JPH06930A - Laminated biaxially oriented polyester film for magnetic recording medium - Google Patents

Abstract

PURPOSE:To inexpensively provide the above polyester film excellent in surface roughness, slip properties and shaving resistance in a form useful for the conservation of resources. CONSTITUTION:In a laminated biaxially oriented polyester film consisting of three layers, a core layer contains fine inert particles A with a mean particle size of 1.0mum or less and each of surface layers contains fine inert particles B having a mean particle size equal to or larger than that of the fine inert particles A in an amount more than the finer inert particles A and the thickness of each of the surface layers is equal to or more than the mean particle size of the fine inert particles A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated biaxially oriented polyester film for magnetic recording media, and more particularly to a laminated biaxially oriented polyester film composed of three layers, which comprises fine inert particles added to the film. Laminated biaxial orientation for magnetic recording media, which is useful for low cost and resource saving while maintaining surface properties such as surface roughness, slipperiness, abrasion resistance and scratch resistance imparted by fine projections on the formed film surface. Regarding polyester film.

[0002]

2. Description of the Related Art Biaxially oriented polyester film represented by polyethylene terephthalate film is widely used as a base film for magnetic recording media such as magnetic tape and floppy disk because of its excellent physical and chemical properties. .

In such a biaxially oriented polyester film, its slipperiness and abrasion resistance are major factors that affect the workability of the film manufacturing process and the processing process in various applications, and further the quality of the product. ing. If these are insufficient, for example, when a magnetic layer is applied to the polyester film surface and is used as a magnetic tape, the friction between the coating roll and the film surface during the application of the magnetic layer is severe, and the abrasion of the film surface due to this is also severe, In extreme cases, wrinkles, scratches, etc. on the film surface occur. Also, even after slitting the film after coating the magnetic layer and processing it into audio, video or computer tape, etc., when it is pulled out from the reel, cassette, etc. Abrasion occurs remarkably between the two, and scratches and distortions are generated, and white powder is generated due to abrasion of the surface of the polyester film, and as a result, loss of a magnetic recording signal, that is, dropout is often a major cause.

Generally, in order to improve the slipperiness of a polyester film, (i) a method of precipitating inactive fine particles from a catalyst residue in a production process in a raw material polymer, and (ii) a method of adding inactive fine particles For example, a method has been adopted in which unevenness is imparted to the film surface by such means as to reduce the contact area with the guide roll. Generally, the larger the size of the fine particles in these films, the greater the improvement in the slipperiness.

On the other hand, in the base film for a magnetic recording medium, the surface of the base film is required to be as flat as possible from the viewpoint of improving electromagnetic conversion characteristics.

To meet the contradictory requirements of improving the slipperiness and improving the electromagnetic conversion characteristics, for example, coarse projections on the film caused by coarse particles present in the fine particles to be added may cause abrasion powder, Focusing on the fact that it sticks to the magnetic surface after coating the magnetic layer and is a factor that deteriorates the electromagnetic conversion characteristics, various improvements such as strengthening classification of fine particles and using originally synthetic particles having a sharp particle size distribution have been proposed. There is.

However, although such a method imparts excellent properties to the film, it also causes a significant increase in cost. That is, when the classification of the fine particles is strengthened, the cut portion becomes unusable and the total cost is increased. In the case of synthetic particles having a sharp particle size distribution, the particle size is generally uniform because the starting materials for the synthesis are high in purity, and the particles are often extremely expensive.

As a countermeasure against this, a method has been proposed in which additive particles for forming protrusions on the surface of the film are unevenly distributed only on the surface of the film, that is, a laminated film. This method forms a thin layer containing particles on the outside of a core layer containing no particles, thereby achieving the same film surface formation as a single layer, while reducing the amount of added particles as a whole film. This is possible, and in this respect, it leads to a reduction in the film manufacturing cost. However, in general, in the method for producing a biaxially oriented polyester film, a molten polyester extruded in a sheet form is cooled and solidified to obtain an unstretched film, which is then subjected to simultaneous biaxial stretching or sequential biaxial stretching to obtain a desired machine. Has acquired the characteristic. At this time, in order to stretch the film in the lateral direction, it is common to grasp the edge portion of the film with a chuck and move it on a rail installed so that the width gradually increases at a predetermined temperature. In order to prevent breakage at the chuck portion, it is customary to make the thickness of the edge portion thicker than the thickness of the central portion. This edge part cannot be a final product and is discarded, which is a problem from the viewpoint of resource saving.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention satisfy the above-mentioned problems, that is, the contradictory requirements of improving the slipperiness of the film surface and improving the electromagnetic conversion characteristics, and at the same time, to save resources and save resources. As a result of conducting research on how to do so, even if particles are contained in the core layer, the particle size of the particles, the thickness of the surface layer, the particle size of the particles contained in the surface layer, and the addition amount are appropriate. Within the range, a laminated biaxial that can be manufactured at low cost, has excellent slip properties and abrasion resistance in a form that helps save resources, has excellent electromagnetic conversion characteristics when used for magnetic recording media, and has few dropouts. The inventors have found that an oriented polyester film can be obtained and have reached the present invention.

[0010]

That is, the present invention has three features.
A laminated biaxially oriented polyester film consisting of layers, wherein the core layer contains inert fine particles A having an average particle diameter of 1.0 μm or less, and the surface layer has an average particle diameter not less than the average particle diameter of the inert fine particles A. The inert fine particles B are contained in an amount larger than that of the inert fine particles A, and the surface layer has a thickness of the inert fine particles A.
It is a laminated biaxially oriented polyester film for a magnetic recording medium, characterized in that

The polyester in the present invention is a polyester having an aromatic dicarboxylic acid as a main acid component and an aliphatic glycol as a main glycol component. Such polyesters are substantially linear and have film forming properties, especially film formation by melt molding. Examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, diphenoxyethane dicarboxylic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid and anthracene dicarboxylic acid. You can Examples of the aliphatic glycol include polymethylene glycol having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and decamethylene glycol, and alicyclic compounds such as cyclohexanedimethanol. Examples thereof include diols.

In the present invention, as the polyester, those having alkylene terephthalate and / or alkylene naphthalate as a main constituent are preferably used.

Among such polyesters, especially polyethylene terephthalate, polyethylene-2,6-naphthalate, etc., for example, 8 of all dicarboxylic acid components are used.
A copolymer in which 0 mol% or more is terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and 80 mol% or more of all glycol components is ethylene glycol is preferable. 20 mol% or less of the total acid component may be the above-mentioned aromatic dicarboxylic acids other than terephthalic acid and / or 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid. An alicyclic dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid can be used. And, 20 mol% or less of the total glycol component can be the above-mentioned glycol other than ethylene glycol, and aromatic diol such as hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl) propane, etc .; 1 An aliphatic diol having an aromatic ring such as 1,4-dihydroxydimethylbenzene; a polyalkylene glycol (polyoxyalkylene glycol) such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can also be used.

The polyester of the present invention includes
Aromatic oxyacids such as hydroxybenzoic acid, ω-
Those in which a component derived from an oxycarboxylic acid such as an aliphatic oxyacid such as hydroxycaproic acid is copolymerized or bonded with 20 mol% or less based on the total amount of the dicarboxylic acid component and the oxycarboxylic acid component are also included.

Further, in the polyester of the present invention,
Amounts in a range that is substantially linear, eg, 2 based on total acid component
Also included are those obtained by copolymerizing a polycarboxylic acid or polyhydroxy compound having a functionality of 3 or more, such as trimellitic acid and pentaerythritol, in an amount of not more than mol%.

The above-mentioned polyester is known per se, and can be produced by a method known per se.
The polyester has an intrinsic viscosity of about 0.4 when measured at 35 ° C. as a solution in o-chlorophenol.
Of about 0.9 are preferred.

The polyester constituting each layer in the laminated biaxially oriented polyester film of the present invention comprises the above polyester, but the polymer in each layer may be the same or different. Among them, it is preferable that they are the same.

The laminated biaxially oriented polyester film of the present invention comprises three layers, and each layer, that is, the core layer and both surface layers, contains inert fine particles. Examples of the inert fine particles include (1) silicon dioxide (including hydrates, silica sand, quartz, etc.); (2) alumina in various crystal forms; (3) SiO ₂
Silicates containing 30% by weight or more of components (for example, amorphous or crystalline clay minerals, aluminosilicates (including calcined products and hydrates), warm asbestos, fly ash, etc.);
(4) Mg, Zn, Zr, and Ti oxides; (5) C
a and Ba sulfate; (6) Li, Ba, and Ca phosphate (including monohydrogen salt and dihydrogen salt): (7) Li,
Benzoates of Na and K; (8) Ca, Ba, Zn,
And Mn terephthalate; (9) Mg, Ca, Ba,
Zn, Cd, Pb, Sr, Mn, Fe, Co, and Ni
Titanate; (10) Ba and Pb chromate;
(11) Carbon (for example, carbon black, graphite, etc.); (12) Glass (for example, glass powder, glass beads, etc.); (13) Carbonate of Ca and Mg; (14) Fluorite; (15) ZnS; ( 16) Heat resistant polymer particles (for example, silicone resin particles, crosslinked acrylic particles, crosslinked polystyrene particles, crosslinked styrene-acrylic particles, crosslinked polyester particles, Teflon particles, polyimide particles, polyimide-amide particles, melamine resin particles, etc.) are preferable. Can be mentioned.

The inert fine particles A contained in the core layer in the present invention are fine particles having an average particle diameter of 1.0 μm or less. If the average particle size exceeds 1.0 μm, protrusion of the fine particles to the film surface appears largely through the surface layer, which makes it difficult to obtain homogeneity of the film surface, which is not preferable.

In the present invention, the surface layer contains a larger amount of the inert fine particles B having an average particle size larger than the average particle size of the inert fine particles A contained in the core layer, more than the content of the inert fine particles A in the core layer. It is important that the thickness of the surface layer is equal to or larger than the average particle diameter of the inert fine particles A contained in the core layer.

The inactive fine particles B contained in the surface layer mainly comprise protrusions on the surface of the film, and have a great effect on the flatness of the film relating to the electromagnetic conversion characteristics when used as a magnetic recording medium, and on the slipperiness and scraping property of the film. Involved. If the average particle size of the inactive fine particles B contained in the surface layer is less than the average particle size of the inactive fine particles A contained in the core layer, the surface of the film formed by the fine particles of the surface layer depends on the thickness of the surface layer. The effect of protrusions due to the protrusion of fine particles in the core layer is remarkable, and the surface roughness of the obtained film is increased, so that the electromagnetic conversion characteristics of the magnetic tape are deteriorated, which is not preferable.

Since the content of the inert fine particles B in the surface layer is higher than the content of the inert fine particles A in the core layer, the characteristics of the projections formed on the film surface are determined by the inert fine particles B and the surface layer This will lead to a thinner thickness. The content of the inert fine particles B is 0.05 to
It is preferably 1.5% by weight. When this content does not satisfy the above range, the slipperiness becomes insufficient and the surface becomes too rough, which makes it unsuitable for magnetic recording media.

Further, if the thickness of the surface layer is smaller than the average particle size of the inert fine particles A contained in the core layer, the protrusion of projections on the film surface by the inert particles A significantly affects the surface property, which is not preferable. The thicker the surface layer is, the less the influence of the fine particles A contained in the core layer on the film surface is reduced. However, the purpose of the present invention is to provide a film having excellent properties in a form that is inexpensive and saves resources. Hard to achieve. The preferable range of the thickness of the surface layer is 1 to 5 times the average particle size of the fine particles contained in the core layer.

The laminated biaxially oriented polyester film of the present invention preferably has a thickness of 10 to 25 μm.

The laminated biaxially oriented polyester film of the present invention can be obtained by a conventionally known method or a method accumulated in the art. For example, it can be obtained by first producing a laminated unstretched film and then biaxially orienting the film. This laminated unstretched film can be manufactured by a conventionally accumulated manufacturing method of a laminated film. For example, a method of laminating a film layer forming a surface and a film layer forming a core layer in a melted state or a cooled and solidified state can be used. More specifically, for example, it can be produced by a method such as coextrusion or extrusion laminating.

The unstretched film laminated by the above-mentioned method can be made into a biaxially oriented film according to the conventional accumulated manufacturing method of a biaxially oriented film. For example, the laminated unstretched film is uniaxially (longitudinal or transverse) at a temperature of (Tg-10) to (Tg + 70) ° C. (however, Tg: glass transition temperature of polyester) of 2.5 to
The film is stretched at a draw ratio of 5.0 times, and then in a direction perpendicular to the above-described stretching direction (when the first stage stretching is the longitudinal direction, the second stage stretching is the transverse direction), Tg (° C)-(Tg + 70) ° C. It can be produced by stretching at a temperature of 2.5 to 5.0 times.
In this case, the area draw ratio is 9 to 22 times, and further 12 to 2
It is preferably doubled. The stretching means may be simultaneous biaxial stretching or sequential biaxial stretching. Further, the biaxially oriented film can be heat-set at a temperature of (Tg + 70) ° C. to Tm (° C.). For example, laminated polyethylene terephthalate film is preferably heat set at 190 to 230 ° C. The heat setting time is, for example, 1 to 60 seconds.

The laminated biaxially oriented polyester film of the present invention can be used as a polymer for the core layer in a simple device such as an edge portion of a biaxially stretched film which cannot be a final product until now if the above-mentioned conditions are satisfied. A laminated biaxially oriented polyester film that can be reused and consequently has excellent surface properties, that is, excellent slidability and abrasion resistance, and excellent electromagnetic conversion properties when used as a magnetic tape is supplied at low cost. It has the characteristic of being able to.

Various physical properties and characteristics in the present invention are measured and defined as follows.

(1) Average Particle Size (DP) Shimadzu CP-50 Model Centrifugal Particle Size Analyzer (Centrifugal Particle S)
ize Analyzer). The particle diameter corresponding to 50 mass% is read from the integrated curve of the particles of each particle diameter calculated based on the obtained centrifugal sedimentation curve and the abundance thereof, and this value is taken as the above average particle diameter (Book Technology ”, published by Nikkan Kogyo Shimbun, 1975, pp. 242-247).

(2) Running friction coefficient of film (μk) The friction coefficient is measured as follows using the apparatus shown in FIG.
In FIG. 1, 1 is an unwind reel, 2 is a tension controller, 3, 5, 6, 8, 9 and 11 are free rollers, 4
Is a tension detector (inlet), 7 is stainless steel SUS
304 fixed rod (outer diameter 5mmφ, surface roughness Ra = 0.02
μm), 10 is a tension detector (outlet), 12 is a guide roller, and 13 is a take-up reel.

In an environment of temperature 20 ° C. and humidity 60%, width 1 /
The film cut into 2 inches is attached to a fixed rod of 7 at an angle θ =
(152/180) π radians (152 °) are brought into contact with each other and moved (rubbed) at a speed of 200 cm per minute. The exit tension (T ₂ : g) when the tension controller 2 is adjusted so that the entrance tension T ₁ is 35 g is detected by the exit tension detector after the film has run 90 m, and the running friction coefficient μk is calculated by the following formula. calculate.

[0032]

[Number 1] μk = (2.303 / θ) log (T 2 / T 1) = 0.868log (T 2/35)

(3) Flatness of film surface Ra (center line average roughness) is measured according to JIS B 0601. Using a stylus type surface roughness meter (SURFCOM3B) manufactured by Tokyo Seimitsu Co., Ltd., the radius of the needle is 2 μm and the load is 0.0
Draw a chart (film surface roughness curve) under the condition of 7 g, extract a portion of the measurement length L from the obtained film surface roughness curve in the direction of its center line, and use the center line of this extracted portion as the X axis. When the roughness curve Y = f (x) is represented with the direction of longitudinal magnification as the Y axis, the value (Ra: μm) given by the following equation is defined as the flatness of the film surface.

[0034]

[Equation 2]

In the present invention, the reference length is 0.25 mm and 8
Ra is expressed as an average value of 5 measured values obtained by removing 3 pieces from the largest value.

(4) High Speed Scratchability and Scrapability A surface roughness Ra obtained by bending the fixing rod 7 into a cylindrical shape of a SUS sintered plate in the same device as that used in FIG. 1 used for measuring the running friction coefficient μk is 0.15 μm. In place of the tape guide, the winding angle is 30 degrees and the inlet tension is 5 at a speed of 300 m / min.
Run 200m so that it will be 0g. The shavings adhering to the tape guide after running and the scratches of the tape after running are evaluated.

<Judgment of shavings> ◎ No shavings are observed. ○ A slight amount of shavings can be seen. △ The presence of shavings can be seen at a glance. × Shavings are badly attached.

<Scratch Judgment> ◎ No scratch is observed. ○ 1 to 5 scratches are seen. Δ 6 to 15 scratches are seen. × 16 or more scratches can be seen.

[0039]

EXAMPLES The present invention will be further described below with reference to examples.

[0040]

Comparative Examples 1 and 2 Dimethyl terephthalate and ethylene glycol, manganese acetate as a transesterification catalyst, antimony trioxide as a polymerization catalyst, phosphorous acid as a stabilizer, and calcium carbonate having an average particle size of 0.60 μm as a lubricant. Fine particles (Comparative Example 1) or calcium carbonate fine particles having an average particle size of 1.2 μm as a lubricant (Comparative Example 2) were added and polymerized by an ordinary method to obtain an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62. Polyethylene terephthalate was obtained. The amount of calcium carbonate fine particles added was 0.30% by weight in Comparative Example 1, and 0.10 in Comparative Example 2.
It was adjusted so that it would be weight%.

1 of the obtained polyethylene terephthalate was used.
After drying at 70 ° C. for 3 hours, it was supplied to an extruder, extruded into a sheet from a die, and cooled to obtain an unstretched film.

The unstretched film thus obtained is preheated at 75 ° C., and further 15 mm between low speed and high speed rolls.
It was heated from above by one IR heater having a surface temperature of 900 ° C., stretched 3.6 times, rapidly cooled, and then supplied to a stenter and stretched laterally 3.9 times at 105 ° C. The obtained biaxially oriented film was heat set at a temperature of 205 ° C. for 5 seconds to obtain a heat set biaxially oriented film having a thickness of 15 μm at the central portion.

Next, the portions (both ends) having different thicknesses, which were gripped by the stenter clip, were cut with a leather blade, the central portion was wound up as a product film, and both ends were separately wound as unused portions. The weight of the unused portion was 32% based on the weight of the product film. The properties of the central product film are shown in Table 1.

[0044]

Example 1 Both ends, which were wound as unused parts in Comparative Example 1, were flaked using a grinder. The obtained flakes were melted by an extruder, extruded into a strand shape, and then cut into pellets to prepare recovered pellets A.

In making a three-layer laminated biaxially oriented polyester film, the polyester used for the surface layer was that used in Comparative Example 1, and the polyester for the core layer was polyethylene terephthalate containing no recovered pellets A and no inert fine particles. Using a mixture of 50% and 50%, the mixture was dried at 170 ° C. for 3 hours in the same manner as in Comparative Example 1, and then fed to separate extruders of a coextrusion film forming machine, and the thickness ratio of surface layer / core layer / surface layer was 1. It was extruded from a three-layer die so as to be 0/13 / 1.0 and cooled to obtain a laminated unstretched film. Then, the product film was obtained by stretching and winding in the same manner as in Comparative Example 1. The properties of the obtained central product film are also shown in Table 1.

[0046]

[Comparative Examples 3 and 4] Both end portions wound as unused portions in Comparative Example 2 were flaked using a grinder. The obtained flakes were melted by an extruder, extruded in a strand shape, and then cut into pellets to prepare recovered pellets B.

In making a laminated biaxially oriented polyester film of three layers, the polyester used for the surface layer was the one used in Comparative Example 1, and the polyester for the core layer was polyethylene terephthalate containing neither the recovered pellets B nor inert fine particles. Using a mixture obtained by mixing 50% and 50% with each other, the mixture was dried at 170 ° C. for 3 hours in the same manner as in Comparative Example 1, and then fed to separate extruders of a coextrusion film forming machine, and the thickness ratio of surface layer / core layer / surface layer was Comparative Example. No. 3 was extruded from a three-layer die so as to have a ratio of 2.0 / 11 / 2.0 and cooled to obtain a laminated unstretched film.
Then, the product film was obtained by stretching and winding in the same manner as in Comparative Example 1. The properties of the obtained central product film are also shown in Table 1.

[0048]

[Table 1]

As can be seen from Table 1, the film according to the present invention is used as a core layer component by passing a film, which has not been used before, at both ends in a biaxial stretching process which has not been used conventionally, through a simple process. However, it shows the same surface characteristics as the single layer film. Further, in the films of Comparative Examples 3 and 4 in which the particle diameter of the core layer does not satisfy the conditions of the present invention, the surface of the laminated biaxially oriented polyester film is roughened by the components of the core layer, and when used as a magnetic recording medium, electromagnetic conversion characteristics are obtained. Is becoming a concern, and at the same time, the abrasion resistance is deteriorated due to the presence of unnecessary protrusions.

[0050]

According to the present invention, it is possible to provide a laminated biaxially oriented polyester film which is excellent in surface properties, slipperiness and abrasion resistance, at a low cost and in a form useful for resource saving.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for measuring a coefficient of dynamic friction for evaluating film running property.

[Explanation of symbols]

 1 Feeding reel 2 Tension controller 3, 5, 6, 8, 9, 11 Free roller 4 Tension detector (entrance) 7 Fixing pin 10 Tension detector (outgoing side) 12 Guide roller 13 Take-up reel

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Claims (2)

[Claims] 1. A laminated biaxially oriented polyester film consisting of three layers, wherein the core layer contains inert fine particles A having an average particle diameter of 1.0 μm or less, and the surface layer has an average particle diameter not less than that of the inert fine particles A. For a magnetic recording medium, characterized in that the content of the inactive fine particles B having an average particle diameter of 1 is larger than the content of the inactive fine particles A, and the thickness of the surface layer is not less than the average particle diameter of the inactive fine particles A. Laminated biaxially oriented polyester film. 2. The content of the inert fine particles B is 0.05 to.
The laminated biaxially oriented polyester film for magnetic recording media according to claim 1, which is 1.5% by weight.