JPH0885193A - Laminated polyester film for pachinko card - Google Patents

Abstract

PURPOSE: To provide a polyester film, prominent for a PACHINKO card. CONSTITUTION: A laminated film is provided with at least one outermost layer (layer A), containing white pigment and having the b-value of less than 5.0 and a coating layer on the surface of the layer A and/or a layer B of co- extrusion laminated biaxially oriented polyester film, having at least one layer of the layer B, containing 1wt.% of polymer reproduced from a recovered used magnetic card, while the value of OD of the laminated film is higher than 0.8.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester multilayer film for pachinko cards.

[0002]

2. Description of the Related Art Currently, as a prepaid card, an NT using a single layer film is used.
Telephone cards of T, orange cards of JR, etc. are widely used for payment of telephone charges and stamps. On the other hand, in the pachinko industry, the use of prepaid cards for pachinko cards, especially for models with a high level of gambling, has been overwhelmingly popular with the support of users under the administrative guidance. However, unlike a telephone card or an orange card, a pachinko card requires an extremely expensive card, and thus it is essential to prevent forgery. On the other hand, pachinko cards are
Since the merit is smaller than that of a telephone card or an orange card, it is desired that the film be as cheap as possible, and disposal of the used card is becoming a problem.

[0003]

Means for Solving the Problems The present inventor has diligently studied the above-mentioned problems, and as a result, multi-layered a polyester film and recovered a used pachinko card,
It has been found that the above problems can be solved by recycling it and using it as a recycled material, and completed the present invention.

That is, the gist of the present invention is to use at least one outermost layer containing a white pigment and having a b value of 5.0 or less (A layer), and to provide a recycled polymer from the collection of used magnetic cards. A laminated film having a coating layer on the A layer surface and / or the B layer surface of a coextrusion laminated biaxially oriented polyester film having at least one layer (B layer) containing 1% by weight or more, and the OD of the laminated film is 0.
It exists in the laminated polyester film for pachinko cards characterized by being 8 or more.

The present invention will be described in more detail below. The coextrusion-laminated biaxially stretched polyester film referred to in the present invention is a coextrusion method in which all layers are comelt extruded from a die, and the extruded product is biaxially stretched and heat set. A stretched and heat-fixed film bonded off-line via an adhesive is not preferable because the flatness of the film is poor and the thickness accuracy of each layer of the film is poor. As a coextrusion method, either a feed block type or a multi-manifold type may be used. However, the feed block type coextrusion method is preferably used because the film thickness of each layer is basically the same. Hereinafter, as the laminated film, a two-layer film and a three-layer film will be mainly described, but the multilayered layers in the present invention are not limited to the two layers and the three layers, and may be a multilayer having more layers. . Especially when the purpose is to prevent forgery,
A multi-layer film having four or more layers can be used together, but a three-layer film is particularly preferable.

The laminated film of the present invention has a layer having a white pigment (A layer) forming at least one surface layer and at least one layer containing a recycled material (B layer). Here, a three-layer film of A / B / A will be described as a representative film, but if necessary, a two-layer film of A / B, A / B / A / B / A, A / C / B, A / C / B /
Various laminated films such as C / A may be used. First,
The layer (A layer) forming the outermost layer having a white pigment will be described. The polyester constituting the layer A is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalene-2,6-dicarboxylic acid, ethylene glycol,
It is a polyester whose main component is an ester with a glycol such as diethylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like. The polyester is obtained by directly polymerizing an aromatic dicarboxylic acid and a glycol, and is subjected to an ester exchange reaction between an aromatic dicarboxylic acid dialkyl ester and a glycol and then polycondensed.
Alternatively, it can be obtained by a method such as polycondensing a diglycol ester of an aromatic dicarboxylic acid.

Typical examples of the polyester include polyethylene terephthalate, polyethylene-2,
Examples thereof include 6-naphthalene dicarboxylate (PEN) and polycyclohexylene dimethylene terephthalate (PCT), with polyethylene terephthalate being the most inexpensive and preferred. Such a polymer may be a homopolymer which is not copolymerized, but may be one of the dicarboxylic acid components.
A copolymerized polyester in which less than 5 mol% is a dicarboxylic acid component other than the main component or less than 10 mol% of the diol component is a diol component other than the main component may be used. Also, if necessary, polymers other than polyester,
For example, nylon, polyolefin or the like may be blended. At the time of polymerization, a polymerization regulator, a crystallization regulator, a plasticizer, a matting agent, a stabilizer and the like may be added, but it is essential to contain a white pigment. That is,
This is because the film of the present invention must be made invisible from the back surface by increasing the hiding power of the film by whitening and preventing the transmission of light rays when it is made into a magnetic card.

As the white pigment, organic polymers such as phenoxy resin, polyolefin and polycarbonate which are dispersed in a so-called sea-island shape to cause light scattering may be used, but in general, talc, kaolin, barium nitrate,
It is preferable to use inorganic particles such as aluminum oxide, calcium carbonate, titanium oxide and silica. Among these, titanium oxide is particularly preferable as the white pigment. The particle size of the inorganic particles used is usually 0.0
It is 1 to 5.0 μm, preferably 0.1 to 0.8 μm. The content of the inorganic particles is usually 5 to 50% by weight, preferably 7 to 20% by weight. If the particle size is too small or the content is too small, the whiteness may be insufficient. If the particle size is too large or the content is too large,
Breakage tends to occur frequently during film formation. As a method of incorporating the white pigment in the polyester film, a method of adding it during the polymerization step of polyester, a method of preliminarily kneading the white pigment into a master batch using an extruder, or the like is adopted, but a particularly preferable method is In this method, a white pigment is directly added and mixed in the extrusion step of the film manufacturing process. As the extruder at that time, a twin-screw extruder with a vent is preferable. In order to improve the dispersibility of particles, a twin-screw extruder with different directions is preferable to a twin-screw extruder with the same direction.
On the other hand, as the particles to be directly added, powder may be used, but addition in water slurry is a preferable method because it is highly quantitative. When titanium oxide is used as the white pigment, silica and a fluorescent whitening agent are preferably used in combination.

Titanium dioxide, which is particularly preferable as the white pigment contained in the polyester A layer in the present invention, may be either anatase type or rutile type in crystal form, but in view of weather resistance, it is of anatase type. Is preferred. Further, for the purpose of improving the dispersion of titanium dioxide in polyester, it is also possible to use titanium dioxide whose surface is treated with an oxide such as aluminum, silicon or zinc or various organic substances. On the other hand, the silica used in combination with titanium dioxide may be crystalline silica or amorphous silica in terms of crystal morphology, and this production method may be either a dry method or a wet method. As the silica, besides pure silica, those containing a metal such as aluminum and magnesium and having a silicon content of 80% or more, and those obtained by surface-treating various metals or organic compounds on the surface of silica can be used. The average particle size of silica used in combination is usually 0.5 to 10 μm.
m, preferably 0.8 to 10 μm, more preferably 1
~ 5 μm. If the average particle size of silica is 0.5 μm or less, the surface of the obtained film tends to be flat and the matting effect tends to be small. If the average particle size of silica is 10 μm or more, the film surface is excessively roughened, and the magnetic recording conversion characteristics of the magnetic card are deteriorated. There is a possibility that problems may occur such as worsening the life of the filter during film production. The content of added silica is
Usually 0.1 to 10% by weight, preferably 0.3 to 2.0
% By weight. When the amount of silica added is 0.1% by weight or less, the film surface is often glossy, and when it is 10% by weight or more, problems occur such that magnetic recording conversion characteristics deteriorate and film breakage during film stretching increases. There is a fear.

The fluorescent whitening agent used in combination with titanium dioxide may be of any type as long as it has a fluorescent peak in the wavelength range of 400 to 500 nm, but suitable examples include Ubitex OB (Ciba Geigy) and OB. -1 (Eastman Co., Ltd.), Mika White (Nippon Kayaku-Mitsubishi Kasei Co., Ltd.) and the like are commercially available. The content of the fluorescent whitening agent added to the polyester is usually 10 to 10,000 ppm, and more preferably 50 to 600 ppm. Titanium dioxide and silica that can be used in the present invention have a particle size adjusted using a refining process before being incorporated into a polyester.
It is preferable to remove coarse particles. As the industrial means of the purification process, for example, a jet mill, a ball mill, etc. can be mentioned as the pulverizing means, and a dry type or wet centrifuge etc. can be mentioned as the classifying means. It should be noted that these means may be used in combination of two or more and purified stepwise. The intrinsic viscosity of the layer A of the film of the present invention is usually 0.55 or more, preferably 0.59 or more in the film state. If the intrinsic viscosity is less than 0.55, the mechanical properties tend to be poor.

The A layer has a b value of 5.0 or less, preferably 3.0 or less, and more preferably 1.0 or less when measured alone. When the b value exceeds 5.0, the whiteness is poor and the sharpness in printing is poor, so that the commercial value is poor, which is not preferable. On the other hand, as the polyester constituting the B layer of the film of the present invention, the same polyester as used in the A layer can be used. However, when the B layer is the outermost layer such as an A / B two-layer film, it is usual to include particles in the B layer. When the layer B does not form the outermost layer, it may be substantially free of particles. The particles to be contained include the above-mentioned kaolin, clay, various calcium carbonates,
Not only well-known inert externally added particles such as various silicon oxides, calcium terephthalate, various aluminum oxides, various titanium dioxides, calcium phosphates, lithium fluoride, etc. Dispersed spherical organic particles, crushed organic particles,
The particles may be any particles such as precipitated particles formed inside the polymer at the time of polyester production by the crosslinked polymer, the alkali metal compound, the alkaline earth metal compound and the like, and may be contained alone or in combination of two or more kinds. The average particle size of the particles is preferably 0.01 to 10 μm, and the addition amount is preferably 0.001 to 30% by weight. An additive other than particles such as a fluorescent whitening agent, a stabilizer, an antioxidant, a colorant, a defoaming agent, and an antistatic agent may be mixed in the B layer.

As a layer for forming the B layer, after collecting used cards of magnetic cards and peeling off the magnetic layer and the like as required, at least 1% by weight or more of the B layer is used as a recycled raw material. It is mandatory. Preferably, 10 to 80
%, And more preferably 20 to 50% by weight. If the amount of the recycled material used is less than 1% by weight, cost reduction, which is one of the objects of the present invention, cannot be expected. In particular, magnetic cards used for pachinko cards are preferable because they are easy to collect. Further, a self-recycled raw material and / or another brand of recycled raw material may be contained in the B layer. At that time, as the content of self and other brand recycled raw materials,
0 to 99% by weight in the B layer is preferable. In particular, as a recycle raw material, at least a part or all of the regenerated raw material may include a regenerated raw material of a film including a so-called in-line coat (ILC) layer, which is combined with a coating layer during the polyester film manufacturing process. Especially when containing ILC recycled materials,
It is preferable to use an antioxidant and / or an optical brightener together. Any method may be used as the method of incorporating the antioxidant or the optical brightening agent, but it is preferable to additionally add it when the recycled chip is produced.

The total amount of the antioxidant and the optical brightener in the B layer is preferably 10% or less. Especially IL
When the C recycled material is used, the ILC composition applied is not particularly limited, but a polyester-based composition, particularly a water-dispersed polyester-based composition is particularly preferable. This is because these compositions are less likely to be decomposed and colored during the recycling process and are easily and uniformly compatible with the polyester as the film raw material. In particular, ILC where it is difficult to mix self-recycled polymer
It is preferable to use a recycled chip of the film for a high-density magnetic tape as described above because of its economical effect. As the antioxidant, it is preferable to use a peroxide decomposing agent that is a secondary antioxidant, especially a phosphorus-based one. Furthermore, it is preferable to use a radical chain inhibitor, especially a hindered phenol-based primary antioxidant together with the secondary antioxidant. B
The intrinsic viscosity of the layer alone is usually 0.50 or more, preferably 0.
It is 54 or more. When the laminated film of the present invention is an A / B two-layer or an A / B / A two-kind three-layer laminated film,
The total thickness of the A layer is usually 5 to 100 μm, preferably 10
˜50 μm. On the other hand, the total film thickness is usually 100
˜250 μm, generally 188 μm.

The OD (optical density), which is an index showing the hiding property of the laminated polyester film of the present invention, must be 0.8 or more. When it is less than 0.8, the appearance of printing is impaired, which is not suitable. OD is preferably 0.9-
It is 1.7. More preferably, it is 1.0 to 1.15. The intrinsic viscosity of the whole film is usually 0.54 or more, preferably 0.58 or more. If the intrinsic viscosity is low, so-called burrs tend to appear when a card is punched out. It is preferable that the particle contents and the film viscosities of the A layer and the B layer satisfy the following expressions.

[0015]

[Number 1] _{| C A -C B | ≦ 25} ··· ( in the above formulas, C _A is the particle content of the layer A, C _B is the particle content of the layer B)

[Equation 2] | [η] _A − [η] _B | ≦ 0.1 (where [η] _A is the intrinsic viscosity of the A layer, and [η] _B is B
Is the intrinsic viscosity of the layer)

If the difference in the particle content and / or the film viscosity is too large, peeling of layers tends to occur when a card is prepared and used as a laminated film, and as a result, durability is improved. May be inferior. The thickness deviation of the film is preferably in the range of 188 ± 2 μ at a specified thickness, for example, 188 μm, and it is particularly important to suppress the thickness deviation in the film width direction to be low. It is also important that the film does not curl. Of course, it is also necessary not to curl after printing or applying the magnetic layer. Therefore, a laminated film symmetric in the thickness direction represented by the A / B / A type is preferable to a laminated film asymmetrical in the thickness direction represented by the A / B type. Further, since curling may occur when the film forming machine is completely symmetrical, the A / B / A ′ type having the same composition as A and A ′ but having different thicknesses is preferable because curl countermeasures can be easily taken.

Since the film of the present invention is used as a prepaid card used for pachinko cards, it is necessary to provide a coating layer on the surface of the A layer and / or the surface of the B layer. The coating layer is preferably obtained by coating a film with a coating liquid containing at least one or more selected from polyurethane, polyester, an acrylic styrene-butadiene copolymer, and an acrylonitrile-butadiene copolymer, and then drying it. As a method for forming the coating layer, a method for forming the biaxially oriented film (ILC described above) is used.
There is a method of forming the biaxially oriented film after production, but the former method is preferable. As a specific example of the former, for example, after applying the thin film forming liquid on the surface of the unstretched film,
Stretch in the biaxial direction. Alternatively, a method of applying the thin film forming liquid on the surface of the uniaxially stretched film and further stretching it in the perpendicular direction may be mentioned, but a method of using these together is also preferable.

When the stretching treatment after coating is not carried out, the adhesion between the coating layer formed and the white polyester film as the base film tends to be weak, and the adhesiveness suitable for practical use may not be obtained. In order to achieve these industrially advantageously, it is preferable to apply them in the biaxially stretched film production process. As an example of such a method, a method of applying a film to a film uniaxially stretched in the longitudinal direction of the film-forming step, stretching the film in a dry or undried state in a direction perpendicular to the uniaxially stretching direction and then performing a heat treatment is a manufacturing cost. It is adopted in terms of aspect, but is not limited to these.

The stretching step for obtaining the above film is
It is preferably carried out at 70 to 160 ° C., and the stretching ratio is at least 4 times or more, preferably 6 to 35 times in terms of area ratio. The stretched film is usually heat-treated at 150 to 250 ° C. Further, in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet, a method of relaxing 0.1 to 20% in the longitudinal direction and the transverse direction is preferably adopted. In particular, the coating solution was applied to a uniaxially stretched white polyester film stretched 2 to 6 times in the longitudinal direction of the film at 70 to 145 ° C. by a roll stretching method, and was appropriately dried or not dried, and then obtained. The coated film is stretched in the transverse direction at 90 to 160 ° C. to 2 to 6 times,
A method of performing heat treatment at 0 to 250 ° C. for 1 to 600 seconds is preferably adopted. According to this method, the coating layer can be dried at the same time as stretching, and the thickness of the coating layer can be reduced according to the stretching ratio, and a film suitable as a white polyester film substrate can be manufactured at a relatively low cost. it can.

A reverse roll coater, a gravure coater, a rod coater, an air doctor coater, etc. shown in "Coating Method" by Yuji Harazaki, Maki Shoten, 1979, is used as a method for applying the above-mentioned coating liquid to a polyester film. be able to. As the coating layer of the film of the present invention, it is preferable to provide an easily printable thin film layer. The easily printable thin film forming agent is not particularly limited as long as it has improved adhesiveness to a printing ink such as water-soluble ink and UV curable ink, and is a water-soluble or water-dispersible polyester-based agent. Preferred examples include a composition, a water-soluble or water-dispersible polyurethane composition, a water-soluble or water-dispersible polyacrylic composition, a water-soluble or water-dispersible styrene-butadiene copolymer, and an acrylonitrile-butadiene copolymer. .

On the other hand, it is preferable to form a double-sided coating layer on the surface opposite to the surface on which the easily printable thin film layer is formed, by forming a thin film layer for enhancing the adhesiveness with the magnetic layer. The method for forming an easily-adhesive thin film with a magnetic layer and the forming agent are the same as the above-mentioned forming method and forming agent for an easily printable thin film, but in particular for a pachinko card, urethane, vinyl chloride, vinyl acetate and iron oxide were contained. It is preferable that the adhesiveness with the magnetic recording composition is improved.

The coating layer of the film of the present invention preferably has antistatic performance. That is, the workability is deteriorated due to the sticking due to the electrification of the film, and a problem such as an ignition accident due to spark discharge occurs. It is also important to prevent the attachment of dust. As a method of imparting antistatic property, a low molecular weight anionic surfactant such as organic sulfonic acid, for example, an antistatic agent such as sodium polystyrene sulfonate is applied to the above-mentioned easy printability and / or easy magnetic layer adhesion coating. It is preferable to mix the agent and apply it in-line. Further, a high molecular weight cationic antistatic agent is used as an antistatic agent, or a polymer containing a resin having a phosphate group or a phosphate group or a polymer having an ionized nitrogen element in its main chain is used as a compounding agent. Is also a preferred method.

Even when the coating layer is formed, it is preferable that the blocking is small. If there is blocking, the film may stick to the film when it is wound and slit after film formation, and in extreme cases, it may be broken.
Further, after printing the magnetic layer, the magnetic layer may be transferred to the opposite surface during printing, which may cause peeling of the magnetic layer.

The coating liquid for obtaining the coating layer of the present invention may contain a crosslinking agent in order to improve the blocking property, water resistance, solvent resistance and mechanical strength of the coating layer. As the cross-linking agent, a methylolated or alkylolated urea-based compound, melamine-based compound, guanamine-based compound, acrylamide-based compound, polyamide-based compound, epoxy compound, oxazoline compound, aziridine compound, blocked isocyanate compound, silane coupling agent, titanium coupling Agents, zirco-aluminate coupling agents, peroxides, heat- or photo-reactive vinyl compounds, photosensitive resins and the like. Further, the coating liquid for obtaining the coating layer of the present invention may contain particles for improving the slipperiness of the coating layer. As the particles, inorganic particles such as colloidal silica, alumina, calcium carbonate, titanium oxide, and fine particles containing a homopolymer or copolymer of polystyrene resin, polyacrylic resin or polyvinyl resin, or a composite of these and a crosslinking component is used. Organic particles represented by crosslinked particles are exemplified.

Further, the coating liquid for obtaining the coating layer of the present invention comprises a defoaming agent, a coating property improving agent, a thickener, a low molecular weight antistatic agent, an organic lubricant, an antioxidant, if necessary. It may contain an ultraviolet absorber, a foaming agent, a dye, a pigment and the like. Further, the coating liquid for obtaining the coating layer of the present invention may contain a small amount of an organic solvent for the purpose of improving the dispersion in water or the film-forming performance, as long as water is the main medium. Good. When the organic solvent is used as a main medium mixed with water, it is necessary to use it in a range that dissolves in water. Examples of the organic solvent include aliphatic or alicyclic alcohols such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol and methyl alcohol, glycols such as propylene glycol, ethylene glycol and diethylene glycol, n-butyl cellosolve, Ethyl cellosolve, methyl cellosolve, glycol derivatives such as propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and amyl acetate, ketones such as methyl ethyl ketone and acetone, N
Examples include, but are not limited to, amides such as methylpyrrolidone. These organic solvents may be used alone or in combination of two or more if necessary.

The thickness of the coating layer of the film of the present invention is usually in the range of 0.02 to 0.5 μm, preferably 0.01 to 0.3 μm, and more preferably the final dry thickness. It is in the range of 0.03 to 0.2 μm. When the thickness of the coating layer is more than 0.5 μm, the films are likely to block each other, and particularly when re-stretching the coating-treated film for the purpose of increasing the strength of the film, it may stick to the roll during the process. It may be easier. The problem of blocking is particularly remarkable when the same antistatic layer is provided on both surfaces of the film. When the thickness of the coating layer is less than 0.02 μm, the effect of improving the adhesiveness tends to be small. In addition, in order to improve the coating property and the adhesive property of the coating agent on the film, the film may be subjected to a chemical treatment or a discharge treatment before the coating. Further, in order to improve the surface characteristics and the like of the coating layer of the biaxially stretched polyester film of the present invention, the coating layer may be subjected to a discharge treatment after the coating layer is formed.

As a method of using a used pachinko card as a regenerated raw material, there is a method of peeling the magnetic layer to form flakes, then drying and melting and pelletizing by a twin-screw extruder. At that time, it is preferable to pelletize with a vent type twin-screw extruder without drying. However, it is costly and difficult to separate the used pachinko cards one by one from the magnetic layer. For example, it is preferable to pelletize the magnetic layers containing the magnetic layers using an extruder manufactured by Elema. Further, in this case, it is more preferable to directly form a laminated film by directly connecting it to the main extruder while directly melting without pelletizing. Next, the method for producing the film of the invention will be specifically described, as long as the constituent requirements of the invention are satisfied,
It is not particularly limited to the following examples.

A polyester (A) containing a predetermined amount of a white pigment (preferably TiO ₂ ), a fluorescent whitening agent and other lubricants.
Layer) and a recycled material of used pachinko cards, self-recycled polyester, recycled polymer of in-line coated film for the purpose or another purpose, or polyester blended with other polymer (B
Layer) and separately dried and melt-extruded from different extruders, and then bonded and laminated in a laminar flow state in the molten polymer channel tube or in the extrusion die, and discharged from the extrusion die and unstretched. Create a laminated film. For drying, it is preferable to use a hopper dryer, a vacuum dryer, a paddle dryer, an oven or the like. Layer B is the main extruder and sub-extruder is A
When used as a layer, it is also a preferred embodiment to use a method in which a sub-extruder is a twin-screw vent extruder and a white pigment or the like is directly added. In particular, when switching between films with different ODs, there is little loss, which contributes to improved productivity. It is also preferable to apply an electrostatic contact method at the time of casting, and also use a liquid application method such as water.

The unstretched laminated film thus obtained is
First, the film is stretched in the longitudinal direction at 70 ° C. to 145 ° C. in a single step or in multiple steps at a rate of 2.0 to 6 times to obtain a longitudinally uniaxially stretched film, and then the coating liquid is sequentially applied to both surfaces of the film, and appropriate drying is performed, Alternatively, without drying, the coated uniaxially stretched film is gripped with a clip and guided to a tenter, and first stretched in the transverse direction at 90 to 160 ° C. to 2.0 to 6.0 times, and then to 150 to
It is preferable to perform heat treatment at 250 ° C. for 1 to 600 seconds. At this time, in the maximum temperature zone of the heat treatment and / or the cooling zone at the exit of the heat treatment, a method of relaxing 0.1 to 20% in the longitudinal direction and / or the lateral direction is preferable. Further, it is also possible to add re-longitudinal stretching and re-transverse stretching if necessary.

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The evaluation method of the film is as follows. (1) Color Tone Color analyzer TC1800M manufactured by Tokyo Denshoku Co., Ltd.
Using the KII type, the color tone was measured as the values of L, a and b according to the method of JIS Z-8277. (2) Optical density (OD) Using a Macbeth densitometer TD-904 type, the transmitted light density under the G filter was measured. (3) Surface Layer Film Thickness of Laminated Film The film cross section was observed with a transmission electron microscope (TEM). That is, a small piece of a film sample was embedded in a resin in which an epoxy resin was mixed with a curing agent and an accelerating agent, and a section having a thickness of about 200 nm was prepared with an ultramicrotome, and used as an observation sample. A micrograph of a cross section of the obtained sample was taken using a transmission electron microscope H-9000 manufactured by Hitachi Ltd., and the thickness of the surface layer was measured. However, the accelerating voltage is 300 kV, the magnification depends on the outermost layer thickness,
It was set in the range of 10,000 times to 100,000 times. The thickness was measured at 50 points, 10 points from the thickest value and 10 points from the thinnest value were deleted, and 30 points were averaged to obtain the measured value.

(4) Average particle size of inert solid particles (electron microscopic method) The average particle size of monodisperse particles was measured by a photographic method using an electron microscope. The magnification was 20000 times. (5) Average particle diameter d ₅₀ ^{cc of} inert solid particles (Coulter counter method) Measured using a Coulter counter TA-II type manufactured by Nikkaki Co., Ltd. The measured value is represented by an equivalent spherical equivalent value (diameter, μm). (6) Surface resistivity (antistatic property) Concentric circular electrode from Yokogawa / Hewlett-Packard Company "1"
A sample was placed on the "6008A (trade name)" (inner electrode 50 mm diameter, outer electrode 70 mm diameter) in an atmosphere of 23 ° C and 50% RH, and a voltage of 100 V was applied. ) ”Was used to measure the surface resistivity of the sample. The criterion is the following, which is the logarithm of the surface resistivity. Less than 10: A (good) 10 or more, less than 13: B (normal) 13 or more: C (defective)

(7) Adhesiveness with UV curable ink UV curable offset ink "FD" manufactured by Toyo Ink Mfg. Co., Ltd.
"OL indigo APN ro" was transferred to a film with a thickness of 2 µm by "RI tester RI-2" which is an offset printing tester manufactured by Akira Seisakusho, and this was irradiated by Ushio Electric Co., Ltd. "UVC-402". / 1HN: 302/1
Through MH ", mercury lamp output 120W / cm, line speed 10m / min, lamp-film spacing 100mm
The ink was cured under the conditions of, and the cellotape peeling test was immediately performed, and the peeled area was evaluated. The judgment criteria are as follows. No peeling: A (good) Some peeling spots: B (normal) Full peeling: C (poor)

(8) Adhesion with magnetic paint The following evaluation paint was applied to a sample film with a wire bar so that the film thickness after drying was 5 μm, dried at 80 ° C. for 2 minutes, and then at 60 ° C. for 24 minutes. Time aged. The adhesive strength of the magnetic layer is 7 cm so that air bubbles do not enter cellophane tape (18 mm width) manufactured by Nichiban Co., Ltd. on the surface of the magnetic layer of the sample.
After affixing a fixed load with a 3 kg manual load roll and sticking it on this, the film was fixed, one end of the cellophane tape was connected to a 500 g weight, and the weight naturally dropped at a distance of 45 cm. , 180 ° direction peeling test was started. Adhesiveness was evaluated according to the following three-stage criteria. Paint does not peel at all: A, paint at less than 10% peels off: B, paint at 10% or more peels off: C

Paint for evaluation Magnetic fine powder X6000 (Titanium industry) 500 parts, polyurethane resin Nipporan 2304 (manufactured by Nippon Polyurethane)
30 parts, vinyl chloride vinyl acetate copolymer 1000GKT (manufactured by Denki Kagaku)
50 parts, 5 parts of lecithin (Kishida chemical reagent), 246 parts of cyclohexanone, 246 parts of methyl isobutyl ketone and 738 parts of methyl ethyl ketone were mixed and dispersed in a sand mill for 1 hour, and then 10 parts of Coronate L as a cross-linking agent was added and well stirred to form a magnetic paint. obtain.

Comparative Example 1 [Production of Polyester A Substantially Free of Particulate Lubricant] 87 parts of terephthalic acid and 42 parts of ethylene glycol were added under normal pressure in the presence of 100 parts of bis- (β-hydroxyethyl) terephthalate oligomer. An esterification reaction was carried out by reacting at 260 ° C. Four hours after the start of the reaction, a polyester oligomer having an esterification rate of 97% was obtained. Next, to 103 parts of the obtained polyester oligomer (corresponding to 100 parts of the final produced polyester), 0.01 part of germanium dioxide and 0.04 parts of tetra-n-butyl orthotitanate.
Add 0355 parts and 0.01 parts orthophosphoric acid to give 250
While increasing the temperature from 120 ° C. to 285 ° C. in 120 minutes and simultaneously reducing the vacuum degree from 760 mmHg to 1 mmHg in 120 minutes, a polycondensation reaction was carried out for 4 hours at 285 ° C. and 1 mmHg to obtain polyester A. The intrinsic viscosity of the obtained polyester was 0.63.

[Production of Polyester B] Polyester B was subjected to solid phase polymerization according to a usual method to obtain polyester B having an intrinsic viscosity of 0.75. [Manufacture of Polyester C, D, E] Polyester A is dried and subjected to a vent type twin-screw extruder to obtain T having an average particle size of 0.3 μm.
Polyester C was obtained by kneading iO ₂ (anatase type titanium oxide) to 40% by weight and chipping. Here, instead of titanium oxide, an optical brightening agent OB-I was added to 1.0
Polyester D was obtained by kneading so as to have a weight% and forming chips. Further, polyester E was obtained by kneading the siloid 72 having an average particle size d ₅₀ ^cc of 2.4 μm so as to be 3.0% by weight and forming a chip.

[Production of Regenerated Polymer F] Comparative Example 1 described later
The regenerated polymer F was obtained by dry-powdering the ears of the laminated film of 1 above and extruding it into chips. [Manufacture of Regenerated Polymer G] Regenerated Polymer G was prepared by extruding the ears of the base film for magnetic recording for Hi-8 metal powder into a dry powder and extruding it into chips. [Manufacture of Regenerated Polymer H] Pachinko cards collected at a pachinko parlor were washed with water, then only the magnetic layer was peeled off, and chips were formed using an extruder manufactured by Elema Co., to obtain regenerated polymer H. [Manufacture of regenerated polymers F ', G', H '] OB as a fluorescent whitening agent when regenerated polymers F, G, H are made into recycled chips
0.05% by weight of -I in the polymer, 1 as a phosphorus-based antioxidant JP310 (a phosphite (tridecyl phosphite) manufactured by Johoku Chemical Co., Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) as antioxidants. The remixed polymers F ′, G ′, and H ′ were obtained by adding the mixture of 1: 1 to 0.35% by weight in the polymer.

[Method for producing laminated polyester film]
Polyester C: Polyester D: Polyester E: Polyester B = 50: 2.0: 16.7: 31.3 (weight ratio) were blended to obtain Blend I. The intrinsic viscosity of Blend I was 0.62. Polyester C: Polyester F: Polyester G: Polyester H
= 12.2: 20: 40: 27.8 (weight ratio) were blended to obtain blend II. The intrinsic viscosity of Blend II was 0.58.

The blend I and the blend II obtained above were stored in separate silos, then dried by a paddle dryer with a nitrogen substitution, and the blend I was fed into the sub-extruder and the blend II was fed into the main extruder. Here, the main extruder used was a normal single extruder, but the sub-extruders used were bent-type twin-screw extruders in different directions. After branching the polymer of the sub-extruder into two layers, the polymer from the main extruder was merged with a feed block through a gear pump filter, and the polymer was taken out through a die onto a casting drum to obtain an unstretched film. An electrostatic contact method was used for casting. The thus obtained two-kind, three-layer laminated unstretched film was fed to a longitudinal stretching roll, and first stretched 2.5 times at a film temperature of 83 ° C. (with IR heater), and then at 1.87 ° C. (with IR heater). The film was stretched 23 times, and the birefringence after longitudinal stretching was adjusted to 0.70. Then, it was held with a clip and led to a tenter, and stretched 3.0 times in the transverse direction at 125 ° C. to obtain a biaxially oriented film. Then, the biaxially oriented film was introduced into a heat setting zone and heat set at 232 ° C. for 10 seconds while relaxing in the width direction by 2%, and the intrinsic viscosity was 0. 8 at 188 μm of two kinds of three layers having a thickness of 15 μm / 158 μm / 15 μm. 60, a film with a thickness deviation in the film width direction of ± 2 or less was obtained. The characteristics and evaluation results of the obtained film are shown in Table 3 below.

Examples 1 and 2 A coating solution having the coating composition shown in Table 1 below was applied to a polyester film after longitudinal stretching and before lateral stretching in Comparative Example 1, and then biaxially treated in the same manner as in Comparative Example 1. A stretched film was obtained. The contents of the coating material abbreviations in Table 1 are as shown in Table 2 below. Further, the composition of the content of the coating layer in Table 1 is the weight ratio of each component in terms of dry solid content. The coating thickness is the dry coating thickness on the surface of the finally obtained biaxially stretched film. Table 3 shows the results of evaluating the characteristics of the obtained film.

[Table 1]

[0041]

[Table 2]

Example 3 A film was produced in the same manner as in Example 1 except that polyester F ′, polyester G ′ and polyester H ′ were used instead of polyester F, polyester G and polyester H used in Example 1, The results of characteristic evaluation of the film are shown in Table 3.

Comparative Example 2 In Example 1, the blend I was polyester C: polyester D: polyester E: polyester B: polyester A = 25: 2.0: 16.7: 31.3: 25, and blend II was polyester. C: Polyester F: Polyester G: Polyester H: Polyester A = 6.
A film having a thickness of 188 μm was obtained in the same manner as in Example 1 except that the ratio was 1: 20: 40: 27.8: 6.1.

Comparative Example 3 In Example 1, both the inner and outer layers were made of polyester C: polyester F: polyester G: polyester H = 12.
2: 20: 40: 27.8 with TiO only in the outer layer
A film having a thickness of 188 μm was obtained in the same manner as in Example 1 except that TiO ₂ was directly added so that the amount of ₂ (anatase type titanium oxide) was 20% by weight.

Comparative Example 4 In Example 1, polyester C: polyester A: polyester D: polyester E: polyester B: polyester H '= 9.5: 7.5: 1.
Example 1 except 0: 6.0: 31.3: 44.7
A film having a thickness of 188 μm was obtained in the same manner as in. When a magnetic card was prepared by coating a magnetic layer on one side and a printing layer on one side of the films of Comparative Examples 1 to 4 and Examples 1 to 3, Examples 1 to 3 are satisfactory as magnetic cards in all respects. At the same time, since it is multi-layered in the thickness direction, it is excellent in forgery prevention. In particular, it collects used cards and reuses them, making it an environmentally friendly product. On the other hand, Comparative Example 1 was inadequate because of poor adhesion of the magnetic layer and the printing layer. Further, the film of Comparative Example 2 had a low whiteness, a poor print finish, and had no commercial value. The films of Comparative Examples 3 and 4 had a yellowish color tone, had poor print finish, and had no commercial value.

[0046]

[Table 3]

[0047]

EFFECTS OF THE INVENTION As in the present invention, the social contribution of reusing a large amount of magnetic cards, especially in a pachinko parlor, is extremely remarkable, and since the place where it is used is specified, it is collected. Since the present invention can provide a valuable example as an environmentally friendly film, which is easy and can recover almost the entire amount, the value of the present invention is high.

Claims (1)

[Claims] 1. A layer containing a white pigment and having a b value of 5.0 or less (A layer) as at least one outermost layer, and containing 1% by weight or more of a recycled polymer from the collection of a used magnetic card. It is a laminated film having a coating layer on the A layer surface and / or the B layer surface of a coextrusion laminated biaxially oriented polyester film having at least one layer (B layer), and the OD of the laminated film is 0.8 or more. A laminated polyester film for pachinko cards, which is characterized in that