JPH08108458A - Laminated polyester film for magnetic card - Google Patents

Abstract

PURPOSE: To provide a pinball game-card of high quality gentle to environment. CONSTITUTION: In a co-extrusion laminated biaxially stretched polyester film having a polyester layer (A-layer) containing white pigment and having a b-value of 5.0 or less as the outermost layer and at least one layer (B-layer) containing 1wt.% or more of a regenerated polymer, a coating layer is provided on the surface of the A-layer and/or the B-layer. The laminated polyester thus constituted for a magnetic card satisfies formula OD>0.8......1 and formula 0<=|CA-CB|<15......2 [wherein CA is the content (wt.%) of the white pigment in the A-layer and CB is the content (wt.%) of the white pigment in the B-layer] at the same time.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As magnetic cards currently used for prepaid cards, NTT telephone cards using a single-layer film, JR orange cards, etc. are used for telephone payment, stamp payment, etc. Widely used in. On the other hand, in the pachinko industry,
Especially for models that are highly gambling, using prepaid cards as pachinko cards has become overwhelmingly popular with the support of users. However, unlike a telephone card or an orange card, a pachinko card requires an extremely expensive card, so it is essential to prevent forgery, and unlike a telephone card or an orange card, a pachinko card is a privately owned card. Since the ratio of the film is extremely small, there is little merit in that respect, and it is desired that the film be as cheap as possible. More often than expected, it was used repeatedly and the durability as a prepaid card came to be required.

[0003]

Means for Solving the Problems The inventors of the present invention have diligently studied the above-mentioned problems and, as a result, have made a polyester film into a multilayer and use a recycled raw material including a used pachinko card to reproduce a white pigment. It has been found that the above problems can be solved by specifying the content of each layer, and the present invention has been completed.

That is, the gist of the present invention is a layer containing a white pigment, wherein the outermost layer is a polyester layer (A layer) having a b value of 5.0 or less, and contains 1% by weight or more of a recycled polymer. A coextrusion laminated biaxially oriented polyester film having at least one layer (B layer), which has a coating layer on the surface of the A layer and / or B layer, and satisfies the following formulas and at the same time: Existing in laminated polyester film.

[Number 2] OD> 0.8 ...... 0 ≦ laminate film _{| C A -C B | <15} ...... ( In the formula, C _A white content in layer A (wt%), C _B
Represents the white content (% by weight) in layer B)

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 (A layer) having a white pigment and forming at least one outermost layer, and at least one layer (B layer) containing a recycled material. Here, A / B / A as a representative film
The three-layer film having the structure of
B two-layer film, A / B / A / B / A, A / C / B,
It may be various laminated films such as A / C / B / C / A. First, the layer forming the outermost layer having a white pigment (A
Layers). The polyester that constitutes the A layer is terephthalic acid, isophthalic acid, naphthalene-2,6
A polyester mainly composed of an ester of an aromatic dicarboxylic acid such as dicarboxylic acid and a glycol such as ethylene glycol, 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 after transesterifying an aromatic dicarboxylic acid dialkyl ester and a glycol,
It can also be obtained by a method such as polycondensation or polycondensation of a diglycol ester of an aromatic dicarboxylic acid.

As typical examples of the polyester, polyethylene terephthalate, polyethylene 2,
6 naphthalene dicarboxylate (PEN), polycyclohexylene dimethylene terephthalate (PCT film) and the like are exemplified, but polyethylene terephthalate is the most inexpensive and preferred. Such a polymer may be a homopolymer which is not copolymerized, but less than 15 mol% of the dicarboxylic acid component 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. It may be a copolyester such as Further, if necessary, a polymer other than polyester, such as nylon or polyolefin, 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, in the film of the present invention, it is necessary to increase the hiding power of the film by whitening it and prevent the transmission of light rays when it is made into a magnetic card so that the printing layer cannot be seen from the back surface.

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.

In the present invention, titanium dioxide, which is particularly preferable as a white pigment to be contained in the polyester A layer, 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. Silica contains metals such as aluminum and magnesium in addition to pure silica,
Those having a silicon content of 80% or more, and those obtained by surface-treating silica with various metals and organic compounds can also be used. The average particle size of silica used in combination is usually 0.5 to 10
μm, preferably 0.8 to 10 μm, more preferably 1 to 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
It is 2.0% by weight. When the amount of silica added is 0.1% by weight or less, the film surface is often glossy.
When the content is more than 10% by weight, there is a possibility that problems such as deterioration of magnetic recording conversion characteristics and increase in film breakage during film stretching may occur.

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), Mika White (Nippon Kayaku-Mitsubishi Kasei) 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 in the film state is usually 0.55 or more, preferably 0.59.
That is all. If the intrinsic viscosity is less than 0.55, the mechanical properties tend to be poor. The A layer has ab value of 5.0 or less, preferably less than 3.0, and more preferably less than 1.0 when measured as the A layer alone. When the b value exceeds 5.0, the whiteness is inferior and the printing lacks clarity.
The product value is inferior and unfavorable. On the other hand, as the polyester constituting the B layer of the film of the present invention, the same polyester as the A layer can be used. However, layer B is A
When forming the outermost layer such as a / B two-layer film, particles are usually contained, but the A / B / A
When the B layer does not form the outermost layer as in the seed three-layer film, it may be substantially free of particles. As the particles to be included, not only known inert externally added particles such as the above-mentioned kaolin, clay, various calcium carbonates, various silicon oxides, calcium terephthalate, various aluminum oxides, various titanium dioxides, calcium phosphates, lithium fluoride, etc. , A high-melting point organic compound insoluble during melt film formation of polyester resin, monodisperse spherical organic particles,
Any type of particles, such as crushed organic particles, crosslinked polymers, and precipitation particles formed inside the polymer during production of polyester by an alkali metal compound, an alkaline earth metal compound, etc., may be used alone or in combination of two or more kinds. Good. 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.

The layer forming the layer B may contain a recycled material after collecting used cards of magnetic cards and peeling off the magnetic layer and the like if necessary. Content is B
It is 1% by weight or more in the layer, more preferably 10 to 80% by weight, and most preferably 20 to 50% by weight. In particular, magnetic cards used for pachinko cards are preferable because they are easy to collect. If it is less than 1% by weight, there is no cost advantage. Furthermore, a self-recycled raw material and / or a recycled raw material of another brand may be contained in the B layer. At that time, the content of self-recycled // other-brand recycled materials is also preferably 1% by weight or more in the B layer. In particular, it is preferable that at least a part or the whole of the recycled raw material contains a regenerated raw material of a film including a so-called in-line coat (ILC) layer that imparts a coating layer during the polyester film manufacturing process. In particular, it can be said that social contribution by reusing magnetic cards that are discharged in large quantities in pachinko parlors is extremely significant. Further, since the place to be used is specified, collection is easy and almost the entire amount can be collected, which can provide a valuable example as an environmentally friendly film.

When the ILC regenerated raw material is contained, it is preferable to use an antioxidant and / or an optical brightening agent together. The antioxidant and / or the optical brightening agent may be contained in any method, but it is preferable that the antioxidant and / or the optical brightening agent are additionally added when the recycled chip is produced. The total amount of the antioxidant and the optical brightener in the B layer may be 10% or less. When an ILC recycled material is used, the ILC composition applied is not limited, but a polyester-based composition is preferable, and 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, it is preferable to use a recycled chip of an ILC film for a high-density magnetic tape in which it is difficult to mix the self-recycled polymer, because it has an 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.

The intrinsic viscosity of layer B alone is usually 0.50 or more,
It is preferably 0.54 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.
It is preferably 10 to 50 μm. On the other hand, the total film thickness is usually 100 to 250 μm, and generally 188 μm.
m and 195 μm. The OD (optical density), which is an index showing the hiding property of the laminated polyester film of the present invention, needs to exceed 0.8. If it is less than 0.8, the aesthetic appearance of printing is impaired, which is unsuitable. The OD is preferably 0.9 to 2.0. More preferably 1.0 to
It is 1.7. 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. Further, the particle contents of the A layer and the B layer must satisfy the following formula.

[0015]

0 ≦ | C _A −C _B | <15 (wherein C _A is the white pigment content (% by weight) in the A layer,
C _B represents the content (% by weight) of the white pigment in the B layer) When the formula is 15 or more, the durability is poor and it is not preferable. It is preferably less than 10, more preferably less than 5. If the difference in the content of the particles is too large, when a card is prepared and used as a laminated film, layer peeling tends to occur, and as a result, the durability may be poor. The thickness deviation of the film is a specified thickness, for example 188
It is preferably in the range of 188 ± 2μ in μm, and it is particularly important to suppress the thickness fluctuation in the film width direction to be low. Furthermore, it is preferable that the film does not curl. Of course, it is also preferable 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, polyurethane, polyester, acrylstyrene-butadiene copolymer, acrylonitrile-butadiene copolymer is formed on at least one surface forming the layer A. It is necessary to have a coating layer obtained by applying a coating solution containing at least one selected from the group and then drying it. As the method for forming the coating film, there are a method of forming the biaxially oriented film (ILC described above) and a method of forming the biaxially oriented film, but the former method is preferable. As a specific example of the former, for example, a thin film forming liquid is applied to the surface of an unstretched film and then stretched in a 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. If the stretching treatment after coating is not performed, the adhesion between the formed coating layer 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 process 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 is 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 is appropriately dried or not dried, and then the uniaxially stretched film. The film is stretched 2 to 6 times in the transverse direction at 90 to 160 ° C.
A method of performing heat treatment at ˜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. As a method of applying the above-mentioned coating liquid to a polyester film, Yuji Harasaki, Maki Shoten, 1979,
A reverse roll coater, a gravure coater, a rod coater, an air doctor coater or the like shown in the "coating method" can be used.

The coating layer of the film of the present invention is preferably a thin film layer having easy printability. 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. A composition, a water-soluble or water-dispersible polyurethane composition,
Water-soluble or water-dispersible polyacrylic compositions, water-soluble or water-dispersible styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and the like are preferable. On the other hand, on the surface opposite to the surface on which the easily printable thin film layer is formed,
It is preferable to form a double-sided coating layer by forming a thin film layer that enhances 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,
It preferably has antistatic ability. 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, zircoaluminate 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 solution for obtaining the coating layer of the film of the present invention contains, if necessary, an antifoaming agent, a coating property improving agent,
It may contain a thickener, a low molecular weight antistatic agent, an organic lubricant, an antioxidant, 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. As the organic solvent, n-
Aliphatic or alicyclic alcohols such as 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 and propylene. Examples include, but are not limited to, glycol derivatives such as 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, and amides such as N-methylpyrrolidone. It is not something that can be done. 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. By the way, as a method of using a used magnetic card, particularly a pachinko card, as a reproduction 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 pachinko card while containing the magnetic layer 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, but the invention is not particularly limited to the following examples as long as the constitutional requirements of the invention are satisfied. A white pigment (preferably TiO ₂ ), a fluorescent whitening agent, and a polyester containing a predetermined amount of a lubricant (A layer), a white material and a recycled material of used pachinko card and / or a self-recycled polyester and / or The in-line coated film for application and / or other applications, the regenerated polymer and / or the polyester (B layer) blended with the other polymer are separately dried and melt-extruded from different extruders, and then the melt-polymer flow path is formed. In a tube or in an extrusion die, the layers are joined and laminated in a laminar flow and discharged from the extrusion die to prepare an unstretched laminated film. For drying, it is preferable to use a hopper dryer, a vacuum dryer, a paddle dryer, an oven or the like. When the B layer is used as the main extruder and the sub extruder is used for the A layer, it is also a preferred embodiment to use a method in which the sub extruder is a twin-screw vent extruder and a white pigment or the like is directly added. Especially OD
Contributes to improved productivity with little loss when switching between different films. 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.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. 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 density of transmitted light 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 Microscope 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} inactive solid particles (Coulter counter method) It was 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 to 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.
It is attached to the length of, and a fixed load is applied with a 3 kg manual load roll on this, the film is fixed, the end of the cellophane tape is connected to a 500 g weight, and the weight naturally falls at a distance of 45 cm. Later, evaluation was performed by a method in which a peel test in the 180 ° direction was started. Adhesiveness was evaluated according to the following three-stage criteria. The paint does not peel off at all. : A The paint of less than 10% peels off. : B 10% or more of the paint peels off. : C evaluation paint 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. (9) Curling property and durable peeling property of magnetic card The prepared magnetic card was placed on a flat surface, and the presence or absence of curling problem was visually observed. In addition, the durability of the card was such that the card did not peel off even if it was bent until it was broken.

Comparative Example 1 (Production of Polyester A Substantially Free of Particulate Lubricant) In the presence of 100 parts of bis- (β-hydroxyethyl) terephthalate oligomer, 87 parts of terephthalic acid and 42 parts of ethylene glycol were added under normal pressure in 260 parts. An esterification reaction was carried out by reacting at ° 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 having an intrinsic viscosity of 0.75 is obtained by solid-state polymerization of the above polyester A.
I got (Production of Polyesters C, D, E) Polyester A is dried, and T having an average particle size of 0.3 μm is produced by a vent type twin-screw extruder.
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 brightener 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) The laminated film of Comparative Example 1 was dried into powder and extruded into chips to obtain Regenerated Polymer F.

(Production of Regenerated Polymer G) Regenerated Polymer G was prepared by extruding the ears of a magnetic recording base film for Hi-8 metal powder into 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. (Manufacturing method of laminated polyester film) Polyester C: Polyester D: Polyester E: Polyester B
= 33: 5: 16: 46 (weight ratio) to give Blend I. Blend I has an intrinsic viscosity of 0.63
Met. Polyester C: Polyester D: Polyester E: Polyester F: Polyester G: Polyester H = 33: 5: 16: 10: 10: 26 (weight ratio) to obtain Blend II. The intrinsic viscosity of Blend II was 0.60. 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 to the sub extruder and the blend II was fed to 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 sent to a longitudinal stretching roll, and the film temperature was set to 83 ° C.
After stretching 2.5 times with (with IR heater), further 8
Stretching 1.23 times at 7 ° C (with IR heater), and after setting the birefringence after longitudinal stretching to 0.70, hold with a clip and guide it to a tenter, and stretch at transversely 3.0 times at 125 ° C. A biaxially oriented film was obtained. Then, the biaxially oriented film is introduced into a heat setting zone, and the width direction is 2% at 232 ° C. for 10 seconds.
Heat setting while relaxing, 15μm / 158μm / 15μ
Intrinsic viscosity of 0.6 at 188 μm with 2 layers and 3 layers of m thickness
A film having a thickness deviation of 0 and a thickness deviation in the film width direction of within ± 2 was obtained. The characteristics and evaluation results of the obtained film are shown in Table 3 below.

Comparative Example 2 Polyester C as Blend 1 in Comparative Example 1:
Polyester D: Polyester E: Polyester B = 5
Blended so as to be 0: 2.0: 16.7: 31.3 (weight ratio), and as blend 2, polyester C: polyester A: polyester B = 12.2: 56.5: 3
A laminated film of 188μ was obtained in the same manner as in Comparative Example 1 except that the blending was performed so as to be 1.3 (weight ratio), which was designated as Comparative Example 2. Comparative Example 3 Polyester C as Blend 1 in Comparative Example 1:
Polyester D: Polyester E: Polyester B = 1
Blended to be 7: 5: 16: 62 (weight ratio),
Polyester C, Polyester D, Polyester E, Polyester F, Polyester G, Polyester H as Blend 2, the amount of titanium oxide in the polymer of Blend 2,
Blending was performed so that the amount of the fluorescent whitening agent and the amount of the siloid particles were the same as in the blend 1, and the other steps were the same as in Comparative Example 1 to obtain a laminated film of 188μ.

Examples 1, 2 and Comparative Example 4 A coating solution having the coating composition shown in Table 1 below was prepared as Comparative Examples 1, 2, and
3 was applied to the polyester film after longitudinal stretching and before transverse stretching, and thereafter, biaxially stretched films were obtained in the same manner as in Comparative Examples 1, 2, and 3 to be Example 1, Comparative Example 4, and Example 2, respectively. . 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.

[0033]

[Table 1]

[0034]

[Table 2]

Comparative Example 5 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 6 In Example 1, 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.

Magnetic films were prepared by coating a magnetic layer on one side and a printing layer on one side of the films of Comparative Examples 1 to 6 and Examples 1 and 2, and Examples 1 and 2 are all points as magnetic cards. In addition to satisfying the requirement, it is excellent in forgery prevention property because it is multi-layered in the thickness direction. In particular, recycled polymer, including used cards, is reused, making it an eco-friendly and inexpensive product. On the other hand, Comparative Examples 1, 2, 3
Was inadequate because of poor adhesion of the magnetic layer and the printing layer. Further, the film of Comparative Example 4 is inferior in durability and is not preferable, and the film of Comparative Example 5 has low whiteness,
The print quality was poor and the product had no commercial value. The film of Comparative Example 6 had a yellowish color tone, had poor print finish, and had no commercial value.

[0037]

[Table 3]

[0038]

Industrial Applicability According to the polyester film of the present invention, a pachinko card of high quality and environment-friendly is provided, and the industrial value of the present invention is high.

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Claims (1)

[Claims] 1. A layer containing a white pigment, wherein the outermost layer is a polyester layer (A layer) having ab value of 5.0 or less, and a layer (B layer) containing 1% by weight or more of a regenerated polymer. A coextrusion laminated biaxially oriented polyester film having at least one layer, which has a coating layer on the surface of its A layer and / or B layer, and simultaneously satisfies the following expressions and: [Number 1] OD of the laminated _{film> 0.8 ...... 0 ≦ | C A} -C B | <15 ...... ( In the formula, C _A white pigment content of the A layer (wt%),
C _B represents the white pigment content (% by weight) in layer _B )