatment of the next step.

The preheating time varies depending on the type of support, heating temperature, etc., but is 10 to 100 seconds, preferably 20 to
60 seconds. As a preheating means, an infrared heater,
Air-conditioning air can be appropriately selected. In the preheating step,
A plurality of idle rollers for transferring the polyester-based support are installed at appropriate positions.

In order to continuously and consistently carry out these surface treatments, coating treatments, preheating treatments, heat treatments, etc., in all of these steps, the support to be subjected to the roll-like treatment is sequentially web-like from the tip. Immediately before the roll-shaped support is conveyed, or at the same time as the conveyance is completed, a so-called turret-type feeding device that joins and conveys the end of the web being conveyed and the leading end web of the roll-like support in a stand-by state, A joining device is provided.

The joining method is preferably a method in which the supports are butted to each other and are joined using an adhesive tape or the like, and the accuracy thereof is as described in JIII Journal of Technical Disclosure No. 6-13721. It is desirable that the bending is within 5 mm / m and the step difference is within 5 mm. Further, an accumulator may be installed in order to perform the bonding operation more stably.

The heat treatment temperature is 50 ° C. or higher and lower than Tg, more preferably Tg-20 ° C. or higher and lower than Tg, and further preferably Tg-15 ° C. or higher and lower than Tg. The heat treatment time is 0.
1 hour or more and 1500 hours or more, preferably 2 hours or more 10
It is preferably 00 hours or less, more preferably 5 hours or more and 400 hours or less. The heat treatment is carried out while continuously winding the polyester support in a roll or is carried to the next step while being subjected to the heat treatment.

When being wound, the so-called winding device for performing this operation is of a turret type, and the polyester base material is wound in a roll shape with a predetermined length, and at the same time, the width of the web being conveyed is increased. In the direction, there is a publicly known rewinding process such as cutting with a traversing cutter or the like, winding the tip of the web around a winding core waiting for rotation, and winding the roll into a roll shape.

Further, an accumulator may be installed in order to carry out the winding and winding operations more stably. Further, as a winding condition during the heat treatment, a so-called taper tension in which the tension gradually decreases according to the winding diameter and / or an elastic roll is brought into contact with the surface of the support that is sequentially wound at an appropriate pressure, or pressure and heating are performed under an appropriate condition. The methods of blowing the air may be combined and set as necessary.

The diameter of the core provided for these is preferably 100 mm or more and 400 mm or less, and the material is not particularly limited as long as it has excellent heat resistance, but FRP, FWP, SU
S, fiber-impregnated resin, or the like is appropriately used. In addition, since the winding core improves heat transfer to the roll-shaped support, it is disclosed in Japanese Patent Application No. 5-3.
As shown in Japanese Patent No. 50670, a heating means may be provided inside the winding core having a hollow structure.

In the heat treatment, as shown in Japanese Patent Application No. 5-350677, the support may be wound up by a winding device under the heat treatment temperature condition and then transferred to a temperature-controlled room under the same treatment temperature condition. . In order to maintain a good winding appearance during winding, the height of the web-shaped polyester support should be 1
It is preferable to have a step of knurling of ˜50 μm, more preferably 3 to 25 μm.

The width of the knurl is 2 to 50 mm, more preferably 7 to 20 mm. Such knurls may be on one side or on both sides and are formed at a temperature of Tg or higher using a pair of knurled rolls.

The polyester-based support which has been subjected to the surface treatment, coating treatment and heat treatment as described above is subjected to the undercoat layer coating treatment step after being heat-preserved in a roll form or while being conveyed in a web form. Will be guided to. In the coating process,
The support to be subjected to the roll-like treatment is sequentially fed out in a web form from the tip, and immediately before or at the end of the conveyance of the roll-like support, the end of the web being conveyed and the roll in the stand-by standby state. A so-called turret type delivery device for joining and conveying the front end web of the support and a joining device may be provided.

When the undercoat layer is formed on the side of the polyester support on which the silver halide emulsion layer is to be formed, gelatin, an organic solvent, and other necessary components are prepared in a predetermined amount and uniformly prepared at 15 to 25 ° C. , Desirably 18-22 ℃
Controlled by a bar type coating device and the coating amount is 10 to 40 cc / m
² , preferably in the range of 25 to 30 cc / m ² .

The coated polyester-based support is immediately dried and conveyed by a known drying method such as an arch dryer type or an air floating type in which the temperature and humidity are controlled appropriately. Then, while the polyester support is being conveyed, a light transmitting magnetic recording layer is immediately formed on the side where the silver halide emulsion layer is not formed.

In forming the light-transmitting magnetic recording layer, a predetermined amount of a magnetic substance, an organic solvent, and other necessary components are uniformly prepared and a coating solution is controlled at 15 to 25 ° C., preferably 18 to 22 ° C. Type coating device or slide hopper type coating device, coating amount of 10 to 40 cc / m ² , preferably 25 to
It is applied in the range of 30 cc / m ² . The polyester support coated with the light-transmitting magnetic recording layer is an arch drier type that is controlled at an appropriate temperature and humidity immediately while being transported.
Dry by known drying method such as air floating method,
Conveyed.

As the necessary components, known lubricants, lubricants, dispersants, hardeners, antistatic agents, abrasives and the like are appropriately selected. Then, while the polyester support is being conveyed, an overcoat layer is immediately formed on the side where the silver halide emulsion layer is not formed.

In forming the overcoat layer, a predetermined amount of an organic solvent and other necessary components are uniformly prepared and the coating solution is controlled to 15 to 25 ° C., preferably 18 to 22 ° C., and coated by a bar type coating device. The amount is 10 to 40 cc / m ² , preferably 25 to 30 cc / m ² . While being conveyed, the polyester support coated with the overcoat layer is immediately dried and conveyed by a known drying method such as an arch dryer type or an air floating type, which is controlled at an appropriate temperature and humidity.

As the necessary components, known slip agents, surfactants, dispersants and the like are appropriately selected.

When the slip agent is added to the coating solution, the slip agent, the dispersant, and other necessary components together with a necessary amount, a uniform amount,
An ultrasonic dispersion device, a high-pressure homogenizer, or the like is used until the particles have a predetermined particle size, and the particles are appropriately dispersed while being controlled at an appropriate temperature and treatment flow rate.

The support used in the coating process according to the present invention has a temperature of 15 to 30 ° C., preferably 18 to 25 ° C.
Must be set to. It is desirable that the difference between the temperature of the coating liquid and the temperature of the support is small from the viewpoints of preventing surface failure due to precipitation of dissolved air in the coating liquid and coating stability. This temperature difference depends on the properties of the coating liquid, the coating speed, etc., but is preferably 5 ° C. or less.

The temperature setting of the polyester support is controlled by using a known means such as a roller having a jacket structure for rotatably supporting the polyester support, and allowing a coolant of an appropriate temperature to pass therethrough. On the number of rollers,
It may be conveyed with an appropriate tension. In coating these, as a means for dealing with the excessive film thickness that inevitably occurs in the initial coating section, as shown in Japanese Patent Application No. 7-104308, a roller whose outer periphery is randomly coated with a stainless wire. It is preferable to employ a method of contacting the polyester support with a polyester-based support at an appropriate pressure and at an appropriate timing to absorb the excess coating liquid.

The treatment temperature is 50 ° C. or higher and lower than the glass transition temperature (Tg) of the polyester support, and the treatment time is 0.1.
In the process of applying heat to the support, which is represented by a heat treatment performed for not less than 1 hour and not more than 1500 hours, during treatment or in the case of winding in a roll, a local end portion or both end portions of the support is locally applied. Such deformation causes deterioration of flatness, coating property, transportability, and product loss. Therefore, as shown in Japanese Patent Application No. 7-19021, only the substantially end portion of the support (Tg -40) -melting point 1-600
The second heating means may be arranged at an appropriate position in the continuous coating process.

Needless to say, the cleanliness is required in the photographic polyester film support provided by the present invention, and the whole process is kept clean and the proper position of the continuous coating process is maintained. In addition, it is essential to install the required number of known dust removers and static eliminators. Further, in the continuous surface treatment, preliminary coating, heat treatment, coating treatment step according to the present invention, a meandering correction device for the support,
It goes without saying that a dancer roller for speed control and tension control for each process, and a feed roller of suction type or rubber lining type are appropriately installed.

Further, in the continuous surface treatment, preliminary coating, heat treatment and coating treatment steps according to the present invention, a known inspection device for monitoring the property of the coated surface and inspecting for any abnormality online is installed at an appropriate place. May be done. Polyester supports used in the present invention include polyethylene naphthalate, polyethylene terephthalate, etc., and these polyesters are polymerized by a known method, pelletized, then sufficiently dried, and melt-extruded with a die. The film is formed into an unstretched film, a predetermined biaxially oriented film is formed by a known biaxial stretching method, and a film having a necessary width slitted in the longitudinal direction is used.

The polyester support used in the present invention is
Thickness is 85 to 120 μm, width is 1000 to 2000 m
m, preferably 50 to 110 μm in thickness and 1000 to 1 in width
It is 500 mm. The photographic polyester film support treated according to the present invention is then formed with the silver halide emulsion layer, the antireflection layer, the protective layer, and other layers finally necessary for the photographic film by a known method, and then a predetermined width. Slit into and spool on the spool inside the cartridge for the required length

[0057]

Embodiments of the present invention will be described below with reference to the drawings. 1 to 3 show the processing steps for producing a photographic polyester film support according to the present invention. That is, the PEN support body 101 wound to a predetermined length is attached to one shaft of the biaxial turret type delivery device 103 and continuously delivered. When the delivery of the PEN support body 101 mounted on the one shaft is completed, the joining device 105 is mounted while being wound around the web rear end of the PEN support body 101 mounted on the one shaft and the other shaft, and stopped. The web end of the new PEN support on standby is butted and joined by the joining tape, and the delivery is continued.

The PEN support 101 is a dust removing and static eliminating device 1
07, meandering correction device and feed roller 10 not shown
After that, the PEN support body 101 is conveyed to a lead-out introduction unit 111 that continuously introduces and introduces the PEN support body 101 between the atmospheric space and the decompression space. The lead-out introduction unit 111 includes a plurality of feed rollers 111a and a plurality of idle rollers 111b arranged in a column.
The pressure detection and control device 117 and the exhaust means 119 that monitor the pressure gauge 113 and control the valve 115 gradually reduce the pressure.

The PEN support 101, which has been introduced into a reduced pressure atmosphere for vacuum surface treatment, is heated by a heating roller 121 as a heating means and then treated by a cylindrical water-cooled electrode 123. The cylindrical water-cooled electrode 123 is disclosed in JP-A-7-305.
The PEN support 101 has the structure shown in Japanese Patent Publication No. 6 and generates a glow discharge by a plurality of counter electrodes.
Is processed in a low temperature plasma atmosphere. After that, it is conveyed to a cooling roll 125 which is a cooling means and cooled to a predetermined temperature, is conveyed again to the introduction / extraction section 111, is gradually pressurized and is introduced into the atmospheric pressure space.

In order to control the heating by the heating roller 121 and the cooling by the cooling roller 125, the temperature after heating and cooling is detected by the thermocouple 127, and the temperature of the heating roller 121 and the cooling roller 125 is detected based on this detection result. A heating roller control means 129 and a cooling roller control means 131 for feedback control of the are provided. The casing for vacuum surface treatment is provided with a mass flow rate setting and introducing device 135 for controlling the mass and flow rate of the gas introduced into the compartment. The mass of the gas in the compartment is analyzed and measured by the mass spectrometer 136, and the mass flow rate setting introduction device 1
35 sets the flow rate of the gas introduced into the compartment based on the analysis measurement result.

Thereafter, the PEN support 101 is appropriately passed through a dust remover, a static eliminator, a meandering correction device, a feed roller 133 and the like (not shown), and then conductive inorganic particles or organic particles, a surfactant, The coating process of the water-based coating liquid, which consists of a hardening agent, a binder and the like, maintains the amount of dissolved air under constant conditions and the liquid temperature under constant conditions. The coating process is executed by the bar coater 137.

After the coating process, the PEN support 101 is transported into the heat insulating casing 139 and dried. PE
The N support 101 is then heated to 200 ° C. from around the temperature Tg.
Preheating treatment is performed by a heating means (not shown) below. Prior to the preliminary heating treatment, the knurling means 141 imparts knurls of a predetermined height to both ends of the PEN support 101.

After completion of the preheating treatment, the PEN support 101
Is heat-treated at a temperature of 50 ° C. or higher and lower than Tg by a heating means (not shown). During the heat treatment, the PEN support body 101 is continuously wound into a roll by the winding device 143.
In this winding, the web-shaped PEN support is cut in the width direction with a traversing cutter or the like, and the leading end of the web is wound around the winding core waiting for rotation, and the winding device 145 and the P wound around the winding core.
This is accomplished by a twin-screw turret device 147 that winds the EN support.

The heat insulating casing 139 is used to control the temperature in each compartment to be subjected to the drying treatment, preheating treatment and heat treatment.
A temperature control wind generation / exhaust / exhaust means 149 is provided along the above.
Further, partition walls for blocking the movement of gas are provided between the compartments, and the PEN support body 101 is transported through a transport port provided in a part of the partition walls.

PEN support 101 wound into a roll
Is attached to a twin-screw turret type delivery device 203 similar to the delivery device 103, and is delivered continuously.
When the delivery of the PEN support 101 is completed, the joining device 20
5 is the PEN support 1 in the same manner as the above joining device 105.
The rear end of the web No. 01 and the front end of the web of the new PEN support are butt-joined with a joining tape, and the feeding is continued.

The PEN support 101 is a dust removing and static eliminating device 1
PEN support 101 via 07 and cooling roller 209
Is conveyed to a bar coater 237 for coating an undercoat layer on the side where the silver halide emulsion layer is formed. After the undercoat layer coating process, the PEN support body 101 is an arch dryer 239.
It is transported to and dried.

After that, the PEN support 101 is subjected to a dust removing and static eliminator 107 and a cooling roller 209, and then a bar coater for coating a light transmissive magnetic recording layer on the side of the PEN support 101 where the silver halide emulsion layer is not formed. It is transported to 337. PEN support 1 after light-transmissive magnetic recording layer coating treatment
01 is conveyed to the arch dryer 239 and dried.

Thereafter, the PEN support body 101 is further subjected to a dust removing and static eliminating device 107 and a cooling roller 209, and an overcoat layer is further coated on the side of the PEN support body 101 coated with the light transmitting magnetic recording layer. Bar coater 43 for
7. After coating the overcoat layer, PEN
The support 101 is conveyed to the arch dryer 239 and dried.

A PEN support 101 coated with an undercoat layer on one side and a light-transmitting magnetic recording layer and an overcoat layer on the other side.
Is a winding device 245 and a biaxial turret device 247,
It is wound in the same manner as the winding device 145 and the biaxial turret device 147.

[0070]

【Example】

(1) Implementation conditions As a support, PEN having a width of 1100 mm and a thickness of 95 μm
Was used, and the processing speed was 25 m / min.

(2) Surface treatment step φ30, surface length 1500, material SUS of Japanese Patent Laid-Open No. 7-305
A plurality of opposed cylindrical water-cooled electrodes as shown in Japanese Patent No. 6 were fixed to the 4-pair insulating part so as to face the support at a distance of 150 mm in the support transport direction. The polyester support is preheated to 120 ° C (distribution ± 1 ° C) in the width direction with an induction heating roll, and the processing pressure is 20P immediately.
a, discharge treatment was performed in an atmosphere of oxygen gas of 150 Pa · m ³ / sec introduced at a treatment speed of 25 m / min and a discharge frequency of 20 kHz.

The discharge treatment intensity was set to a discharge treatment voltage of 1000V or 3000V. The discharge processing voltage, current, and power were monitor-controlled by known methods. Immediately after discharge treatment, 40
The polyester support was cooled to a temperature of ℃ with a water-cooled roll. The surface temperature of the polyester support during the treatment was measured with a radiation thermometer to control the heating / cooling means.

Further, the pressure of the processing atmosphere was measured with a Baratron type vacuum gauge to control the capacity of the exhaust means. In addition, oxygen gas was set and introduced by a mass flow controller and monitored and controlled by a mass spectrometer.

(3) Coating Step During the vacuum glow discharge treatment and the heat treatment, a coating solution comprising conductive inorganic particles or organic particles, a surfactant, a hardener, a binder, etc. is applied on the anti-emulsion surface by a bar coater. It was made to dry by the work and arch dryer. The coating liquid used was a conductive fine particle containing SnO ₂ as a main component, and a known surfactant and hardener were prepared in an aqueous gelatin solution.

The coating solution was immediately used after reducing the dissolved oxygen amount to 50% of the saturated dissolved oxygen amount in a decompression tank depressurized to 3 kPa and keeping it at 30 ° C. The system for supplying the coating solution was a circulation system, and the system was continuously returned to the vacuum tank. The coating amount was 7 cc / m ² , the coating speed was 25 m / min, and the drying temperature was 120 ° C.

(4) Knurling process: Width 10 mm and height 10 μ on both ends of the polyester support.
m knurled over the entire length. At this time, the temperature of the pressing die (roll having a pair of irregularities) was 150 ° C., and the pressing pressure was 2 kgf.

(5) Preliminary Heat Treatment A polyester support was passed through the casing set at 140 ° C. with warm air at a conveying speed of 20 m / min for 20 seconds while being rotatably supported by an idle roller.

(6) Heat treatment The polyester support was treated under an atmosphere of Tg-20 ° C.
A roll having a diameter of 300 mm and having heat resistance was continuously wound in a roll length of 2500 m. The take-up device is a turret type, and at the same time when the polyester support has a predetermined length and is wound into a roll shape, the web being conveyed is cut in the width direction by a traversing cutter or the like, and the tip of the web is cut. The operation of winding the roll around the winding core waiting for rotation and winding the roll into a roll was repeated sequentially, and the wound roll was immediately transferred to a temperature-controlled room at the same condition as the treatment temperature.

The heat treatment time was set to 50 hours, and then gradually cooled to room temperature.

(7) Undercoat layer coating treatment On a PEN support which has been heat-treated in a roll form, gelatin, an organic solvent and other known necessary components are uniformly prepared in a predetermined amount on the side where a silver halide emulsion layer is formed. 20 times the applied liquid
Controlled at ~ 22 ℃, 28cc / applied amount with bar type applicator
It was applied in the range of m ² .

The coated PEN support was immediately heated to temperature 1
It was dried by an arch dryer controlled at 20 ± 2 ° C.

(8) Light-Transmissive Magnetic Recording Layer Coating Treatment While transporting the PEN support which has been heat-treated in a roll state, a magnetic substance, an organic solvent and other necessary components are provided on the side where the silver halide emulsion layer is not immediately formed. The coating solution prepared in a predetermined amount was uniformly controlled at 20 to 22 ° C., and was coated with a bar coating device at a coating amount of 25 cc / m ² .

The PEN support coated with the magnetic recording layer was immediately dried by an arch dryer controlled at a temperature of 120 ± 2 ° C.

(9) Coating treatment of overcoat layer Then, while transporting the PEN support, immediately, a slip agent,
A predetermined amount of the organic solvent and other necessary components are uniformly prepared, and the coating liquid is controlled at 20 ° C.
It was applied at cc / m ² . The PEN support coated with the overcoat layer was immediately conveyed to a temperature of 120 ±
It was dried by an arch dryer controlled at 2 ° C.

When the slip agent is added to the coating solution, the slip agent, the dispersant, and other necessary components together with a necessary amount, a uniform amount,
The particles were repeatedly dispersed with an ultrasonic dispersion device until a predetermined particle size was obtained. In these continuous coating steps,
The support temperature was controlled at 25 ° C using a water-cooled jacket roller.

(10) Evaluation Table 1 shows the evaluation results of a photographic film having a photosensitive layer formed on a photographic polyester film support prepared by the continuous continuous production method according to the present invention.

[0087]

[Table 1]

(10-1) Blocking Evaluation The heat-treated roll was visually evaluated while being fed out.
Those that did not result in cleavage were rated as Δ, and those in which blocking occurred and cleavage occurred were rated as x. ○ is the level at which it can be put to practical use.

(10-2) Adhesion Evaluation After the undercoat layer was coated and the photosensitive layer was simultaneously coated in multiple layers by a known method, six cuts were formed on the surface of the photosensitive layer at intervals of 6 mm in length and width, and an adhesive tape (manufactured by Nitto Denko Corporation , Knit tape)
Affixed, peeled off in the direction of 180 degrees, and the peeled area is 1%
Less than ⊚, less than 3% were evaluated as ◯, less than 5% of the peeled area was evaluated as Δ, and 5% or more of the peeled area was evaluated as x. ⊚ to ∘ are levels that can be put to practical use.

In Table 1, levels 1 and 2 are those produced by the process according to the invention. Level 3 is manufactured by a conventional batch process in which each process is a separate process by a conventional technique. In Level 3, good results can be obtained, but since there are multiple processes,
A sending process and a winding process are required for each process, vacuum exhaust / release to the atmosphere is required for each level in vacuum processing, and equipment for transporting semi-finished product rolls between each processing process is required. It was extremely disadvantageous in terms of installation cost, installation space, required time, etc.

Levels 4 and 5 are heat-treated by performing only vacuum glow treatment in a separate process according to the conventional technique. In the production method according to the present invention, good results were obtained for both blocking and adhesion.

In this example, the treatment speed was 25 m / min, the winding length was 2500 m, and the introduced gas species was oxygen, and the heating temperature of the support before the glow treatment was 120 ° C. The case where the cooling temperature was 40 ° C. was mentioned. In addition, in the coating process, the amount of dissolved oxygen was reduced to 50% compared to the saturated amount of dissolved oxygen, and the coating liquid kept at 30 ° C was applied with a bar coater at an application amount of 7 cc / m ² and an application speed of 20 m / min. Details were mentioned when the conditions to

However, the present invention is not limited to this, and the processing speed is 20 to 200 m / min, and the winding length is 5.
0 to 6000 m, the gas type is air, ammonia, etc., the heating temperature of the support is 80 to 180 ° C., and the cooling temperature is 20 to 50.
In addition, the dissolved oxygen amount is reduced in the range of 10 to 70% in comparison with the saturated dissolved oxygen amount under the coating conditions, and the liquid temperature is 20 to
Good results could be obtained even when the coating amount was 40 ° C. and the coating amount was 0.1 to 20 cc / min.

(10-3) Required time evaluation When the vacuum surface treatment was continuously and consistently compared with the batch type processing time, the turret type feeding device could not be installed in the vacuum device in the batch type and the coating, It is extremely inefficient in that the support cannot be continuously conveyed to the heat treatment step. Table 2 shows the comparison results of the time required for one roll when the coating layer was treated by repeatedly sharing the same coating device as the time required for the continuous coating treatment according to the present invention.

[0095]

[Table 2]

In any case, the preparation time of the coating liquid, the dryer heating time, and the time for the cooling roll to reach a predetermined temperature are not included. As shown in Table 2, according to the continuous coating process of the present invention, the required time can be significantly shortened.

(10-4) Evaluation of surface condition of coated surface In Table 3, the surface condition of the photographic polyester film support was limited to scratches and winding defects, and the results of a visual sensory test were carried out. The results obtained by comparing the case where the same coating apparatus is repeatedly used and the case where the same coating apparatus is repeatedly used are shown. For the surface condition evaluation, the support after the coating treatment was sampled every 200 m with a total width of 1 m.

[0098]

[Table 3]

○ No occurrence at all △ There is some occurrence, but it can be used as the final photographic film ▲ Frequent occurrence is close to the limit of use, and some measure is required to use it as the final photographic film Required × Not usable as the final photo film

As shown in Table 3, the continuous coating treatment is
It is more stable than repeated coating.

(10-5) Evaluation of Application Stability Table 4 shows the results of ΔT defined by substrate temperature-coating solution temperature and application stability of the coating solution.

[0102]

[Table 4]

○ Stable △ Slightly unstable ▲ Unstable × Remarkably unstable

In this embodiment described above, the parameters of the process conditions are limited for the purpose of explanation, but the method for producing the photographic polyester film support according to the present invention is not limited to this. For example, the processing speed is 10-100
Good results can be obtained between m / min.

[0105]

As described above, according to the method for producing a photographic polyester film support according to the present invention, the continuous coating treatment is employed, so that the photographic polyester is complicated and difficult in quality stability. The film support can be manufactured efficiently and stably.

[Brief description of drawings]

FIG. 1 is a process drawing showing each process involved in the production of a photographic polyester film support.

FIG. 2 is a process drawing showing each process involved in producing a photographic polyester film support.

FIG. 3 is a process chart showing a continuous coating process according to the method for producing a photographic polyester film support of the present invention.

[Explanation of symbols]

 101 PEN support 103, 203 Delivery device 105, 205 Coupling device 107 Dust removal, static eliminator 109, 133 Feed roller 111 Induction / emission device 113 Pressure gauge 115 Valve 117 Pressure detection, control device 119 Exhaust means 121 Heating roller 123 Cylindrical water cooling electrode 125 Water-cooling roller 127 Thermocouple 129 Heating roller control means 131 Cooling roller control means 135 Mass flow rate setting introduction device 136 Mass spectrometer 137 Bar coater 139 Heat insulation casing 141 Knurling processing means 143 Winding device 145, 245 Winding device 147, 247 Biaxial turret Device 149 Generation of temperature control air, air supply / exhaust means 209 Cooling roll 239 Arch dryer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08J 7/04 CFD C08J 7/04 CFDG C09D 5/24 PQW C09D 5/24 PQW G03C 1/00 G03C 1/00 E 1/81 1/81 1/91 1/91

Claims (22)

[Claims] 1. A vacuum surface treatment for at least one surface of a web-shaped polyester support which is continuously conveyed,
Preliminary coating treatment and continuous heat treatment under conditions of 50 ° C. or more and glass transition temperature (Tg) or less and treatment time of 0.1 hour or more and 1500 hours or less in a state in which the support is wound into a roll. After that, an undercoat layer is applied to the silver halide emulsion layer forming surface of the polyester support, and then the light transmitting magnetic recording layer and the overcoat are applied to the silver halide emulsion layer forming surface of the polyester support. A method for producing a photographic polyester film support, characterized in that the layers are applied in that order. 2. The method for producing a photographic polyester film support according to claim 1, wherein the vacuum surface treatment is a glow discharge treatment in vacuum. 3. The water-based coating prepared by the pre-coating treatment in a predetermined amount together with conductive inorganic particles or organic particles, a surfactant, a hardener, a binder and other necessary components on the anti-emulsion coating surface. The method for producing a photographic polyester film support according to claim 1, which comprises applying a liquid and drying it to form a conductive layer. 4. The method, when performing the vacuum glow discharge treatment, includes a step of continuously guiding the polyester support in an air space to a vacuum space and a step of performing the vacuum glow discharge treatment. 1. A method for producing a photographic polyester film support as described in 1 or 2. 5. In the step of performing the vacuum glow discharge treatment, the generated power in the discharge power source and the consumed power in the discharge part are monitored so that the ratio of the consumed power to the generated power can be maintained at 0.9 or more. The method for producing a photographic polyester film support according to claim 1, 2 or 4, which is monitored and controlled. 6. In the step of performing the vacuum glow discharge treatment, an arbitrary kind of gas in a simple substance or a mixed state is externally supplied from 10 to 300 Pa.
m ³ / sec is introduced, the processing pressure atmosphere is changed, and the processing pressure atmosphere is monitored and controlled.
A method for producing a photographic polyester film support described in 2, 4, or 5. 7. The step of performing the vacuum glow discharge treatment, wherein the polyester support just before the vacuum glow discharge treatment is heated, and further the polyester support just after the vacuum glow discharge treatment is cooled. The method for producing a photographic polyester film support according to claim 1, 2, 4, 5, or 6. 8. In the coating step, the amount of dissolved air is 70% or less of the amount of saturated air, and the liquid temperature is 20 to 40.
The method for producing a photographic polyester film support according to claim 1 or 3, wherein an aqueous coating liquid maintained and controlled at a temperature of 0 ° C is used. 9. The resistance of the conductive layer is 10 exp3 to 10.
The method for producing a photographic polyester film support according to claim 1, 3 or 8, wherein exp12 Ω is set. 10. The fine particles used in the conductive layer are Zn and T.
i, Sn, Al, In, Si, Mg, Ba, Mo, W,
V as a main component and its volume resistivity is 0 Ω / cm or more 10
The method for producing a photographic polyester film support according to claim 1, 3, 8 or 9, characterized in that the exp is 7 Ω / cm or less. 11. The method for producing a photographic polyester film support according to claim 1, wherein the heat treatment is performed for 2 hours or more and 1000 hours or less. 12. The undercoat layer coating liquid is prepared in a predetermined amount together with gelatin, an organic solvent, a binder, and other necessary components, and the undercoat layer coating treatment is a bar treatment. Using a mold coating device,
The method for producing a photographic polyester film support according to claim 1, wherein the coating amount is in the range of 10 to 40 cc / m ² and the temperature of the liquid is 15 to 25 ° C. 13. A liquid used for coating the light transmissive magnetic recording layer, together with a magnetic substance, an organic solvent, and other necessary components.
Each of them is composed of a dispersion liquid which is preliminarily and uniformly mixed in a predetermined amount, and the light-transmissive magnetic recording layer coating treatment uses a slide hopper type coating device or a bar type coating device, Application amount is 10-40cc / m ²
2. The method for producing a photographic polyester film support according to claim 1, wherein the temperature of the liquid is 15 to 25 ° C. 14. A liquid used for coating the overcoat layer, which comprises an organic solvent, a slip agent, and other necessary components, each of which is a dispersion liquid which is uniformly mixed in a predetermined amount. The overcoat layer coating treatment is carried out using a bar type coating apparatus, the coating amount is in the range of 10 to 40 cc / m ² , and the temperature of the liquid is 15 to 25 ° C. Claim 1 characterized by
A method for producing the described photographic polyester film support. 15. The polyester-based support is previously maintained at 20 to 30 ° C. when the undercoat layer and / or the magneto-optical recording layer and / or the overcoat layer are applied. 1. A method for producing a photographic polyester film support as described in 1, 12, 13 or 14. 16. At least one set of a dust removing device for removing dust adhering to the surface of a web-shaped polyester-based support which is being continuously conveyed is installed at least one set. A method for producing the described photographic polyester film support. 17. A web-type polyester support which is being continuously conveyed, and at least one set of static eliminator for removing electric charges applied to the surface of the support is installed. A method for producing the described photographic polyester film support. 18. The photographic polyester film according to claim 1, further comprising a step of subjecting both ends of the web-shaped polyester support to knurling with a height of 1 to 50 μm before the heat treatment. A method for manufacturing a support. 19. The polyester support has a thickness of 8
5. The method for producing a photographic polyester film support according to claim 1, wherein the support has a width of 5 to 120 [mu] m and a width of 1000 to 1500 mm. 20. A web-shaped poly-ether that is continuously conveyed.
For photographic film that heat-treats a stell-based support at a specified temperature
In the method for producing a support, the polyester-based support
Vacuum glow discharge treatment, coating treatment on at least one side of
And the heat treatment are continuously performed in the order, and
The heat treatment is applied in a state where the support is wound into a roll.
In the vacuum glow discharge treatment, any species from the outside
Maintaining the processing pressure at a constant level for single or mixed gases
10-300 Pa · m with holding ^Three/ Sec introduction and processing pressure
Photo-polyes, characterized by changing the power atmosphere
A method for producing a telfilm support. 21. The vacuum glow discharge treatment continuously introduces the polyester-based support from the atmosphere into a vacuum,
21. The method for producing a photographic polyester film support according to claim 20, wherein the introduced support is subjected to vacuum glow discharge treatment. 22. In the vacuum glow discharge process, the generated power of the discharge power source and the power consumption of the discharge unit are monitored,
22. The method for producing a photographic polyester film support according to claim 20, wherein the ratio of power consumption to generated power is maintained at 0.9 or more.