JP2541684B2 - Biaxially oriented polyester film for magnetic recording media - Google Patents

Description

TECHNICAL FIELD The present invention relates to a biaxially oriented polyester film for magnetic recording media, and more specifically, it contains specific colloidal silica particles and heat resistant polymer particles, and a film is formed by these particles. The present invention relates to a biaxially oriented polyester film for a magnetic recording medium, which has improved slipperiness, abrasion resistance and scratch resistance due to protrusions formed on the surface.

[Prior Art] Biaxially oriented polyester films typified by polyethylene terephthalate films are widely used for magnetic recording media because of their excellent physical and chemical properties.

In a biaxially oriented polyester film, its slipperiness and abrasion resistance are major factors that affect the workability of the film manufacturing process and processing process and the product quality. If these are insufficient, for example, when a magnetic layer is applied to the surface of a biaxially oriented polyester film and used as a magnetic tape, the friction between the coating roll and the film surface is severe and shavings are generated, or scratches are generated on the film surface. To do. Even when used for VTRs and data cartridges, shavings and scratches are generated in the process of winding the cassette at high speed, which causes signal loss (D / O).

Especially in VTR applications, metal guides or plastic guides whose surfaces have not been sufficiently finished may be used for the guide posts that have recently been fixed in the cassette for the purpose of cost reduction. In the case of a magnetic tape without a coat, a conventional technique for improving the slipperiness and the sharpness of a film, for example, a method of adding inorganic particles such as silicon oxide, titanium dioxide, calcium carbonate, talc, clay, and calcined kaolin (for example, (See Japanese Laid-Open Patent Publication No. 54-57562) or a method of precipitating fine particles containing calcium, lithium or phosphorus in the polymerization system (see, for example, Japanese Patent Publication No. 52-32914), in the step of winding the cassette at high speed, shavings and This improvement is required because scratches occur and the D / O level increases.

[Object of the Invention] The object of the present invention is to provide excellent slip resistance and excellent abrasion resistance and scratch resistance even at high-speed winding of a tape into a cassette using a metal guide or a plastic guide whose surface is not sufficiently finished. Another object of the present invention is to provide a biaxially oriented polyester film for a magnetic recording medium.

According to the present invention, a biaxially oriented polyester film having heat-resistant polymer particles having an average particle size of 0.03 to 1.5 μm is provided. 0.001-0.5
Weight%, independent existence rate is 80% or more, average particle size is 0.30μ
0.05 to 2.0% by weight of colloidal silica particles of m or less
The distribution curve of the projections formed on the film surface by these particles in the range where the height (x: μm) is 0.05 μm or more and the number of projections (y: pieces / mm ² ) is 30 pieces / mm ² or more. Is the following formula A-11.4x + 4 <log y <-10.0x + 5 ... A And the change in the running friction coefficient of the film (Δμ
It is achieved by a biaxially oriented polyester film for magnetic recording media, characterized in that k) is less than 0.15.

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 formability, especially film formability by melt molding. Examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, diphenoxyethane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, and anthracene dicarboxylic acid. Can be. Examples of the aliphatic glycol include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol,
Examples thereof include polymethylene glycol having 2 to 10 carbon atoms such as hexamethylene glycol and decamethylene glycol, and alicyclic diols such as cyclohexanedimethanol.

In the present invention, as the polyester, for example, one having alkylene terephthalate and / or alkylene naphthalate as a main constituent component is preferably used.

Among such polyesters, in particular, polyethylene terephthalate, polyethylene-2,6-naphthalate, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid account for 80 mol% or more of all dicarboxylic acid components, and 80 mol% or more for all glycol components. Copolymers in which is ethylene glycol are preferred. 20 mol% or less of the total acid component can be the above aromatic dicarboxylic acids other than terephthalic acid and / or 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid. ;
It can be an alicyclic dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid. Further, 20 mol% or less of the total glycol component may be the above-mentioned glycol other than ethylene glycol, and, for example, hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl)
Aromatic diols such as propane; Aliphatic diols having an aromatic ring such as 1,4-dihydroxydimethylbenzene;
Polyethylene glycol, polypropylene glycol,
It may also be a polyalkylene glycol (polyoxyalkylene glycol) such as polytetramethylene glycol.

In the polyester of the present invention, a component derived from an oxycarboxylic acid such as an aromatic oxyacid such as hydroxybenzoic acid, an aliphatic oxyacid such as ω-hydroxycaproic acid, a dicarboxylic acid component and an oxycarboxylic acid component. Those which are copolymerized or bonded at 20 mol% or less based on the total amount of

Further, in the polyester of the present invention, a tricarboxylic or polyfunctional polycarboxylic acid or polyhydroxy compound such as trimellitic acid, pentamer or the like is added in an amount in a substantially linear range, for example, an amount of 2 mol% or less based on all acid components. A copolymer of erythritol and the like is also included.

The above polyester is known per se and can be produced by a method known per se.

The above-mentioned polyester has an intrinsic viscosity of about 0.4-measured as a solution in o-chlorophenol at 35 ° C.
A value of about 0.9 is preferred.

The biaxially oriented polyester film of the present invention has a large number of fine protrusions on its surface. These fine projections are derived from a large number of substantially inactive heat-resistant polymer particles and colloidal silica particles contained in polyester in a dispersed state.

In the present invention, the projections formed on the film surface by these particles have a height (x: μm) of 0.05 μm or more and the number of projections (y: pieces / mm ² ) in the range of 30 pieces / mm ² or more. It is important that the distribution curve satisfies the following formula A.

-11.4x + 4 <log y <-10.0x + 5 ... A If the protrusion distribution curve does not satisfy the above formula A, the magnetic tape surface will become rough when used as a magnetic tape without a back coat, and even if a magnetic layer is provided, the surface of the magnetic layer becomes rough due to the presence of large protrusions, resulting in electromagnetic characteristics. Is insufficient, which is not preferable for magnetic recording media.

In the present invention, the heat-resistant polymer particles used for forming the surface protrusions have a 5% weight loss temperature of 31% under the protrusion gas atmosphere.
It is preferably 0 ° C or higher, more preferably 330 ° C or higher, and particularly preferably 350 ° C or higher. Examples of such particles include silicon resin particles, crosslinked acrylic resin particles, crosslinked polystyrene particles, crosslinked polyester particles, Teflon particles, and polyimide particles. Of these, silicone resin particles are preferable.

The heat-resistant polymer particles have an average particle size of 0.3 to 1.5 μm, and this amount is 0.001 to polyester.
0.5% by weight. A preferable average particle diameter is 0.5 to 1.0 μm, and a preferable content is 0.005 to 0.3% by weight. When the average particle diameter of the heat-resistant polymer particles is less than 0.3 μm, the height of the protrusions formed is insufficient, and the slipperiness of the obtained film is insufficient. On the other hand, if the average particle size exceeds 1.5 μm, the height of the protrusions formed becomes too large, and the film surface becomes too rough for use as a magnetic recording medium, which is not preferable. Further, the addition content of the heat resistant polymer particles is 0.00
If it is less than 1% by weight, the number of projections formed is insufficient and the slipperiness becomes insufficient. On the other hand, if the content of addition exceeds 0.5% by weight, the film surface becomes too rough and it is not suitable for magnetic recording media. .

It is preferable that the heat-resistant polymer particles are spherical-like in shape and have a sharp particle size distribution. Particularly, the volume shape factor (f) and the particle size distribution ratio (γ) satisfy the following formulas B and C. Is preferred.

0.4 <fπ / 6 ... B 1 <γ <1.4… C In the present invention, colloidal silica particles are used in combination with the heat-resistant polymer particles, and the colloidal silica particles form fine protrusions between the high protrusions formed by the heat-resistant polymer particles on the film surface. Due to the presence of these protrusions, the friction coefficient of the background of the film is reduced even when contacting with a metal guide or plastic guide whose surface is not sufficiently finished, and in combination with the high protrusions formed by heat-resistant polymer particles, excellent resistance is achieved. It is considered that it exhibits abrasion resistance and scratch resistance.

Colloidal silica particles have an independent existence rate in the film.
The average particle size is 80% or more and 0.30 μm or less.
This amount is 0.05 to 2.0% by weight with respect to the polyester.
If the average particle size of the colloidal silica particles exceeds 0.30 μm, the projections formed become too large, and the sharpness during high-speed contact with the friction body deteriorates, which is not desirable. If the content of colloidal silica particles added is less than 0.05% by weight, the number of protrusions formed on the background is insufficient and improvement in abrasion resistance and scratch resistance cannot be expected. The protrusions of colloidal silica particles overlap,
Scrap resistance deteriorates. Furthermore, it is also important that 80% or more of the colloidal silica particles are independent in the film, and if this is not satisfied, the abrasion resistance deteriorates.

Colloidal silica particles are powder weight ratio 100-3000ppm Na
It is preferable that it contains If the Na content is outside the above range, the effect of improving scratch resistance may be poor,
The independent existence rate of particles in the film is lowered, and the abrasion resistance is apt to be deteriorated. Regarding the method for producing the colloidal silica, there are a dialysis method using Na silicate as a starting material, an electrolysis method, a salt precipitation method and a method of producing an active silica sol by an ion exchange resin, and then polymerizing the same. Ion exchange resin-polymerization methods are most preferred.

When producing the biaxially oriented polyester film of the present invention, in order to intimately mix the heat resistant polymer particles and the colloidal silica particles with the polyester, these fine particles are used in a polymerization kettle before or during the polymerization of the polyester, The pellets may be sufficiently kneaded with the polyester in the extruder when pelletizing after the completion of the polymerization, or in the extruder when the sheet is melt-extruded.

Biaxially oriented polyester film of the present invention, for example,
Melting polyester at a temperature of melting point (Tm: ° C.) to (Tm + 70) ° C. to obtain an unstretched film having an intrinsic viscosity of 0.35 to 0.9 dl / g, the unstretched film being uniaxially (longitudinal or transverse) ( Tg-10) to (Tg + 70) ° C. (where Tg: glass transition temperature of polyester) is stretched at a draw ratio of 2.5 to 5.0, and then in the direction perpendicular to the stretching direction (when the first stage stretching is in the longitudinal direction). Is the Tg at the second stage stretching is in the transverse direction)
It can be produced by stretching at a temperature of (° C)-(Tg + 70) ° C at a draw ratio of 2.5 to 5.0 times. In this case, the area stretching ratio is 9 to
It is preferably 22 times, more preferably 12 to 22 times. The stretching means may be simultaneous biaxial stretching or sequential biaxial stretching.

In addition, the biaxially oriented film is (Tg + 70) ℃ ~ Tm (℃)
Can be heat-set at a temperature of For example, a polyethylene terephthalate film is preferably heat set at 190 to 230 ° C. The heat setting time is, for example, 1 to 60 seconds.

The biaxially oriented polyester film of the present invention has excellent slipperiness and also has excellent abrasion resistance and scratch resistance even when traveling with a metal guide or a plastic guide whose surface is not sufficiently finished, It is extremely useful for magnetic recording media.

Incidentally, various physical properties and characteristics in the present invention are measured and defined as follows.

(1) Average particle size (DP) Shimadzu CP-50 type Centrifugal particle size analyzer (Centrifugal Particle Siz
e Analyser). The particle size corresponding to 50 mass percent is read from the integrated curve of particles of each particle size and its abundance calculated based on the obtained centrifugal sedimentation curve, and this value is defined as the average particle size described above (Book “Particle Size Measurement Technology, published by Nikkan Kogyo Shimbun, 1975, pp. 242 to 247).

(2) Particle size distribution ratio (γ) Based on the centrifugal sedimentation curve obtained in the measurement of the average particle size of the particles, an integrated curve of the particles of each particle size and their abundance is calculated and drawn, The particle size corresponding to the cumulative particle weight of 25% (D ₂₅ ) and the particle size corresponding to the cumulative particle weight of 75% (D ₇₅ ) are read from the larger one, and the former value is used as the latter value. (D ₂₅ / D ₇₅ ) and calculate the particle size distribution ratio (γ) of each particle.

(3) Coefficient of running friction of film (μk) It 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 a stainless steel SUS304 fixed rod (outside). Diameter 5 mmφ, 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 the environment of temperature of 20 ℃ and humidity of 60%, the film cut into 1/2 inch width is brought into contact with the fixed rod of 7 at the angle θ = (152/181) π radial (152 °) and the speed of 200cm / min. Move (rub) with. When the tension controller 2 is adjusted so that the inlet tension T ₁ is 35g, the outlet tension (T ₂ : g) is detected by the outlet tension detector after the film has run 90m, and the running friction coefficient μk is calculated by the following formula. calculate.

.mu.k = a (2.303 / θ) log (T 2 / T 1) = 0.868log (T 2/35) (4) a device for measuring a running friction coefficient change in the running friction coefficient of the film (Derutamyuk) above (3) A film of 10 m length is repeatedly run 50 times with the moving speed of the film being 2 m / min. The first friction coefficient at that time is μk ₁ , 5
Δμk is calculated by the following formula, with the friction coefficient at the 0th time being μk ₅₀ .

Δμk = μk ₅₀ −μk ₁ (5) Flatness Ra (center line average roughness) of the film surface is measured according to JIS B 0601. Stylus type surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd. (SURFCOM3
Using B), make a chart (film surface roughness curve) under the condition of a needle radius of 2μ and a load of 0.07g, and measure the length L from the obtained film surface roughness curve toward the center line. When the roughness curve Y = f (x) is expressed with the center line of the extracted portion as the X axis and the vertical direction as the Y axis, the value (Ra: μm) given by Is defined as the flatness of.

In the present invention, eight pieces are measured with the reference length set to 0.25 mm, and Ra is expressed as an average value of five pieces obtained by removing three pieces from the larger value.

(6) Protrusion distribution on the film surface Using a three-dimensional roughness meter (SE-30K), Kosaka Laboratory, needle diameter 2
μmR, stylus pressure 30 mg, measurement length 1 mm, sampling pitch 2 μm, cutoff 0.25 mm, vertical magnification 20,000 times, horizontal magnification 200 times, number of scanning lines 150 Make the image original (three-dimensional).

When the profile is cut on a plane perpendicular to the thickness direction of the film, the plane where the total cross-sectional area of the profile of each protrusion is 70% of the area of the measurement area of the film is the reference level (0 level). , Y is the number of protrusions cut when cut on a plane parallel to the plane of the reference level and separated by a distance x in the height direction of the protrusions. x
Is sequentially increased or decreased, and the number of y at that time is read and plotted on a graph to draw a protrusion distribution curve.

(7) Volumetric shape factor (f) Photograph of particles with a scanning electron microscope, for example, at 5000 times
10 field of view photography, for example, Luzex 50 image analysis processor
Using 0 (manufactured by Nippon Regulator), the average value of the maximum diameters is measured for each field of view, and the average value of 10 fields of view is calculated and designated as D.

The average volume {V = (π / 6) d ³ } of the particles is obtained from the average particle diameter d of the particles obtained in the above measurement method (1), and the shape factor f is calculated by the following equation.

In the formula f = v / D ³ , v represents the average volume (μm ³ ) per particle, and D represents the average maximum particle size (μm) of the particles.

(8) Independent abundance of particles The biaxially oriented polyester film obtained by film formation was fixed on a sample stage for a scanning electron microscope, and a sputtering device manufactured by JEOL Ltd. (JFC-1100 type ion sputtering device) was used. Then, the film surface is subjected to ion etching treatment under the following conditions. Install the sample stage in the benger, raise the vacuum to about 10 ^-3 Torr and raise the voltage to 0.25k.
Ion etching is performed at V and current of 12.5 mA for about 10 minutes. Further, gold sputtering is applied to the film surface by the same apparatus to form a gold thin film layer of about 200 Å, and measurement is performed at a magnification of 20,000 times using a scanning electron microscope. The measurement is performed randomly in 100 fields of view, and the total number of confirmed particles a and the number of aggregated and exfoliated particles b (which causes voids over the entire width between adjacent particles due to stretching stress during film formation) are calculated by the following formula. Ask for.

(9) Scraping and scratching In the same device as that used in FIG. 1 used to measure the running friction coefficient of the film, instead of the stainless steel SUS304 fixed rod of 7, the SUS sintered plate was bent into a cylindrical shape and fixed at 6φ. Using a rod with a surface roughness Ra of 0.15 μm and a 6φ tape guide of carbon black-containing polyacetal manufactured by Dai-ichi Seiko Co., at an angle of 30 degrees and an inlet tension of 50 g / 1/2 inch at a speed of 300 m / min. And run for 200m.

The shavings adhering to the guide after running and the scratches of the tape after running are evaluated.

<Judgment of shavings> ◎ No shavings can be seen at all ○ Slightly shavings can be seen △ The existence of shavings can be seen at a glance × Shavings are badly attached <Scratch judgment> ◎ Scratches can be seen at all No ○ 1 to 5 scratches were found △ 6 to 15 scratches were found × 16 or more scratches were found (10) Na content in the colloidal silica powder Hydrogen fluoride was added to the colloidal silica powder Using an acid, dissolve completely and quantify Na by atomic absorption method to determine the Na content in the powder.

[Examples] Hereinafter, the present invention will be described with reference to Examples.

Examples 1 and 2 and Comparative Examples 1 to 4 Dimethyl terephthalate and ethylene glycol,
Manganese acetate was used as a transesterification catalyst, antimony trioxide was used as a polymerization catalyst, phosphorous acid was used as a stabilizer, and the additive particles shown in Table 1 were added as a lubricant. Polymerization was carried out by a conventional method to obtain an intrinsic viscosity (orthochlorophenol , 35 ℃) 0.6
2 polyethylene terephthalate was obtained.

This polyethylene terephthalate pellet is heated to 170 ° C.
After drying for 3 hours in the extruder hopper, melt temperature 280
It was melted at ˜300 ° C., and the molten polymer was extruded through a 1 mm slit die onto a rotary cooling drum having a surface finish of about 0.3 s and a surface temperature of 20 ° C. to obtain an unstretched film of 200 μm.

The unstretched film obtained in this way is preheated at 75 ° C, and further between low-speed and high-speed rolls at a temperature of 15mm above 900 ° C.
The sheet was heated by one IR heater having a surface temperature of, stretched 3.6 times, quenched, and then supplied to a stenter, and stretched 3.9 times horizontally at 105 ° C. 2 obtained biaxially oriented film
Heat setting was performed for 5 seconds at a temperature of 05 ° C. to obtain a heat setting biaxially oriented film having a thickness of 14.2 μm.

The properties of the 14.2 μm biaxially oriented polyester film thus obtained are shown in Table 1.

When the projection distribution curve of the obtained film was examined, those of Examples 1 and 2 and Comparative Examples 1, 2 and 4 satisfy the following formula (A), and those of Comparative Example 3 The number y of protrusions (number / mm ² ) did not satisfy the relation of log y <-10.0x + 5 for the entire range of the regulation.

-11.4x + 4 <log y <-10.0x + 5 ... A As is clear from Table 1, the one according to the present invention has an excellent surface property for a magnetic recording medium and is excellent in slipperiness and has a sufficiently finished surface. Even metal guides and plastic guides that have not been prepared have excellent abrasion resistance and scratch resistance, and have extremely excellent properties as a biaxially oriented polyester film for magnetic recording media.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for measuring the running friction coefficient of a film. The symbols in the figure are as follows. 1: Unwind reel, 2: Tension controller, 4: Tension detector (entrance), 7: Fixed rod, 10: Tension detector (exit), 13: Take-up reel.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G11B 5/704 G11B 5/704 // B29K 67:00 B29L 7:00 (72) Inventor Hideo Kato 3-37-19 Koyama, Sagamihara City, Kanagawa Prefecture, within the Sagamihara Research Center, Teijin Limited (56) References JP-A-2-251538 (JP, A) JP-A-2-31321 (JP, A)

Claims (3)

(57) [Claims] 1. A biaxially oriented polyester film, wherein 0.001 to 0.5% by weight of heat-resistant polymer particles having an average particle size of 0.3 to 1.5 μm, and an independent abundance ratio are contained.
Colloidal silica particles having an average particle size of 80% or more and 0.30 μm or less are present in an amount of 0.05 to 2.0% by weight, and the height (x: μm) of the protrusions formed on the film surface by these particles.
Is 0.05 μm or more and the number of protrusions (y: pieces / mm ² ) is 30 pieces / mm ² or more, the distribution curve satisfies the following expression A, and the change in the running friction coefficient (Δμk) of the film is less than 0.15. A biaxially oriented polyester film for a magnetic recording medium. -11.4x + 4 <log y <-10.0x + 5 ... A 2. The biaxially oriented magnetic recording medium according to claim 1, wherein the volumetric shape factor (f) and the particle size distribution ratio (γ) of the heat resistant polymer particles satisfy the following formulas B and C. Polyester film. 0.4 <fπ / 6 ... B 1 <γ <1.4… C 3. Colloidal silica particles having a powder weight ratio of 100 to 3
The biaxially oriented polyester film for a magnetic recording medium according to claim 1, which contains 000 ppm of Na.